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Sample records for natural geochemical analogues

  1. Microbial Diversity in Engineered Haloalkaline Environments Shaped by Shared Geochemical Drivers Observed in Natural Analogues

    PubMed Central

    Warren, Lesley A.; Kendra, Kathryn E.

    2015-01-01

    Microbial communities in engineered terrestrial haloalkaline environments have been poorly characterized relative to their natural counterparts and are geologically recent in formation, offering opportunities to explore microbial diversity and assembly in dynamic, geochemically comparable contexts. In this study, the microbial community structure and geochemical characteristics of three geographically dispersed bauxite residue environments along a remediation gradient were assessed and subsequently compared with other engineered and natural haloalkaline systems. In bauxite residues, bacterial communities were similar at the phylum level (dominated by Proteobacteria and Firmicutes) to those found in soda lakes, oil sands tailings, and nuclear wastes; however, they differed at lower taxonomic levels, with only 23% of operational taxonomic units (OTUs) shared with other haloalkaline environments. Although being less diverse than natural analogues, bauxite residue harbored substantial novel bacterial taxa, with 90% of OTUs nonmatchable to cultured representative sequences. Fungal communities were dominated by Ascomycota and Basidiomycota, consistent with previous studies of hypersaline environments, and also harbored substantial novel (73% of OTUs) taxa. In bauxite residues, community structure was clearly linked to geochemical and physical environmental parameters, with 84% of variation in bacterial and 73% of variation in fungal community structures explained by environmental parameters. The major driver of bacterial community structure (salinity) was consistent across natural and engineered environments; however, drivers differed for fungal community structure between natural (pH) and engineered (total alkalinity) environments. This study demonstrates that both engineered and natural terrestrial haloalkaline environments host substantial repositories of microbial diversity, which are strongly shaped by geochemical drivers. PMID:25979895

  2. Natural geochemical analogues of the near field of high-level nuclear waste repositories

    SciTech Connect

    Apps, J.A.

    1995-09-01

    United States practice has been to design high-level nuclear waste (HLW) geological repositories with waste densities sufficiently high that repository temperatures surrounding the waste will exceed 100{degrees}C and could reach 250{degrees}C. Basalt and devitrified vitroclastic tuff are among the host rocks considered for waste emplacement. Near-field repository thermal behavior and chemical alteration in such rocks is expected to be similar to that observed in many geothermal systems. Therefore, the predictive modeling required for performance assessment studies of the near field could be validated and calibrated using geothermal systems as natural analogues. Examples are given which demonstrate the need for refinement of the thermodynamic databases used in geochemical modeling of near-field natural analogues and the extent to which present models can predict conditions in geothermal fields.

  3. Distribution and geochemical characterization of coalbed gases at excavation fields at natural analogue site area Velenje Basin, Slovenia

    NASA Astrophysics Data System (ADS)

    Kanduč, Tjaša; Žigon, Stojan; Grassa, Fausto; Sedlar, Jerneja; Zadnik, Ivo; Zavšek, Simon

    2016-04-01

    Unconventional gas resources, including coal bed methane and shale gas, are a growing part of the global energy mix, which has changed the economic and strategic picture for gas consuming and producing countries, including the USA, China and Australia that, together are responsible for around half the currently recoverable unconventional gas resources. However, CBM production was often hindered by low permeability and mineralization in cleats and fractures, necessitating the development of cost effective horizontal drilling and completion techniques. Geochemical and isotopic monitoring of coalbed gases at excavation fields in Velenje Basin started in year 2000, with the aim to obtain better insights into the origin of coalbed gases. Results from active excavation fields in the mining areas Pesje and Preloge in the year period 2014-2015 are presented in this study. Composition and isotopic composition of coalbed gases were determined with mass - spectrometric methods. The chemical (methane, carbon dioxide, nitrogen) and isotopic composition of carbon in methane and carbon dioxide in the Velenje Basin vary and depend on the composition of the source of coalbed gas before excavation, advancement of the working face, depth of the longwall face, pre-mining activity and newly mined activity. The basic gas components determined in excavation fields are carbon dioxide and methane. Knowledge of the stable isotope geochemistry of coal bed and shale gas and the related production water is essential to determine not only gas origins but also the dominant methanogenic pathway in the case of microbial gas. Concentrations of methane at active excavation fields are changing from 1.8 to 63.9 %, concentrations of carbon dioxide are changing from 36.1 to 98.2% and CDMI (Carbon Dioxide Methane Index) index from 0.2 to 100 %. Isotopic composition of carbon dioxide is changing from -11.0 to -1.9‰ , isotopic composition of methane from -71.8 to -43.3‰ , isotopic composition of

  4. The Valles natural analogue project

    SciTech Connect

    Stockman, H.; Krumhansl, J.; Ho, C.; McConnell, V.

    1994-12-01

    The contact between an obsidian flow and a steep-walled tuff canyon was examined as an analogue for a highlevel waste repository. The analogue site is located in the Valles Caldera in New Mexico, where a massive obsidian flow filled a paleocanyon in the Battleship Rock tuff. The obsidian flow provided a heat source, analogous to waste panels or an igneous intrusion in a repository, and caused evaporation and migration of water. The tuff and obsidian samples were analyzed for major and trace elements and mineralogy by INAA, XRF, X-ray diffraction; and scanning electron microscopy and electron microprobe. Samples were also analyzed for D/H and {sup 39}Ar/{sup 4O} isotopic composition. Overall,the effects of the heating event seem to have been slight and limited to the tuff nearest the contact. There is some evidence of devitrification and migration of volatiles in the tuff within 10 meters of the contact, but variations in major and trace element chemistry are small and difficult to distinguish from the natural (pre-heating) variability of the rocks.

  5. Macrolactam analogues of macrolide natural products.

    PubMed

    Hügel, Helmut M; Smith, Andrew T; Rizzacasa, Mark A

    2016-12-07

    The chemical modification of macrolide natural products into aza- or lactam analogues is a strategy employed to improve their metabolic stability and biological activity. The methods for the synthesis of several lactam analogues of macrolide natural products are highlighted and aspects of their biological properties presented.

  6. Natural analogues of nuclear waste glass corrosion.

    SciTech Connect

    Abrajano, T.A. Jr.; Ebert, W.L.; Luo, J.S.

    1999-01-06

    This report reviews and summarizes studies performed to characterize the products and processes involved in the corrosion of natural glasses. Studies are also reviewed and evaluated on how well the corrosion of natural glasses in natural environments serves as an analogue for the corrosion of high-level radioactive waste glasses in an engineered geologic disposal system. A wide range of natural and experimental corrosion studies has been performed on three major groups of natural glasses: tektite, obsidian, and basalt. Studies of the corrosion of natural glass attempt to characterize both the nature of alteration products and the reaction kinetics. Information available on natural glass was then compared to corresponding information on the corrosion of nuclear waste glasses, specifically to resolve two key questions: (1) whether one or more natural glasses behave similarly to nuclear waste glasses in laboratory tests, and (2) how these similarities can be used to support projections of the long-term corrosion of nuclear waste glasses. The corrosion behavior of basaltic glasses was most similar to that of nuclear waste glasses, but the corrosion of tektite and obsidian glasses involves certain processes that also occur during the corrosion of nuclear waste glasses. The reactions and processes that control basalt glass dissolution are similar to those that are important in nuclear waste glass dissolution. The key reaction of the overall corrosion mechanism is network hydrolysis, which eventually breaks down the glass network structure that remains after the initial ion-exchange and diffusion processes. This review also highlights some unresolved issues related to the application of an analogue approach to predicting long-term behavior of nuclear waste glass corrosion, such as discrepancies between experimental and field-based estimates of kinetic parameters for basaltic glasses.

  7. Long-term predictions using natural analogues

    SciTech Connect

    Ewing, R.C.

    1995-09-01

    One of the unique and scientifically most challenging aspects of nuclear waste isolation is the extrapolation of short-term laboratory data (hours to years) to the long time periods (10{sup 3}-10{sup 5} years) required by regulatory agencies for performance assessment. The direct validation of these extrapolations is not possible, but methods must be developed to demonstrate compliance with government regulations and to satisfy the lay public that there is a demonstrable and reasonable basis for accepting the long-term extrapolations. Natural systems (e.g., {open_quotes}natural analogues{close_quotes}) provide perhaps the only means of partial {open_quotes}validation,{close_quotes} as well as data that may be used directly in the models that are used in the extrapolation. Natural systems provide data on very large spatial (nm to km) and temporal (10{sup 3}-10{sup 8} years) scales and in highly complex terranes in which unknown synergisms may affect radionuclide migration. This paper reviews the application (and most importantly, the limitations) of data from natural analogue systems to the {open_quotes}validation{close_quotes} of performance assessments.

  8. Naturalness in an emergent analogue spacetime.

    PubMed

    Liberati, Stefano; Visser, Matt; Weinfurtner, Silke

    2006-04-21

    Effective field theories (EFTs) have been widely used as a framework in order to place constraints on the Planck suppressed Lorentz violations predicted by various models of quantum gravity. There are, however, technical problems in the EFT framework when it comes to ensuring that small Lorentz violations remain small--this is the essence of the "naturalness" problem. Herein we present an "emergent" spacetime model, based on the "analogue gravity" program, by investigating a specific condensed-matter system. Specifically, we consider the class of two-component BECs subject to laser-induced transitions between the components, and we show that this model is an example for Lorentz invariance violation due to ultraviolet physics. Furthermore, our model explicitly avoids the naturalness problem, and makes specific suggestions regarding how to construct a physically reasonable quantum gravity phenomenology.

  9. Natural analogue studies of the role of colloids, natural organics and microorganisms on radionuclide transport

    SciTech Connect

    McCarthy, J.F.

    1994-10-01

    Colloids may be important as a geochemical transport mechanism for radionuclides at geological repositories if they are (1) present in the groundwater, (2) stable with respect to both colloidal and chemical stabilities, (3) capable of adsorbing radionuclides, especially if the sorption is irreversible, and (4) mobile in the subsurface. The available evidence from natural analogue and other field studies relevant to these issues is reviewed, as is the potential role of mobile microorganisms ({open_quotes}biocolloids{close_quotes}) on radionuclide migration. Studies have demonstrated that colloids are ubiquitous in groundwater, although colloid concentrations in deep, geochemically stable systems may be too low to affect radionuclide transport. However, even low colloid populations cannot be dismissed as a potential concern because colloids appear to be stable, and many radionuclides that adsorb to colloids are not readily desorbed over long periods. Field studies offer somewhat equivocal evidence concerning colloid mobility and cannot prove or disprove the significance of colloid transport in the far-field environment. Additional research is needed at new sites to properly represent a repository far-field. Performance assessment would benefit from natural analogue studies to examine colloid behavior at sites encompassing a suite of probable groundwater chemistries and that mimic the types of formations selected for radioactive waste repositories.

  10. U.S. Nuclear Regulatory Commission natural analogue research program

    SciTech Connect

    Kovach, L.A.; Ott, W.R.

    1995-09-01

    This article describes the natural analogue research program of the U.S. Nuclear Regulatory Commission (US NRC). It contains information on the regulatory context and organizational structure of the high-level radioactive waste research program plan. It also includes information on the conditions and processes constraining selection of natural analogues, describes initiatives of the US NRC, and describes the role of analogues in the licensing process.

  11. Variation of Geochemical Signatures and Correlation of Biomarkers in Icelandic Mars Analogue Environments

    NASA Astrophysics Data System (ADS)

    Gentry, D.; Amador, E. S.; Cable, M. L.; Cantrell, T.; Chaudry, N.; Cullen, T.; Duca, Z. A.; Jacobsen, M. B.; McCaig, H. C.; Murukesan, G.; Rennie, V.; Schwieterman, E. W.; Stevens, A. H.; Tan, G.; Yin, C.; Stockton, A.; Cullen, D.; Geppert, W.

    2015-12-01

    Exploration missions to Mars rely on rovers to perform deep analyses over small sampling areas; however, landing site selection is done using large-scale but low-resolution remote sensing data. Using Earth analogue environments to estimate the small-scale spatial and temporal distributions of key geochemical signatures and (for habitability studies) biomarkers helps ensure that the chosen sampling strategies meet mission science goals. We conducted two rounds of analogue expeditions to recent Icelandic lava fields. In July 2013, we tested correlation between three common biomarker assays: cell quantification via fluorescence microscopy, ATP quantification via bioluminescence, and quantitative PCR with universal primer sets. Sample sites were nested at four spatial scales (1 m, 10 m, 100 m, and > 1 km) and homogeneous at 'remote imaging' resolution (overall temperature, apparent moisture content, and regolith grain size). All spatial scales were highly diverse in ATP, bacterial 16S, and archaeal 16S DNA content; nearly half of sites were statistically different in ATP content at α = 0.05. Cell counts showed significant variation at the 10 m and 100 m scale; at the > 1 km scale, the mean counts were not distinguishable, but the median counts were, indicating differences in underlying distribution. Fungal 18S DNA content similarly varied at 1 m, 10 m, and 100 m scales only. Cell counts were not correlated with ATP or DNA content at any scale. ATP concentration and DNA content for all three primer sets were positively correlated. Bacterial DNA content was positively correlated with archaeal and fungal DNA content, though archaeal correlation was weak. Fungal and archaeal correlation was borderline. In July 2015, we repeated the sampling strategy, with the addition of a smaller-scale sampling grid of 10 cm and a third > 1 km location. This expedition also measured reflectance of the tephra cover and preserved mineral samples for future Raman spectroscopy in order to

  12. Río tinto: a geochemical and mineralogical terrestrial analogue of Mars.

    PubMed

    Amils, Ricardo; Fernández-Remolar, David; The Ipbsl Team

    2014-09-15

    The geomicrobiological characterization of the water column and sediments of Río Tinto (Huelva, Southwestern Spain) have proven the importance of the iron and the sulfur cycles, not only in generating the extreme conditions of the habitat (low pH, high concentration of toxic heavy metals), but also in maintaining the high level of microbial diversity detected in the basin. It has been proven that the extreme acidic conditions of Río Tinto basin are not the product of 5000 years of mining activity in the area, but the consequence of an active underground bioreactor that obtains its energy from the massive sulfidic minerals existing in the Iberian Pyrite Belt. Two drilling projects, MARTE (Mars Astrobiology Research and Technology Experiment) (2003-2006) and IPBSL (Iberian Pyrite Belt Subsurface Life Detection) (2011-2015), were developed and carried out to provide evidence of subsurface microbial activity and the potential resources that support these activities. The reduced substrates and the oxidants that drive the system appear to come from the rock matrix. These resources need only groundwater to launch diverse microbial metabolisms. The similarities between the vast sulfate and iron oxide deposits on Mars and the main sulfide bioleaching products found in the Tinto basin have given Río Tinto the status of a geochemical and mineralogical Mars terrestrial analogue.

  13. Río Tinto: A Geochemical and Mineralogical Terrestrial Analogue of Mars

    PubMed Central

    Amils, Ricardo; Fernández-Remolar, David

    2014-01-01

    The geomicrobiological characterization of the water column and sediments of Río Tinto (Huelva, Southwestern Spain) have proven the importance of the iron and the sulfur cycles, not only in generating the extreme conditions of the habitat (low pH, high concentration of toxic heavy metals), but also in maintaining the high level of microbial diversity detected in the basin. It has been proven that the extreme acidic conditions of Río Tinto basin are not the product of 5000 years of mining activity in the area, but the consequence of an active underground bioreactor that obtains its energy from the massive sulfidic minerals existing in the Iberian Pyrite Belt. Two drilling projects, MARTE (Mars Astrobiology Research and Technology Experiment) (2003–2006) and IPBSL (Iberian Pyrite Belt Subsurface Life Detection) (2011–2015), were developed and carried out to provide evidence of subsurface microbial activity and the potential resources that support these activities. The reduced substrates and the oxidants that drive the system appear to come from the rock matrix. These resources need only groundwater to launch diverse microbial metabolisms. The similarities between the vast sulfate and iron oxide deposits on Mars and the main sulfide bioleaching products found in the Tinto basin have given Río Tinto the status of a geochemical and mineralogical Mars terrestrial analogue. PMID:25370383

  14. Naturally occurring crystalline phases: analogues for radioactive waste forms

    SciTech Connect

    Haaker, R.F.; Ewing, R.C.

    1981-01-01

    Naturally occurring mineral analogues to crystalline phases that are constituents of crystalline radioactive waste forms provide a basis for comparison by which the long-term stability of these phases may be estimated. The crystal structures and the crystal chemistry of the following natural analogues are presented: baddeleyite, hematite, nepheline; pollucite, scheelite;sodalite, spinel, apatite, monazite, uraninite, hollandite-priderite, perovskite, and zirconolite. For each phase in geochemistry, occurrence, alteration and radiation effects are described. A selected bibliography for each phase is included.

  15. Using a Natural Analogue to Investigate Chemical Reactions Associated with Carbon Dioxide Sequestration

    NASA Astrophysics Data System (ADS)

    Navarre-Sitchler, A.; Kaszuba, J.; Thyne, G.

    2008-12-01

    Capture and storage of carbon dioxide in deep underground geologic formations (geologic carbon sequestration) is currently the most advanced technology for reducing or mitigating anthropogenic carbon dioxide emissions. There are a number of scientific challenges associated with injection and storage of large amounts of CO2 in geologic formations. Understanding the chemical reactions that can occur among reservoir rocks, aqueous fluids, and supercritical carbon dioxide ± other gasses is one of these challenges. Natural analogues to CO2 sequestration are systems where carbon dioxide has been stored over geologic time scales. By studying these analogues we can determine important chemical reactions between the host rock and stored gases. The Moxa Arch is a structural feature located in the southern end of the greater Green River Basin, Wyoming. Carbon dioxide and methane were emplaced in Paleozoic rocks, including the 1000 feet thick Mississippian age Madison Limestone, of the Moxa Arch through natural processes. Concentrations of carbon dioxide in the emplaced gas in these formations vary in the region of the Moxa Arch from 70-95% and are as low as ~ 15% in gas producing areas outside of the Moxa Arch. Methane, hydrogen sulfide and helium comprise the balance of the gas compositons. Geochemical reaction path and reactive transport models based upon the mineralogy of 12 core samples collected from three wells completed in the Madison Limestone near the Moxa Arch will be presented. These models help identify potential geochemical reactions between reservoir minerals and stored gasses.

  16. Facile Synthesis of Natural Alkoxynaphthalene Analogues from Plant Alkoxybenzenes.

    PubMed

    Tsyganov, Dmitry V; Krayushkin, Mikhail M; Konyushkin, Leonid D; Strelenko, Yuri A; Semenova, Marina N; Semenov, Victor V

    2016-04-22

    Analogues of the bioactive natural alkoxynaphthalene pycnanthulignene D were synthesized by an efficient method. The starting plant allylalkoxybenzenes (1) are easily available from the plant essential oils of sassafras, dill, and parsley. The target 1-arylalkoxynaphthalenes (5) exhibited antiproliferative activity in a phenotypic sea urchin embryo assay.

  17. Magnesite formation in playas: A natural analogue for carbon sequestration

    NASA Astrophysics Data System (ADS)

    Power, Ian; Harrison, Anna; Wilson, Siobhan; Dipple, Gregory; Fallon, Stewart

    2015-04-01

    Non-marine carbonate deposits are of renewed interest as natural analogues for carbon sequestration and storage. Specifically, the sequestration of anthropogenic carbon dioxide (CO2)in Mg-carbonate minerals is being actively investigated as a strategy for reducing greenhouse gas emissions1. In northern British Columbia, hydromagnesite-magnesite playas (hectare-scale) have formed since the last deglaciation, suggesting that these minerals possess a level of stability required for long-term carbon storage2. Quantitative mineralogical and hydrogeochemical data, as well as microscopy and field observations, were used to formulate a comprehensive facies model that describes the depositional environments for the formation of these playas. Over several millennia, there have been transitions from deposition of siliciclastic to subaqueous Ca-Mg-carbonate to subaerial Mg-carbonate sediments3,4. Consequently, a complex assemblage of carbonate minerals is present within the playas including magnesite [MgCO3], the most stable Mg-carbonate for storing CO2. Magnesite precipitation at near-surface temperatures is kinetically inhibited due to the strong hydration of Mg2+ ions in solution5. Thus, understanding the rates of, and controls on, magnesite formation at low temperatures remains a challenge. Magnesite abundances at the surface (1 to 41 wt.%) and at depth (1 to 86 wt.%) within the playas are highly variable4. There is a propensity for hydrated Mg-carbonate minerals to undergo transformation to less hydrated, more stable forms (lansfordite > nesquehonite > dypingite > hydromagnesite)5; however, stable, radiogenic, and clumped isotope6 data as well as electron microscopy demonstrate that magnesite formation is likely dominated by direct precipitation from aqueous solution in the shallow subsurface (~3-10 ° C). An observed variation in magnesite crystal morphology with depth is attributed to different crystal growth mechanisms induced by changes in magnesite saturation state

  18. THE PENA BLANCA NATURAL ANALOGUE PERFORMANCE ASSESSMENT MODEL

    SciTech Connect

    G. Saulnier and W. Statham

    2006-04-16

    The Nopal I uranium mine in the Sierra Pena Blanca, Chihuahua, Mexico serves as a natural analogue to the Yucca Mountain repository. The Pena Blanca Natural Analogue Performance Assessment Model simulates the mobilization and transport of radionuclides that are released from the mine and transported to the saturated zone. The Pena Blanca Natural Analogue Performance Assessment Model uses probabilistic simulations of hydrogeologic processes that are analogous to the processes that occur at the Yucca Mountain site. The Nopal I uranium deposit lies in fractured, welded, and altered rhyolitic ash-flow tuffs that overlie carbonate rocks, a setting analogous to the geologic formations at the Yucca Mountain site. The Nopal I mine site has the following analogous characteristics as compared to the Yucca Mountain repository site: (1) Analogous source--UO{sub 2} uranium ore deposit = spent nuclear fuel in the repository; (2) Analogous geology--(i.e. fractured, welded, and altered rhyolitic ash-flow tuffs); (3) Analogous climate--Semiarid to arid; (4) Analogous setting--Volcanic tuffs overlie carbonate rocks; and (5) Analogous geochemistry--Oxidizing conditions Analogous hydrogeology: The ore deposit lies in the unsaturated zone above the water table.

  19. THE PENA BLANCA NATURAL ANALOGUE PERFORMANCE ASSESSMENT MODEL

    SciTech Connect

    G.J. Saulnier Jr; W. Statham

    2006-03-10

    The Nopal I uranium mine in the Sierra Pena Blanca, Chihuahua, Mexico serves as a natural analogue to the Yucca Mountain repository. The Pena Blanca Natural Analogue Performance Assessment Model simulates the mobilization and transport of radionuclides that are released from the mine and transported to the saturated zone. the Pena Blanca Natural Analogue Model uses probabilistic simulations of hydrogeologic processes that are analogous to the processes that occur at the Yucca Mountain site. The Nopal I uranium deposit lies in fractured, welded, and altered rhyolitic ash flow tuffs that overlie carbonate rocks, a setting analogous to the geologic formations at the Yucca Mountain site. The Nopal I mine site has the following characteristics as compared to the Yucca Mountain repository site. (1) Analogous source: UO{sub 2} uranium ore deposit = spent nuclear fuel in the repository; (2) Analogous geologic setting: fractured, welded, and altered rhyolitic ash flow tuffs overlying carbonate rocks; (3) Analogous climate: Semiarid to arid; (4) Analogous geochemistry: Oxidizing conditions; and (5) Analogous hydrogeology: The ore deposit lies in the unsaturated zone above the water table. The Nopal I deposit is approximately 8 {+-} 0.5 million years old and has been exposed to oxidizing conditions during the last 3.2 to 3.4 million years. The Pena Blanca Natural Analogue Model considers that the uranium oxide and uranium silicates in the ore deposit were originally analogous to uranium-oxide spent nuclear fuel. The Pena Blanca site has been characterized using field and laboratory investigations of its fault and fracture distribution, mineralogy, fracture fillings, seepage into the mine adits, regional hydrology, and mineralization that shows the extent of radionuclide migration. Three boreholes were drilled at the Nopal I mine site in 2003 and these boreholes have provided samples for lithologic characterization, water-level measurements, and water samples for laboratory

  20. Interglacial analogues of the Holocene and its natural near future

    NASA Astrophysics Data System (ADS)

    Yin, Qiuzhen; Berger, André

    2015-07-01

    In an attempt to find potential interglacial analogues of our present interglacial and its natural future, five interglacials (MIS-1, 5, 9, 11 and 19) are studied in terms of their astronomical characteristics, greenhouse gases concentration and climate simulated using both snapshot and transient experiments. Transient simulations covering a full range of obliquity, precession and eccentricity allow to develop an OPE index to estimate the climate sensitivity to astronomical forcing. They also show that obliquity and precession have different weight on the annual mean temperature and precipitation of different latitudinal zones, leading to varying phasing of these climate variables between different latitudes. However, the variations in boreal summer temperature of different latitudes (except the Southern Ocean) are in phase and are dominated by precession. All the interglacials are shown to be warmer than the natural climate of the present day and of the next centuries during boreal summer and for the annual mean temperature with varying duration and intensity. Such warming is mainly caused by changes in insolation, unlike the present global warming which mainly results from anthropogenic CO2 increase. The exceptionally long duration of MIS-11 is confirmed by our simulations, and it is demonstrated to be related to the long-lasting low eccentricity and high CO2 concentration and to the anti-phase relationship between obliquity maximum and precession minimum during MIS-11. As far as the variations of annual and seasonal temperatures are concerned, both snapshot and transient simulations show that MIS-19 is the best analogue of the present interglacial. MIS-11 is also a decent analogue when the impact of insolation alone is considered, but it is warmer than MIS-1 when the impact of CO2 is additionally included. Due to the large amplitude in the variations of insolation, MIS-5 and MIS-9 can hardly be considered as an analogue of the natural present-day climate and of

  1. Natural analogue studies as supplements to biomineralization research

    SciTech Connect

    McNeil, M.B.

    1995-09-01

    Chemical reactions can alter the chemistry and crystal structure of solid objects over archeological or geological times, while preserving external physical shapes. The reactions resulting in these structures offer natural analogues to laboratory experiments in biomineralization and to biologically influenced alteration of nuclear waste packages, and thus, they offer the only available way of validating models that purport waste package behavior over archaeological or geological times. Potential uses of such analogues in the construction and validation of hypothetical mechanisms of microbiological corrosion and biomineralization are reviewed. Evidence from such analogues suggests that biofilms can control materials alteration in ways usually overlooked. The newly hypothesized mechanisms involve control by biofilms of the cation flow near the solid surface and offer plausible mechanisms for the formation of mixed-cation minerals under conditions that would lead to dealloying in abiotic experiments; they also account for the formation of unusual minerals [such as posnjakite, Cu{sub 4}SO{sub 4}(OH){sub 6{center_dot}}H{sub 2}O] and mineral morphologies unusual in corrosion [malachite, Cu{sub 2}CO{sub 3}(OH){sub 2}, rarely forms botryoidally under corrosion conditions and its occasional presence on archaeological objects that appear to have undergone microbiological corrosion may be related to biofilm phenomena].

  2. Pena blanca natural analogue project: summary of activities

    SciTech Connect

    Levy, Schon S; Goldstein, Steven J; Abdel - Fattah, Amr I

    2010-12-08

    The inactive Nopal I uranium mine in silicic tuff north of Chihuahua City, Chihuahua, Mexico, was studied as a natural analogue for an underground nuclear-waste repository in the unsaturated zone. Site stratigraphy was confirmed from new drill core. Datafrom site studies include chemical and isotopic compositions of saturated- and unsaturated-zone waters. A partial geochronology of uranium enrichment and mineralization was established. Evidence pertinent to uranium-series transport in the soil zone and changing redox conditions was collected. The investigations contributed to preliminary, scoping-level performance assessment modeling.

  3. Pena Blanca Natural Analogue Project: Summary of activities

    SciTech Connect

    Levy, S.; Goldstein, S.; Dobson, P.F.; Goodell, P.; Ku, T.-L.; Abdel-Fattah, A.; Saulnier, G.; Fayek, M.; de la Garza, R.

    2011-02-01

    The inactive Nopal I uranium mine in silicic tuff north of Chihuahua City, Chihuahua, Mexico, was studied as a natural analogue for an underground nuclear-waste repository in the unsaturated zone. Site stratigraphy was confirmed from new drill cores. Data from site studies include chemical and isotopic compositions of saturated- and unsaturated-zone waters. A partial geochronology of uranium enrichment and mineralization was established. Evidence pertinent to uranium-series transport in the soil zone and changing redox conditions was collected. The investigations contributed to preliminary, scoping-level performance assessment modeling.

  4. Natural Bacterial Communities Serve as Quantitative Geochemical Biosensors

    PubMed Central

    Smith, Mark B.; Rocha, Andrea M.; Smillie, Chris S.; Olesen, Scott W.; Paradis, Charles; Wu, Liyou; Campbell, James H.; Fortney, Julian L.; Mehlhorn, Tonia L.; Lowe, Kenneth A.; Earles, Jennifer E.; Phillips, Jana; Joyner, Dominique C.; Elias, Dwayne A.; Bailey, Kathryn L.; Hurt, Richard A.; Preheim, Sarah P.; Sanders, Matthew C.; Yang, Joy; Mueller, Marcella A.; Brooks, Scott; Watson, David B.; Zhang, Ping; He, Zhili; Dubinsky, Eric A.; Adams, Paul D.; Arkin, Adam P.; Fields, Matthew W.; Zhou, Jizhong; Alm, Eric J.

    2015-01-01

    ABSTRACT Biological sensors can be engineered to measure a wide range of environmental conditions. Here we show that statistical analysis of DNA from natural microbial communities can be used to accurately identify environmental contaminants, including uranium and nitrate at a nuclear waste site. In addition to contamination, sequence data from the 16S rRNA gene alone can quantitatively predict a rich catalogue of 26 geochemical features collected from 93 wells with highly differing geochemistry characteristics. We extend this approach to identify sites contaminated with hydrocarbons from the Deepwater Horizon oil spill, finding that altered bacterial communities encode a memory of prior contamination, even after the contaminants themselves have been fully degraded. We show that the bacterial strains that are most useful for detecting oil and uranium are known to interact with these substrates, indicating that this statistical approach uncovers ecologically meaningful interactions consistent with previous experimental observations. Future efforts should focus on evaluating the geographical generalizability of these associations. Taken as a whole, these results indicate that ubiquitous, natural bacterial communities can be used as in situ environmental sensors that respond to and capture perturbations caused by human impacts. These in situ biosensors rely on environmental selection rather than directed engineering, and so this approach could be rapidly deployed and scaled as sequencing technology continues to become faster, simpler, and less expensive. PMID:25968645

  5. Natural bacterial communities serve as quantitative geochemical biosensors

    DOE PAGES

    Smith, Mark B.; Rocha, Andrea M.; Smillie, Chris S.; ...

    2015-05-12

    Biological sensors can be engineered to measure a wide range of environmental conditions. Here we show that statistical analysis of DNA from natural microbial communities can be used to accurately identify environmental contaminants, including uranium and nitrate at a nuclear waste site. In addition to contamination, sequence data from the 16S rRNA gene alone can quantitatively predict a rich catalogue of 26 geochemical features collected from 93 wells with highly differing geochemistry characteristics. We extend this approach to identify sites contaminated with hydrocarbons from the Deepwater Horizon oil spill, finding that altered bacterial communities encode a memory of prior contamination,more » even after the contaminants themselves have been fully degraded. We show that the bacterial strains that are most useful for detecting oil and uranium are known to interact with these substrates, indicating that this statistical approach uncovers ecologically meaningful interactions consistent with previous experimental observations. Future efforts should focus on evaluating the geographical generalizability of these associations. Taken as a whole, these results indicate that ubiquitous, natural bacterial communities can be used as in situ environmental sensors that respond to and capture perturbations caused by human impacts. These in situ biosensors rely on environmental selection rather than directed engineering, and so this approach could be rapidly deployed and scaled as sequencing technology continues to become faster, simpler, and less expensive. Here we show that DNA from natural bacterial communities can be used as a quantitative biosensor to accurately distinguish unpolluted sites from those contaminated with uranium, nitrate, or oil. These results indicate that bacterial communities can be used as environmental sensors that respond to and capture perturbations caused by human impacts.« less

  6. Natural bacterial communities serve as quantitative geochemical biosensors

    SciTech Connect

    Smith, Mark B.; Rocha, Andrea M.; Smillie, Chris S.; Olesen, Scott W.; Paradis, Charles; Wu, Liyou; Campbell, James H.; Fortney, Julian L.; Mehlhorn, Tonia L.; Lowe, Kenneth A.; Earles, Jennifer E.; Phillips, Jana; Techtmann, Steve M.; Joyner, Dominique C.; Elias, Dwayne A.; Bailey, Kathryn L.; Hurt, Richard A.; Preheim, Sarah P.; Sanders, Matthew C.; Yang, Joy; Mueller, Marcella A.; Brooks, Scott; Watson, David B.; Zhang, Ping; He, Zhili; Dubinsky, Eric A.; Adams, Paul D.; Arkin, Adam P.; Fields, Matthew W.; Zhou, Jizhong; Alm, Eric J.; Hazen, Terry C.

    2015-05-12

    Biological sensors can be engineered to measure a wide range of environmental conditions. Here we show that statistical analysis of DNA from natural microbial communities can be used to accurately identify environmental contaminants, including uranium and nitrate at a nuclear waste site. In addition to contamination, sequence data from the 16S rRNA gene alone can quantitatively predict a rich catalogue of 26 geochemical features collected from 93 wells with highly differing geochemistry characteristics. We extend this approach to identify sites contaminated with hydrocarbons from the Deepwater Horizon oil spill, finding that altered bacterial communities encode a memory of prior contamination, even after the contaminants themselves have been fully degraded. We show that the bacterial strains that are most useful for detecting oil and uranium are known to interact with these substrates, indicating that this statistical approach uncovers ecologically meaningful interactions consistent with previous experimental observations. Future efforts should focus on evaluating the geographical generalizability of these associations. Taken as a whole, these results indicate that ubiquitous, natural bacterial communities can be used as in situ environmental sensors that respond to and capture perturbations caused by human impacts. These in situ biosensors rely on environmental selection rather than directed engineering, and so this approach could be rapidly deployed and scaled as sequencing technology continues to become faster, simpler, and less expensive. Here we show that DNA from natural bacterial communities can be used as a quantitative biosensor to accurately distinguish unpolluted sites from those contaminated with uranium, nitrate, or oil. These results indicate that bacterial communities can be used as environmental sensors that respond to and capture perturbations caused by human impacts.

  7. Monitoring of Geoengineering Effects and their Natural and Anthropogenic Analogues

    NASA Astrophysics Data System (ADS)

    Duren, R. M.; Robock, A.; Stephens, G. L.; MacMynowski, D. G.

    2011-12-01

    A number of climate intervention concepts, referred to as "geoengineering," are being considered as an alternative approach to managing climate change. However, before we go down the path of deliberate climate intervention including precursor field-experiments, it is essential that we take the necessary steps to validate our understanding that underpins any of the proposed intervention concepts in order to understand all likely consequences and put in place the necessary strategies for monitoring the expected and unintended consequences of such intervention. The Keck Institute for Space Studies (KISS) is undertaking a project to identify specific priorities for improved scientific understanding and focused efforts to address selected priorities. The KISS project does not advocate the deployment of geoengineering or monitoring systems for potential field experiments but is rather a precautionary study with the following goals: 1) enumeration of where major gaps in our understanding exist in solar radiation management (SRM) approaches, 2) identification of the research that would be required to improve understanding of such impacts including modeling and observation of natural and anthropogenic analogues to geoengineering, and 3) a preliminary assessment of where gaps exist in observations of relevance to SRMs and what is needed to fill such gaps. This study focuses primarily on SRM rather than other proposed geoengineering techniques such as carbon dioxide removal from the atmosphere because there exist a number of analogues to the SRMs that currently operate on Earth that provide a unique opportunity to assess our understanding of the response of the climate system to associated changes in solar radiation. Additionally, the processes related to these analogues are also fundamental to understanding climate change itself being of central relevance to how climate is forced by aerosol and respond through clouds, among other influences (e.g., such research has potential

  8. Matsushiro Earthquake Swarm (1965-1967) as a Natural Analogue of CO2 Storage and Leakage

    NASA Astrophysics Data System (ADS)

    Yamamoto, K.; Koide, H.; Tosha, T.; Todaka, N.; Nakanishi, S.; Aoyagi, R.; Benson, S.; Rutqvist, J.; Lewicki, J.

    2006-12-01

    The Matsushiro basin, Nagano city, Central Japan, is a unique natural analogue site of the CO2 storage and leakage through fault. From May 1966 to February 1967, ten million tons of CO2-bearing water discharged through surface ruptures and springs midst an earthquake swarm. The swarm began in August 1965 and the active period lasted two years followed by three-year relatively silent term. The location of water and CO2 discharge was concentrated in a narrow strip along the main focal fault. Weak seismic activities, CO2 bearing hot spa, and bubbles in rice paddy are observed, so the low intensity activities seem to continue. The fault is a left-lateral strike-slip fault striking NW-SE. Surface upheaval up to 90 cm and lateral motion corresponding to the strike-slip fault were observed. Based on this and additional geophysical evidence, some past studies adopted the idea that the upward water migration in the fault played a major role in the occurrence of the earthquake through the dilatancy mechanism. In this model, the earthquakes are assumed to follow the preceding hydrological and hydraulic phenomena such as water migration to the fractures in rock mass, reducing effective stress, and shear failures with increasing permeability. The authors anticipate that also CO2 played some vital roles in the phenomena observed at Matsushiro, and we could learn the CO2 behaviour in the underground condition. We assume that the fault and CO2 bearing water interacted through chemo-physical (precipitation/dissolution of carbonate and phase change) and mechanical (CO2 pressure induced stress and permeability change in the fault) processes, and affected the flow characters, seismicity, and the initiation and termination of the activities. For the investigation, geochemical surveys were carried out in the area to characterize present day surface CO2 flux. Geochemical and geomechanical modelling are being conducted for the quantitative understanding of the mechanisms. Also, water

  9. Final report of the Peña Blanca natural analogue project

    SciTech Connect

    Levy, Schön S.; Goldstein, Steven Joel; Abdel-Fattah, Amr I.; Amato, Ronald S.; Anthony, Elizabeth; Cook, Paul; Dobson, Patrick F.; Fayek, Mostafa; French, Diana; Garza, Rodrigo de; Ghezzehei, Teamrat; Goodell, Philip C.; Harder, Steven H.; Ku, Teh-Lung; Luo, Shangde; Murrell, Michael Tildon; Norman, Deborah E.; Nunn, Andrew J.; Oliver, Ronald; Pekar-Carpenter, Katrina; Rearick, Michael Sean; Ren, Minghua; Reyes-Cortes, Ignacio; Pineda, Jose Alfredo; Saulnier, George; Tarimala, Sowmitri; Walton, John

    2016-10-04

    The Peña Blanca region, 50 km north of Chihuahua City, Chihuahua, México, was a target of uranium exploration and mining by the Mexican government. After mining ceased in 1981, researchers became interested in this region as a study area for subsurface uranium migration with relevance to geologic disposal of nuclear waste. Many studies related to this concept were conducted at the Nopal I mine site located on a cuesta (hill) of the Sierra Peña Blanca. This site has geologic, tectonic, hydrologic, and geochemical similarities to Yucca Mountain, Nevada, a formerly proposed site for a high-level nuclear-waste repository in the unsaturated zone. The U.S. Department of Energy (U.S. DOE), Office of Civilian Radioactive Waste Management (OCRWM), sponsored studies at Nopal I in the 1990s and supported the drilling of three research wells – PB1, PB2, and PB3 – at the site in 2003. Beginning in 2004, the Peña Blanca Natural Analogue Project was undertaken by U.S. DOE, OCRWM to develop a three-dimensional conceptual model of the transport of uranium and its radiogenic daughter products at the Nopal I site.

  10. Non-natural acetogenin analogues as potent Trypanosoma brucei inhibitors

    PubMed Central

    Florence, Gordon J.; Fraser, Andrew L.; Gould, Eoin R.; King, Elizabeth F.; Menzies, Stefanie K.; Morris, Joanne C.; Tulloch, Lindsay B.; Smith, Terry K.

    2015-01-01

    A series of novel bis-tetrahydropyran 1,4-triazole analogues based on the acetogenin framework display low micromolar trypanocidal activities towards both bloodstream and insect forms of Trypanosoma brucei, the causative agent of African sleeping sickness. A divergent synthetic strategy was adopted for the synthesis of the key tetrahydropyran intermediates to enable rapid access to diastereochemical variation either side of the 1,4-triazole core. The resulting diastereomeric analogues displayed varying degrees of trypanocidal activity and selectivity in structure activity relationship studies. PMID:25145275

  11. New synthetic strategies towards psammaplin A, access to natural product analogues for biological evaluation.

    PubMed

    Baud, Matthias G J; Leiser, Thomas; Meyer-Almes, Franz-Josef; Fuchter, Matthew J

    2011-02-07

    New synthetic routes towards the natural product psammaplin A were developed with the particular view to preparing diverse analogues for biological assessment. These routes utilize cheap and commercially available starting materials, and allowed access to psammaplin A analogues not accessible via currently reported methods. Preliminary biological studies revealed these compounds to be the most potent non peptidic inhibitors of the enzyme histone deacetylase 1 (HDAC1, class I) discovered so far. Interestingly, psammaplin A and our synthetic analogues show class I selectivity in vitro, an important feature for the design and synthesis of future isoform selective inhibitors.

  12. Synthesis and biological evaluation of new salvinorin A analogues incorporating natural amino acids.

    PubMed

    Fichna, Jakub; Lewellyn, Kevin; Yan, Feng; Roth, Bryan L; Zjawiony, Jordan K

    2011-01-01

    The synthesis and in vitro evaluation of a new series of salvinorin A analogues substituted at the C(2) position with natural amino acids is reported. Compound 12, containing Val, displayed high affinity and full agonist activity at the kappa-opioid receptor. Analogues with bulky and/or aromatic residues were inactive, showing the importance of size and electronegativity of C(2)-substituents for binding affinity of salvinorin A derivatives.

  13. Sansanmycin natural product analogues as potent and selective anti-mycobacterials that inhibit lipid I biosynthesis.

    PubMed

    Tran, Anh T; Watson, Emma E; Pujari, Venugopal; Conroy, Trent; Dowman, Luke J; Giltrap, Andrew M; Pang, Angel; Wong, Weng Ruh; Linington, Roger G; Mahapatra, Sebabrata; Saunders, Jessica; Charman, Susan A; West, Nicholas P; Bugg, Timothy D H; Tod, Julie; Dowson, Christopher G; Roper, David I; Crick, Dean C; Britton, Warwick J; Payne, Richard J

    2017-03-01

    Tuberculosis (TB) is responsible for enormous global morbidity and mortality, and current treatment regimens rely on the use of drugs that have been in use for more than 40 years. Owing to widespread resistance to these therapies, new drugs are desperately needed to control the TB disease burden. Herein, we describe the rapid synthesis of analogues of the sansanmycin uridylpeptide natural products that represent promising new TB drug leads. The compounds exhibit potent and selective inhibition of Mycobacterium tuberculosis, the etiological agent of TB, both in vitro and intracellularly. The natural product analogues are nanomolar inhibitors of Mtb phospho-MurNAc-pentapeptide translocase, the enzyme responsible for the synthesis of lipid I in mycobacteria. This work lays the foundation for the development of uridylpeptide natural product analogues as new TB drug candidates that operate through the inhibition of peptidoglycan biosynthesis.

  14. Synthesis and Neurotrophic Activity Studies of Illicium Sesquiterpene Natural Product Analogues.

    PubMed

    Richers, Johannes; Pöthig, Alexander; Herdtweck, Eberhardt; Sippel, Claudia; Hausch, Felix; Tiefenbacher, Konrad

    2017-03-02

    Neurotrophic natural products hold potential as privileged structures for the development of therapeutic agents against neurodegeneration. However, only a few studies have been conducted to investigate a common pharmacophoric motif and structure-activity relationships (SARs). Here, an investigation of structurally more simple analogues of neurotrophic sesquiterpenes of the illicium family is presented. A concise synthetic route enables preparation of the carbon framework of (±)-Merrilactone A and (±)-Anislactone A/B on a gram scale. This has allowed access to a series of structural analogues by modification of the core structure, including variation of oxidation levels and alteration of functional groups. In total, 15 derivatives of the natural products have been synthesized and tested for their neurite outgrowth activities. Our studies indicate that the promising biological activity can be retained by structurally simpler natural product analogues, which are accessible by a straightforward synthetic route.

  15. Sansanmycin natural product analogues as potent and selective anti-mycobacterials that inhibit lipid I biosynthesis

    NASA Astrophysics Data System (ADS)

    Tran, Anh T.; Watson, Emma E.; Pujari, Venugopal; Conroy, Trent; Dowman, Luke J.; Giltrap, Andrew M.; Pang, Angel; Wong, Weng Ruh; Linington, Roger G.; Mahapatra, Sebabrata; Saunders, Jessica; Charman, Susan A.; West, Nicholas P.; Bugg, Timothy D. H.; Tod, Julie; Dowson, Christopher G.; Roper, David I.; Crick, Dean C.; Britton, Warwick J.; Payne, Richard J.

    2017-03-01

    Tuberculosis (TB) is responsible for enormous global morbidity and mortality, and current treatment regimens rely on the use of drugs that have been in use for more than 40 years. Owing to widespread resistance to these therapies, new drugs are desperately needed to control the TB disease burden. Herein, we describe the rapid synthesis of analogues of the sansanmycin uridylpeptide natural products that represent promising new TB drug leads. The compounds exhibit potent and selective inhibition of Mycobacterium tuberculosis, the etiological agent of TB, both in vitro and intracellularly. The natural product analogues are nanomolar inhibitors of Mtb phospho-MurNAc-pentapeptide translocase, the enzyme responsible for the synthesis of lipid I in mycobacteria. This work lays the foundation for the development of uridylpeptide natural product analogues as new TB drug candidates that operate through the inhibition of peptidoglycan biosynthesis.

  16. Sansanmycin natural product analogues as potent and selective anti-mycobacterials that inhibit lipid I biosynthesis

    PubMed Central

    Tran, Anh T.; Watson, Emma E.; Pujari, Venugopal; Conroy, Trent; Dowman, Luke J.; Giltrap, Andrew M.; Pang, Angel; Wong, Weng Ruh; Linington, Roger G.; Mahapatra, Sebabrata; Saunders, Jessica; Charman, Susan A.; West, Nicholas P.; Bugg, Timothy D. H.; Tod, Julie; Dowson, Christopher G.; Roper, David I.; Crick, Dean C.; Britton, Warwick J.; Payne, Richard J.

    2017-01-01

    Tuberculosis (TB) is responsible for enormous global morbidity and mortality, and current treatment regimens rely on the use of drugs that have been in use for more than 40 years. Owing to widespread resistance to these therapies, new drugs are desperately needed to control the TB disease burden. Herein, we describe the rapid synthesis of analogues of the sansanmycin uridylpeptide natural products that represent promising new TB drug leads. The compounds exhibit potent and selective inhibition of Mycobacterium tuberculosis, the etiological agent of TB, both in vitro and intracellularly. The natural product analogues are nanomolar inhibitors of Mtb phospho-MurNAc-pentapeptide translocase, the enzyme responsible for the synthesis of lipid I in mycobacteria. This work lays the foundation for the development of uridylpeptide natural product analogues as new TB drug candidates that operate through the inhibition of peptidoglycan biosynthesis. PMID:28248311

  17. Comparison of natural aquifer geochemical variability with uncertainty from model-predicted CO2 induced geochemical changes: How detectable is leakage from carbon sequestration sites?

    NASA Astrophysics Data System (ADS)

    Navarre-Sitchler, A. K.; Moore, J.

    2012-12-01

    Leakage of CO2 from underground formations poses risk to the storage permanence goal of 99% of injected CO2 remaining sequestered from the atmosphere, which is needed to mitigate potential global climate change. Additionally, leaked CO2 that invades overlying shallow aquifers may cause deleterious changes to groundwater quality and pose risks to environmental and human health. For these reasons, technologies for monitoring, measurement and accounting of injected CO2 are necessary for regulation and permitting of CO2 sequestration operations. Changes in groundwater geochemistry induced by CO2 leakage offer a potential diagnostic tool for identifying leakage into shallow aquifers. In order to confidently use geochemical parameters as indicators of leakage, however, natural variability in geochemical concentrations and uncertainty in predicted geochemical changes induced by CO2 leakage must be quantitatively evaluated. For leakage monitoring, spatial variability of geochemical parameters such as alkalinity, pH, and specific conductivity is less relevant than temporal variability of these parameters within a given well. We used geochemical data from the Ohio Environmental Protection Agency, Ambient Ground Water Monitoring Network to characterize geochemical variability within individual wells. We selected wells from limestone, sandstone, and unconsolidated aquifers with ≥15 samples (typically annual) and statistically analyzed variability in alkalinity, pH, and specific conductance using median and interquartile range (IQR) to avoid influence by outliers and non-gaussian distributions. Neither the medians nor the IQRs showed correlation with well depth, sampling month, or number of samples. Our results indicate that variability in alkalinity and pH (4 - 12%) within individual wells is lower than specific conductance (28 - 32%), and thus, alkalinity and pH potentially provide more robust indicators. Uncertainty in predicted alkalinity and pH changes due to uncertainty

  18. Natural analogue synthesis report, TDR-NBS-GS-000027 rev00 icn02

    SciTech Connect

    Simmons, A.; Nieder-Westermann, G.; Stuckless, J.; Dobson, P.; Unger, A.J.A.; Kwicklis, E.; Lichtner, P.; Carey, B.; Wolde, G.; Murrel,M.; Kneafsey, T.J.; Meijer, A.; Faybishenko, B.

    2002-04-01

    The purpose of this report is to present analogue studies and literature reviews designed to provide qualitative and quantitative information to test and provide added confidence in process models abstracted for performance assessment (PA) and model predictions pertinent to PA. This report provides updates to studies presented in the Yucca Mountain Site Description (CRWMS M&O 2000 [151945], Section 13) and new examples gleaned from the literature, along with results of quantitative studies conducted specifically for the Yucca Mountain Site Characterization Project (YMP). The intent of the natural analogue studies was to collect corroborative evidence from analogues to demonstrate additional understanding of processes expected to occur during postclosure at a potential Yucca Mountain repository. The report focuses on key processes by providing observations and analyses of natural and anthropogenic (human-induced) systems to improve understanding and confidence in the operation of these processes under conditions similar to those that could occur in a nuclear waste repository. The process models include those that represent both engineered and natural barrier processes. A second purpose of this report is to document the various applications of natural analogues to geologic repository programs, focusing primarily on the way analogues have been used by the YMP. This report is limited to providing support for PA in a confirmatory manner and to providing corroborative inputs for process modeling activities. Section 1.7 discusses additional limitations of this report. Key topics for this report are analogues to emplacement drift degradation, waste form degradation, waste package degradation, degradation of other materials proposed for the engineered barrier, seepage into drifts, radionuclide flow and transport in the unsaturated zone (UZ), analogues to coupled thermal-hydrologic-mechanical-chemical processes, saturated zone (SZ) transport, impact of radionuclide release

  19. Synthesis and characterization of a small analogue of the anticancer natural product leinamycin.

    PubMed

    Keerthi, Kripa; Rajapakse, Anuruddha; Sun, Daekyu; Gates, Kent S

    2013-01-01

    Leinamycin (1) is a Streptomyces-derived natural product that displays nanomolar IC(50) values against human cancer cell lines. In the work described here, we report the synthesis and characterization of a small leinamycin analogue 19 that closely resembles the 'upper-right quadrant' of the natural product, consisting of an alicyclic 1,2-dithiolan-3-one 1-oxide heterocycle connected to an alkene by a two-carbon linker. The results indicate that this small analogue contains the core set of functional groups required to enable thiol-triggered generation of both redox active polysulfides and an episulfonium ion intermediate via the complex reaction cascade first seen in the natural product leinamycin. The small leinamycin analogue 19 caused thiol-triggered oxidative DNA strand cleavage in a manner similar to the natural product, but did not alkyate duplex DNA effectively. This highlights the central role of the 18-membered macrocycle of leinamycin in driving efficient DNA alkylation by the natural product.

  20. Multi-isotope tracing of CO2 leakage and water-rock interaction in a natural CCS analogue.

    NASA Astrophysics Data System (ADS)

    Kloppmann, Wolfram; Gemeni, Vasiliki; Lions, Julie; Koukouzas, Nikolaos; Humez, Pauline; Vasilatos, Charalampos; Millot, Romain; Pauwels, Hélène

    2015-04-01

    Natural analogues of CO2 accumulation and, potentially, leakage, provide a highly valuable opportunity to study (1) geochemical processes within a CO2-reservoir and the overlying aquifers or aquicludes, i.e. gas-water-rock interactions, (2) geology and tightness of reservoirs over geological timescales, (3) potential or real leakage pathways, (3) impact of leakage on shallow groundwater resources quality, and (4) direct and indirect geochemical indicators of gas leakage (Lions et al., 2014, Humez et al., 2014). The Florina Basin in NW Macedonia, Greece, contains a deep CO2-rich aquifer within a graben structure. The graben filling consists of highly heterogeneous Neogene clastic sediments constituted by components from the adjacent massifs including carbonates, schists, gneiss as well as some ultramafic volcanic rocks. Clay layers are observed that isolate hydraulically the deep, partly artesian aquifer. Organic matter, in form of lignite accumulations, is abundant in the Neogene series. The underlying bedrocks are metamorphic carbonates and silicate rocks. The origin of the CO2 accumulation is controversial (deep, partially mantle-derived D'Allessandro et al., 2008 or resulting from thermal decomposition of carbonates, Hatziyannis and Arvanitis, 2011). Groundwaters have been sampled from springs and borewells over 3 years at different depths. First results on major, minor and trace elements give evidence of water-rock interaction, mainly with carbonates but also with ultramafic components but do not indicate that CO2-seepage is the principal driver of those processes (Gemeni et al., submitted). Here we present isotope data on a selection of groundwaters (δ2H , δ18O, δ13CTDIC, 87Sr/86Sr, δ11B, δ7Li). Stable isotopes of water indicate paleo-recharge for some of the groundwaters, limited exchange with gaseous CO2 and, in one case, possibly thermal exchange processes with silicates. Sr isotope ratios vary between marine ratios and radiogenic values indicating

  1. In Vitro Neuroprotective and Anti-Inflammatory Activities of Natural and Semi-Synthetic Spirosteroid Analogues.

    PubMed

    García-Pupo, Laura; Zaldo-Castro, Armando; Exarchou, Vassiliki; Tacoronte-Morales, Juan Enrique; Pieters, Luc; Vanden Berghe, Wim; Nuñez-Figueredo, Yanier; Delgado-Hernández, René

    2016-07-29

    Two spirosteroid analogues were synthesized and evaluated for their in vitro neuroprotective activities in PC12 cells, against glutamate-induced excitotoxicity and mitochondrial damage in glucose deprivation conditions, as well as their anti-inflammatory potential in LPS/IFNγ-stimulated microglia primary cultures. We also evaluated the in vitro anti-excitotoxic and anti-inflammatory activities of natural and endogenous steroids. Our results show that the plant-derived steroid solasodine decreased PC12 glutamate-induced excitotoxicity, but not the cell death induced by mitochondrial damage and glucose deprivation. Among the two synthetic spirosteroid analogues, only the (25R)-5α-spirostan-3,6-one (S15) protected PC12 against ischemia-related in vitro models and inhibited NO production, as well as the release of IL-1β by stimulated primary microglia. These findings provide further insights into the role of specific modifications of the A and B rings of sapogenins for their neuroprotective potential.

  2. Potential impacts on groundwater resources of deep CO2 storage: natural analogues for assessing potential chemical effects

    NASA Astrophysics Data System (ADS)

    Lions, J.; Gale, I.; May, F.; Nygaard, E.; Ruetters, H.; Beaubien, S.; Sohrabi, M.; Hatzignatiou, D. G.; CO2GeoNet Members involved in the present study Team

    2011-12-01

    Carbon dioxide Capture and Storage (CCS) is considered as one of the promising options for reducing atmospheric emissions of CO2 related to human activities. One of the main concerns associated with the geological storage of CO2 is that the CO2 may leak from the intended storage formation, migrate to the near-surface environment and, eventually, escape from the ground. This is a concern because such leakage may affect aquifers overlying the storage site and containing freshwater that may be used for drinking, industry and agriculture. The IEA Greenhouse Gas R&D Programme (IEAGHG) recently commissioned the CO2GeoNet Association to undertake a review of published and unpublished literature on this topic with the aim of summarizing 'state of the art' knowledge and identifying knowledge gaps and research priorities in this field. Work carried out by various CO2GeoNet members was also used in this study. This study identifies possible areas of conflict by combining available datasets to map the global and regional superposition of deep saline formations (DSF) suitable for CO2 storage and overlying fresh groundwater resources. A scenario classification is developed for the various geological settings where conflict could occur. The study proposes two approaches to address the potential impact mechanisms of CO2 storage projects on the hydrodynamics and chemistry of shallow groundwater. The first classifies and synthesizes changes of water quality observed in natural/industrial analogues and in laboratory experiments. The second reviews hydrodynamic and geochemical models, including coupled multiphase flow and reactive transport. Various models are discussed in terms of their advantages and limitations, with conclusions on possible impacts on groundwater resources. Possible mitigation options to stop or control CO2 leakage are assessed. The effect of CO2 pressure in the host DSF and the potential effects on shallow aquifers are also examined. The study provides a review of

  3. Non-Natural Sugar Analogues: Chemical Probes for Metabolic Oligosaccharide Engineering

    NASA Astrophysics Data System (ADS)

    Aich, Udayanath; Yarema, Kevin J.

    Metabolic oligosaccharide engineering (MOE) is a rapidly growing technology emerging from the field of chemical biology that allows novel chemical functionalities to be biosynthetically installed into the carbohydrates of living cells and animals. Since pioneering efforts to modulate sialic acid display through the use of non-natural N-acetyl-D-mannosamine (ManNAc) analogues were reported 15 years ago, monosaccharide probes have been developed to manipulate N-acetyl-D-galactosamine (GalNAc), N-acetyl-D-glucosamine (GlcNAc), and fucose-containing glycans. The 'first generation' of analogues, comprised of a series of ManNAc derivatives with elongated N-acyl chains, demonstrated pathway permissivity and the ability of this methodology to impinge on biological processes ranging from pathogen binding to gene expression and cell adhesion. Later analogues have incorporated chemical function groups including ketones, azides, thiols, and alkyne not normally found in carbohydrates. These groups serve as 'tags' for the subsequent use of chemoselective ligation reactions to further elaborate the chemical properties of the cell surface and thereby greatly expand the potential of MOE technology to offer control over biological processes.

  4. Geochemical profile of a layered outcrop in the Atacama analogue using laser-induced breakdown spectroscopy: Implications for Curiosity investigations in Gale

    NASA Astrophysics Data System (ADS)

    Sobron, Pablo; Lefebvre, Catherine; Leveille, Richard; Koujelev, Alex; Haltigin, Timothy; Du, Hongwei; Wang, Alian; Cabrol, Nathalie; Zacny, Kris; Craft, Jack

    2013-05-01

    performed laboratory laser-induced breakdown spectroscopy (LIBS) and laser Raman spectroscopy measurements on samples from a layered outcrop from the Atacama Desert, Chile. This outcrop is a terrestrial morphological and possibly mineralogical analogue for similar formations that will likely be investigated by the Curiosity rover at Gale Crater. Our results demonstrate that fast LIBS analysis can generate semiquantitative chemical profiles in subminute times using automated data processing tools. Therefore, the LIBS instrument can be an invaluable tactical tool on the Curiosity rover for remote, rapid geochemical survey of layered outcrops, thus serving daily operational needs. The derived chemical profiles, supported by the range of minerals identified by Raman spectroscopy, is consistent with the products of a continental evaporitic lake. In the framework of future surface exploration on Mars, a combined Raman/LIBS investigation may provide a rapid mineralogical/chemical evaluation of targets that can be useful for selecting samples to be eventually collected for sample return purposes or for selecting sample sites to be drilled in the search for astrobiology-relevant species.

  5. Geochemical Responses to Anthropogenic and Natural Influences in Ebinur Lake Sediments of Arid Northwest China

    PubMed Central

    Wu, Jinglu; Abuduwaili, Jilili; Liu, Wen

    2016-01-01

    Geochemical concentrations were extracted for a short sediment core from Ebinur Lake, located in arid northwest China, and mathematical methods were used to demonstrate the complex pattern of the geochemical anomalies resulting from the temporal changes in natural and anthropogenic forces on the lake sediments. The first element assemblage (C1) (aluminum, potassium, iron, magnesium, beryllium, etc.) was predominantly terrigenous; among the assemblage, total phosphorus and titanium were generally consistent with aluminum except with regards to their surface sequences, which inferred the differences of source regions for terrigenous detrital material led to this change around ca. 2000AD. The second assemblage (C2) (calcium and strontium) was found to have a negative relationship with aluminum through a cluster analysis. The third assemblage (C3) included sodium and magnesium, which were influenced by the underwater lake environment and deposited in the Ebinur depression. The concentration ratio of C1/(C1+C2) was used as an indicator for denudation amount of detrital materials, which was supported by the values of magnetic susceptibility. The enrichment factors for heavy metals suggested that the influence of human activities on heavy-metal enrichment in Ebinur Lake region was not severe over the past century. Prior to the 1960s, geochemical indicators suggested a stable lacustrine environment with higher water levels. Beginning in the 1960s, high agricultural water demand resulted in rapid declines in lake water level, with subsequent increases of lake water salinity, as evidenced by enhanced sodium concentration in lake core sediments. During this period, anthropogenic activity also enhanced the intensity of weathering and the denudation of the Ebinur watershed. PMID:27176765

  6. Flavone-based analogues inspired by the natural product simocyclinone D8 as DNA gyrase inhibitors.

    PubMed

    Verghese, Jenson; Nguyen, Thuy; Oppegard, Lisa M; Seivert, Lauren M; Hiasa, Hiroshi; Ellis, Keith C

    2013-11-01

    The increasing occurrence of drug-resistant bacterial infections in the clinic has created a need for new antibacterial agents. Natural products have historically been a rich source of both antibiotics and lead compounds for new antibacterial agents. The natural product simocyclinone D8 (SD8) has been reported to inhibit DNA gyrase, a validated antibacterial drug target, by a unique catalytic inhibition mechanism of action. In this work, we have prepared simplified flavone-based analogues inspired by the complex natural product and evaluated their inhibitory activity and mechanism of action. While two of these compounds do inhibit DNA gyrase, they do so by a different mechanism of action than SD8, namely DNA intercalation.

  7. Geochemical evidence for possible natural migration of Marcellus Formation brine to shallow aquifers in Pennsylvania

    PubMed Central

    Warner, Nathaniel R.; Jackson, Robert B.; Darrah, Thomas H.; Osborn, Stephen G.; Down, Adrian; Zhao, Kaiguang; White, Alissa; Vengosh, Avner

    2012-01-01

    The debate surrounding the safety of shale gas development in the Appalachian Basin has generated increased awareness of drinking water quality in rural communities. Concerns include the potential for migration of stray gas, metal-rich formation brines, and hydraulic fracturing and/or flowback fluids to drinking water aquifers. A critical question common to these environmental risks is the hydraulic connectivity between the shale gas formations and the overlying shallow drinking water aquifers. We present geochemical evidence from northeastern Pennsylvania showing that pathways, unrelated to recent drilling activities, exist in some locations between deep underlying formations and shallow drinking water aquifers. Integration of chemical data (Br, Cl, Na, Ba, Sr, and Li) and isotopic ratios (87Sr/86Sr, 2H/H, 18O/16O, and 228Ra/226Ra) from this and previous studies in 426 shallow groundwater samples and 83 northern Appalachian brine samples suggest that mixing relationships between shallow ground water and a deep formation brine causes groundwater salinization in some locations. The strong geochemical fingerprint in the salinized (Cl > 20 mg/L) groundwater sampled from the Alluvium, Catskill, and Lock Haven aquifers suggests possible migration of Marcellus brine through naturally occurring pathways. The occurrences of saline water do not correlate with the location of shale-gas wells and are consistent with reported data before rapid shale-gas development in the region; however, the presence of these fluids suggests conductive pathways and specific geostructural and/or hydrodynamic regimes in northeastern Pennsylvania that are at increased risk for contamination of shallow drinking water resources, particularly by fugitive gases, because of natural hydraulic connections to deeper formations. PMID:22778445

  8. Geochemical evidence for possible natural migration of Marcellus Formation brine to shallow aquifers in Pennsylvania.

    PubMed

    Warner, Nathaniel R; Jackson, Robert B; Darrah, Thomas H; Osborn, Stephen G; Down, Adrian; Zhao, Kaiguang; White, Alissa; Vengosh, Avner

    2012-07-24

    The debate surrounding the safety of shale gas development in the Appalachian Basin has generated increased awareness of drinking water quality in rural communities. Concerns include the potential for migration of stray gas, metal-rich formation brines, and hydraulic fracturing and/or flowback fluids to drinking water aquifers. A critical question common to these environmental risks is the hydraulic connectivity between the shale gas formations and the overlying shallow drinking water aquifers. We present geochemical evidence from northeastern Pennsylvania showing that pathways, unrelated to recent drilling activities, exist in some locations between deep underlying formations and shallow drinking water aquifers. Integration of chemical data (Br, Cl, Na, Ba, Sr, and Li) and isotopic ratios ((87)Sr/(86)Sr, (2)H/H, (18)O/(16)O, and (228)Ra/(226)Ra) from this and previous studies in 426 shallow groundwater samples and 83 northern Appalachian brine samples suggest that mixing relationships between shallow ground water and a deep formation brine causes groundwater salinization in some locations. The strong geochemical fingerprint in the salinized (Cl > 20 mg/L) groundwater sampled from the Alluvium, Catskill, and Lock Haven aquifers suggests possible migration of Marcellus brine through naturally occurring pathways. The occurrences of saline water do not correlate with the location of shale-gas wells and are consistent with reported data before rapid shale-gas development in the region; however, the presence of these fluids suggests conductive pathways and specific geostructural and/or hydrodynamic regimes in northeastern Pennsylvania that are at increased risk for contamination of shallow drinking water resources, particularly by fugitive gases, because of natural hydraulic connections to deeper formations.

  9. Radiation-Induced Defects in Kaolinite as Tracers of Past Occurrence of Radionuclides in a Natural Analogue of High Level Nuclear Waste Repository

    NASA Astrophysics Data System (ADS)

    Allard, T.; Fourdrin, C.; Calas, G.

    2007-05-01

    Understanding the processes controlling migrations of radioelements at the Earth's surface is an important issue for the long-term safety assessment of high level nuclear waste repositories (HLNWR). Evidence of past occurrence and transfer of radionuclides can be found using radiation-induced defects in minerals. Clay minerals are particularly relevant because of their widespread occurrence at the Earth's surface and their finely divided nature which provides high contact area with radioactive fluids. Owing to its sensitivity to radiations, kaolinite can be used as natural, in situ dosimeter. Kaolinite is known to contain radiation-induced defects which are detected by Electron Paramagnetic Resonance. They are differentiated by their nature, their production kinetics and their thermal stability. One of these defects is stable at the scale of geological periods and provides a record of past radionuclide occurrence. Based on artificial irradiations, a methodology has been subsequently proposed to determine paleodose cumulated by kaolinite since its formation. The paleodose can be used to derive equivalent radioelement concentrations, provided that the age of kaolinite formation can be constrained. This allows quantitative reconstruction of past transfers of radioelements in natural systems. An example is given for the Nopal I U-deposit (Chihuahua, Mexico), hosted in hydrothermally altered volcanic tufs and considered as analogue of the Yucca Mountain site. The paleodoses experienced by kaolinites were determined from the concentration of defects and dosimetry parameters of experimental irradiations. Using few geochemical assumption, a equivalent U-content responsible for defects in kaolinite was calculated from the paleodose, a dose rate balance and model ages of kaolinites constrained by tectonic phases. In a former study, the ages were assumptions derived from regional tectonic events. In thepresent study, ages of mineralization events are measured from U

  10. Crystallization and Stress Relaxation in Highly Stretched Samples of Natural Rubber and its Synthetic Analogue

    SciTech Connect

    Tosaka,M.; Kawakami, D.; Senoo, K.; Kohjiya, S.; Toki, S.; Hsiao, B.

    2006-01-01

    Vulcanizates of natural rubber (NR) and its synthetic analogue (IR) were quickly stretched to 6 times the original length. The post stretch relaxation of tensile stress and the development of strain-induced crystallization (SIC) were studied by simultaneous measurements of the stress and the diffraction intensities using the synchrotron X-ray source. In the range of 8 s, NR crystallized much faster than IR. Accordingly, the origin of the superior toughness of NR was thought to come from the ability of rapid SIC. Time constants of the post-stretch crystallization were estimated from the X-ray study. Then the crystallization time constants were used to decompose the contribution of SIC from the total magnitude of the post-stretch relaxation. The contribution of SIC was dominant for the total magnitude of the post-stretch relaxation during several seconds.

  11. Nematicidal activity of natural ester compounds and their analogues against pine wood nematode, Bursaphelenchus xylophilus.

    PubMed

    Seo, Seon-Mi; Kim, Junheon; Koh, Sang-Hyun; Ahn, Young-Joon; Park, Il-Kwon

    2014-09-17

    In this study, we evaluated the nematicidal activity of natural ester compounds against the pine wood nematode, Bursaphelenchus xylophilus, to identify candidates for the development of novel, safe nematicides. We also tested the nematicidal activity of synthesized analogues of these ester compounds to determine the structure-activity relationship. Among 28 ester compounds tested, isobutyl 2-methylbutanoate, 3-methylbutyl 2-methylbutanoate, 3-methylbutyl tiglate, 3-methyl-2-butenyl 2-methylbutanoate, and pentyl 2-methylbutanoate showed strong nematicidal activity against the pine wood nematode at a 1 mg/mL concentration. The other ester compounds showed weak nematicidal activity. The LC50 values of 3-methylbutyl tiglate, isobutyl 2-methylbutanoate, 3-methylbutyl 2-methylbutanoate, 3-methyl-2-butenyl 2-methylbutanoate, and pentyl 2-methylbutanoate were 0.0218, 0.0284, 0.0326, 0.0402, and 0.0480 mg/mL, respectively. The ester compounds described herein merit further study as potential nematicides for pine wood nematode control.

  12. Antibacterial Optimization of 4-Aminothiazolyl Analogues of the Natural Product GE2270 A: Identification of the Cycloalkylcarboxylic Acids

    SciTech Connect

    LaMarche, Matthew J.; Leeds, Jennifer A.; Amaral, Kerri; Brewer, Jason T.; Bushell, Simon M.; Dewhurst, Janetta M.; Dzink-Fox, JoAnne; Gangl, Eric; Goldovitz, Julie; Jain, Akash; Mullin, Steve; Neckermann, Georg; Osborne, Colin; Palestrant, Deborah; Patane, Michael A.; Rann, Elin M.; Sachdeva, Meena; Shao, Jian; Tiamfook, Stacey; Whitehead, Lewis; Yu, Donghui

    2012-11-09

    4-Aminothiazolyl analogues of the antibiotic natural product GE2270 A (1) were designed, synthesized, and optimized for their activity against Gram positive bacterial infections. Optimization efforts focused on improving the physicochemical properties (e.g., aqueous solubility and chemical stability) of the 4-aminothiazolyl natural product template while improving the in vitro and in vivo antibacterial activity. Structure-activity relationships were defined, and the solubility and efficacy profiles were improved over those of previous analogues and 1. These studies identified novel, potent, soluble, and efficacious elongation factor-Tu inhibitors, which bear cycloalkylcarboxylic acid side chains, and culminated in the selection of development candidates amide 48 and urethane 58.

  13. Using Natural Geochemical Tracers to Discern the Dominant Sources of Freshwater into Biscayne Bay, Southeast Florida

    NASA Astrophysics Data System (ADS)

    Stalker, J. C.; Price, R. M.; Swart, P. K.

    2005-05-01

    Biscayne Bay is a sub-tropical estuary located on the carbonate platform of south Florida. The water occupying Biscayne Bay is a balance of saltwater influx from the open ocean and freshwater inputs from precipitation, surface water runoff, and submarine groundwater discharge. The bays watershed includes a total of 3 million inhabitants, the major urban centers of Miami and Ft. Lauderdale, as well as the Everglades system. With the development of south Florida, the natural diffuse groundwater and stream flow into the bay has been replaced by a large system of canals and levees in an effort to control flooding and drain swampland. The Comprehensive Everglades Restoration Plan includes changes in the freshwater deliveries to Biscayne Bay from point-source discharges via canals to non-point source discharges via wetlands and groundwater flow. The balance of salinity in Biscayne Bay effects sensitive seagrass and tidal ecosystems including numerous species of corals and other biota. A comprehensive understanding of the flow of freshwater into the bay is crucial to future planned developments and restorations. The goal of this study is to use naturally occurring geochemical constituents as tracers to identify and quantify the sources of freshwater, i.e. rainfall, canal flow, and groundwater, discharge to Biscayne Bay. In this study, discrete samples of precipitation, canal water, terrestrial groundwater, marine groundwater, and bay surface water are collected monthly and analyzed for the stable isotopes of hydrogen and oxygen as well as for major cations and anions. Initial results indicate that fresh groundwater has an isotopic signature (del 18O = -2.66 per mil, del D, -7.60 per mil) similar to rainfall (del 18O = -2.86 per mil, del D =-4.78 per mil). In contrast canal water has a heavy isotopic signature (del 18O = -0.46 per mil, del D = -2.48 per mil) due to evaporation. Thus it is possible to use stable isotopes of oxygen and hydrogen to separate canal water from

  14. Encapsulation of piceatannol, a naturally occurring hydroxylated analogue of resveratrol, by natural and modified cyclodextrins.

    PubMed

    Matencio, Adrián; García-Carmona, Francisco; López-Nicolás, José Manuel

    2016-05-18

    In this work, an in-depth study of the interaction between piceatannol (a type of stilbene with high biological activity) and different natural and modified cyclodextrins (CDs) is made, using steady state fluorescence. This bioactive molecule forms a 1 : 1 complex with all the natural (α-CD, β-CD and γ-CD) and modified (HP-β-CD, HE-β-CD and M-β-CD) CDs tested. Among natural CDs, the interaction of piceatannol with β-CD was the most efficient. However, the modified CDs showed higher encapsulation constants (KF) than β-CD, except M-β-CD; the highest KF being found for HP-β-CD (14 048 ± 702 M(-1)). The encapsulation of piceatannol in the internal cavity of CDs showed a strong dependence on pH and temperature. The interaction between HP-β-CD and piceatannol was less effective in the pH region where the stilbene begins to suffer the deprotonation of its hydroxyl group. Moreover, the values of KF decreased as the system temperature increased. To obtain information on the mechanism involved in the piceatannol affinity for CD, the thermodynamic parameters of the complexation (ΔH°, ΔS° and ΔG°) were studied, the results showed a negative entropy (-3.7 ± 0.2 J mol(-1) K(-1)), enthalpy (-24.6 ± 1.2 kJ mol(-1)) and Gibbs free energy change at 25 °C (-23.5 ± 1.2 J mol(-1)). Finally, molecular docking calculations provided further insights into how the different interactions influence the complexation constant. A high degree of correlation was observed between the computed scores and experimental values.

  15. Nature or nurture of coplanar Tatooines: the aligned circumbinary Kuiper belt analogue around HD 131511

    NASA Astrophysics Data System (ADS)

    Kennedy, Grant M.

    2015-02-01

    A key discovery of the Kepler mission is of the circumbinary planets known as `Tatooines', which appear to be well aligned with their host stars' orbits. Whether this alignment is due to initially coplanar circumbinary planet-forming discs (i.e. nature), or subsequent alignment of initially misaligned discs by warping the inner disc or torquing the binary (i.e. nurture), is not known. Tests of which scenario dominates may be possible by observing circumbinary Kuiper belt analogues (`debris discs'), which trace the plane of the primordial disc. Here, the 140 au diameter circumbinary debris disc around HD 131511 is shown to be aligned to within 10° of the plane of the near edge-on 0.2 au binary orbit. The stellar equator is also consistent with being in this plane. If the primordial disc was massive enough to pull the binary into alignment, this outcome should be common and distinguishing nature versus nurture will be difficult. However, if only the inner disc becomes aligned with the binary, the HD 131511 system was never significantly misaligned. Given an initial misalignment, the ˜ Gyr main-sequence lifetime of the star allows secular perturbations to align the debris disc out to 100 au at the cost of an increased scaleheight. The observed debris disc scaleheight limits any misalignment to less than 25°. With only a handful known, many more such systems need to be characterized to help test whether the alignment of circumbinary planets is nature or nurture.

  16. The comparative toxicity to soil invertebrates of natural chemicals and their synthetic analogues.

    PubMed

    Whitaker, J; Chaplow, J S; Potter, E; Scott, W A; Hopkin, S; Harman, M; Sims, I; Sorokin, N

    2009-07-01

    The introduction of Registration, Evaluation and Authorisation of Chemicals (REACH), requires companies to register and risk assess all substances produced or imported in volumes of >1 tonne per year. Extrapolation methods which use existing data for estimating the effects of chemicals are attractive to industry, and comparative data are therefore increasingly in demand. Data on natural toxic chemicals could be used for extrapolation methods such as read-across. To test this hypothesis, the toxicity of natural chemicals and their synthetic analogues were compared using standardised toxicity tests. Two chemical pairs: the napthoquinones, juglone (natural) and 1,4-naphthoquinone (synthetic); and anthraquinones, emodin (natural) and quinizarin (synthetic) were chosen, and their comparative effects on the survival and reproduction of collembolans, earthworms, enchytraeids and predatory mites were assessed. Differences in sensitivity between the species were observed with the predatory mite (Hypoaspis aculeifer) showing the least sensitivity. Within the chemical pairs, toxicity to lethal and sub-lethal endpoints was very similar for the four invertebrate species. The exception was earthworm reproduction, which showed differential sensitivity to the chemicals in both naphthoquinone and anthraquinone pairs. Differences in toxicity identified in the present study may be related to degree of exposure and/or subtle differences in the mode of toxic action for the chemicals and species tested. It may be possible to predict differences by identifying functional groups which infer increased or decreased toxicity in one or other chemical. The development of such techniques would enable the use of read-across from natural to synthetic chemicals for a wider group of compounds.

  17. The effect of sterilization on biological, organic geochemical and morphological information in natural samples

    NASA Technical Reports Server (NTRS)

    Hochstein, L. I.; Kvenvolden, K. A.; Philpott, D. E.

    1974-01-01

    The loss of biological, organic geochemical, and morphological science information that may occur should a Mars surface sample be sterilized prior to return to earth is examined. Results of experimental studies are summarized.

  18. Novel Firmicutes Group Implicated in the Dechlorination of Two Chlorinated Xanthones, Analogues of Natural Organochlorines

    PubMed Central

    Krzmarzick, Mark J.; Miller, Hanna R.; Yan, Tao

    2014-01-01

    Although the abundance and diversity of natural organochlorines are well established, much is still unknown about the degradation of these compounds. Triplicate microcosms were used to determine whether, and which, bacterial communities could dechlorinate two chlorinated xanthones (2,7-dichloroxanthone and 5,7-dichloro-1,3-dihydroxylxanthone), analogues of a diverse class of natural organochlorines. According to quantitative-PCR (qPCR) results, several known dechlorinating genera were either not present or not enriched during dechlorination of the xanthones. Denaturing gradient gel electrophoresis, however, indicated that several Firmicutes were enriched in the dechlorinating cultures compared to triplicate controls amended with nonchlorinated xanthones. One such group, herein referred to as the Gopher group, was further studied with a novel qPCR method that confirmed enrichment of Gopher group 16S rRNA genes in the dechlorinating cultures. The enrichment of the Gopher group was again tested with two new sets of triplicate microcosms. Enrichment was observed during chlorinated xanthone dechlorination in one set of these triplicate microcosms. In the other set, two microcosms showed clear enrichment while a third did not. The Gopher group is a previously unidentified group of Firmicutes, distinct from but related to the Dehalobacter and Desulfitobacterium genera; this group also contains clones from at least four unique cultures capable of dechlorinating anthropogenic organochlorines that have been previously described in the literature. This study suggests that natural chlorinated xanthones may be effective biostimulants to enhance the remediation of pollutants and highlights the idea that novel genera of dechlorinators likely exist and may be active in bioremediation and the natural cycling of chlorine. PMID:24296507

  19. XAFS And Molecular Dynamics Study of Natural Minerals, Analogues of Ceramics for Nuclear Waste Storage

    SciTech Connect

    Harfouche, M.; Farges, F.; Crocombette, J.P.; Flank, A.M.; /SLAC, SSRL

    2006-10-27

    Natural actinides (U and Th) are harmful for the crystalline structure of natural minerals, due to their irradiation. Natural minerals can then become amorphous to x-ray diffraction ('metamict') after being irradiated throughout a long period of time (10{sup 8} years). Then, they are used as natural analogues of ceramics for nuclear waste storage. XAFS studies were performed in zircon, monazite and titanite to understand the effect of radiation damage on the local structure around Th, U, Zr and P and compared to available molecular dynamics (MD) simulations. In zircon, a local expansion around actinides (when substituting for Zr) is found. The radial expansion is a function of the metamictisation degree: up to {approx}4 {angstrom} in crystalline zircon and larger in the metamict counterparts. Ab-initio calculations (FEFF7) were performed around Zr ({approx}23000 sites) and around U (1000 to 3000 sites) in various crystalline and alpha-decay damaged zircon MD simulations. The calculated averaged EXAFS spectra confirms this expansion, which validates the use of the potentials used in the simulations as well as the alpha decay damage model considered in these MD simulations. Tetravalent actinides were found to be 8-coordinated in the undamaged structure, whereas their coordination drops to 7 in the damaged structures. In contrast to zircon, no local expansion around actinides in monazite was detected, despite some polymerization around P is measured (related to radiation damage). Finally, in some phases (such as titanite), actinides are found as oxyde-type clusters (ThO{sub 2}, UO{sub 2}). Consequently, actinides do not 'systematically' substitute for major actions in these structure, in contrast to the common belief in mineralogy.

  20. Restoration of estuarine wetlands via "managed realignment": the use of natural analogues.

    NASA Astrophysics Data System (ADS)

    Cundy, A.

    2003-04-01

    A proposed management response to rising sea-levels for low-relief coastal areas is the managed-realignment approach, where existing coastal defences are repositioned landward, and protective wetlands allowed to develop on the abandoned land. This technique has been applied with varying degrees of success at a number of coastal sites, and, in the U.K. at least, its use is increasing as coastal management authorities move away from hard engineering approaches towards more "natural" coastal and floodplain management. Studies of the response of low-lying coastal areas to the managed-realignment approach, and the subsequent restoration of intertidal wetlands, have tended to rely on short-term (< 5 years) studies of erosion and accretion, vegetation change, and changes in sediment chemistry. While the short-term response to breaching is important, it is essential to complement these studies with an understanding of the medium-term (decadal) response of low-lying coasts to sudden inundation to allow effective site selection and management. This medium-term response may be assessed using sedimentary and geomorphological studies at coastal sites which have been historically breached and flooded, which provide natural analogues for the managed realignment process. This paper illustrates this approach using data from two contrasting sites in southern England (Pagham Harbour and part of the Hamble estuary), which were flooded in the early 20th century following breaching of flood defences. Sediments at both sites retain a record of environmental change following marine inundation, and sedimentary studies, combined with documentary evidence, have been used to examine post-breaching marsh stability, variations in sediment accumulation rate, and vegetation colonisation and dieback over varying timescales. Historically-breached sites such as Pagham Harbour and the Hamble estuary are relatively common around European coasts, and these provide important natural laboratories within

  1. Heterogeneous seepage at the Nopal I natural analogue site, Chihuahua, Mexico

    NASA Astrophysics Data System (ADS)

    Dobson, Patrick F.; Ghezzehei, Teamrat A.; Cook, Paul J.; Rodríguez-Pineda, J. Alfredo; Villalba, Lourdes; de La Garza, Rodrigo

    2012-02-01

    A study of seepage occurring in an adit at the Nopal I uranium mine in Chihuahua, Mexico, was conducted as part of an integrated natural analogue study to evaluate the effects of infiltration and seepage on the mobilization and transport of radionuclides. An instrumented seepage collection system and local automated weather station permit direct correlation between local precipitation events and seepage. Field observations recorded between April 2005 and December 2006 indicate that seepage is highly heterogeneous with respect to time, location, and quantity. Seepage, precipitation, and fracture data were used to test two hypotheses: (1) that fast flow seepage is triggered by large precipitation events, and (2) that an increased abundance of fractures and/or fracture intersections leads to higher seepage volumes. A few zones in the back adit recorded elevated seepage volumes immediately following large (>20 mm/day) precipitation events, with transit times of less than 4 h through the 8-m thick rock mass. In most locations, there is a 1-6 month time lag between the onset of the rainy season and seepage, with longer times observed for the front adit. There is a less clear-cut relation between fracture abundance and seepage volume; processes such as evaporation and surface flow along the ceiling may also influence seepage.

  2. Heterogeneous seepage at the Nopal I natural analogue site, Chihuahua, Mexico

    SciTech Connect

    Dobson, Patrick F.; Cook, Paul J.; Ghezzehei, Teamrat A.; Rodriguez, J. Alfredo; Villalba, Lourdes; de la Garza, Rodrigo

    2008-10-25

    An integrated field, laboratory, and modeling study of the Pena Blanca (Chihuahua, Mexico) natural analogue site is being conducted to evaluate processes that control the mobilization and transport of radionuclides from a uranium ore deposit. One component of this study is an evaluation of the potential for radionuclide transport through the unsaturated zone (UZ) via a seepage study in an adit at the Nopal I uranium mine, excavated 10 m below a mined level surface. Seasonal rainfall on the exposed level surface infiltrates into the fractured rhyolitic ash-flow tuff and seeps into the adit. An instrumented seepage collection system and local automated weather station permit direct correlation between local precipitation events and seepage within the Nopal I +00 adit. Monitoring of seepage within the adit between April 2005 and December 2006 indicates that seepage is highly heterogeneous with respect to time, location, and quantity. Within the back adit area, a few zones where large volumes of water have been collected are linked to fast flow path fractures (0-4 h transit times) presumably associated with focused flow. In most locations, however, there is a 1-6 month time lag between major precipitation events and seepage within the adit, with longer residence times observed for the front adit area. Seepage data obtained from this study will be used to provide input to flow and transport models being developed for the Nopal I hydrogeologic system.

  3. Geochemical Controls on Natural Attenuation of Arsenic Solubilized by Human-Induced Alterations

    NASA Astrophysics Data System (ADS)

    Bilgin, A.; Hering, J. G.; Harrington, J.; Horst, J.; Burris, D.; Reisinger, H. J.

    2005-12-01

    Naturally-occurring arsenic (As) in soils can be solubilized into groundwater as a result of anthropogenic changes in subsurface redox conditions. However, the presence of As in groundwater may not lead to human exposure if As is attenuated before intercepting a water source. Dissolved As can be attenuated by sorption and precipitation processes whose effectiveness may be strongly influenced by redox transformations. Anaerobic bioremediation has been employed at a site in the Northeastern U.S. to treat a tetrachloroethene (PCE) plume in groundwater. An organic carbon source is injected via a transect of wells oriented perpendicular to groundwater flow. The resulting anaerobic reducing zone extends 30 meters down gradient of the injection transect. At the down gradient edge of the reducing zone, dissolved As and Fe concentrations have been observed at over 0.7 milligrams per liter (mg/L) and 450 mg/L, respectively. However, 60 m down gradient (and outside of the reducing zone), As and Fe concentrations have been maintained at levels below their detection limits (0.005 mg/L and 1 mg/L) for over 900 days, demonstrating natural attenuation of As. The sorption of As onto Fe and Mn oxyhydroxides under changing geochemical conditions is investigated by using the reactive transport modeling program Geochemist's Work Bench (GWB). Down gradient conditions are simulated where reduced constituents of contaminated groundwater react with Fe(III) and Mn(III, IV) oxyhydroxides in the soil/aquifer matrix or with dissolved oxygen in uncontaminated groundwater at the periphery of the reducing zone. Dissolved Fe(II) and Mn(II) are re-oxidized and precipitate as oxyhydroxide coatings on the soil or aquifer sediments. These coatings then serve as sorbents for both As(III) and As(V). Simulations allow us to examine As sequestration as a function of groundwater composition (e.g., pH and competing sorbates such as phosphate) and of the rate and extent of the precipitation of Fe(III) and Mn

  4. Total Synthesis of Vinblastine, Vincristine, Related Natural Products, and Key Structural Analogues

    PubMed Central

    Ishikawa, Hayato; Colby, David A.; Seto, Shigeki; Va, Porino; Tam, Annie; Kakei, Hiroyuki; Rayl, Thomas J.; Hwang, Inkyu; Boger, Dale L.

    2009-01-01

    Full details of the development of a direct coupling of catharanthine with vindoline to provide vinblastine are described along with key mechanistic and labeling studies. Following an Fe(III)-promoted coupling reaction initiated by generation of a presumed catharanthine radical cation that undergoes a subsequent oxidative fragmentation and diastereoselective coupling with vindoline, addition of the resulting reaction mixture to an Fe(III)–NaBH4/air solution leads to oxidation of the C15′–C20′ double bond and reduction of the intermediate iminium ion directly providing vinblastine (40–43%) and leurosidine (20–23%), its naturally occurring C20′ alcohol isomer. The yield of coupled products, which exclusively possess the natural C16′ stereochemistry, approaches or exceeds 80% and the combined yield of the isomeric C20′ alcohols is >60%. Preliminary studies of Fe(III)–NaBH4/air oxidation reaction illustrate a generalizable trisubstituted olefin scope, identified alternatives to O2 trap at the oxidized carbon, provides a unique entry into C20′ functionalized vinblastines, and affords initial insights into the observed C20′ diastereoselectivity. The first disclosure of the use of exo-catharanthine proceeding through Δ19′,20′-anhydrovinblastine in such coupling reactions is also detailed with identical stereochemical consequences. Incorporating either a catharanthine N-methyl group or a vindoline N-formyl group precludes Fe(III)-promoted coupling, whereas the removal of the potentially key C16 methoxy group of vindoline does not adversely impact the coupling efficiency. Extension of these studies provided a total synthesis of vincristine (2) via N-desmethylvinblastine (36, also a natural product), 16-desmethoxyvinblastine (44) and 4-desacetoxy-16-desmethoxyvinblastine (47) both of which we can now suggest are likely natural products produced by C. roseus, desacetylvinblastine (62) and 4-desacetoxyvinblastine (59), as well as a series of key

  5. Natural analogues for CO2 storage sites - analysis of a global dataset

    NASA Astrophysics Data System (ADS)

    Miocic, Johannes; Gilfillan, Stuart; McDermott, Christopher; Haszeldine, R. Stuart

    2013-04-01

    Carbon Capture and Storage is the only industrial scale technology currently available to reduce CO2 emissions from fossil-fuelled power plants and large industrial source to the atmosphere and thus mitigate climate change. CO2 is captured at the source and transported to subsurface storage sites, such as depleted oil and gas fields or saline aquifers. In order to have an effect on emissions and to be considered safe it is crucial that the amount of CO2 leaking from storage sites to shallow aquifers or the surface remains very low (<1% over 1000 years). Some process that influence the safety of a reservoir, such as CO2-rock-brine interactions, can be studied using experiments on both laboratory and field-scale. However, long-term processes such as the development of leakage pathways can only be understood by either predictive modelling or by studying natural CO2 reservoirs as analogues for long term CO2 storage sites. Natural CO2 reservoirs have similar geological trapping mechanisms as anticipated for CO2 storage sites and often have held CO2 for a geological period of time (millions of years) without any indication for leakage. Yet, migration of CO2 from reservoirs to the surface is also common and evidenced by gas seeps such as springs and soil degassing. We have compiled and analysed a dataset comprising of more than 50 natural CO2 reservoirs from different settings all around the globe to provide an overview of the factors that are important for the retention of CO2 in the subsurface and what processes lead to leakage of CO2 from the reservoir. Initial results indicate that if the reservoir is found to be leaking, CO2 migration is along faults and not through caprock layers. This indicates that faults act as fluid pathways and play an important role when characterizing a storage site. Additionally, it appears that overpressure of the overburden and the state of CO2 in the reservoir influence the likelihood of migration and hence the safety of a reservoir.

  6. Fe and O isotope composition of meteorite fusion crusts: Possible natural analogues to chondrule formation?

    NASA Astrophysics Data System (ADS)

    Hezel, Dominik C.; Poole, Graeme M.; Hoyes, Jack; Coles, Barry J.; Unsworth, Catherine; Albrecht, Nina; Smith, Caroline; RehkäMper, Mark; Pack, Andreas; Genge, Matthew; Russell, Sara S.

    2015-02-01

    Meteorite fusion crust formation is a brief event in a high-temperature (2000-12,000 K) and high-pressure (2-5 MPa) regime. We studied fusion crusts and bulk samples of 10 ordinary chondrite falls and 10 ordinary chondrite finds. The fusion crusts show a typical layering and most contain vesicles. All fusion crusts are enriched in heavy Fe isotopes, with δ56Fe values up to +0.35‰ relative to the solar system mean. On average, the δ56Fe of fusion crusts from finds is +0.23‰, which is 0.08‰ higher than the average from falls (+0.15‰). Higher δ56Fe in fusion crusts of finds correlate with bulk chondrite enrichments in mobile elements such as Ba and Sr. The δ56Fe signature of meteorite fusion crusts was produced by two processes (1) evaporation during atmospheric entry and (2) terrestrial weathering. Fusion crusts have either the same or higher δ18O (0.9-1.5‰) than their host chondrites, and the same is true for Δ17O. The differences in bulk chondrite and fusion crust oxygen isotope composition are explained by exchange of oxygen between the molten surface of the meteorites with the atmosphere and weathering. Meteorite fusion crust formation is qualitatively similar to conditions of chondrule formation. Therefore, fusion crusts may, at least to some extent, serve as a natural analogue to chondrule formation processes. Meteorite fusion crust and chondrules exhibit a similar extent of Fe isotope fractionation, supporting the idea that the Fe isotope signature of chondrules was established in a high-pressure environment that prevented large isotope fractionations. The exchange of O between a chondrule melt and an 16O-poor nebula as the cause for the observed nonmass dependent O isotope compositions in chondrules is supported by the same process, although to a much lower extent, in meteorite fusion crusts.

  7. Preliminary delineation of natural geochemical reactions, Snake River Plain aquifer system, Idaho National Engineering Laboratory and vicinity, Idaho

    SciTech Connect

    Knobel, L.L.; Bartholomay, R.C.; Orr, B.R.

    1997-05-01

    The U.S. Geological Survey, in cooperation with the U.S. Department of Energy, is conducting a study to determine the natural geochemistry of the Snake River Plain aquifer system at the Idaho National Engineering Laboratory (INEL), Idaho. As part of this study, a group of geochemical reactions that partially control the natural chemistry of ground water at the INEL were identified. Mineralogy of the aquifer matrix was determined using X-ray diffraction and thin-section analysis and theoretical stabilities of the minerals were used to identify potential solid-phase reactants and products of the reactions. The reactants and products that have an important contribution to the natural geochemistry include labradorite, olivine, pyroxene, smectite, calcite, ferric oxyhydroxide, and several silica phases. To further identify the reactions, analyses of 22 representative water samples from sites tapping the Snake River Plain aquifer system were used to determine the thermodynamic condition of the ground water relative to the minerals in the framework of the aquifer system. Principal reactions modifying the natural geochemical system include congruent dissolution of olivine, diopside, amorphous silica, and anhydrite; incongruent dissolution of labradorite with calcium montmorillonite as a residual product; precipitation of calcite and ferric oxyhydroxide; and oxidation of ferrous iron to ferric iron. Cation exchange reactions retard the downward movement of heavy, multivalent waste constituents where infiltration ponds are used for waste disposal.

  8. Decomposition of sodium formate and L- and D-alanine in the Pampas de La Joya soils: Implications as a new geochemical analogue to Martian regolith

    NASA Astrophysics Data System (ADS)

    Valdivia-Silva, Julio E.; Navarro-González, Rafael; Rosa, José De La; McKay, Christopher P.

    2012-03-01

    The organic compounds on the Martian surface are still undetectable by the previous Viking mission that has been sent to Mars even though they are expected to be there by exogenous and/or endogenous synthesis. The high abiotic reactivity has been the most acceptable explanation for the apparently absence of organic matter in the regolith.Earth soils that have geochemical properties similar to those expected on the surface of Mars could help to decipher this question on the surface and shallow subsurface of the Red Planet. This work aims to demonstrate that the place known as the Pampas de La Joya desert in southern Peru, contains soils that have nonbiological chemical decomposition mechanisms of organic compounds under conditions of the Viking Labeled Release Experiment (LRx). We compare the organic decomposition kinetics of these hyper-arid soils with those seen in samples from arid and semiarid regions of the Atacama Desert, and data obtained by Viking LRx in the Martian regolith. 13Carbon-labeled organic compounds (sodium formate, D-, and L-alanine) were added in aqueous solution to different soil samples in order to analyze the evolved carbon dioxide (13CO2) generated during their degradation. As expected, there were significant differences in the evolved gas behavior between soil samples under similar experimental conditions. When sodium formate was added to hyper-arid samples, there was a peak of 13CO2 gas released demonstrating high oxidation activity in the soil. Heat treatment of soil samples did not completely eliminate the CO2 production. An increase in the decomposition rates ˜7 days after the first addition of organics showed a response consistent with biological activity. The addition of D- and L-alanine demonstrated that the production of 13CO2 due to biological decomposition began 5-8 days after incubation. Our results suggest that these soils from Pampas de La Joya present at least two types of oxidants, a thermostable one which is highly

  9. The Werkendam natural CO2 accumulation: An analogue for CO2 storage in depleted oil reservoirs

    NASA Astrophysics Data System (ADS)

    Bertier, Pieter; Busch, Andreas; Hangx, Suzanne; Kampman, Niko; Nover, Georg; Stanjek, Helge; Weniger, Philipp

    2015-04-01

    The Werkendam natural CO2 accumulation is hosted in the Röt (Early Triassic) sandstone of the West Netherlands Basin, at a depth of 2.8 km, about 20 km south-east of Rotterdam (NL). This reservoir, in a fault-bound structure, was oil-filled prior to charging with magmatic CO2 in the early Cretaceous. It therefore offers a unique opportunity to study long-term CO2-water-rock interactions in the presence of oil. This contribution will present the results of a detailed mineralogical and geochemical characterisation of core sections from the Werkendam CO2 reservoir and an adjacent, stratigraphically equivalent aquifer. X-ray diffraction combined with X-ray fluorescence spectrometry revealed that the reservoir samples contain substantially more feldspar and more barite and siderite than those from the aquifer, while the latter have higher hematite contents. These differences are attributed to the effects hydrocarbons and related fluids on diagenesis in the closed system of the CO2 reservoir versus the open-system of the aquifer. Petrophysical analyses yielded overall higher and more anisotropic permeability for the reservoir samples, while the porosity is overall not significantly different from that of their aquifer equivalents. The differences are most pronounced in coarse-grained sandstones. These have low anhydrite contents and contain traces of calcite, while all other analyzed samples contain abundant anhydrite, dolomite/ankerite and siderite, but no calcite. Detailed petrography revealed mm-sized zones of excessive primary porosity. These are attributed to CO2-induced dissolution of precompactional, grain-replacive anhydrite cement. Diagenetic dolomite/ankerite crystals are covered by anhedral, epitaxial ankerite, separated from the crystals by bitumen coats. Since these carbonates were oil-wet before CO2-charging, the overgrowths are interpreted to have grown after CO2-charging. Their anhedral habit suggests growth in a 2-phase water-CO2 system. Isotopic

  10. A natural analogue for CO2 leakage: The release and fate of CO2 at the Jan Mayen vent fields (AMOR)

    NASA Astrophysics Data System (ADS)

    Baumberger, T.; Lilley, M. D.; Pedersen, R. B.; Thorseth, I. H.

    2013-12-01

    Carbon dioxide capture and storage (CCS) is seen as a new possible technique for reducing the emission of industrial CO2 to the atmosphere. To evaluate the risks of sub-seabed CO2 storage, the European Commission is supporting the international and multi-disciplinary ECO2 project. Among other objectives, this project is dealing with evaluating the likelihood of leakage and the resulting possible impacts on marine ecosystems. In the framework of the ECO2 project, the release and dispersal of CO2 have been studied at several natural seep sites. In this study, we present geochemical data collected at the natural CO2 leakage analogue, Jan Mayen vent fields (JMVF). The basalt-hosted JMVF are located at 71° N on the southern end of the ultra-slow spreading Mohns Ridge, which is part of the Arctic Mid-Ocean Ridge (AMOR) system. The JMVF are composed of several venting sites, spread over a large area. These venting areas include focused high-temperature venting and diffuse low-temperature fluid flow vents as well as areas where free gas bubbles are released. Over the past few years, we have repeatedly visited and extensively sampled these vent fields to study the release and fate of CO2 in this natural seep area. One of our main objectives was to constrain the CO2 content of the widely emitted gas and to study its dispersion and fate in the water column. We have also investigated hydrate formation, which is observed at various locations. The venting fluids are chemically characterized by CO2 concentrations of up to 110 mmol/kg, having an associated isotopic composition representing a mantle carbon source. Thus, the CO2 concentrations measured at the JMVF represent the high-end compared to the concentration range of most other basalt-hosted hydrothermal mid-ocean ridge systems. Even though the concentrations of the emitted CO2 vary over time and with the type of venting (focused flow, diffuse flow or bubbles), the overall release is continuously high. The dispersion of the

  11. A comparative study on the crystal structure of bicycle analogues to the natural phytotoxin helminthosporins

    NASA Astrophysics Data System (ADS)

    Barbosa, Luiz Cláudio de Almeida; Teixeira, Robson Ricardo; Nogueira, Leonardo Brandão; Maltha, Celia Regina Alvares; Doriguetto, Antônio Carlos; Martins, Felipe Terra

    2016-02-01

    Herein we described structural insights of a series of analogues to helminthosporin phytotoxins. The key reaction used to prepare the compounds corresponded to the [3 + 4] cycloaddition between the oxyallyl cation generated from 2,4-dibromopentan-3-one and different furans. Their structures were confirmed upon IR, NMR and X-ray diffraction analyses. While bicycles 7, 8 and 9 crystallize in the centrosymmetric monoclinic space group P21/c, compound 10 was solved in the noncentrosymmetric orthorhombic space group P212121. The solid materials obtained were shown to be racemic crystals (7, 8, 9) or racemic conglomerate (10). In all compounds, there is formation of a bicycle featured by fused tetrahydropyranone and 2,5-dihydrofuran rings. They adopt chair and envelope conformations, respectively. Crystal packing of all compounds is stabilized through C-H•••O contacts. Conformational aspects as well as similarities and differences among the crystal structures of the synthesized analogues are discussed.

  12. Analogue modelling of inclined, brittle-ductile transpression: Testing analytical models through natural shear zones (external Betics)

    NASA Astrophysics Data System (ADS)

    Barcos, L.; Díaz-Azpiroz, M.; Balanyá, J. C.; Expósito, I.; Jiménez-Bonilla, A.; Faccenna, C.

    2016-07-01

    The combination of analytical and analogue models gives new opportunities to better understand the kinematic parameters controlling the evolution of transpression zones. In this work, we carried out a set of analogue models using the kinematic parameters of transpressional deformation obtained by applying a general triclinic transpression analytical model to a tabular-shaped shear zone in the external Betic Chain (Torcal de Antequera massif). According to the results of the analytical model, we used two oblique convergence angles to reproduce the main structural and kinematic features of structural domains observed within the Torcal de Antequera massif (α = 15° for the outer domains and α = 30° for the inner domain). Two parallel inclined backstops (one fixed and the other mobile) reproduce the geometry of the shear zone walls of the natural case. Additionally, we applied digital particle image velocimetry (PIV) method to calculate the velocity field of the incremental deformation. Our results suggest that the spatial distribution of the main structures observed in the Torcal de Antequera massif reflects different modes of strain partitioning and strain localization between two domain types, which are related to the variation in the oblique convergence angle and the presence of steep planar velocity - and rheological - discontinuities (the shear zone walls in the natural case). In the 15° model, strain partitioning is simple and strain localization is high: a single narrow shear zone is developed close and parallel to the fixed backstop, bounded by strike-slip faults and internally deformed by R and P shears. In the 30° model, strain partitioning is strong, generating regularly spaced oblique-to-the backstops thrusts and strike-slip faults. At final stages of the 30° experiment, deformation affects the entire model box. Our results show that the application of analytical modelling to natural transpressive zones related to upper crustal deformation

  13. The project De Caldas International Project: An example of a large-scale radwaste isolation natural analogue study

    SciTech Connect

    Shea, M.

    1995-09-01

    The proper isolation of radioactive waste is one of today`s most pressing environmental issues. Research is being carried out by many countries around the world in order to answer critical and perplexing questions regarding the safe disposal of radioactive waste. Natural analogue studies are an increasingly important facet of this international research effort. The Pocos de Caldas Project represents a major effort of the international technical and scientific community towards addressing one of modern civilization`s most critical environmental issues - radioactive waste isolation.

  14. Radon in underground waters as a natural analogue to study the escape of CO2 in geological repositories.

    PubMed

    Martín Sánchez, A; Ruano Sánchez, A B; de la Torre Pérez, J; Jurado Vargas, M

    2015-11-01

    Activity concentrations of dissolved (222)Rn and (226)Ra were measured in several underground aquifers, which are candidates for repositories or for the study of analogue natural escapes of CO2. The concentration of both radionuclides in water was determined using liquid scintillation counting. The values obtained for the (222)Rn concentrations varied from 0 to 150 Bq l(-1), while the levels of (226)Ra were in general very low. This indicates that (222)Rn is coming from the decay of the undissolved (226)Ra existing in the rocks and deep layers of the aquifers, being later transported by diffusion in water.

  15. Synthesis and Anti-Tuberculosis Activity of the Marine Natural Product Caulerpin and Its Analogues

    PubMed Central

    Canché Chay, Cristina I.; Gómez Cansino, Rocío; Espitia Pinzón, Clara I.; Torres-Ochoa, Rubén O.; Martínez, Roberto

    2014-01-01

    Caulerpin (1a), a bis-indole alkaloid from the marine algal Caulerpa sp., was synthesized in three reaction steps with an overall yield of 11%. The caulerpin analogues (1b–1g) were prepared using the same synthetic pathway with overall yields between 3% and 8%. The key reaction involved a radical oxidative aromatic substitution involving xanthate (3) and 3-formylindole compounds (4a–4g). All bis-indole compounds synthesized were evaluated against the Mycobacterium tuberculosis strain H37Rv, and 1a was found to display excellent activity (IC50 0.24 µM). PMID:24681629

  16. Putting the Fizz in the Fissure: Geochemical and Geomechanical Effects of Carbonated Brine in a Natural Fracture

    NASA Astrophysics Data System (ADS)

    Smith, M. M.; Walsh, S. D.; Carroll, S.

    2012-12-01

    The increased mobility and buoyancy of CO2, coupled with rising demands for renewable energy production, make it an attractive alternative heat-exchange fluid in lieu of water for use in enhanced geothermal systems (EGS). However, the geochemical impact of elevated CO2 levels on these engineered systems and the consequent effects on reservoir capacity and system permeability are poorly-constrained at present, leading to uncertainty in predictions of longer-term reservoir performance. For example, consistently high levels of aqueous CO2 cycling through the subsurface may result in relatively rapid and extensive dissolution of pH-sensitive minerals, with an increased risk of secondary alteration phase precipitation (e.g., oxides, clays, and/or carbonate minerals) and adverse effects on EGS resource productivity. If, however, injected CO2-rich fluids traverse the system primarily through fracture networks, other factors such as accessibly reactive surface areas, fracture asperity susceptibility, and fracture surface/wallrock exchange may also factor into the ultimate evolution of reservoir permeability. To evaluate the comparative impacts of both geochemistry and geomechanics in sustaining fracture network flow under conditions relevant to CO2-EGS, a 60-day core-flooding experiment was conducted on a naturally fractured and chemically complex greywacke core sample exposed to CO2-acidified brine at 200C and 25MPa. The objective of this study was to investigate the potential effects of using CO2 as a heat-exchange fluid on fracture flow and reaction within a pre-existing well-characterized fracture representative of reactivated fractures targeted for stimulation in many EGS projects. Over the course of the experiment, changes in solution chemistry and pressure/permeability were monitored. In addition, pre- and post-reaction three-dimensional high-resolution X-ray computed tomography (XRCT) imaging was used to determine changes in fracture aperture and geometry as well

  17. Revisiting AI-2 quorum sensing inhibitors: direct comparison of alkyl-DPD analogues and a natural product fimbrolide.

    PubMed

    Lowery, Colin A; Abe, Takumi; Park, Junguk; Eubanks, Lisa M; Sawada, Daisuke; Kaufmann, Gunnar F; Janda, Kim D

    2009-11-04

    Quorum sensing (QS) systems have been discovered in a wide variety of bacteria, and mediate both intra- and interspecies communication. The AI-2-based QS system represents the most studied of these proposed interspecies systems and has been shown to regulate diverse functions such as bioluminescence, expression of virulence factors, and biofilm formation. As such, the development of modulatory compounds, both agonists and antagonists, is of great interest for the study of unknown AI-2-based QS systems and the potential treatment of bacterial infections. The fimbrolide class of natural products has exhibited excellent inhibitory activity against AI-2-based QS and as such may be considered the "gold standard" of AI-2 inhibitors. Thus, we sought to include a fimbrolide as a control compound for our recently developed alkyl-DPD panel of AI-2 modulators. Herein, we present a revised synthesis of a commonly studied fimbrolide as well as a direct comparison between the fimbrolide and alkyl-DPD analogues. We demonstrate that our alkyl-DPD analogues are more potent inhibitors of QS in both Vibrio harveyi and Salmonella typhimurium, the two organisms with defined AI-2 QS systems, and in doing so call into question the widely accepted use of fimbrolide-derived compounds as the "gold standard" of AI-2 inhibition.

  18. A natural analogue for high-level waste in tuff: Chemical analysis and modeling of the Valles site

    SciTech Connect

    Stockman, H.W.; Krumhansl, J.L.; Ho, C.K.; Kovach, L.; McConnell, V.S.

    1995-03-01

    The contact between an obsidian flow and a steep-walled tuff canyon was examined as an analogue for a high-level waste repository. The analogue site is located in the Valles Caldera in New Mexico, where a massive obsidian flow filled a paleocanyon in the Battleship Rock Tuff. The obsidian flow provided a heat source, analogous to waste panels or an igneous intrusion in a repository, and caused evaporation and migration of water. The tuff and obsidian samples were analyzed for major and trace elements and mineralogy by INAA, XRF, x-ray diffraction, and scanning electron microscopy and electron microprobe. Samples were also analyzed for D/H and {sup 39}Ar/{sup 40}Ar isotopic composition. Overall, the effects of the heating event seem to have been slight and limited to the tuff nearest the contact. There is some evidence of devitrification and migration of volatiles in the tuff within 10 m of the contact, but variations in major and trace element chemistry are small and difficult to distinguish from the natural (pre-heating) variability of the rocks.

  19. Contributions of natural arsenic sources to surface waters on a high grade arsenic-geochemical anomaly (French Massif Central).

    PubMed

    Bossy, A; Grosbois, C; Hendershot, W; Beauchemin, S; Crouzet, C; Bril, H

    2012-08-15

    The subwatershed studied drains a non-exploited area of the St-Yrieix-la-Perche gold mining district (French Massif Central) and it is located on an arsenic (As) geochemical anomaly. In this context, it is important to know the geochemical processes involved in the transfer of As from solid environmental compartments to the aquatic system. The stream showed a temporal variation of dissolved As (As(d)) content from 69.4 μg.L(-1) in the low flow period to 7.5 μg.L(-1) in the high flow period. Upstream, ground- and wetland waters had As(d) concentrations up to 215 and 169 μg.L(-1), respectively. The main representative As sources were determined at the subwatershed scale with in-situ monitoring of major and trace element contents in different waters and single extraction experiments. The As sources to stream water could be regrouped into two components: (i) one As-rich group (mainly in the low flow period) with groundwater, gallery exploration outlet waters and wetland waters, and (ii) one As-poor group (mainly in the high flow period) with rainwaters and soil solutions. In the soil profile, As(d) showed a significant decrease from 52.4 μg.L(-1) in the 0-5 cm superficial soil horizon to 14.4 μg.L(-1) in the 135-165 cm deep soil horizon. This decrease may be related to pedogenic processes and suggests an evolution of As-bearing phase stability through the soil profile. Quantification of As(d) fluxes at the subwatershed scale showed that groundwater was the major input (>80%) of As(d) to surface water. Moreover, natural weathering of the As-rich solid phases showed an impact on the As release, mainly from superficial soil horizons with runoff contributing about 5% to As input in surface water.

  20. The geochemical nature of the Archean Ancient Gneiss Complex and Granodiorite Suite, Swaziland: a preliminary study

    USGS Publications Warehouse

    Hunter, D.R.; Barker, F.; Millard, H.T.

    1978-01-01

    The Ancient Gneiss Complex (AGC) of Swaziland, an Archean gray gneiss complex, lies southeast and south of the Barberton greenstone belt and includes the most structurally complex and highly metamorphosed portions of the eastern Kaapvaal craton. The AGC is not precisely dated but apparently is older than 3.4 Ga. The AGC consists of three major units: (a) a bimodal suite of closely interlayered siliceous, low-K gneisses and metabasalt; (b) homogeneous tonalite gneiss; and (c) interlayered siliceous microcline gneiss, metabasalt, and minor metasedimentary rocks - termed the metamorphite suite. A geologically younger gabbro-diorite-tonalite-trondhjemite suite, the Granodiorite Suite, is spatially associated with the AGC and intrusive into it. The bimodal suite consists largely of two types of low-K siliceous gneiss: one has SiO2 14%, low Rb/Sr ratios, and depleted heavy rare earth elements (REE's); the other has SiO2 > 75%, Al2O3 < 13%, high Rb/Sr ratios, and relatively abundant REE's except for negative Eu anomalies. The interlayered metabasalt ranges from komatiitic to tholeiitic compositions. Lenses of quartz monzonitic gneiss of K2O/Na2O close to 1 form a minor part of the bimodal suite. Tonalitic to trondhjemitic migmatite locally is abundant and has major-element abundances similar to those of non-migmatitic varieties. The siliceous gneisses of the metamorphic suite show low Al2O, K2O/Na2O ratios of about 1, high Rb/Sr ratios, moderate REE abundances and negative Eu anomalies. K/Rb ratios of siliceous gneisses of the bimodal suite are very low (???130); of the tonalitic gneiss, low (???225); of the siliceous gneiss of the metamorphite suite, moderate (???300); and of the Granodiorite Suite, high (???400). Rocks of the AGC differ geochemically in several ways from the siliceous volcanic and hypabyssal rocks of the Upper Onverwacht Group and from the diapirs of tonalite and trondhjemite that intrude the Swaziland Group. ?? 1978.

  1. A Natural Analogue for Thermal-Hydrological-Chemical Coupled Processes at the Proposed Nuclear Waste Repository at Yucca Mountain, Nevada

    SciTech Connect

    Bill Carey; Gordon Keating; Peter C. Lichtner

    1999-08-01

    Dike and sill complexes that intruded tuffaceous host rocks above the water table are suggested as natural analogues for thermal-hydrologic-chemical (THC) processes at the proposed nuclear waste repository at Yucca Mountain, Nevada. Scoping thermal-hydrologic calculations of temperature and saturation profiles surrounding a 30-50 m wide intrusion suggest that boiling conditions could be sustained at distances of tens of meters from the intrusion for several thousand years. This time scale for persistence of boiling is similar to that expected for the Yucca Mountain repository with moderate heat loading. By studying the hydrothermal alteration of the tuff host rocks surrounding the intrusions, insight and relevant data can be obtained that apply directly to the Yucca Mountain repository and can shed light on the extent and type of alteration that should be expected. Such data are needed to bound and constrain model parameters used in THC simulations of the effect of heat produced by the waste on the host rock and to provide a firm foundation for assessing overall repository performance. One example of a possible natural analogue for the repository is the Paiute Ridge intrusive complex located on the northeastern boundary of the Nevada Test Site, Nye County, Nevada. The complex consists of dikes and sills intruded into a partially saturated tuffaceous host rock that has stratigraphic sequences that correlate with those found at Yucca Mountain. The intrusions were emplaced at a depth of several hundred meters below the surface, similar to the depth of the proposed repository. The tuffaceous host rock surrounding the intrusions is hydrothermally altered to varying extents depending on the distance from the intrusions. The Paiute Ridge intrusive complex thus appears to be an ideal natural analogue of THC coupled processes associated with the Yucca Mountain repository. It could provide much needed physical and chemical data for understanding the influence of heat

  2. Informatic search strategies to discover analogues and variants of natural product archetypes.

    PubMed

    Johnston, Chad W; Connaty, Alex D; Skinnider, Michael A; Li, Yong; Grunwald, Alyssa; Wyatt, Morgan A; Kerr, Russell G; Magarvey, Nathan A

    2016-03-01

    Natural products are a crucial source of antimicrobial agents, but reliance on low-resolution bioactivity-guided approaches has led to diminishing interest in discovery programmes. Here, we demonstrate that two in-house automated informatic platforms can be used to target classes of biologically active natural products, specifically, peptaibols. We demonstrate that mass spectrometry-based informatic approaches can be used to detect natural products with high sensitivity, identifying desired agents present in complex microbial extracts. Using our specialised software packages, we could elaborate specific branches of chemical space, uncovering new variants of trichopolyn and demonstrating a way forward in mining natural products as a valuable source of potential pharmaceutical agents.

  3. An interregional analysis of natural vegetation analogues using ERTS-1 imagery

    NASA Technical Reports Server (NTRS)

    Poulton, C. E.; Welch, R. I.

    1973-01-01

    The identification of ecological analogs of natural vegetation and food crops using ERTS-1 imagery is discussed. Signatures of four natural vegetation analogs have been determined from color photography. Color additive techniques to improve the photointerpretation are examined. Tests were conducted at test sites in Louisiana, California, and Colorado.

  4. Migratory Patterns of American Shad (Alosa Sapidissima) Revealed by Natural Geochemical Tags in Otoliths

    DTIC Science & Technology

    2007-02-01

    geographic indicators of natal origins of monarch butterflies in eastern North America. Oecologia 120: 397-404. Hoff, G.R., & Fuiman, L.A. 1995... butterflies (Chamberlain et al. 1997; Hobson et al. 1999; Rubenstein et al. 2002). Such remarkable movements are not restricted to terrestrial... butterflies have been successfully studied using natural gradients in hydrogen, carbon, and nitrogen isotope ratios that are recorded in feather and wing

  5. Characterization of U-series disequilibria at the Pena Blanca natural analogue site, Chihuahua, Mexico

    SciTech Connect

    Wong, V.; Goodell, P.C.; Anthony, E.Y.

    1999-07-01

    The purpose of this study was to evaluate radionuclide migration from a uranium-mineralized breccia pipe. The site provides an excellent opportunity to evaluate radionuclide mobility in a geochemical environment similar to that around the proposed high-level waste repository at Yucca Mountain, Nevada. Samples represent fracture-infillings from both within and outside the breccia pipe. Mineral assemblages within the fractures include (1) pure kaolinite, (2) a mixture of iron-oxyhydroxides (goethite and hematite) with associated alunite and jarosite, which the authors refer to as the Fe-mineral assemblage, and (3) carbonates. Uranophane, weeksite, soddyite, and boltwoodite are associated with samples from within the breccia zone. The authors obtain radionuclide activities from gamma-ray rather than alpha spectroscopy, and the methodology for these measurements is presented in detail. Plots of {sup 230}Th/{sup 238}U vs. {sup 226}Ra/{sup 230}Th show three distinct mobility trends. (1) The majority of the Fe-mineral samples from within the breccia pipe yield values between 1.0 and 1.1 for both ratios, (2) Fe-mineral samples from outside the ore zone and a kaolinite from within the ore zone have {sup 230}Th/{sup 238}U of 0.58 to 0.83 and {sup 226}Ra/{sup 230}Th of 1.09 to 1.42, and (3) some Fe-mineral samples from within the breccia pipe have values of 1.2 and 0.9 respectively. These data, combined with those from other studies at Pena Blanca suggest that U and Ra are sometimes mobile in the near-surface environment and that multiple episodes of enrichment and leaching are required to explain the trends.

  6. Obsidians and tektites: Natural analogues for water diffusion in nuclear waste glasses

    SciTech Connect

    Mazer, J.J.; Bates, J.K.; Bradley, C.R.; Stevenson, C.M.

    1991-11-01

    Projected scenarios for the proposed Yucca Mountain repository include significant periods of time when high relative humidity atmospheres will be present, thus the reaction processes of interest will include those known to occur under these conditions. The ideal natural analog for the proposed Yucca Mountain repository would consist of natural borosilicate glasses exposed to expected repository conditions for thousands of years; however, the prospects for identifying such an analog are remote, but an important caveat for using natural analog studies is to relate the reaction processes in the analog to those in the system of interest, rather than a strict comparison of the glass compositions. In lieu of this, identifying natural glasses that have reacted via reaction processes expected in the repository is the most attractive option. The goal of this study is to quantify molecular water diffusion in the natural analogs obsidian and tektites. Results from this study can be used in assessing the importance of factors affecting molecular water diffusion in nuclear waste glasses, relative to other identified reaction processes. In this way, a better understanding of the long-term reaction mechanism can be developed and incorporated into performance assessment models. 17 refs., 4 figs.

  7. Naturally occurring arsenic in groundwater and identification of the geochemical sources in the Duero Cenozoic Basin, Spain

    NASA Astrophysics Data System (ADS)

    Gómez, J. J.; Lillo, J.; Sahún, B.

    2006-09-01

    Arsenic concentrations surpassing potability limit of 10 μg/L in the groundwater supplies of an extensive area in the Duero Cenozoic Basin (central Spain) have been detected and the main sources of arsenic identified. Arsenic in 514 samples of groundwater, having mean values of 40.8 μg/L, is natural in origin. Geochemical analysis of 553 rock samples, assaying arsenic mean values of 23 mg/kg, was performed. Spatial coincidence between the arsenic anomaly in groundwater and the arsenic lithogeochemical distribution recorded in the Middle Miocene clayey organic-rich Zaratan facies illustrates that the rocks of this unit are the main source of arsenic in groundwater. The ferricretes associated to the Late Cretaceous-Middle Miocene siliciclastics also constitute a potential arsenic source. Mineralogical study has identified the presence of arsenic in iron oxides, authigenic pyrite, manganese oxides, inherited titanium-iron oxides, phyllosilicates and organomineral compounds. Arsenic mobilization to groundwater corresponds to arsenic desorption from iron and manganese oxides and from organic matter.

  8. Microbial effects on the release and attenuation of arsenic in the shallow subsurface of a natural geochemical anomaly.

    PubMed

    Drahota, Petr; Falteisek, Lukáš; Redlich, Aleš; Rohovec, Jan; Matoušek, Tomáš; Cepička, Ivan

    2013-09-01

    Critical factors leading to arsenic release and attenuation from the shallow subsurface were studied with multidisciplinary approach in the natural gold-arsenic geochemical anomaly at Mokrsko (Czech Republic). The results show that microbial reduction promotes arsenic release from Fe(III) (hydr)oxides and Fe(III) arsenates, thereby enhancing dissolved arsenic in the shallow groundwater at average concentration of 7.76 mg/L. In the organic-rich aggregates and wood particles, however, microbial sulfate reduction triggers the formation of realgar deposits, leading to accumulation of As in the distinct organic-rich patches of the shallow subsurface. We conclude that precipitation of realgar in the shallow subsurface of soil/sediment depends on specific and non-trivial combination of water and rock chemistry, microbial community composition and spatial organisation of the subsurface zone, where speciation in saturated environments varied on a centimeter scale from reduced (decomposed wood, H2S and realgar present) to oxidized (goethite and arsenate minerals are present).

  9. Geochemical Evidence for Possible Natural Migration of Marcellus Formation Brine to Shallow Aquifers in Pennsylvania

    NASA Astrophysics Data System (ADS)

    Warner, N. R.; Darrah, T. H.; Jackson, R. B.; Osborn, S.; Down, A.; Vengosh, A.

    2012-12-01

    The acceleration in production of natural gas from shale formations through horizontal drilling and hydraulic fracturing has altered the landscape of domestic energy production in the USA. Yet shale gas exploration has generated an increased awareness of risks to drinking water quality amid concerns for the possible migration of stray gas or hydraulic fracturing fluid and/or flowback brine to shallow drinking water aquifers. The degree to which shallow drinking water is at risk from hydraulic fracturing could depend upon the hydraulic connectivity between the shale gas formations and the surface. In this study, we analyzed the geochemistry of over 400 water samples located across six counties of northeastern Pennsylvania in the three principle aquifers, two Upper Devonian Age bedrock aquifers (Catskill and Lock Haven) and one Quaternary Age (Alluvium) that overlie the Marcellus Formation. Based on a detailed analysis of major (Br, Cl, Na, Mg, Ba, and Sr) and trace (Li) element geochemistry, coupled with utilization of a specific spectrum of isotopic tracers (87Sr/86Sr, 228Ra/ 226Ra, 2H/H, 18O/16O), we identify a salinized (Cl> 20 mg/L) shallow groundwater type which suggests conservative mixing relationships between fresh shallow groundwater and an underlying brine. Identification of the brine source is complicated as many of the brines in the northern Appalachian Basin likely share a common origin as the expelled remnants of the formation of the Silurian Salina evaporate deposits. To determine the ultimate source of the diluted brine we compared the observed geochemistry to over 80 brines produced from northern Appalachian Basin formations. The shallow salinized groundwater most closely resembles diluted produced water from the Middle Devonian Marcellus Formation. The 18O/16O and 2H/H of the salinized groundwater indicate that the brine is likely diluted with post-glacial (<10,000 ybp) meteoric water. Combined, these data indicate that hydraulic connections

  10. IMPACTS OF SOLUBILITY AND OTHER GEOCHEMICAL PROCESSES ON RADIONUCLIDE RETARDATION IN THE NATURAL SYSTEM

    SciTech Connect

    B. Arnold

    2005-08-02

    This report documents results and findings of a study of solubility/co-precipitation effects and enhanced sorption due to variations in redox conditions on radionuclide transport in the natural system (BSC 2005 [DIRS 173951]; BSC 2005 [DIRS 173859]) conducted in response to DOE Contracting Officer Authorization Letter 05-001, Item d (Mitchell 2005 [DIRS 173265]). The purpose of this study is to assess the potential impacts of precipitation and enhanced sorption due to variations in redox conditions on radionuclide transport in the saturated zone (SZ) at Yucca Mountain. The information presented in this report is intended to aid in assessing the conservatism in the SZ transport model for supporting the total system performance assessment (TSPA) calculations. A similar study was performed for the impact of solubility/precipitation on radionuclide transport in the unsaturated zone (UZ). However, because the unsaturated zone is under predominantly oxidizing conditions and that the radionuclides released from the engineered barrier system are not expected to precipitate in the UZ for the reasons described below, it was concluded that the effect on unsaturated zone transport is not significant to warrant a detailed study. Solubility limiting conditions for neptunium in the UZ are expected to be similar to the conditions for neptunium solubility in the waste emplacement drift invert, where Np{sub 2}O{sub 5} is recommended as the controlling solid phase (BSC 2005 [DIRS 174566], Section 6.6.1). Solubility limits for neptunium inside the waste package, however, are expected to be controlled by NpO{sub 2} (BSC 2005 [DIRS 174566], Section 6.6.1). The solubility limits for Np2O5 are generally much higher than for NpO{sub 2} (BSC 2005 [DIRS 174566], Tables 6.6-4 and 6.6-7). Therefore, the low concentrations of neptunium releases from waste packages are unlikely to be affected by solubility limits in the unsaturated zone. The SZ is part of the Lower Natural Barrier to the

  11. Geochemical and strontium isotope characterization of produced waters from Marcellus Shale natural gas extraction.

    PubMed

    Chapman, Elizabeth C; Capo, Rosemary C; Stewart, Brian W; Kirby, Carl S; Hammack, Richard W; Schroeder, Karl T; Edenborn, Harry M

    2012-03-20

    Extraction of natural gas by hydraulic fracturing of the Middle Devonian Marcellus Shale, a major gas-bearing unit in the Appalachian Basin, results in significant quantities of produced water containing high total dissolved solids (TDS). We carried out a strontium (Sr) isotope investigation to determine the utility of Sr isotopes in identifying and quantifying the interaction of Marcellus Formation produced waters with other waters in the Appalachian Basin in the event of an accidental release, and to provide information about the source of the dissolved solids. Strontium isotopic ratios of Marcellus produced waters collected over a geographic range of ~375 km from southwestern to northeastern Pennsylvania define a relatively narrow set of values (ε(Sr)(SW) = +13.8 to +41.6, where ε(Sr) (SW) is the deviation of the (87)Sr/(86)Sr ratio from that of seawater in parts per 10(4)); this isotopic range falls above that of Middle Devonian seawater, and is distinct from most western Pennsylvania acid mine drainage and Upper Devonian Venango Group oil and gas brines. The uniformity of the isotope ratios suggests a basin-wide source of dissolved solids with a component that is more radiogenic than seawater. Mixing models indicate that Sr isotope ratios can be used to sensitively differentiate between Marcellus Formation produced water and other potential sources of TDS into ground or surface waters.

  12. Geochemical and Strontium Isotope Characterization of Produced Waters from Marcellus Shale Natural Gas Extraction

    SciTech Connect

    Elizabeth C. Chapman,† Rosemary C. Capo,† Brian W. Stewart,*,† Carl S. Kirby,‡ Richard W. Hammack,§ Karl T. Schroeder,§ and Harry M. Edenborn

    2012-02-24

    Extraction of natural gas by hydraulic fracturing of the Middle Devonian Marcellus Shale, a major gas-bearing unit in the Appalachian Basin, results in significant quantities of produced water containing high total dissolved solids (TDS). We carried out a strontium (Sr) isotope investigation to determine the utility of Sr isotopes in identifying and quantifying the interaction of Marcellus Formation produced waters with other waters in the Appalachian Basin in the event of an accidental release, and to provide information about the source of the dissolved solids. Strontium isotopic ratios of Marcellus produced waters collected over a geographic range of ∼375 km from southwestern to northeastern Pennsylvania define a relatively narrow set of values (εSr SW = +13.8 to +41.6, where εSr SW is the deviation of the 87Sr/86Sr ratio from that of seawater in parts per 104); this isotopic range falls above that of Middle Devonian seawater, and is distinct from most western Pennsylvania acid mine drainage and Upper Devonian Venango Group oil and gas brines. The uniformity of the isotope ratios suggests a basin-wide source of dissolved solids with a component that is more radiogenic than seawater. Mixing models indicate that Sr isotope ratios can be used to sensitively differentiate between Marcellus Formation produced water and other potential sources of TDS into ground or surface waters.

  13. Geochemical and Strontium Isotope Characterization of Produced Waters from Marcellus Shale Natural Gas Extraction

    SciTech Connect

    Chapman, Elizabeth C; Capo, Rosemary C.; Stewart, Brian W.; Kirby, Carl S.; Hammack, Richard W.; Schroeder, Karl T.; Edenborn, Harry M.

    2012-03-20

    Extraction of natural gas by hydraulic fracturing of the Middle Devonian Marcellus Shale, a major gas-bearing unit in the Appalachian Basin, results in significant quantities of produced water containing high total dissolved solids (TDS). We carried out a strontium (Sr) isotope investigation to determine the utility of Sr isotopes in identifying and quantifying the interaction of Marcellus Formation produced waters with other waters in the Appalachian Basin in the event of an accidental release, and to provide information about the source of the dissolved solids. Strontium isotopic ratios of Marcellus produced waters collected over a geographic range of 375 km from southwestern to northeastern Pennsylvania define a relatively narrow set of values (ε{sub Sr}{sup SW} = +13.8 to +41.6, where ε{sub Sr}{sup SW} is the deviation of the {sup 87}Sr/{sup 86}Sr ratio from that of seawater in parts per 10{sup 4}); this isotopic range falls above that of Middle Devonian seawater, and is distinct from most western Pennsylvania acid mine drainage and Upper Devonian Venango Group oil and gas brines. The uniformity of the isotope ratios suggests a basin-wide source of dissolved solids with a component that is more radiogenic than seawater. Mixing models indicate that Sr isotope ratios can be used to sensitively differentiate between Marcellus Formation produced water and other potential sources of TDS into ground or surface waters.

  14. The Antei uranium deposit: A natural analogue of an SNF repository and an underground geodynamic laboratory in granite

    NASA Astrophysics Data System (ADS)

    Laverov, N. P.; Petrov, V. A.; Poluektov, V. V.; Nasimov, R. M.; Hammer, J.; Burmistrov, A. A.; Shchukin, S. I.

    2008-10-01

    The estimation of the long-term stability of crystalline rock massifs with respect to natural and technogenic loads in the course of long-term storage of spent nuclear fuel (SNF) is a special area of surveys at underground research laboratories (URLs). In parallel with these surveys, data on uranium deposits—natural analogues of repositories of SNF consisting of 95% UO2—are used for obtaining insight into the dynamics of radionuclide migration and validating barrier properties of host rocks. Examples of URLs located in granitic massifs of Sweden (Äspö), Canada (Whiteshell), Switzerland (Grimsel), Japan (Mizunami), and Finland (ONKALO), as well as the El Berrocal (Spain), Palmottu (Finland), Sanerliu (China), and Kamaishi (Japan) deposits, are considered in the paper. The objects listed above are distinct in tectonic settings, geology, control of ore mineralization, redox conditions of uranium migration, and character and intensity of filtration and transportation, which predetermine the direction and specific features of research conducted therein. A variant in which a URL and a natural analogue are combined in one object is especially promising for validation of safe long-term isolation of SNF. The Antei vein-stockwork uranium deposit in the southeastern Transbaikal region, localized in Paleozoic granite at a depth of 400 1000 m and opened by mine workings at six levels, is such an object. Its geological features, stress-strain state, and infrastructure of mine workings offer an opportunity to study the entire spectrum of processes proceeding in near-and far-field of an SNF repository. The structural geology, mineralogy and petrography, and petrophysical and tectonophysical features of the deposit at its three lower levels are considered. The sequence of metasomatic alteration of rocks and the dynamics of formation of ore-bearing faults that crosscut prototectonic elements, as well as relationships of physicomechanical properties of rocks as a function of

  15. Geochemical gradients in soil O-horizon samples from southern Norway: Natural or anthropogenic?

    USGS Publications Warehouse

    Reimann, C.; Englmaier, P.; Flem, B.; Gough, L.; Lamothe, P.; Nordgulen, O.; Smith, D.

    2009-01-01

    Forty soil O- and C-horizon samples were collected along a south-to-north transect extending inland for approximately 200 km from the southern tip of Norway. The elements As, Au, Bi, Cd, Cu, Ga, Ge, Hf, Hg, In, Mg, Mn, Mo, Na, Ni, Pb, Sb, Se, V, W, Zn and Zr all show a distinct decrease in concentration in soil O-horizons with increasing distance from the coast. The elements showing the strongest coastal enrichment, some by more than an order of magnitude compared to inland samples, are Au, Bi, As, Pb, Sb and Sn. Furthermore, the elements Cd (median O-/median C-horizon = 31), C, Sb, Ag, K, S, Ge (10), Hg, Pb, As, Bi, Sr (5), Se, Au, Ba, Na, Zn, P, Cu and Sn (2) are all strongly enriched in the O-horizon when compared to the underlying C-horizon. Lead isotope ratios, however, do not show any gradient with distance from the coast (declining Pb concentration). Along a 50 km topographically steep east-west transect in the centre of the survey area, far from the coast but crossing several vegetation zones, similar element enrichment patterns and concentration gradients can be observed in the O-horizon. Lead isotope ratios in the O-horizon correlate along both transects with pH and the C/N-ratio, both proxies for the quality of the organic material. Natural conditions in southern Norway, related to climate and vegetation, rather than long range atmospheric transport of air pollutants (LRT), cause the observed features. ?? 2008 Elsevier Ltd.

  16. Geochemical variability of natural soils and reclaimed minespoil soils in the San Juan Basin, New Mexico

    USGS Publications Warehouse

    Gough, L.P.; Severson, R.C.

    1981-01-01

    An inventory of total-and extractable-element concentrations in soils was made for three areas of the San Juan Basin in New Mexico: (1) the broad area likely to be affected by energy-related development. (2) an area of soils considered to have potential for use as topsoil in mined-land reclamation. and (3) an area of the San Juan coal mine that has been regraded. topsoiled, and revegetated. Maps made of concentrations of 16 elements in area 1 soils show no gradational pattern across the region. Further. these maps do not correspond to those showing geology or soil types. Sodic or saline problems, and a possible but unproven deficiency of zinc available to plants. may make some of the soils in this area undesirable for use as topsoil in mined-land reclamation. Taxonomic great groups of soil in this area cannot be distinguished because each great group tends to have a large within-group variability if compared to the between-group variability. In area 2 the major soils sampled were of the Sheppard. Shiprock. and Doak association. These soils are quite uniform in chemical composition and are not greatly saline or sodic. As in area 1 soils. zinc deficiency may cause a problem in revegetating most of these soils. It is difficult to distinguish soil taxonomic families by using their respective chemical compositions. because of small between-family variability. Topsoil from a reclaimed area of the San Juan mine (area 3) most closely resembles the chemical composition of natural C horizons of soil from area 1. Spoil material that has not been topsoiled is likely to cause sodic-and saline-related problems in revegetation and may cause boron toxicity in plants. Topsoiling has apparently ameliorated these potential problems for plant growth on mine spoil. Total and extractable concentrations for elements and other parameters for each area of the San Juan Basin provide background information for the evaluation of the chemical quality of soils in each area.

  17. Stratigraphic and geochemical controls on naturally occurring arsenic in groundwater, eastern Wisconsin, USA

    NASA Astrophysics Data System (ADS)

    Schreiber, M. E.; Simo, J. A.; Freiberg, P. G.

    High arsenic concentrations (up to 12,000μg/L) have been measured in groundwater from a confined sandstone aquifer in eastern Wisconsin. The main arsenic source is a sulfide-bearing secondary cement horizon (SCH) that has variable thickness, morphology, and arsenic concentrations. Arsenic occurs in pyrite and marcasite as well as in iron oxyhydroxides but not as a separate arsenopyrite phase. Nearly identical sulfur isotopic signatures in pyrite and dissolved sulfate and the correlation between dissolved sulfate, iron, and arsenic concentrations suggest that sulfide oxidation is the dominant process controlling arsenic release to groundwater. However, arsenic-bearing oxyhydroxides can potentially provide another arsenic source if reducing conditions develop or if they are transported as colloids in the aquifer. Analysis of well data indicates that the intersection of the SCH with static water levels measured in residential wells is strongly correlated with high concentrations of arsenic in groundwater. Field and laboratory data suggest that the most severe arsenic contamination is caused by localized borehole interactions of air, water, and sulfides. Although arsenic contamination is caused by oxidation of naturally occurring sulfides, it is influenced by water-level fluctuations caused by municipal well pumping or climate changes, which can shift geographic areas in which contamination occurs. Résumé De fortes concentrations en arsenic, jusqu'à 12000μg/L, ont été mesurées dans l'eau souterraine d'un aquifère gréseux captif, dans l'est du Wisconsin. La principale source d'arsenic est un horizon à cimentation secondaire (SCH) comportant des sulfures, dont l'épaisseur, la morphologie et les concentrations en arsenic sont variables. L'arsenic est présent dans la pyrite et dans la marcassite, de même que dans des oxy-hydroxydes de fer, mais non pas dans une phase séparée d'arsénopyrite. Les signatures isotopiques du soufre presque identiques dans la

  18. Natural glass analogues to alteration of nuclear waste glass: A review and recommendations for further study

    SciTech Connect

    McKenzie, W.F.

    1990-01-01

    The purpose of this report is to review previous work on the weathering of natural glasses; and to make recommendations for further work with respect to studying the alteration of natural glasses as it relates quantifying rates of dissolution. the first task was greatly simplified by the published papers of Jercinovic and Ewing (1987) and Byers, Jercinovic, and Ewing (1987). The second task is obviously the more difficult of the two and the author makes no claim of completeness in this regard. Glasses weather in the natural environment by reacting with aqueous solutions producing a rind of secondary solid phases. It had been proposed by some workers that the thickness of this rind is a function of the age of the glass and thus could be used to estimate glass dissolution rates. However, Jercinovic and Ewing (1987) point out that in general the rind thickness does not correlate with the age of the glass owing to the differences in time of contact with the solution compared to the actual age of the sample. It should be noted that the rate of glass dissolution is also a function of the composition of both the glass and the solution, and the temperature. Quantification of the effects of these parameters (as well as time of contact with the aqueous phase and flow rates) would thus permit a prediction of the consequences of glass-fluid interactions under varying environmental conditions. Defense high- level nuclear waste (DHLW), consisting primarily of liquid and sludge, will be encapsulated by and dispersed in a borosilicate glass before permanent storage in a HLW repository. This glass containing the DHLW serves to dilute the radionuclides and to retard their dispersion into the environment. 318 refs.

  19. Novel peptide chemistry in terrestrial animals: natural luciferin analogues from the bioluminescent earthworm Fridericia heliota.

    PubMed

    Dubinnyi, Maxim A; Tsarkova, Aleksandra S; Petushkov, Valentin N; Kaskova, Zinaida M; Rodionova, Natalja S; Kovalchuk, Sergey I; Ziganshin, Rustam H; Baranov, Mikhail S; Mineev, Konstantin S; Yampolsky, Ilia V

    2015-03-02

    We report isolation and structure elucidation of AsLn5, AsLn7, AsLn11 and AsLn12: novel luciferin analogs from the bioluminescent earthworm Fridericia heliota. They were found to be highly unusual modified peptides, comprising either of the two tyrosine-derived chromophores, CompX or CompY and a set of amino acids, including threonine, gamma-aminobutyric acid, homoarginine, and unsymmetrical N,N-dimethylarginine. These natural compounds represent a unique peptide chemistry found in terrestrial animals and rise novel questions concerning their biosynthetic origin.

  20. New time-resolved micro-photoluminescence spectroscopy of natural and synthetic analogue minerals

    NASA Astrophysics Data System (ADS)

    Panczer, G.; Ollier, N.; Champagnon, B.; Gaft, M.

    2003-04-01

    Minerals as well as geomaterials often present light emissions under UV or visible excitations. This property called photoluminescence is due to low concentration impurities such as the rare earths, the transition elements and the lanthanides. The induced color is used for ore prospection but only spectroscopic analyses indicate the nature of the emitted centers. However natural samples contained numerous luminescent centers simultaneously and with regular steady-state measurements (such as in cathodoluminescence) all the emissions are often over lapping. In order to record the contributions of each separate center, it is possible to use time-resolved measurements based on the decay time of the emissions and using pulsed laser excitation. Some characteristic examples will be presented on apatites, zircons as well as gemstones. Geomaterials present as well micro scale heterogeneities (growth zoning, inclusions, devitrification, microphases...). Precise identification and optical effects of such heterogeneities have to be taken into account. To reach the microscale using photo luminescence studies, a microscope has be modified to allowed pulsed laser injection (from UV to visible), beam focus with micro scale resolution on the sample (<10 μm), as well as time resolved collection of micro fluorescence. Such equipment allows now undertaking time-resolved measurements of microphases. Applications on geomaterials will be presented.

  1. Natural compounds of the strobilurin series and their synthetic analogues as cell respiration inhibitors

    NASA Astrophysics Data System (ADS)

    Zakharychev, Vladimir V.; Kovalenko, Leonid V.

    1998-06-01

    A group of fungicidal antibiotics, β-methoxyacrylic acid derivatives (strobilurins, oudemansins, and myxothiazols), their producers, and mechanisms of action are considered. The fungicidal activity of these compounds is based on the suppression of cell respiration of fungi in the bc1-complex of cytochromes. They also manifest other biological activities that are not always coupled with inhibition of respiration. Studies of the structure of the natural methoxyacrylates has made it possible to create a novel class of synthetic agricultural fungicides with enhanced stability, high activity, and a broad spectrum of action. The main regularities of the structure-activity relationship and methods of synthesis of these compounds are discussed. The bibliography includes 159 references.

  2. Insights into the nature of cometary organic matter from terrestrial analogues

    NASA Astrophysics Data System (ADS)

    Court, Richard W.; Sephton, Mark A.

    2012-04-01

    The nature of cometary organic matter is of great interest to investigations involving the formation and distribution of organic matter relevant to the origin of life. We have used pyrolysis-Fourier transform infrared (FTIR) spectroscopy to investigate the chemical effects of the irradiation of naturally occurring bitumens, and to relate their products of pyrolysis to their parent assemblages. The information acquired has then been applied to the complex organic matter present in cometary nuclei and comae. Amalgamating the FTIR data presented here with data from published studies enables the inference of other comprehensive trends within hydrocarbon mixtures as they are progressively irradiated in a cometary environment, namely the polymerization of lower molecular weight compounds; an increased abundance of polycyclic aromatic hydrocarbon structures; enrichment in 13C; reduction in atomic H/C ratio; elevation of atomic O/C ratio and increase in the temperature required for thermal degradation. The dark carbonaceous surface of a cometary nucleus will display extreme levels of these features, relative to the nucleus interior, while material in the coma will reflect the degree of irradiation experienced by its source location in the nucleus. Cometary comae with high methane/water ratios indicate a nucleus enriched in methane, favouring the formation of complex organic matter via radiation-induced polymerization of simple precursors. In contrast, production of complex organic matter is hindered in a nucleus possessing a low methane/water ration, with the complex organic matter that does form possessing more oxygen-containing species, such as alcohol, carbonyl and carboxylic acid functional groups, resulting from reactions with hydroxyl radicals formed by the radiolysis of the more abundant water. These insights into the properties of complex cometary organic matter should be of particular interest to both remote observation and space missions involving in situ

  3. Natural glass from Deccan volcanic province: an analogue for radioactive waste form

    NASA Astrophysics Data System (ADS)

    Rani, Nishi; Shrivastava, J. P.; Bajpai, R. K.

    2015-11-01

    Deccan basaltic glass is associated with the differentiation centres of the vast basaltic magmas erupted in a short time span. Its suitability as a radioactive waste containment chiefly depends on alteration behaviour; however, detailed work is needed on this glass. Therefore, the basaltic glass was treated under hydrothermal-like conditions and then studied to understand its alteration. Moreover, comparison of these results with the naturally altered glass is also documented in this paper. Solutions as well as residue obtained after glass alteration experiments were analysed. Treated glass specimens show partial to complete release of all the ions during alteration; however, abundant release of Si and Na ions is noticed in case of almost all the specimens and the ionic release is of the order of Na > Si > K > Ca > Al = Mg > Fe > Mn > Ti. Scanning electron images of the altered residue show morphologies of smectite, montmorillonite and illite inside as well as outside of the secondary layers, and represent paragenesis of alteration minerals. It has been noticed that the octahedral cation occupancies of smectite are consistent with the dioctahedral smectite. The secondary layer composition indicates retention for Si, Al, and Mg ions, indicating their fixation in the alteration products, but remarkably high retention of Ti, Mn and Fe ions suggests release of very small amount of these elements into the solution. By evolution of the secondary layer and retention of less soluble ions, the obstructive effect of the secondary layer increases and the initial constant release rate begins slowly to diminish with the proceeding time. It has been found that devitrification of glass along the cracks, formation of spherulite-like structures and formation of yellowish brown palagonite, chlorite, calcite, zeolite and finally white coloured clays yielded after experiments that largely correspond to altered obsidian that existed in the natural environment since inception ~66 Ma ago.

  4. Geochemical evidence concerning the nature of the source region to the Middle Proterozoic Granite-Rhyolite Province

    SciTech Connect

    Shuster, R.D. . Dept. Geography Mueller, P.A.; Heatherington, A.L. . Dept. Geology)

    1992-01-01

    The mostly buried 1.5--1.3 Ga old Granite-Rhyolite Province of the midcontinent of North America, is characterized by extensive, undeformed silicic volcanic rocks and related epizonal granitic plutons. Thirty-three previously dated samples from a wide geographic range (Michigan to Colorado) have been analyzed to determine their chemical and Nd and Pb isotopic compositions in order to constrain source regions and processes involved in the formation of these rocks. Major and trace element analyses of these rocks indicate their anorogenic nature, with relatively high Ce/Nb and Y/Nb ratios, as well as relatively high Ga/Al ratios. Geochemically, these rocks are similar to the A2 granites of Eby (1992), which are thought to be generated from the melting of crust which has experienced at least one cycle of subduction-related magmatism. Rare earth element and Pb isotopic data suggest melting at middle to shallow depths. The isotopic data (Nd and Pb) indicate little to no contribution of Archean crust to the source of these rocks. Initial Pb isotopic ratios (208Pb/204Pb) suggest a low Th/U ratio in the source, which contrasts strongly with high Th/U ratios of the Wyoming Province. The Pb isotopic ratios for these rocks are variable, but cluster about the orogene plumbotectonics curve. The variability in the data suggest sources which are variable in their U/Pb ratios and/or ages. The isotopic data are consistent with the existence of a proposed lithospheric boundary which trend NE-SW through the Granite-Rhyolite Province and separates 1.65 Ga old lithosphere (to the NW) from 1.5 Ga old lithosphere (to the SE). Samples analyzed from either side of this boundary have different isotopic signatures. Many of the samples appear to be derived from sources which are only slightly older than the crystallization ages of the granites themselves.

  5. Evidence of alkali rich melt reactions with mantle peridotite : Natural observations and experimental analogues

    NASA Astrophysics Data System (ADS)

    Grant, T. B.; Milke, R.; Wunder, B.

    2012-04-01

    The Heldburg Phonolite, (Thuringia, Germany) is peculiar in its nature due to its absence of a Eu anomaly, and hence lack of feldspar fractionation, as well as the presence of spinel lherzolite xenocrysts. These observations suggest a higher than normal (mantle) pressure of origin, and its potential as a metasomatic agent at depth is explored in this work. Disequilibrium between the phonolite and its entrained upper mantle xenocrysts resulted in the development of secondary reaction rim assemblages of; (1) phlogopite + minor diopside around olivine, (2) pargasitic amphibole, phlogopite and minor diopside around orthopyroxene. We document both the natural rims and the attempts to reproduce them under experimental conditions, in order to elucidate the likely origin of the phonolite and its efficacy for metasomatising the upper mantle. Platinum capsules were loaded with mixtures of crushed mineral separates, (of pure synthetic forsterite, San Carlos olivine, synthetic enstatite or a natural enstatite from Kilosa, Tanzania) with a synthetic Fe-free phonolite melt in a 16:84% weight ratio, respectively. Experiments were run in a piston cylinder apparatus with CaF2 as the pressure medium. In addition to varying PT conditions, a wide range of water contents were tested (0-14wt%). It was found that pressures of 10-14 kbar, and temperatures of 900-1000°C, satisfy the conditions at which the reactions can form, thus, it is likely that the phonolite existed at upper mantle conditions. Water must be present to stabilize the desired hydrous phases, with >6wt% required at 900°C and 10 kbar. The destabilization of feldspar is also essential to the process, hence higher water contents are needed at the lowest PT conditions compared to 4-5 wt. % H2O at greater PT. The formation of amphibole around enstatite appears to be affected by sluggish reaction kinetics and the orientation of the host pyroxene, sometimes leading to diopside single rims. Furthermore we note some of the

  6. Tracing the CO2 source and migration in natural analogues from different geological contexts

    NASA Astrophysics Data System (ADS)

    Battani, A.; Jean Luc, F.; Philippe, S.; Nadine, E.; Olivier, V.; Elodie, J.

    2009-12-01

    Naturally occurring CO2 fields allow studying long-term fluid-rock interactions, and the processes of CO2 migration, useful for the prediction of CO2 behavior in industrial storage sites. Two different provinces showing both leaking systems (hydrothermal areas) and well confined systems (stable sedimentary basins) have been studied. The first province concerns the French CO2 province of Massif Central (volcanic events, seismic activity, high geothermal gradient) and the stable Valence basin. The other study was devoted to the Basin and Range province, USA, with hydrothermal, high seismic and volcanic activity, a high geothermal gradient (Soda Springs; Idaho, Sevier basin), and the non-hydrothermal stable area of the Colorado plateau (Green River, San Rafael anticline and Springerville). The aim is to link the CO2 sources and its subsurface migration to the geological context. In hydrothermal areas, the mesured helium isotopic ratio (R/Ra) is high (close to the mantle ratio), while the CO2/3He ratios move dramatically towards crustal values. In this context, isotopic and elemental noble gas data show that the gas migrates very fast from depth. In more confined areas (natural CO2 fields), the CO2 shows a more important proportion of radiogenic gases (4He) (crustal helium isotopic ratios) and the associated CO2/3He ratios are in the MORB range, or “mantle derived”. We try to explain the apparent discrepancy between the CO2/3He and the R/Ra values in both areas. As a primary assumption, the source of CO2 could be localized in the extensional zones of high geothermal gradient with important seismicity. We suggest that the pseudotachylites formed by frictional melting associated with each seismic event supply an instantaneous crustal CO2.amount to the initial magmatic CO2. This justifies the coeval increase of the CO2/3He ratios without any significant modification in the helium isotopic ratios (instantaneous, no time for 4He production). Moreover, the contact

  7. Natural Occurring Silks and Their Analogues as Materials for Nerve Conduits.

    PubMed

    Radtke, Christine

    2016-10-20

    Spider silk and its synthetic derivatives have a light weight in combination with good strength and elasticity. Their high cytocompatibility and low immunogenicity make them well suited for biomaterial products such as nerve conduits. Silk proteins slowly degrade enzymatically in vivo, thus allowing for an initial therapeutic effect such as in nerve scaffolding to facilitate endogenous repair processes, and then are removed. Silks are biopolymers naturally produced by many species of arthropods including spiders, caterpillars and mites. The silk fibers are secreted by the labial gland of the larvae of some orders of Holometabola (insects with pupa) or the spinnerets of spiders. The majority of studies using silks for biomedical applications use materials from silkworms or spiders, mostly of the genus Nephila clavipes. Silk is one of the most promising biomaterials with effects not only in nerve regeneration, but in a number of regenerative applications. The development of silks for human biomedical applications is of high scientific and clinical interest. Biomaterials in use for biomedical applications have to meet a number of requirements such as biocompatibility and elicitation of no more than a minor inflammatory response, biodegradability in a reasonable time and specific structural properties. Here we present the current status in the field of silk-based conduit development for nerve repair and discuss current advances with regard to potential clinical transfer of an implantable nerve conduit for enhancement of nerve regeneration.

  8. Natural Occurring Silks and Their Analogues as Materials for Nerve Conduits

    PubMed Central

    Radtke, Christine

    2016-01-01

    Spider silk and its synthetic derivatives have a light weight in combination with good strength and elasticity. Their high cytocompatibility and low immunogenicity make them well suited for biomaterial products such as nerve conduits. Silk proteins slowly degrade enzymatically in vivo, thus allowing for an initial therapeutic effect such as in nerve scaffolding to facilitate endogenous repair processes, and then are removed. Silks are biopolymers naturally produced by many species of arthropods including spiders, caterpillars and mites. The silk fibers are secreted by the labial gland of the larvae of some orders of Holometabola (insects with pupa) or the spinnerets of spiders. The majority of studies using silks for biomedical applications use materials from silkworms or spiders, mostly of the genus Nephila clavipes. Silk is one of the most promising biomaterials with effects not only in nerve regeneration, but in a number of regenerative applications. The development of silks for human biomedical applications is of high scientific and clinical interest. Biomaterials in use for biomedical applications have to meet a number of requirements such as biocompatibility and elicitation of no more than a minor inflammatory response, biodegradability in a reasonable time and specific structural properties. Here we present the current status in the field of silk-based conduit development for nerve repair and discuss current advances with regard to potential clinical transfer of an implantable nerve conduit for enhancement of nerve regeneration. PMID:27775616

  9. The Bengamides: A Mini-Review of Natural Sources, Analogues, Biological Properties, Biosynthetic Origins, and Future Prospects

    PubMed Central

    2017-01-01

    This review focuses entirely on the natural bengamides and selected synthetic analogues that have inspired decades of research. Bengamide A was first reported in 1986 from the sponge Jaspis cf. coriacea, and bengamide-containing sponges have been gathered from many biogeographic sites. In 2005, a terrestrial Gram-negative bacterium, Myxococcus virescens, was added as a source for bengamides. Biological activity data using varying bengamide-based scaffolds has enabled fine-tuning of structure–activity relationships. Molecular target finding contributed to the creation of a synthetic “lead” compound, LAF389, that was the subject of a phase I anticancer clinical trial. Despite clinical trial termination, the bengamide compound class is still attracting worldwide attention. Future breakthroughs based on the bengamide scaffold are possible and could build on their nanomolar in vitro and positive in vivo antiproliferative and antiangiogenic properties. Bengamide molecular targets include methionine aminopeptidases (MetAP1 and MetAP2) and nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB). A mixed PKS/NRPS biosynthetic gene cluster appears to be responsible for creation of the bengamides. This review highlights that the bengamides have driven inspirational studies and that they will remain relevant for future research, even 30 years after the discovery of the first structures. PMID:28185457

  10. The Bengamides: A Mini-Review of Natural Sources, Analogues, Biological Properties, Biosynthetic Origins, and Future Prospects.

    PubMed

    White, Kimberly N; Tenney, Karen; Crews, Phillip

    2017-03-24

    This review focuses entirely on the natural bengamides and selected synthetic analogues that have inspired decades of research. Bengamide A was first reported in 1986 from the sponge Jaspis cf. coriacea, and bengamide-containing sponges have been gathered from many biogeographic sites. In 2005, a terrestrial Gram-negative bacterium, Myxococcus virescens, was added as a source for bengamides. Biological activity data using varying bengamide-based scaffolds has enabled fine-tuning of structure-activity relationships. Molecular target finding contributed to the creation of a synthetic "lead" compound, LAF389, that was the subject of a phase I anticancer clinical trial. Despite clinical trial termination, the bengamide compound class is still attracting worldwide attention. Future breakthroughs based on the bengamide scaffold are possible and could build on their nanomolar in vitro and positive in vivo antiproliferative and antiangiogenic properties. Bengamide molecular targets include methionine aminopeptidases (MetAP1 and MetAP2) and nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB). A mixed PKS/NRPS biosynthetic gene cluster appears to be responsible for creation of the bengamides. This review highlights that the bengamides have driven inspirational studies and that they will remain relevant for future research, even 30 years after the discovery of the first structures.

  11. The Haughton Impact Structure as an Analogue to Mars: Polygons and the Nature of Their Depositional Environment

    NASA Astrophysics Data System (ADS)

    Godin, E.; Osinski, G. R.

    2016-09-01

    Thermal contraction polygons can differ in definition, aspect, shape, and size. Three types of deposits with respectively distinct polygons near Haughton Impact Structure (Devon Island, NU, Canada) were investigated as analogues to polygons on Mars.

  12. Natural and industrial analogues for release of CO2 from storagereservoirs: Identification of features, events, and processes and lessonslearned

    SciTech Connect

    Lewicki, Jennifer L.; Birkholzer, Jens; Tsang, Chin-Fu

    2006-03-03

    The injection and storage of anthropogenic CO{sub 2} in deep geologic formations is a potentially feasible strategy to reduce CO{sub 2} emissions and atmospheric concentrations. While the purpose of geologic carbon storage is to trap CO{sub 2} underground, CO{sub 2} could migrate away from the storage site into the shallow subsurface and atmosphere if permeable pathways such as well bores or faults are present. Large-magnitude releases of CO{sub 2} have occurred naturally from geologic reservoirs in numerous volcanic, geothermal, and sedimentary basin settings. Carbon dioxide and natural gas have also been released from geologic CO{sub 2} reservoirs and natural gas storage facilities, respectively, due to influences such as well defects and injection/withdrawal processes. These systems serve as natural and industrial analogues for the potential release of CO{sub 2} from geologic storage reservoirs and provide important information about the key features, events, and processes (FEPs) that are associated with releases, as well as the health, safety, and environmental consequences of releases and mitigation efforts that can be applied. We describe a range of natural releases of CO{sub 2} and industrial releases of CO{sub 2} and natural gas in the context of these characteristics. Based on this analysis, several key conclusions can be drawn, and lessons can be learned for geologic carbon storage. First, CO{sub 2} can both accumulate beneath, and be released from, primary and secondary reservoirs with capping units located at a wide range of depths. Both primary and secondary reservoir entrapments for CO{sub 2} should therefore be well characterized at storage sites. Second, many natural releases of CO{sub 2} have been correlated with a specific event that triggered the release, such as magmatic fluid intrusion or seismic activity. The potential for processes that could cause geomechanical damage to sealing cap rocks and trigger the release of CO{sub 2} from a storage

  13. Natural and industrial analogues for leakage of CO2 from storagereservoirs: identification of features, events, and processes and lessonslearned

    SciTech Connect

    Lewicki, Jennifer L.; Birkholzer, Jens; Tsang, Chin-Fu

    2006-02-28

    The injection and storage of anthropogenic CO2 in deepgeologic formations is a potentially feasible strategy to reduce CO2emissions and atmospheric concentrations. While the purpose of geologiccarbon storage is to trap CO2 underground, CO2 could migrate away fromthe storage site into the shallow subsurface and atmosphere if permeablepathways such as well bores or faults are present. Large-magnitudereleases of CO2 have occurred naturally from geologic reservoirs innumerous volcanic, geothermal, and sedimentary basin settings. Carbondioxide and natural gas have also been released from geologic CO2reservoirs and natural gas storage facilities, respectively, due toinfluences such as well defects and injection/withdrawal processes. Thesesystems serve as natural and industrial analogues for the potentialrelease of CO2 from geologic storage reservoirs and provide importantinformation about the key features, events, and processes (FEPs) that areassociated with releases, as well as the health, safety, andenvironmental consequences of releases and mitigation efforts that can beapplied. We describe a range of natural releases of CO2 and industrialreleases of CO2 and natural gas in the context of these characteristics.Based on this analysis, several key conclusions can be drawn, and lessonscan be learned for geologic carbon storage. First, CO2 can bothaccumulate beneath, and be released from, primary and secondaryreservoirs with capping units located at a wide range of depths. Bothprimary and secondary reservoir entrapments for CO2 should therefore bewell characterized at storage sites. Second, many natural releases of CO2have been correlated with a specific event that triggered the release,such as magmatic fluid intrusion or seismic activity. The potential forprocesses that could cause geomechanical damage to sealing cap rocks andtrigger the release of CO2 from a storage reservoir should be evaluated.Third, unsealed fault and fracture zones may act as fast and directconduits

  14. IRON PRECIPITATION AND ARSENIC ATTENUATION - ASSESSMENT OF ARSENIC NATURAL ATTENUATION OF THE SUBSURFACE USING A GEOCHEMICAL MODEL (PHREEQC)

    EPA Science Inventory

    Laboratory experiments show that amorphous and poorly crystallized ferric iron hydroxides have much greater capacity to attenuate arsenic compared to clays and other aluminosilicate minerals. Studies (e.g., Lin and Qvarfort, 1996) showed that a sudden change in geochemical condit...

  15. Global profiling and rapid matching of natural products using diagnostic product ion network and in silico analogue database: Gastrodia elata as a case study.

    PubMed

    Lai, Chang-Jiang-Sheng; Zha, Liangping; Liu, Da-Hui; Kang, Liping; Ma, Xiaojing; Zhan, Zhi-Lai; Nan, Tie-Gui; Yang, Jian; Li, Fajie; Yuan, Yuan; Huang, Lu-Qi

    2016-07-22

    Rapid discovery of novel compounds of a traditional herbal medicine is of vital significance for pharmaceutical industry and plant metabolic pathway analysis. However, discovery of unknown or trace natural products is an ongoing challenge. This study presents a universal targeted data-independent acquisition and mining strategy to globally profile and effectively match novel natural product analogues from an herbal extract. The famous medical plant Gastrodia elata was selected as an example. This strategy consists of three steps: (i) acquisition of accurate parent and adduct ions (PAIs) and the product ions data of all eluting compounds by untargeted full-scan MS(E) mode; (ii) rapid compound screening using diagnostic product ions (DPIs) network and in silico analogue database with SUMPRODUCT function to find novel candidates; and (iii) identification and isomerism discrimination of multiple types of compounds using ClogP and ions fragment behavior analyses. Using above data mining methods, a total of 152 compounds were characterized, and 70 were discovered for the first time, including series of phospholipids and novel gastroxyl derivatives. Furthermore, a number of gastronucleosides and phase II metabolites of gastrodin and parishins were discovered, including glutathionylated, cysteinylglycinated and cysteinated compounds, and phosphatidylserine analogues. This study extended the application of classical DPIs filter strategy and developed a structure-based screening approach with the potential for significant increase of efficiency for discovery and identification of trace novel natural products.

  16. An analogue peptide from the Cancer/Testis antigen PASD1 induces CD8+ T cell responses against naturally processed peptide.

    PubMed

    Hardwick, Nicola; Buchan, Sarah; Ingram, Wendy; Khan, Ghazala; Vittes, Gisella; Rice, Jason; Pulford, Karen; Mufti, Ghulam; Stevenson, Freda; Guinn, Barbara-ann

    2013-01-01

    We have previously identified the novel Cancer/Testis antigen PASD1 by immunoscreening a testis library with pooled acute myeloid leukemia (AML) patient sera. To develop a cytotoxic T lymphocyte (CTL)-inducing vaccine, we have now investigated the carboxy-terminal region, known to contain serological determinants, for MHC class I (HLA-A⋆0201)-binding peptides. Algorithm-selected natural peptides failed to show detectable HLA-A⋆0201 binding in T2 assays. However, anchor-modified analogue peptides showed enhanced binding, with decreased off-rates. Analogue peptide-loaded antigen-presenting cells (APCs) induced IFN-γ production by T cells from normal donors and patients. In addition, peptide-specific T cells could be expanded from cancer patients by stimulation with the PASD1 analogue peptide Pa14. For clinical application, a DNA fusion gene vaccine encoding Pa14 was designed and tested in "humanized" mice. Splenocytes from vaccinated mice showed in vitro cytotoxicity against tumour cells, either exogenously loaded with the corresponding wild-type peptide (Pw8) or expressing endogenously processed PASD1 protein. We show for the first time that a DNA vaccine encoding an altered PASD1 epitope can induce CTLs to target the natural peptide expressed by human tumour cells.

  17. Studies on mimicry of naturally occurring annonaceous acetogenins: non-THF analogues leading to remarkable selective cytotoxicity against human tumor cells.

    PubMed

    Zeng, Bu-Bing; Wu, Yikang; Jiang, Sheng; Yu, Qian; Yao, Zhu-Jun; Liu, Zhong-Hai; Li, Hong-Yan; Li, Yan; Chen, Xiao-Guang; Wu, Yu-Lin

    2003-01-03

    A class of structurally simplified analogues of the naturally occurring annonaceous acetogenins were developed, amongst which some non-THF analogues showed remarkable cytotoxicities against tumor cell lines, as well as good selectivity between human tumor cells and normal cells. The synthetic routes were significantly shortened because of the removal of the chiral centers bearing the THF rings on the natural templates. This simplification also provides access to the parallel synthesis of these mimics by a combinatorial strategy. The remaining stereogenic centers at the positions alpha to the ethereal links were introduced by the Chiron approach from the easily accessible chiral building blocks 6a and/or 6b, made in turn from L-ascorbic acid or D-mannitol, while the one in the butenolide segment was taken from L-lactate. All four diastereomeric non-THF analogues 2a-2d showed remarkable activity against the HCT-8 cell line, and better differentiation was found when testing against the HT-29 cell line. It was also discovered that both the butenolide and ethylene glycol subunits play essential roles in the cytotoxicities against tumor cell lines, while the 10-substituted hydroxy group and the absolute configuration of methyl group at the butenolide moiety are less important for their activity.

  18. Lessons from Natural CO2 Leakage Analogue Site Studies and their Application to Secure CO2 Storage and Monitoring

    NASA Astrophysics Data System (ADS)

    Han, W.; McPherson, B. J.; Kim, K.; Chae, G.; Yum, B.

    2011-12-01

    At CO2 injection sites, CO2 leakage from the storage formation could be catastrophic. CO2 is a highly compressible fluid, typically injected at high pressure and temperature conditions. If this compressed CO2 reaches highly permeable conduits such as faults and fractures, CO2 could leak unabated to other formations (e.g. fresh water aquifers) and/or to the surface. Assuming a fast-flow path to the surface, CO2 escaping from the storage formation instantaneously reaches the surface while experiencing adiabatic expansion, which results in Joule-Thomson cooling. The addressed eruptive mechanisms are analogues to natural CO2 eruption mechanisms, which are found in CO2-driven cold-water geysers around the world. A notable example of a CO2-driven cold-water geyser is the Crystal Geyser in central Utah. The fluid mechanics of this regularly erupting geyser was investigated by instrumenting its conduit with pressure, temperature, pH, EC, and dissolved oxygen sensors, measuring every 1 minute during and between eruptions. Results of these measurements suggest that the time-scale of a single-eruption cycle is composed of four successive eruption types with two recharge periods ranging from 30 to 40 hours. Current eruption patterns exhibit a bimodal distribution although previous measurements and anecdotal evidence suggests that this pattern was different prior to recent seismic activity. This cold geyser's eruptions are regular and predictable, and reflect pressure, temperature, EC, pH, and dissolved oxygen changes resulting from Joule-Thomson cooling, endothermic CO2 exsolution, and exothermic CO2 dissolution. Specifically, the perturbation of pressure and temperature data observed at the Crystal Geyser suggested the possibility of using temperature sensing technology within the observation well at the engineered CO2 sequestration site. With the lessons learned from the Crystal Geyser studies, we established the theoretical framework of temperature changes caused by CO2

  19. Total Synthesis of Vinblastine, Related Natural Products, and Key Analogues and Development of Inspired Methodology Suitable for the Systematic Study of Their Structure–Function Properties

    PubMed Central

    2015-01-01

    Conspectus Biologically active natural products composed of fascinatingly complex structures are often regarded as not amenable to traditional systematic structure–function studies enlisted in medicinal chemistry for the optimization of their properties beyond what might be accomplished by semisynthetic modification. Herein, we summarize our recent studies on the Vinca alkaloids vinblastine and vincristine, often considered as prototypical members of such natural products, that not only inspired the development of powerful new synthetic methodology designed to expedite their total synthesis but have subsequently led to the discovery of several distinct classes of new, more potent, and previously inaccessible analogues. With use of the newly developed methodology and in addition to ongoing efforts to systematically define the importance of each embedded structural feature of vinblastine, two classes of analogues already have been discovered that enhance the potency of the natural products >10-fold. In one instance, remarkable progress has also been made on the refractory problem of reducing Pgp transport responsible for clinical resistance with a series of derivatives made accessible only using the newly developed synthetic methodology. Unlike the removal of vinblastine structural features or substituents, which typically has a detrimental impact, the additions of new structural features have been found that can enhance target tubulin binding affinity and functional activity while simultaneously disrupting Pgp binding, transport, and functional resistance. Already analogues are in hand that are deserving of full preclinical development, and it is a tribute to the advances in organic synthesis that they are readily accessible even on a natural product of a complexity once thought refractory to such an approach. PMID:25586069

  20. Analogue Gravity.

    PubMed

    Barceló, Carlos; Liberati, Stefano; Visser, Matt

    2011-01-01

    Analogue gravity is a research programme which investigates analogues of general relativistic gravitational fields within other physical systems, typically but not exclusively condensed matter systems, with the aim of gaining new insights into their corresponding problems. Analogue models of (and for) gravity have a long and distinguished history dating back to the earliest years of general relativity. In this review article we will discuss the history, aims, results, and future prospects for the various analogue models. We start the discussion by presenting a particularly simple example of an analogue model, before exploring the rich history and complex tapestry of models discussed in the literature. The last decade in particular has seen a remarkable and sustained development of analogue gravity ideas, leading to some hundreds of published articles, a workshop, two books, and this review article. Future prospects for the analogue gravity programme also look promising, both on the experimental front (where technology is rapidly advancing) and on the theoretical front (where variants of analogue models can be used as a springboard for radical attacks on the problem of quantum gravity).

  1. Natural Analogues - One Way to Help Build Public Confidence in the Predicted Performance of a Mined Geologic Repository for Nuclear Waste

    SciTech Connect

    Stuckless, J. S.

    2002-02-26

    The general public needs to have a way to judge the predicted long-term performance of the potential high-level nuclear waste repository at Yucca Mountain. The applicability and reliability of mathematical models used to make this prediction are neither easily understood nor accepted by the public. Natural analogues can provide the average person with a tool to assess the predicted performance and other scientific conclusions. For example, hydrologists with the Yucca Mountain Project have predicted that most of the water moving through the unsaturated zone at Yucca Mountain, Nevada will move through the host rock and around tunnels. Thus, seepage into tunnels is predicted to be a small percentage of available infiltration. This hypothesis can be tested experimentally and with some quantitative analogues. It can also be tested qualitatively using a variety of analogues such as (1) well-preserved Paleolithic to Neolithic paintings in caves and rock shelters, (2) biological remains preserved in caves and rock shelters, and (3) artifacts and paintings preserved in man-made underground openings. These examples can be found in materials that are generally available to the non-scientific public and can demonstrate the surprising degree of preservation of fragile and easily destroyed materials for very long periods of time within the unsaturated zone.

  2. The role of natural glasses as analogues in projecting the long-term alteration of high-level nuclear waste glasses: Part 1

    SciTech Connect

    Mazer, J.J.

    1993-12-31

    The common observation of glasses persisting in natural environments for long periods of time (up to tens of millions of years) provides compelling evidence that these materials can be kinetically stable in a variety of subsurface environments. This paper reviews how natural and historical synthesized glasses can be employed as natural analogues for understanding and projecting the long-term alteration of high-level nuclear waste glasses. The corrosion of basaltic glass results in many of the same alteration features found in laboratory testing of the corrosion of high-level radioactive waste glasses. Evidence has also been found indicating similarities in the rate controlling processes, such as the effects of silica concentration on corrosion in groundwater and in laboratory leachates. Naturally altered rhyolitic glasses and tektites provide additional evidence that can be used to constrain estimates of long-term waste glass alteration. When reacted under conditions where water is plentiful, the corrosion for these glasses is dominated by network hydrolysis, while the corrosion is dominated by molecular water diffusion and secondary mineral formation under conditions where water contact is intermittent or where water is relatively scarce. Synthesized glasses that have been naturally altered result in alkali-depleted alteration features that are similar to those found for natural glasses and for nuclear waste glasses. The characteristics of these alteration features appear to be dependent on the alteration conditions which affect the dominant reaction processes during weathering. In all cases, care must be taken to ensure that the information being provided by natural analogues is related to nuclear waste glass corrosion in a clear and meaningful way.

  3. Extending the structure-activity relationship study of marine natural ningalin B analogues as P-glycoprotein inhibitors.

    PubMed

    Yang, Chao; Wong, Iris L K; Peng, Kai; Liu, Zhen; Wang, Peng; Jiang, Tingfu; Jiang, Tao; Chow, Larry M C; Wan, Sheng Biao

    2017-01-05

    In the present study, a total of 25 novel ningalin B analogues were synthesized and evaluated for their P-gp modulating activity in a P-gp overexpressed breast cancer cell line LCC6MDR. Preliminary structure-activity study shows that A ring and its two methoxy groups are important pharmacophores for P-gp inhibiting activity. Among all derivatives, 23 is the most potent P-gp modulator with EC50 of 120-165 nM in reversing paclitaxel, DOX, vinblastine and vincristine resistance. It is relatively safe to use with selective index at least greater than 606 compared to verapamil. Mechanistic study demonstrates that compound 23 reverses P-gp mediated drug resistance by inhibiting transport activity of P-gp, thereby restoring intracellular drug accumulation. In summary, our study demonstrates that ningalin B analogue 23 is a non-cytotoxic and effective P-gp chemosensitizer that can be used in the future for reversing P-gp mediated clinical cancer drug resistance.

  4. Hydrologic and geochemical data collected near Skewed Reservoir, an impoundment for coal-bed natural gas produced water, Powder River Basin, Wyoming

    USGS Publications Warehouse

    Healy, Richard W.; Rice, Cynthia A.; Bartos, Timothy T.

    2012-01-01

    The Powder River Structural Basin is one of the largest producers of coal-bed natural gas (CBNG) in the United States. An important environmental concern in the Basin is the fate of groundwater that is extracted during CBNG production. Most of this produced water is disposed of in unlined surface impoundments. A 6-year study of groundwater flow and subsurface water and soil chemistry was conducted at one such impoundment, Skewed Reservoir. Hydrologic and geochemical data collected as part of that study are contained herein. Data include chemistry of groundwater obtained from a network of 21 monitoring wells and three suction lysimeters and chemical and physical properties of soil cores including chemistry of water/soil extracts, particle-size analyses, mineralogy, cation-exchange capacity, soil-water content, and total carbon and nitrogen content of soils.

  5. Of the necessity of knowledge of the natural pedo-geochemical background content in the evaluation of the contamination of soils by trace elements.

    PubMed

    Baize, D; Sterckeman, T

    2001-01-08

    In order to evaluate the contamination of the Dornach (Switzerland) site within the framework of the CEEM-Soil project, each participating team was allowed to take a maximum of 15 samples. The French team's sampling was organized in such a way as to answer the following questions: (i) what is the natural concentration of the soils at this site (local pedo-geochemical background content)?; (ii) what are the levels of Cd, Cu, Pb and Zn contamination of the soil?; (iii) what is the depth reached by the surface contamination that is derived from atmospheric fallout?; (iv) how is the contamination spread along the longest axis of the area under study? The relationships between total Fe and the trace metals have allowed local variations in the natural pedo-geochemical background content to be detected and thus permitted the anthropogenic contamination to be estimated. There would appear to be a low level of Pb contamination over all the site investigated (an increase of the order of 5-10 mg kg(-1) on the background level), limited to the surface humus-bearing layers. There is also a significant contamination by Cu over all of the site (an increase of the order of 30-40 mg kg(-1)). This contamination has remained in the surface horizons (0-20 cm). Very high Zn and Cd concentrations have been found in the four surface (0-4 cm) and deep horizons (15-70 cm) taken under the forest and very much lower values in the samples taken from cultivated soils. The most likely explanation is an unequal inheritance between the upper part of the site (wooded with thinner very clayey soils) and the lower cultivated part of the site (with thicker less clayey soils developed in a loamy material). For various reasons, it seems unlikely that a contamination of the wooded part should be so much higher than the cultivated part due to the interception of atmospheric dust by the trees. The local pedo-geochemical background Cd and Zn content of the upper wooded part proved to be clearly higher than

  6. Geochemical, mineralogical and microbiological characteristics of sediment from a naturally reduced zone in a uranium-contaminated aquife

    SciTech Connect

    Campbell, K M; K Kukkadapu, R K; Qafoku, N P; Peacock, A D; Lesher, E; Williams, K H; Bargar, J R; Wilkins, M J; Figueroa, L; Ranville, J; Davis, J A; Long, P E

    2012-05-23

    Localized zones or lenses of naturally reduced sediments have the potential to play a significant role in the fate and transport of redox-sensitive metals and metalloids in aquifers. To assess the mineralogy, microbiology and redox processes that occur in these zones, several cores from a region of naturally occurring reducing conditions in a U-contaminated aquifer (Rifle, CO) were examined. Sediment samples from a transect of cores ranging from oxic/suboxic Rifle aquifer sediment to naturally reduced sediment were analyzed for U and Fe content, oxidation state, and mineralogy; reduced S phases; and solid-phase organic C content using a suite of analytical and spectroscopic techniques on bulk sediment and size fractions. Solid-phase U concentrations were higher in the naturally reduced zone, with a high proportion of the U present as U(IV). The sediments were also elevated in reduced S phases and Fe(II), indicating it is very likely that U(VI), Fe(III), and SO4 reduction has occurred or is occurring in the sediment. The microbial community was assessed using lipid- and DNA-based techniques, and statistical redundancy analysis was performed to determine correlations between the microbial community and the geochemistry. Increased concentrations of solid-phase organic C and biomass in the naturally reduced sediment suggests that natural bioreduction is stimulated by a zone of increased organic C concentration associated with fine-grained material and lower permeability to groundwater flow. Characterization of the naturally bioreduced sediment provides an understanding of the natural processes that occur in the sediment under reducing conditions and how they may impact natural attenuation of radionuclides and other redox sensitive materials. Results also suggest the importance of recalcitrant organic C for maintaining reducing conditions and U immobilization.

  7. Geochemical, mineralogical and microbiological characteristics of sediment from a naturally reduced zone in a uranium-contaminated aquifer

    SciTech Connect

    Campbell, Kate M.; Kukkadapu, Ravi K.; Qafoku, Nikolla; Peacock, Aaron D.; Lesher, E.; Williams, Kenneth H.; Bargar, John R.; Wilkins, Michael J.; Figueroa, Linda A.; Ranville, James; Davis, James; Long, Philip E.

    2012-05-23

    Localized zones or lenses of naturally reduced sediments have the potential to play a significant role in the fate and transport of redox-sensitive metals and metalloids in aquifers. To assess the mineralogy, microbiology, and redox processes that occur in these zones, we examined several cores from a region of naturally occurring reducing conditions in a uranium-contaminated aquifer (Rifle, CO). Sediment samples from a transect of cores ranging from oxic/suboxic Rifle aquifer sediment to naturally reduced sediment were analyzed for uranium and iron content, oxidation state, and mineralogy, reduced sulfur phases, and solid phase organic carbon content using a suite of analytical and spectroscopic techniques on bulk sediment and size fractions. Solid-phase uranium concentrations were higher in the naturally reduced zone, with a high proportion of the uranium present as reduced U(IV). The sediments were also elevated in reduced sulfur phases and Fe(II), indicating it is very likely that U(VI), Fe(III), and sulfate reduction occurred or is occurring in the sediment. The microbial community was assessed using lipid- and DNA-based techniques, and statistical redundancy analysis was performed to determine correlations between the microbial community and the geochemistry. Increased concentration of solid phase organic carbon and biomass in the naturally reduced sediment suggests that natural bioreduction is stimulated by a zone of increased organic carbon concentration associated with fine-grained material and lower permeability to groundwater flow. Characterization of the naturally bioreduced sediment provides an understanding of the natural processes that occur in the sediment under reducing conditions and how they may impact natural attenuation of radionuclides and other redox sensitive materials. Results also suggest the importance of recalcitrant organic carbon for maintaining reducing conditions and uranium immobilization.

  8. Geochemical, mineralogical and microbiological characteristics of sediment from a naturally reduced zone in a uranium-contaminated aquifer

    SciTech Connect

    Campbell, K. M.; Kukkadapu, R. K.; Qafoku, N. P.; Peacock, A. D.; Lesher, E.; Williams, K. H.; Bargar, J. R.; Wilkins, M. J.; Figueroa, L.; Ranville, J.; Davis, J. A.; Long, P. E.

    2012-08-01

    Localized zones or lenses of naturally reduced sediments have the potential to play a significant role in the fate and transport of redox-sensitive metals and metalloids in aquifers. To assess the mineralogy, microbiology and redox processes that occur in these zones, several cores from a region of naturally occurring reducing conditions in a U-contaminated aquifer (Rifle, CO) were examined. Sediment samples from a transect of cores ranging from oxic/suboxic Rifle aquifer sediment to naturally reduced sediment were analyzed for U and Fe content, oxidation state, and mineralogy; reduced S phases; and solid-phase organic C content using a suite of analytical and spectroscopic techniques on bulk sediment and size fractions. Solid-phase U concentrations were higher in the naturally reduced zone, with a high proportion of the U present as U(IV). The sediments were also elevated in reduced S phases and Fe(II), indicating it is very likely that U(VI), Fe(III), and SO4 reduction has occurred or is occurring in the sediment. The microbial community was assessed using lipid- and DNA-based techniques, and statistical redundancy analysis was performed to determine correlations between the microbial community and the geochemistry. Increased concentrations of solid-phase organic C and biomass in the naturally reduced sediment suggests that natural bioreduction is stimulated by a zone of increased organic C concentration associated with fine-grained material and lower permeability to groundwater flow. Characterization of the naturally bioreduced sediment provides an understanding of the natural processes that occur in the sediment under reducing conditions and how they may impact natural attenuation of radionuclides and other redox sensitive materials. Results also suggest the importance of recalcitrant organic C for maintaining reducing conditions and U immobilization.

  9. Geological and geochemical criteria for the continental nature of the Mendeleev Rise (the Arctic Ocean) from the data of drilling and dredging of seabed rock material

    NASA Astrophysics Data System (ADS)

    Morozov, Andrey; Petrov, Oleg; Kremenetskiy, Alexander; Kashubin, Sergey; Rekant, Pavel; Gusev, Eugene; Shokalskiy, Sergey; Shevchenko, Sergey; Sergeev, Sergey; Artyushkov, Eugene

    2013-04-01

    The results are presented of geological and geophysical studies on the Mendeleev Rise at 10 test sites at 79°N to 83°N (expedition "Arktika-2012" in August-September 2012). During the expedition, for the first time, three boreholes were drilled in the bedrocks of the Mendeleev Rise basement at a depth of 1700-2600 m, and more than 20 thousand fragments of seabed rock material were dredged. Among them carbonate-bearing rocks including dolomite with relicts of trilobites and ostracoderms (D3-C) constitute up 65 %. Up to 20% are terrigenous rocks with a predominance of quartz sandstones. Magmatic rocks constitute 10-15% of the samples (including 8% of gabbro-dolerite and 2 % of granite) with 5% of metamorphic rocks. The boreholes revealed magmatic mafic rocks of basalt to basaltic andesite to trachyandesite series (SiO2-48-58% K2O+Na2O-3,4-9,2%) including epigenically altered volcanic breccias. All fragments of magmatic mafic rocks have a similar mineral and chemical composition and are grouped with gabbro dolerite (SiO2-49-51%, K2O+Na2O-2,5-3,0%). Preliminary results of mineralogic, geochemical and of isotopic geochemical (ICP-OEC, ICP-MS, RFA, Sm-Nd, Rb-Sr, EPMA and others) analyses suggest the continental nature of the studied rocks and show a distinct difference from rocks of the Gakkel Ridge in the Eurasian part of the ocean, which are of the oceanic origin. U-Pb dating of zircons from the core rocks and seabed rock material (SIMS SHRIMP II) indicate a wide range of their formation age: 2940-995, 639-385 and 303-203 Ma and thus suggest that they belong to volcanogenic terrigeneous carbonate-bearing bed of the ancient platform composing the floor of Amerasian part of the Arctic Ocean.

  10. Geochemical processes and the effects of natural organic solutes on the solubility of selenium in coal-mine backfill samples from the Powder River basin, Wyoming

    USGS Publications Warehouse

    See, R.B.; Reddy, K.J.; Vance, G.F.; Fadlelmawla, A.A.; Blaylock, M.J.

    1995-01-01

    Geochemical processes and the effects of natural organic solutes on the solubility of selenium in coal-mine backfill aquifers were investigated. Backfill and ground-water samples were collected at coal mines in the Powder River Basin, Wyoming. Backfill was generally dominated by aluminum (14,400 to 49,000 mg/kg (milligrams per kilogram)), iron (3,330 to 23,200 mg/kg), and potassium (7,950 to 18,000 mg/kg). Backfill saturated-paste selenium concentrations ranged from 1 to 156 mg/kg (microsiemens per kilogram). Ground-water total selenium concentrations ranged from 3 to 125 mg/L. Dissolved organic carbon in all ground-water samples was dominated by hydrophobic and hydrophilic acids (38 to 84 percent). Selenite sorption/desorption experiments were conducted using background solutions of distilled-deionized water, 0.1 molar calcium chloride, and isolated hydrophobic and hydrophilic acids. Selenite sorption was larger when 0.1 molar calcium chloride was used. The addition of hydrophilic acid decreased selenite sorption more than the addition of hydrophobic acids. Geochemical modelling was used to predict the solid phases controlling dissolved selenium concentrations and to evaluate the effects of dissolved organic carbon on selenium solubility. Results suggested that 55 to 90 percent of selenium in backfill precipitation/dissolution extracts was dominated by magnesium selenate ion pairs. Dissolved organic carbon had little effect on selenium speciation. A redox chamber was constructed to control Eh and pH in water and backfill-core sample suspensions. The response of selenite and selenate in water samples to redox conditions did not follow thermodynamic predictions. Reduction of selenate in water samples did not occur at any of the redox levels tested.

  11. Geochemical analysis of atlantic rim water, carbon county, wyoming: New applications for characterizing coalbed natural gas reservoirs

    USGS Publications Warehouse

    McLaughlin, J.F.; Frost, C.D.; Sharma, Shruti

    2011-01-01

    Coalbed natural gas (CBNG) production typically requires the extraction of large volumes of water from target formations, thereby influencing any associated reservoir systems. We describe isotopic tracers that provide immediate data on the presence or absence of biogenic natural gas and the identify methane-containing reservoirs are hydrologically confined. Isotopes of dissolved inorganic carbon and strontium, along with water quality data, were used to characterize the CBNG reservoirs and hydrogeologic systems of Wyoming's Atlantic Rim. Water was analyzed from a stream, springs, and CBNG wells. Strontium isotopic composition and major ion geochemistry identify two groups of surface water samples. Muddy Creek and Mesaverde Group spring samples are Ca-Mg-S04-type water with higher 87Sr/86Sr, reflecting relatively young groundwater recharged from precipitation in the Sierra Madre. Groundwaters emitted from the Lewis Shale springs are Na-HCO3-type waters with lower 87Sr/86Sr, reflecting sulfate reduction and more extensive water-rock interaction. To distinguish coalbed waters, methanogenically enriched ??13CDIC wasused from other natural waters. Enriched ??13CDIC, between -3.6 and +13.3???, identified spring water that likely originates from Mesaverde coalbed reservoirs. Strongly positive ??13CDIC, between +12.6 and +22.8???, identified those coalbed reservoirs that are confined, whereas lower ??13CDIC, between +0.0 and +9.9???, identified wells within unconfined reservoir systems. Copyright ?? 2011. The American Association of Petroleum Geologists. All rights reserved.

  12. Linked metatranscriptomic and geochemical data indicate microbial succession in naturally reduced aquifer sediments dominated by H2-oxidizing Comamonadaceae

    NASA Astrophysics Data System (ADS)

    Jewell, T. N. M.; Karaoz, U.; Bill, M.; Chakraborty, R.; Brodie, E.; Williams, K. H.; Beller, H. R.

    2015-12-01

    In this study, we sought to better understand what natural organic matter fuels heterotrophic microbial communities in the anoxic subsurface at the Rifle (CO) site and what genes may be diagnostic of that activity. We conducted a 20-day microcosm experiment with naturally reduced zone (NRZ) sediments and collected replicate samples every 5 days for omics (metagenome and metatranscriptome) and biogeochemical measurements (e.g., continuous CO2 production, H2, CH4, acetate, DOC, Fe(II), sulfate, NH4+, spectroscopic analyses of sediment OM). No electron donors were added other than the NRZ sediment, which is enriched in organic matter relative to typical Rifle aquifer material. The microcosms were constructed and incubated under anaerobic conditions in serum bottles with a N2headspace. Biogeochemical measurements indicate that the decomposition of native organic matter occurred in different phases, including depletion of DOC and release of CO2 during the first week of incubation, followed by a pulse of acetogenesis and methanogenesis after 2 weeks (with acetogenesis dominating carbon flux after 2 weeks). While H2 remained below detection levels throughout the study, a peak of [NiFe] uptake hydrogenase, acetyl-CoA synthetase, urease, and nitrate reductase transcripts belonging to the Comamonadaceae family occurred at day 15. Some members of Comamonadaceae are facultative H2-oxidizing chemolithoautotrophs and fix carbon via the acetogenic Wood-Ljungdahl pathway. Comamonadaceae plateaued at 73% of the metagenome at this time and represented 69% of the metatranscriptome, succeeding the S-oxidizing Sulfurimonas genus. Sulfurimonas species were the dominant group at day 0, accounting for 43% of the metagenome and 25% of the metatranscriptome, decreasing to 11% in both the metagenome and metatranscriptome by day 10. Less abundant but still present were transcripts for genes involved in cellulose degradation (glycosyl hydrolases), and glycolysis (phosphofructokinase

  13. Geochemical survey of Levante Bay, Vulcano Island (Italy), a natural laboratory for the study of ocean acidification.

    PubMed

    Boatta, F; D'Alessandro, W; Gagliano, A L; Liotta, M; Milazzo, M; Rodolfo-Metalpa, R; Hall-Spencer, J M; Parello, F

    2013-08-30

    Shallow submarine gas vents in Levante Bay, Vulcano Island (Italy), emit around 3.6t CO2 per day providing a natural laboratory for the study of biogeochemical processes related to seabed CO2 leaks and ocean acidification. The main physico-chemical parameters (T, pH and Eh) were measured at more than 70 stations with 40 seawater samples were collected for chemical analyses. The main gas vent area had high concentrations of dissolved hydrothermal gases, low pH and negative redox values all of which returned to normal seawater values at distances of about 400m from the main vents. Much of the bay around the vents is corrosive to calcium carbonate; the north shore has a gradient in seawater carbonate chemistry that is well suited to studies of the effects of long-term increases in CO2 levels. This shoreline lacks toxic compounds (such as H2S) and has a gradient in carbonate saturation states.

  14. Geochemical and Isotopic Analysis of Escaped Natural Gases in Hydraulically Fractured and non-Fractured sites in Cumberland Forest, Tennessee

    NASA Astrophysics Data System (ADS)

    Ajayi, M.; Ayers, J. C.; Hornberger, G. M.

    2015-12-01

    Methane (CH4) in the atmosphere accounts for 18% of the climate warming attributed to greenhouse gases. The rapid growth in high volume hydraulic fracturing (HVHF) technologies to procure natural gas raises concern for possible fugitive methane leaks. We measure the flux and carbon isotope composition of methane emitted from the soil into the atmosphere at two geologically similar sites in eastern Tennessee (Morgan Co.), one with HVHF ongoing and the other currently undeveloped. Our objective is to quantify potential non-point source emissions of microbial and thermogenic methane, which are principally distinguished by their δ13C signatures. Using cavity ring down spectroscopy (Picarro G2201-i) we collect rapid (~1 Hz) real-time measurements of methane emissions. The Picarro can measure fluxes of CH4 and CO2 at discrete locations by measuring their concentrations within a static and closed chamber that allows the gases to accumulate over time. Additionally, the mobility of the Picarro instrument permits the continuous collection of data, enabling broad spatial coverage. Applying geostatistical techniques to these data can highlight heterogeneities in the emissions of methane. Trends of where, how much, and what type of methane is escaping from the soil in environments with and without HVHF activities illustrate how to compare and contrast points as well as areas to assess the impact of this extensively implemented method of fossil fuel development.

  15. Clastic dikes of the Hatrurim basin (western flank of the Dead Sea) as natural analogues of alkaline concretes: Mineralogy, solution chemistry, and durability

    NASA Astrophysics Data System (ADS)

    Sokol, E. V.; Gaskova, O. L.; Kozmenko, O. A.; Kokh, S. N.; Vapnik, E. A.; Novikova, S. A.; Nigmatulina, E. N.

    2014-11-01

    This study shows that the mineral assemblages from clastic dikes in areas adjacent to the Dead Sea graben may be considered as natural analogues of alkaline concretes. The main infilling material of the clastic dikes is composed of well-sorted and well-rounded quartz sand. The cement of these hard rocks contains hydroxylapophyllite, tacharanite, calcium silicate hydrates, opal, calcite, and zeolite-like phases, which is indicative of a similarity of the natural cementation processes and industrial alkaline concrete production from quartz sands and industrial alkaline cements. The quartz grains exhibit a variety of reaction textures reflecting the interaction with alkaline solutions (opal and calcium hydrosilicate overgrowths; full replacement with apophyllite or thomsonite + apophyllite). The physicochemical analysis and reconstruction of the chemical composition of peralkaline Ca, Na, and K solutions that formed these assemblages reveal that the solutions evolved toward a more stable composition of zeolite-like phases, which are more resistant to long-term chemical weathering and atmospheric corrosion. The 40Ar/39Ar age of 6.2 ± 0.7 Ma obtained for apophyllite provides conclusive evidence for the high corrosion resistance of the assemblages consisting of apophyllite and zeolite-like phases.

  16. Progression of natural attenuation processes at a crude-oil spill site . I. Geochemical evolution of the plume

    USGS Publications Warehouse

    Cozzarelli, I.M.; Bekins, B.A.; Baedecker, M.J.; Aiken, G.R.; Eganhouse, R.P.; Tuccillo, M.E.

    2001-01-01

    A 16-year study of a hydrocarbon plume shows that the extent of contaminant migration and compound-specific behavior have changed as redox reactions, most notably iron reduction, have progressed over time. Concentration changes at a small scale, determined from analysis of pore-water samples drained from aquifer cores, are compared with concentration changes at the plume scale, determined from analysis of water samples from an observation well network. The small-scale data show clearly that the hydrocarbon plume is growing slowly as sediment iron oxides are depleted. Contaminants, such as ortho-xylene that appeared not to be moving downgradient from the oil on the basis of observation well data, are migrating in thin layers as the aquifer evolves to methanogenic conditions. However, the plume-scale observation well data show that the downgradient extent of the Fe2+ and BTEX plume did not change between 1992 and 1995. Instead, depletion of the unstable Fe (III) oxides near the subsurface crude-oil source has caused the maximum dissolved iron concentration zone within the plume to spread at a rate of approximately 3 m/year. The zone of maximum concentrations of benzene, toluene, ethylbenzene and xylene (BTEX) has also spread within the anoxic plume. In monitoring the remediation of hydrocarbon-contaminated ground water by natural attenuation, subtle concentration changes in observation well data from the anoxic zone may be diagnostic of depletion of the intrinsic electron-accepting capacity of the aquifer. Recognition of these subtle patterns may allow early prediction of growth of the hydrocarbon plume. Copyright ?? 2001 .

  17. Geophysical and geochemical nature of relaminated arc-derived lower crust underneath oceanic domain in southern Mongolia

    NASA Astrophysics Data System (ADS)

    Guy, Alexandra; Schulmann, Karel; Janoušek, Vojtech; Štípská, Pavla; Armstrong, Robin; Belousova, Elena; Dolgopolova, Alla; Seltmann, Reimar; Lexa, Ondrej; Jiang, Yingde; Hanžl, Pavel

    2016-04-01

    The Central Asian Orogenic Belt (CAOB) in southern Mongolia consists of E-W trending Neoproterozoic cratons and Silurian-Devonian oceanic tectonic zones. Previous study revealed that the Early Paleozoic accretionary wedge and the oceanic tectonic zone are underlain by a layer giving a homogeneous gravity signal. Forward gravity modelling suggests that this layer is not formed of high-density material typical of lower oceanic crust but is composed of low- to intermediate-density rocks resembling continental crust. The nature of this lower crust is constrained by the whole-rock geochemistry and zircon Hf isotopic signature of abundant Late Carboniferous high-K calc-alkaline and Early Permian A-type granitoids intruding the two Early Paleozoic domains. It is possible to explain the genesis of these granitoids by anatexis of juvenile, metaigneous (tonalitic-gabbroic) rocks of Late Cambrian age, the source of which is presumed to lie in the "Khantaishir" arc (520-495Ma) further north. In order to test this hypothesis, the likely modal composition and density of Khantaishir arc-like protoliths are thermodynamically modelled at granulite- and higher amphibolite-facies conditions. It is shown that the current average density of the lower crust inferred by gravity modelling (2730 ±20kg/m3) matches best metamorphosed leucotonalite to diorite. Based on these results, it is now proposed that Mongolian CAOB has an architecture in which the accretionary wedge and oceanic upper crust is underlain by allochthonous lower crust that originated in a Cambrian arc. A tectonic model explaining relamination of allochthonous felsic to intermediate lower crust beneath mafic upper crust is proposed.

  18. X-ray absorption fine-structure spectroscopy studies of Fe sites in natural human neuromelanin and synthetic analogues.

    PubMed Central

    Kropf, A J; Bunker, B A; Eisner, M; Moss, S C; Zecca, L; Stroppolo, A; Crippa, P R

    1998-01-01

    X-ray absorption fine-structure spectroscopy is used to study the local environment of the iron site in natural (human) neuromelanin extracted from substantia nigra tissue and in various synthetic neuromelanins. All the materials show Fe centered in a nearest neighbor sixfold (distorted) oxygen octahedron; the Fe-O distances, while slightly different in the natural and synthetic neuromelanin, are both approximately 2.0 A. Appreciable differences arise, however, in the second (and higher) coordination shells. In this case the synthetic melanin has the four planar oxygens bound to carbon rings with Fe-C distances of approximately 2.82 and 4.13 A; the human sample does not show the 2.82 A link but instead indicates a double shell at approximately 3.45 and 3.78 A. PMID:9826634

  19. Synthesis of psymberin analogues: probing a functional correlation with the pederin/mycalamide family of natural products.

    PubMed

    Jiang, Xin; Williams, Noelle; De Brabander, Jef K

    2007-01-18

    In this letter we describe an efficient synthesis of "psympederin", a hybrid between the novel antitumor natural product psymberin and the blister beetle toxin pederin. Evaluation of antiproliferative activity reveals that the dihydroisocoumarin fragment is important for psymberin toxicity and the cyclic pederate fragment is important for pederin/mycalamide toxicity. On the basis of preliminary results described herein, we speculate that, despite their structural resemblance, psymberin and pederin/mycalamide induce toxicity through different mechanisms. [reaction: see text].

  20. Synthesis of withasomnines and their non-natural analogues from aldehydes and 4-nitro-1-butanol in three steps.

    PubMed

    Verma, Deepti; Kumar, Rahul; Namboothiri, Irishi N N

    2013-04-05

    Total synthesis of all three pyrazole-based withasomnine alkaloids and selected examples of their non-natural analogs has been achieved from readily available aldehydes and 4-nitro-1-butanol in three steps. Since 4-nitro-1-butanol in turn is prepared in two steps via Michael addition of nitromethane to acrylate followed by borane reduction of the ester group and the key 1,3-dipolar cycloaddition step is carried out with commercially available TMSCHN2, this approach is a very convenient and economical one.

  1. Comparison of shallow aquifer and soil gas monitoring approaches for detecting CO2 leakage at a natural analogue site in France

    NASA Astrophysics Data System (ADS)

    Widory, D.; Gal, F.; Proust, E.; Mayer, B.

    2011-12-01

    Natural analogue sites where geologic CO2 is leaking to the surface provide excellent opportunities to test approaches suitable for monitoring for potential CO2 leakage at carbon capture and storage sites. We tested isotope monitoring approaches for CO2 detection in shallow aquifers and the overlying soil zone at a CO2 analogue site near Sainte-Marguerite in the Massif Central (France). The Sainte-Marguerite area is located in the southern part of the Limagne graben (French Massif Central). The basement, composed of highly fractured granite, outcrops toward the west of the study area, notably around the Saladis spring. An intercalated arkosic permeable interval between fractured granite and Oligocene marls and limestones acts as a stratiform drain for fluid migration while the overlying thick Oligocene interval is impermeable and acts as a seal. The Allier river bed is located near the contact between the basement and the sedimentary rocks. Deep CO2-ladden fluids migrate through the arkose interval toward the Sainte-Marguerite area and sustain a number of local springs. The Sainte-Marguerite area is known for the travertine deposits associated with the CO2-rich natural springs. We collected water samples and effervescent gases at the springs as well as soil gases for chemical and isotopic analyses. The analytical parameters included major anions and cations, δ13C & δ18O of CO2, δD & δ18O of H2O and δ13C of dissolved inorganic carbon (DIC). Preliminary results revealed that δ13C values of CO2 in most groundwater and soil samples were similar. Oxygen isotope measurements revealed equilibrium between CO2 and H2O-oxygen in most samples, but except for a limited number of samples, δ18O values of water did not deviate significantly from the local meteoric water line. Our preliminary results suggest that both the groundwater and the soil sampling approaches should be capable of detecting leakage of CO2 provided that the leaking gas has a distinct isotopic

  2. Synthesis of high-mannose oligosaccharide analogues through click chemistry: true functional mimics of their natural counterparts against lectins?

    PubMed

    François-Heude, Marc; Méndez-Ardoy, Alejandro; Cendret, Virginie; Lafite, Pierre; Daniellou, Richard; Ortiz Mellet, Carmen; García Fernández, José M; Moreau, Vincent; Djedaïni-Pilard, Florence

    2015-01-26

    Terminal "high-mannose oligosaccharides" are involved in a broad range of biological and pathological processes, from sperm-egg fusion to influenza and human immunodeficiency virus infections. In spite of many efforts, their synthesis continues to be very challenging and actually represents a major bottleneck in the field. Whereas multivalent presentation of mannopyranosyl motifs onto a variety of scaffolds has proven to be a successful way to interfere in recognition processes involving high-mannose oligosaccharides, such constructs fail at reproducing the subtle differences in affinity towards the variety of protein receptors (lectins) and antibodies susceptible to binding to the natural ligands. Here we report a family of functional high-mannose oligosaccharide mimics that reproduce not only the terminal mannopyranosyl display, but also the core structure and the branching pattern, by replacing some inner mannopyranosyl units with triazole rings. Such molecular design can be implemented by exploiting "click" ligation strategies, resulting in a substantial reduction of synthetic cost. The binding affinities of the new "click" high-mannose oligosaccharide mimics towards two mannose specific lectins, namely the plant lectin concanavalin A (ConA) and the human macrophage mannose receptor (rhMMR), have been studied by enzyme-linked lectin assays and found to follow identical trends to those observed for the natural oligosaccharide counterparts. Calorimetric determinations against ConA, and X-ray structural data support the conclusion that these compounds are not just another family of multivalent mannosides, but real "structural mimics" of the high-mannose oligosaccharides.

  3. The role of anthropogenic and natural factors in shaping the geochemical evolution of groundwater in the Subei Lake basin, Ordos energy base, Northwestern China.

    PubMed

    Liu, Fei; Song, Xianfang; Yang, Lihu; Han, Dongmei; Zhang, Yinghua; Ma, Ying; Bu, Hongmei

    2015-12-15

    Groundwater resources are increasingly exploited for industrial and agricultural purposes in many arid regions globally, it is urgent to gain the impact of the enhanced anthropogenic pressure on the groundwater chemistry. The aim of this study was to acquire a comprehensive understanding of the evolution of groundwater chemistry and to identify the impact of natural and anthropogenic factors on the groundwater chemistry in the Subei Lake basin, Northwestern China. A total of 153 groundwater samples were collected and major ions were measured during the three campaigns (August and December 2013, May 2014). At present, the major hydrochemical facies in unconfined groundwater are Ca-Mg-HCO3, Ca-Na-HCO3, Na-Ca-HCO3, Na-HCO3, Ca-Mg-SO4 and Na-SO4-Cl types, while the main hydrochemical facies in confined groundwater are Ca-Mg-HCO3, Ca-Na-HCO3, Na-Ca-HCO3, Ca-HCO3 and Na-HCO3 types. Relatively greater seasonal variation can be observed in the chemical constituents of confined groundwater than that of unconfined groundwater. Rock weathering predominates the evolution of groundwater chemistry in conjunction with the cation exchange, and the dissolution/precipitation of gypsum, halite, feldspar, calcite and dolomite are responsible for the chemical constituents of groundwater. Anthropogenic activities can be classified as: (1) groundwater overexploitation; (2) excessive application of fertilizers in agricultural areas. Due to intensive groundwater pumping, the accelerated groundwater mineralization resulted in the local changes in hydrochemical facies of unconfined groundwater, while the strong mixture, especially a large influx of downward leakage from the unconfined aquifer into the confined aquifer, played a vital role in the fundamental variation of hydrochemical facies in confined aquifer. The nitrate contamination is mainly controlled by the local hydrogeological settings coupled with the traditional flood irrigation. The deeper insight into geochemical evolution of

  4. A combined methodology using electrical resistivity tomography, ordinary kriging and porosimetry for quantifying total C trapped in carbonate formations associated with natural analogues for CO2 leakage

    NASA Astrophysics Data System (ADS)

    Prado-Pérez, A. J.; Aracil, E.; Pérez del Villar, L.

    2014-06-01

    Currently, carbon deep geological storage is one of the most accepted methods for CO2 sequestration, being the long-term behaviour assessment of these artificial systems absolutely essential to guarantee the safety of the CO2 storage. In this sense, hydrogeochemical modelling is being used for evaluating any artificial CO2 deep geological storage as a potential CO2 sinkhole and to assess the leakage processes that are usually associated with these engineered systems. Carbonate precipitation, as travertines or speleothems, is a common feature in the CO2 leakage scenarios and, therefore, is of the utmost importance to quantify the total C content trapped as a stable mineral phase in these carbonate formations. A methodology combining three classical techniques such as: electrical resistivity tomography, geostatistical analysis and mercury porosimetry is described in this work, which was developed for calculating the total amount of C trapped as CaCO3 associated with the CO2 leakages in Alicún de las Torres natural analogue (Granada, Spain). The proposed methodology has allowed estimating the amount of C trapped as calcite, as more than 1.7 Mt. This last parameter, focussed on an artificial CO2 deep geological storage, is essential for hydrogeochemical modellers when evaluating whether CO2 storages constitute or not CO2 sinkholes. This finding is extremely important when assessing the long-term behaviour and safety of any artificial CO2 deep geological storage.

  5. A Nucleotide-Analogue-Induced Gain of Function Corrects the Error-Prone Nature of Human DNA Polymerase iota

    SciTech Connect

    Ketkar, Amit; Zafar, Maroof K.; Banerjee, Surajit; Marquez, Victor E.; Egli, Martin; Eoff, Robert L.

    2012-10-25

    Y-family DNA polymerases participate in replication stress and DNA damage tolerance mechanisms. The properties that allow these enzymes to copy past bulky adducts or distorted template DNA can result in a greater propensity for them to make mistakes. Of the four human Y-family members, human DNA polymerase iota (hpol{iota}) is the most error-prone. In the current study, we elucidate the molecular basis for improving the fidelity of hpol{iota} through use of the fixed-conformation nucleotide North-methanocarba-2{prime}-deoxyadenosine triphosphate (N-MC-dATP). Three crystal structures were solved of hpol{iota} in complex with DNA containing a template 2{prime}-deoxythymidine (dT) paired with an incoming dNTP or modified nucleotide triphosphate. The ternary complex of hpol{iota} inserting N-MC-dATP opposite dT reveals that the adenine ring is stabilized in the anti orientation about the pseudo-glycosyl torsion angle, which mimics precisely the mutagenic arrangement of dGTP:dT normally preferred by hpol{iota}. The stabilized anti conformation occurs without notable contacts from the protein but likely results from constraints imposed by the bicyclo[3.1.0]hexane scaffold of the modified nucleotide. Unmodified dATP and South-MC-dATP each adopt syn glycosyl orientations to form Hoogsteen base pairs with dT. The Hoogsteen orientation exhibits weaker base-stacking interactions and is less catalytically favorable than anti N-MC-dATP. Thus, N-MC-dATP corrects the error-prone nature of hpol{iota} by preventing the Hoogsteen base-pairing mode normally observed for hpol{iota}-catalyzed insertion of dATP opposite dT. These results provide a previously unrecognized means of altering the efficiency and the fidelity of a human translesion DNA polymerase.

  6. Sonic and resistivity measurements on Berea sandstone containing tetrahydrofuran hydrates: a possible analogue to natural-gas-hydrate deposits. [Tetrahydrofuran hydrates

    SciTech Connect

    Pearson, C.; Murphy, J.; Halleck, P.; Hermes, R.; Mathews, M.

    1983-01-01

    Deposits of natural gas hydrates exist in arctic sedimentary basins and in marine sediments on continental slopes and rises. However, the physical properties of such sediments are largely unknown. In this paper, we report laboratory sonic and resistivity measurements on Berea sandstone cores saturated with a stoichiometric mixture of tetrahydrofuran (THF) and water. We used THF as the guest species rather than methane or propane gas because THF can be mixed with water to form a solution containing proportions of the proper stoichiometric THF and water. Because neither methane nor propane is soluble in water, mixing the guest species with water sufficiently to form solid hydrate is difficult. Because THF solutions form hydrates readily at atmospheric pressure it is an excellent experimental analogue to natural gas hydrates. Hydrate formation increased the sonic P-wave velocities from a room temperature value of 2.5 km/s to 4.5 km/s at -5/sup 0/C when the pores were nearly filled with hydrates. Lowering the temperature below -5/sup 0/C did not appreciably change the velocity however. In contrast, the electrical resistivity increases nearly two orders of magnitude upon hydrate formation and continues to increase more slowly as the temperature is further decreased. In all cases the resistivities are nearly frequency independent to 30 kHz and the loss tangents are high, always greater than 5. The dielectric loss shows a linear decrease with frequency suggesting that ionic conduction through a brine phase dominates at all frequencies, even when the pores are nearly filled with hydrates. We find that the resistivities are strongly a function of the dissolved salt content of the pore water. Pore water salinity also influences the sonic velocity, but this effect is much smaller and only important near the hydrate formation temperature.

  7. Long-term effects of CO2 on the mechanical behaviour of faults - a study of samples from a natural CO2 analogue (Entrada Sandstone, Utah, USA)

    NASA Astrophysics Data System (ADS)

    Hangx, S. J. T.; Bakker, E.; Spiers, C. J.

    2012-04-01

    In an attempt to reduce CO2 emissions, CO2 capture and storage in depleted oil and gas reservoirs is seen as one of the most important mitigation strategies. However, in order to achieve safe storage on geological timescales, it is key to maintain integrity of the caprock and any faults penetrating the seal. One of the largest uncertainties lies in the prediction of the effects of fluid-rock interaction on the mechanical integrity and sealing capacity of the reservoir-seal system in the very long term, i.e. on timescales of the order of 103 or 104 years. As chemical interactions in the rock/CO2/brine system are slow, their long-term effects on rock composition, microstructure, mechanical properties and transport properties cannot be properly reproduced in laboratory experiments. One way of addressing this issue is to conduct experiments on reservoir, caprock and fault rock samples taken from natural CO2 reservoir-seal systems, which can serve as natural analogues for CO2 storage fields. The transport and mechanical properties of these rock samples, which have reacted with CO2 over geological timescales, can then be compared with data obtained for laterally equivalent materials that are unaffected by CO2. The observed changes in rock properties can subsequently be used as input for numerical models aimed at assessing the long-term effects of CO2 on reservoir compaction, caprock damage, fault reactivation and fault permeability. We assessed the mechanical behaviour and transport properties of fault rocks. To this end, we performed triaxial direct shear experiments at room temperature under nominally dry conditions, at normal stresses up to 90 MPa and shear velocities of 0.22 -10.9 μm/s. Simulated fault rocks were prepared by crushing material obtained from surface outcrops of the Entrada Sandstone, one of the CO2-bearing formations from an analogue field under the Colorado Plateau, Utah, USA. Three types of starting material were obtained: 1) red-coloured samples

  8. SEDIMENT GEOCHEMICAL MODEL

    EPA Science Inventory

    Until recently, sediment geochemical models (diagenetic models) have been only able to explain sedimentary flux and concentration profiles for a few simplified geochemical cycles (e.g., nitrogen, carbon and sulfur). However with advances in numerical methods, increased accuracy ...

  9. Chemical-mechanical coupling observed for depleted oil reservoirs subjected to long-term CO2-exposure - A case study of the Werkendam natural CO2 analogue field

    NASA Astrophysics Data System (ADS)

    Hangx, Suzanne; Bakker, Elisenda; Bertier, Pieter; Nover, Georg; Busch, Andreas

    2015-10-01

    Geological storage of CO2 is one of the most promising technologies to rapidly reduce anthropogenic emissions of carbon dioxide. In order to ensure storage integrity, it is important to understand the effect of long-term CO2/brine/rock interactions on the mechanical behaviour of a storage complex. As most of these reactions are too slow to reproduce on laboratory timescales, we studied a natural CO2 analogue reservoir (the Röt Fringe Sandstone, Werkendam field, the Netherlands; 125-135 Ma of CO2-exposure) and its unreacted counterpart. We focused on CO2-induced mineralogical and porosity-permeability changes, and their effect on mechanical behaviour of both intact rock and simulated fault gouge. Overall, CO2-exposure did not lead to drastic mineralogical changes. The CO2-exposed material shows a stronger dependence of permeability on porosity, which is attributed to differences in diagenesis (closed-system diagenesis and hydrocarbon emplacement) taking place before CO2 charging. The limited extent of reaction was in part the result of bitumen coatings protecting specific mineral phases from reaction. In local, mm-sized zones displaying significant anhydrite cement dissolution, enhanced porosity was observed. For most of the reservoir the long-term mechanical behaviour after CO2-exposure could be described by the behaviour of the unreacted sandstone, while these more 'porous' zones had a lower rock strength. In addition, CO2-exposure did not affect the fault friction behaviour, and slip is expected to result in stable sliding. Simple stress path calculations predict that reservoir failure due to depletion and injection is unlikely, even for the 'porous' zones, nor will fault reactivation occur for realistic injection scenarios.

  10. A hydrological and geochemical analysis of chromium mobilization from serpentinized ultramafic rocks and serpentine soils at the McLaughlin Natural Reserve, Lake County, California

    NASA Astrophysics Data System (ADS)

    McClain, C.; Maher, K.; Fendorf, S.

    2011-12-01

    (VI) concentrations vary from < 2.5-22 μg/L, where the highest concentrations were found in seeps emanating from fractured serpentinite and in tributaries to Hunting Creek. Aqueous Cr is mostly present as Cr(VI) (likely CrO42- and MgCrO4), which is consistent with the high pH (7.98-8.72). A reactive transport approach, constrained by solid and fluid data, was used to assess the geochemical transformations that occur along flow paths in order to evaluate the coupling between hydrologic and biogeochemical processes. Similar ultramafic rocks and terrains occur in belts along the Coast Range and the Foothills to the Sierra Nevada and in the Klamath Mountains. Creeks and rivers draining these ultramafic terrains have transported Cr-bearing sediments to the Central Valley, (and other densely populated sedimentary basins and alluvial plains) where they are now widely distributed both at the surface and buried underground, interlaced with aquifer materials. This study highlights the importance of using a holistic approach that considers multiple length scales to understand the factors that control Cr distribution and speciation in natural waters.

  11. TAPIR--Finnish national geochemical baseline database.

    PubMed

    Jarva, Jaana; Tarvainen, Timo; Reinikainen, Jussi; Eklund, Mikael

    2010-09-15

    In Finland, a Government Decree on the Assessment of Soil Contamination and Remediation Needs has generated a need for reliable and readily accessible data on geochemical baseline concentrations in Finnish soils. According to the Decree, baseline concentrations, referring both to the natural geological background concentrations and the diffuse anthropogenic input of substances, shall be taken into account in the soil contamination assessment process. This baseline information is provided in a national geochemical baseline database, TAPIR, that is publicly available via the Internet. Geochemical provinces with elevated baseline concentrations were delineated to provide regional geochemical baseline values. The nationwide geochemical datasets were used to divide Finland into geochemical provinces. Several metals (Co, Cr, Cu, Ni, V, and Zn) showed anomalous concentrations in seven regions that were defined as metal provinces. Arsenic did not follow a similar distribution to any other elements, and four arsenic provinces were separately determined. Nationwide geochemical datasets were not available for some other important elements such as Cd and Pb. Although these elements are included in the TAPIR system, their distribution does not necessarily follow the ones pre-defined for metal and arsenic provinces. Regional geochemical baseline values, presented as upper limit of geochemical variation within the region, can be used as trigger values to assess potential soil contamination. Baseline values have also been used to determine upper and lower guideline values that must be taken into account as a tool in basic risk assessment. If regional geochemical baseline values are available, the national guideline values prescribed in the Decree based on ecological risks can be modified accordingly. The national geochemical baseline database provides scientifically sound, easily accessible and generally accepted information on the baseline values, and it can be used in various

  12. Geochemical and Sr-Nd isotope evidences of the suprasubduction nature of mesozoic magmatism in the Mongol-Okhotsk Sector of the Pacific Fold Belt

    NASA Astrophysics Data System (ADS)

    Derbeko, I. M.; Chugaev, A. V.; Oleinikova, T. I.; Bortnikov, N. S.

    2016-02-01

    In this article we present geochemical and isotope characteristics of rocks of the Unerikan, Selitkan and Aezop-Yamalin volcano-plutonic zones of the eastern termination of the Mongol-Okhotsk Orogenic Belt. The obtained data demonstrate that the Mesozoic igneous rocks of the Mongol-Okhotsk sector of the Pacific Folded Belt were formed due to the melting of the continental crust in a tectonic setting corresponding to a suprasubduction one.

  13. Assessment of CO2 discharge in a spring using time-variant stable carbon isotope data as a natural analogue study of CO2 leakage

    NASA Astrophysics Data System (ADS)

    Yu, Soonyoung; Chae, Gitak; Jo, Minki; Kim, Jeong-Chan; Yun, Seong-Taek

    2015-04-01

    CO2-rich springs have been studied as a natural analogue of CO2 leakage through shallow subsurface environment, as they provide information on the behaviors of CO2 during the leakage from geologic CO2 storage sites. For this study, we monitored the δ13C values as well as temperature, pH, EC, DO, and alkalinity for a CO2-rich spring for 48 hours. The water samples (N=47) were collected every hour in stopper bottles without headspace to avoid the interaction with air and the CO2 degassing. The δ13C values of total dissolved inorganic carbon (TDIC) in the water samples were analyzed using a cavity ring-down spectroscopy (CRDS) system (Picarro). The values of δ13CTDIC, temperature, pH, EC, DO, and alkalinity were in the range of -9.43 ~ -8.91 o 12.3 ~ 13.2oC, 4.86 ~ 5.02, 186 ~ 189 μS/cm, 1.8 ~ 3.4 mg/L, and 0.74 ~ 0.95 meq/L, respectively. The concentrations of TDIC calculated using pH and alkalinity values were between 22.5 and 34.8 mmol/L. The δ13CTDIC data imply that dissolved carbon in the spring was derived from a deep-seated source (i.e., magmatic) that was slightly intermixed with soil CO2. Careful examination of the time-series variation of measured parameters shows the following characteristics: 1) the δ13CTDIC values are negatively correlated with pH (r = -0.59) and positively correlated with TDIC (r = 0.58), and 2) delay times of the change of pH and alkalinity following the change of δ13CTDIC values are 0 and -3 hours, respectively; the pH change occurs simultaneously with the change of δ13CTDIC, while the alkalinity change happens before 3 hours. Our results indicate that the studied CO2-rich spring is influenced by the intermittent supply of deep-seated CO2. [Acknowledgment] This work was financially supported by the fundamental research project of KIGAM and partially by the "Geo-Advanced Innovative Action (GAIA) Project (2014000530003)" from Korea Ministry of Environment (MOE).

  14. Design and Synthesis of Analogues of Marine Natural Product Galaxamide, an N-methylated Cyclic Pentapeptide, as Potential Anti-Tumor Agent in Vitro

    PubMed Central

    Lunagariya, Jignesh; Zhong, Shenghui; Chen, Jianwei; Bai, Defa; Bhadja, Poonam; Long, Weili; Liao, Xiaojian; Tang, Xiaoli; Xu, Shihai

    2016-01-01

    Herein, we report design and synthesis of novel 26 galaxamide analogues with N-methylated cyclo-pentapeptide, and their in vitro anti-tumor activity towards the panel of human tumor cell line, such as, A549, A549/DPP, HepG2 and SMMC-7721 using MTT assay. We have also investigated the effect of galaxamide and its representative analogues on growth, cell-cycle phases, and induction of apoptosis in SMMC-7721 cells in vitro. Reckon with the significance of conformational space and N-Me aminoacid (aa) comprising this compound template, we designed the analogues with modification in N-Me-aa position, change in aa configuration from l to d aa and substitute one Leu-aa to d/l Phe-aa residue with respective to the parent structure. The efficient solid phase parallel synthesis approach is employed for the linear pentapeptide residue containing N-Me aa, followed by solution phase macrocyclisation to afford target cyclo pentapeptide compounds. In the present study, all galaxamide analogues exhibited growth inhibition in A549, A549/DPP, SMMC-7721 and HepG2 cell lines. Compounds 6, 18, and 22 exhibited interesting activities towards all cell line tested, while Compounds 1, 4, 15, and 22 showed strong activity towards SMMC-7221 cell line in the range of 1–2 μg/mL IC50. Flow cytometry experiment revealed that galaxamide analogues namely Compounds 6, 18, and 22 induced concentration dependent SMMC-7721 cell apoptosis after 48 h. These compounds induced G0/G1 phase cell-cycle arrest and morphological changes indicating induction of apoptosis. Thus, findings of our study suggest that the galaxamide and its analogues 6, 18 and 22 exerted growth inhibitory effect on SMMC-7721 cells by arresting the cell cycle in the G0/G1 phase and inducing apoptosis. Compound 1 showed promising anti-tumor activity towards SMMC-7721 cancer cell line, which is 9 and 10 fold higher than galaxamide and reference DPP (cisplatin), respectively. PMID:27598177

  15. Design and Synthesis of Analogues of Marine Natural Product Galaxamide, an N-methylated Cyclic Pentapeptide, as Potential Anti-Tumor Agent in Vitro.

    PubMed

    Lunagariya, Jignesh; Zhong, Shenghui; Chen, Jianwei; Bai, Defa; Bhadja, Poonam; Long, Weili; Liao, Xiaojian; Tang, Xiaoli; Xu, Shihai

    2016-09-03

    Herein, we report design and synthesis of novel 26 galaxamide analogues with N-methylated cyclo-pentapeptide, and their in vitro anti-tumor activity towards the panel of human tumor cell line, such as, A549, A549/DPP, HepG2 and SMMC-7721 using MTT assay. We have also investigated the effect of galaxamide and its representative analogues on growth, cell-cycle phases, and induction of apoptosis in SMMC-7721 cells in vitro. Reckon with the significance of conformational space and N-Me aminoacid (aa) comprising this compound template, we designed the analogues with modification in N-Me-aa position, change in aa configuration from l to d aa and substitute one Leu-aa to d/l Phe-aa residue with respective to the parent structure. The efficient solid phase parallel synthesis approach is employed for the linear pentapeptide residue containing N-Me aa, followed by solution phase macrocyclisation to afford target cyclo pentapeptide compounds. In the present study, all galaxamide analogues exhibited growth inhibition in A549, A549/DPP, SMMC-7721 and HepG2 cell lines. Compounds 6, 18, and 22 exhibited interesting activities towards all cell line tested, while Compounds 1, 4, 15, and 22 showed strong activity towards SMMC-7221 cell line in the range of 1-2 μg/mL IC50. Flow cytometry experiment revealed that galaxamide analogues namely Compounds 6, 18, and 22 induced concentration dependent SMMC-7721 cell apoptosis after 48 h. These compounds induced G0/G1 phase cell-cycle arrest and morphological changes indicating induction of apoptosis. Thus, findings of our study suggest that the galaxamide and its analogues 6, 18 and 22 exerted growth inhibitory effect on SMMC-7721 cells by arresting the cell cycle in the G0/G1 phase and inducing apoptosis. Compound 1 showed promising anti-tumor activity towards SMMC-7721 cancer cell line, which is 9 and 10 fold higher than galaxamide and reference DPP (cisplatin), respectively.

  16. Fluid-rock interactions in CO2-saturated, granite-hosted geothermal systems: Implications for natural and engineered systems from geochemical experiments and models

    NASA Astrophysics Data System (ADS)

    Lo Ré, Caroline; Kaszuba, John P.; Moore, Joseph N.; McPherson, Brian J.

    2014-09-01

    Hydrothermal experiments were conducted and geochemical models constructed to evaluate the geochemical and mineralogical response of fractured granite and granite + epidote in contact with thermal water, with and without supercritical CO2, at 250 °C and 25-45 MPa. Illite ± smectite ± zeolite(?) precipitate as secondary minerals at the expense of K-feldspar, oligoclase, and epidote. Illite precipitates in experiments reacting granite and granite + epidote with water; metastable smectite forms in the experiments injected with supercritical CO2. Waters are supersaturated with respect to quartz and saturated with respect to chalcedony in CO2-charged experiments, but neither mineral formed. Carbonate formation is predicted for experiments injected with supercritical CO2, but carbonate only formed during cooling and degassing of the granite + epidote + CO2 experiment. Experimental results provide insight into the buffering capacity of granites as well as the drivers of clay formation. Metastable smectite in the experiments is attributed to high water-rock ratios, high silica activities, and high CO2 and magnesium-iron concentrations. Smectite precipitation in supercritical CO2-bearing geothermal systems may affect reservoir permeability. Silicate formation may create or thicken caps within or on the edges of geothermal reservoirs. Carbonate formation, as desired for carbon sequestration projects coinciding with geothermal systems, may require extended periods of time; cooling and degassing of CO2-saturated waters leads to carbonate precipitation, potentially plugging near-surface production pathways.

  17. Investigation of natural and anthropogenic hydrocarbon inputs in sediments using geochemical markers. II. Sao Sebastião, SP--Brazil.

    PubMed

    Medeiros, Patricia Matheus; Bícego, Márcia Caruso

    2004-12-01

    The São Sebastião Channel, NE São Paulo State, Brazil, is an area of environmental interest of that state not only because of the tourism, but also because of the presence of the most important oil terminal of Brazil, the PETROBRAS Maritime Terminal (DTCS). Sediment samples were collected at 15 sites in the channel, extracted and analyzed by GC/FID and GC/MS for composition and levels of the following organic geochemical markers: aliphatic hydrocarbons (normal and isoprenoid alkanes), petroleum biomarkers, linear alkylbenzenes (LABs) and polycyclic aromatic hydrocarbons (PAHs). The total concentrations varied from 0.04 to 8.53 micorg g(-1) for aliphatics, from 51.1 to 422.0 ng g(-1) for petroleum biomarkers, from 12.6 to 27.7 ng g(-1) for LABs and from 20.4 to 200.3 ng g(-1) for PAHs. The PETROBRAS Maritime Terminal (DTCS), Sao Sebastião Harbor and sewage outfalls along the area had clear influences on the geochemical marker concentrations, especially at locales in the central and north parts of the channel.

  18. Composition of natural gas and crude oil produced from 10 wells in the Lower Silurian "Clinton" Sandstone, Trumbull County, Ohio: Chapter G.7 in Coal and petroleum resources in the Appalachian basin: distribution, geologic framework, and geochemical character

    USGS Publications Warehouse

    Burruss, Robert A.; Ryder, Robert T.; Ruppert, Leslie F.; Ryder, Robert T.

    2014-01-01

    Natural gases and associated crude oils in the “Clinton” sandstone, Medina Group sandstones, and equivalent Tuscarora Sandstone in the northern Appalachian basin are part of a regional, continuous-type or basin-centered accumulation. The origin of the hydrocarbon charge to regional continuoustype accumulations is poorly understood. We have analyzed the molecular and stable isotopic composition of gases and oils produced from 10 wells in the “Clinton” sandstone in Trumbull County, Ohio, in an initial attempt to identify the characteristics of the accumulated fluids. The analyses show that the fluids have remarkably uniform compositions that are similar to previously published analyses of oils (Cole and others, 1987) and gases (Laughrey and Baldasarre, 1998) in Early Silurian reservoirs elsewhere in Ohio; however, geochemical parameters in the oils and gases suggest that the fluids have experienced higher levels of thermal stress than the present-day burial conditions of the reservoir rocks. The crude oils have an unusual geochemical characteristic: they do not contain detectable levels of sterane and triterpane biomarkers. The origin of these absences is unknown.

  19. The mechanism of phosphorylation of natural nucleosides and anti-HIV analogues by nucleoside diphosphate kinase is independent of their sugar substituents.

    PubMed

    Hutter, Michael C; Helms, Volkhard

    2002-07-02

    The reaction mechanism of the phosphoryl transfer catalyzed by dinucleoside diphosphate kinase from Dictyostelium discoideum is investigated by semiempirical AM1 molecular orbital computation of an active site model system on the basis of various X-ray crystallographic structures. The computational results suggest that the phosphoryl transfer from adenosine triphosphate to the His122 residue is accompanied by the simultaneous shift of a proton from the histidine residue to one of the oxygen atoms of the gamma phosphate group. This involves a doubly protonated His122 residue whilst this residue is neutral in its ternary complex with ADP and the transition state analogue AlF(3). The proposed mechanism is thus analogous to that of phosphoryl transfer by cyclic adenosine monophosphate dependent protein kinase and uridine/cytidine monophosphate kinase as found in our earlier work and clarifies the role of the ribose 3'-OH group. Furthermore, the energetics of phosphoryl transfer onto other nucleoside analogues such as 3'-azido-3'-deoxythymidine-diphosphate and 2',3'-dideoxy-2',3'-didehydro-thymidine-diphosphate are investigated. The calculated reaction barriers for the phosphorylation of the diphosphates by the enzyme are all within a range of 13.1 kJ mol(-1), which suggests that variations in the activation energies alone cannot account for the experimentally observed differences in enzymatic activity. Consequences for the design of new anti-HIV nucleoside analogues are discussed. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2268/2002/f360_s.pdf or from the author.

  20. Characterizing the Influence of Flow Regime and Landcover on the Geochemical Nature and Magnitude of Riverine Phosphorus and Trace Metal Loads

    NASA Astrophysics Data System (ADS)

    Rosenberg, B.; Schroth, A. W.

    2014-12-01

    Within aquatic systems, phosphorus (P) is a common limiting nutrient present in low bioavailable concentrations. Colloidal and particulate phases of the trace metals manganese (Mn) and iron (Fe) are common scavengers of phosphate in the freshwater environment, and the distribution and stability of such phases is thought to influence the bioavailability of P. The partitioning and flux of P and TM in rivers can be driven by the geochemical source of these constituents, as well as the hydrologic/biogeochemical pathways active within the watershed, both of which vary based on hydrologic condition and landcover. This study investigates how different landcovers (suburban, agricultural, forested, glacial) contribute to P and TM flux and partitioning during high-flow events (snowmelt, glacial melt, storms). High-resolution water and suspended sediment sampling was conducted during snowmelt in Vermont, as well as during summer storms and baseflow conditions. In Alaska, samples were collected during baseflow, glacial melt, and storm events to provide additional data from other landcovers and hydrologic systems. Initial analyses suggest that the size fraction, loading, and relative lability of water and suspended sediment pools of TM and P are strongly influenced by both land cover and seasonality/hydrology. Samples collected during snowmelt in VT show high concentrations of dissolved and potentially bioavailable particulate P at the start of melt that decrease over time. Coupled with high discharge events, a substantial load of labile P is delivered during this particular high flow period. As snowmelt transitions to baseflow conditions, with intermittent storms the character of the suspended sediment changes drastically, with lower total concentrations of P and TM as well as a lower proportion of extractable P (bound to easily reduced oxyhydroxides) to total sediment P. This study highlights that the snowmelt period is not only important from an overall all load standpoint

  1. Ecstasy analogues found in cacti.

    PubMed

    Bruhn, Jan G; El-Seedi, Hesham R; Stephanson, Nikolai; Beck, Olof; Shulgin, Alexander T

    2008-06-01

    Human interest in psychoactive phenethylamines is known from the use of mescaline-containing cacti and designer drugs such as Ecstasy. From the alkaloid composition of cacti we hypothesized that substances resembling Ecstasy might occur naturally. In this article we show that lophophine, homopiperonylamine and lobivine are new minor constituents of two cactus species, Lophophora williamsii (peyote) and Trichocereus pachanoi (San Pedro). This is the first report of putatively psychoactive phenethylamines besides mescaline in these cacti. A search for further biosynthetic analogues may provide new insights into the structure-activity relationships of mescaline. An intriguing question is whether the new natural compounds can be called "designer drugs."

  2. Survey of Analogue Spacetimes

    NASA Astrophysics Data System (ADS)

    Visser, Matt

    Analogue spacetimes (and more boldly, analogue models both of and for gravity), have attracted significant and increasing attention over the last decade and a half. Perhaps the most straightforward physical example, which serves as a template for most of the others, is Bill Unruh's model for a dumb hole,(mute black hole, acoustic black hole), wherein sound is dragged along by a moving fluid—and can even be trapped behind an acoustic horizon. This and related analogue models for curved spacetimes are useful in many ways: analogue spacetimes provide general relativists with extremely concrete physical models to help focus their thinking, and conversely the techniques of curved spacetime can sometimes help improve our understanding of condensed matter and/or optical systems by providing an unexpected and countervailing viewpoint. In this chapter, I shall provide a few simple examples of analogue spacetimes as general background for the rest of the contributions.

  3. Nature of the lowest electron transitions in styryl bases benzothiazole derivatives and analogues bearing para-methoxy and -trifluoromethyl substituents in phenylyne moiety

    NASA Astrophysics Data System (ADS)

    Navozenko, O. M.; Naumenko, A. P.; Yashchuk, V. M.; Bricks, J. L.; Slominskii, Yu. L.; Ryabitskii, A. B.; Kachkovsky, O. D.

    2016-06-01

    Combined quantum-chemical and spectral investigation of cyanine bases derivatives of thiastyryls as well as their analogues with dimethylamino, metoxy and trifluorine-methyl substituents has been fulfilled. The calculations have shown that going from cationic styryl/metoxystyryl to the corresponding neutral bases is accompanied by substantial change of the equilibrium molecular geometry and charge distribution at atoms, while the experimental absorption band undergoes the essential hypsochromic shift. It is established that introducing on the donor groups in the bases causes negligible change of the carbon-carbon bond and atomic charges in the main chromophore, in contrast to the substantial changes of the magnitude and direction state dipole moments in both ground and excited states. It is found that the bases with the donor groups in benzthiazole moiety and with acceptor CF3 substituent demonstrate the inversion of the direction of the dipole moment. Based on the spectral and quantum-chemical study, one has proposed that some widening of the spectral bands is connected with the vibronic interaction, not with the second electron transition.

  4. Developing a robust geochemical and reactive transport model to evaluate possible sources of arsenic at the CO[subscript 2] sequestration natural analog site in Chimayo, New Mexico

    SciTech Connect

    Viswanathan, Hari; Dai, Zhenxue; Lopano, Christina; Keating, Elizabeth; Hakala, J. Alexandra; Scheckel, Kirk G.; Zheng, Liange; Gutherie, George D.; Pawar, Rajesh

    2012-10-24

    Migration of carbon dioxide (CO{sub 2}) from deep storage formations into shallow drinking water aquifers is a possible system failure related to geologic CO{sub 2} sequestration. A CO{sub 2} leak may cause mineral precipitation/dissolution reactions, changes in aqueous speciation, and alteration of pH and redox conditions leading to potential increases of trace metal concentrations above EPA National Primary Drinking Water Standards. In this study, the Chimayo site (NM) was examined for site-specific impacts of shallow groundwater interacting with CO{sub 2} from deep storage formations. Major ion and trace element chemistry for the site have been previously studied. This work focuses on arsenic (As), which is regulated by the EPA under the Safe Drinking Water Act and for which some wells in the Chimayo area have concentrations higher than the maximum contaminant level (MCL). Statistical analysis of the existing Chimayo groundwater data indicates that As is strongly correlated with trace metals U and Pb indicating that their source may be from the same deep subsurface water. Batch experiments and materials characterization, such as: X-ray diffraction (XRD), scanning electron microscopy (SEM), and synchrotron micro X-ray fluorescence ({mu}-XRF), were used to identify As association with Fe-rich phases, such as clays or oxides, in the Chimayo sediments as the major factor controlling As fate in the subsurface. Batch laboratory experiments with Chimayo sediments and groundwater show that pH decreases as CO{sub 2} is introduced into the system and buffered by calcite. The introduction of CO{sub 2} causes an immediate increase in As solution concentration, which then decreases over time. A geochemical model was developed to simulate these batch experiments and successfully predicted the pH drop once CO{sub 2} was introduced into the experiment. In the model, sorption of As to illite, kaolinite and smectite through surface complexation proved to be the key reactions in

  5. Energy-constrained open-system magmatic processes IV: Geochemical, thermal and mass consequences of energy-constrained recharge, assimilation and fractional crystallization (EC-RAFC)

    NASA Astrophysics Data System (ADS)

    Bohrson, Wendy A.; Spera, Frank J.

    2003-02-01

    A wealth of geochemical and petrological data provide evidence that the processes of fractional crystallization, assimilation, and magma recharge (replenishment) dominate the chemical signatures of many terrestrial igneous rocks. Previous work [Spera and Bohrson, 2001; Bohrson and Spera, 2001] has established the importance of integrating energy, species and mass conservation into simulations of complex magma chamber processes. An extended version of the energy-constrained formulation, Energy-Constrained Recharge, Assimilation, Fractional Crystallization (EC-RAFC), tracks mass and compositional variations of melt, cumulates, and enclaves in a magma body undergoing simultaneous recharge, assimilation, and fractional crystallization [Spera and Bohrson, 2002]. Because many EC-RAFC results are distinct from those predicted by extant RAFC formulations, the primary goal of this paper is to present a range of geochemical and mass relationships for selected cases that highlight issues relevant to modern petrology. Among the plethora of petrologic problems that have important, well-documented analogues in nature are the geochemical distinctions that arise when a magma body undergoes continuous versus episodic recharge, the connection between erupted magmas and associated cumulate bodies, the behavior of recharge-fractionation dominated systems (RFC), thermodynamic conditions that promote the formation of enclaves versus cumulates, and the conditions under which magma bodies may be described as chemically homogeneous. Investigation of the effects of continuous versus episodic recharge for mafic magma undergoing RAFC in the lower crust indicates that the resulting geochemical trends for melt and solids are sensitive to the intensity and composition of recharge, suggesting that EC-RAFC may be used as a tool to distinguish the nature of the recharge events. Compared to the record preserved in melts, the geochemical and mass characteristics of solids associated with particular

  6. Energy-constrained open-system magmatic processes IV: Geochemical, thermal and mass consequences of energy-constrained recharge, assimilation and fractional crystallization (EC-RAFC)

    SciTech Connect

    Wendy A. Bohrson Department of Geological Sciences, Central Washington University, Ellensburg, Washington, 98926, USA; Frank J. Spera Institute for Crustal Studies and Department of Geological Sciences, University of California, Santa Barbara, California, 93106, USA

    2003-07-01

    A wealth of geochemical and petrological data provide evidence that the processes of fractional crystallization, assimilation, and magma recharge (replenishment) dominate the chemical signatures of many terrestrial igneous rocks. Previous work [ Spera and Bohrson, 2001 ; Bohrson and Spera, 2001 ] has established the importance of integrating energy, species and mass conservation into simulations of complex magma chamber processes. An extended version of the energy-constrained formulation, Energy-Constrained Recharge, Assimilation, Fractional Crystallization (EC-RAFC), tracks mass and compositional variations of melt, cumulates, and enclaves in a magma body undergoing simultaneous recharge, assimilation, and fractional crystallization [ Spera and Bohrson, 2002 ]. Because many EC-RAFC results are distinct from those predicted by extant RAFC formulations, the primary goal of this paper is to present a range of geochemical and mass relationships for selected cases that highlight issues relevant to modern petrology. Among the plethora of petrologic problems that have important, well-documented analogues in nature are the geochemical distinctions that arise when a magma body undergoes continuous versus episodic recharge, the connection between erupted magmas and associated cumulate bodies, the behavior of recharge-fractionation dominated systems (RFC), thermodynamic conditions that promote the formation of enclaves versus cumulates, and the conditions under which magma bodies may be described as chemically homogeneous. Investigation of the effects of continuous versus episodic recharge for mafic magma undergoing RAFC in the lower crust indicates that the resulting geochemical trends for melt and solids are sensitive to the intensity and composition of recharge, suggesting that EC-RAFC may be used as a tool to distinguish the nature of the recharge events. Compared to the record preserved in melts, the geochemical and mass characteristics of solids associated with

  7. Reflectance spectroscopy of natural organic solids, iron sulfides and their mixtures as refractory analogues for Rosetta/VIRTIS' surface composition analysis of 67P/CG

    NASA Astrophysics Data System (ADS)

    Moroz, Lyuba V.; Markus, Kathrin; Arnold, Gabriele; Henckel, Daniela; Kappel, David; Schade, Ulrich; Rousseau, Batiste; Quirico, Eric; Schmitt, Bernard; Capaccioni, Fabrizio; Bockelee-Morvan, Dominique; Filacchione, Gianrico; Érard, Stéphane; Leyrat, Cedric; VIRTIS Team

    2016-10-01

    Analysis of 0.25-5 µm reflectance spectra provided by the Visible and InfraRed Thermal Imaging Spectrometer (VIRTIS) onboard Rosetta orbiter revealed that the surface of 67P/CG is dark from the near-UV to the IR and is enriched in refractory phases such as organic and opaque components. The broadness and complexity of the ubiquitous absorption feature around 3.2 µm suggest a variety of cometary organic constituents. For example, complex hydrocarbons (aliphatic and polycyclic aromatic) can contribute to the feature between 3.3 and 3.5 µm and to the low reflectance of the surface in the visible. Here we present the 0.25-5 µm reflectance spectra of well-characterized terrestrial hydrocarbon materials (solid oil bitumens, coals) and discuss their relevance as spectral analogues for a hydrocarbon part of 67P/CG's complex organics. However, the expected low degree of thermal processing of cometary hydrocarbons (high (H+O+N+S)/C ratios and low carbon aromaticities) suggests high IR reflectance, intense 3.3-3.5 µm absorption bands and steep red IR slopes that are not observed in the VIRTIS spectra. Fine-grained opaque refractory phases (e.g., iron sulfides, Fe-Ni alloys) intimately mixed with other surface components are likely responsible for the low IR reflectance and low intensities of absorption bands in the VIRTIS spectra of the 67P/CG surface. In particular, iron sulfides are common constituents of cometary dust, "cometary" chondritic IDPs, and efficient darkening agents in primitive carbonaceous chondrites. Their effect on reflectance spectra of an intimate mixture is strongly affected by grain size. We report and discuss the 0.25-5 µm reflectance spectra of iron sulfides (meteoritic troilite and several terrestrial pyrrhotites) ground and sieved to various particle sizes. In addition, we present reflectance spectra of several intimate mixtures of powdered iron sulfides and solid oil bitumens. Based on the reported laboratory data, we discuss the ability of

  8. Template polymerization of nucleotide analogues

    NASA Technical Reports Server (NTRS)

    Orgel, L. E.

    1991-01-01

    Recent work on the template-directed reactions of the natural D-nucleotides has made it clear that l-nucleotides and nucleotide-like derivatives of other sugars would strongly inhibit the formation of long oligonucleotides. Consequently, attention is focusing on molecules simpler than nucleotides that might have acted as monomers of an information transfer system. We have begun a general exploration of the template directed reactions of diverse peptide analogues. I will present work by Dr. Taifeng Wu on oxidative oligomerization of phosphorothioates and of Dr. Mary Tohidi on the cyclic polymerization of nucleoside and related cyclic pyrophosphates.

  9. Geochemical Interpretation of Collision Volcanism

    NASA Astrophysics Data System (ADS)

    Pearce, Julian

    2014-05-01

    collision type with extreme LILE and significant HFSE enrichment relative to MORB and with large negative Nb-Ta and Ti anomalies. Post-collision volcanism is usually ascribed to combinations of slab detachment, delamination, and slab roll back (orogenic) and extension (post-orogenic). The magma source is typically conductively-heated, sub-continental mantle lithosphere with composition and depth of melting depending on the nature and evolution of the collision zone in question. Geochemical patterns may be similar to those of syn-collision basalts or of intraplate, continental basalts - or transitional between these. This variability in space and time, though problematic for geochemical fingerprinting, can give clues to the polarity and development of the collision zone, for example by highlighting the distribution of subduction-modified mantle lithosphere and hence of pre-collision subduction zones. One characteristic common to this setting is a high crustal input resulting from the presence of a hot, thick 'crustal chemical filter' which is evident on geochemical projections that highlight AFC-type processes. Using this, and other, geochemical features it is possible to develop methodologies to at least partly see through the complexity of collision terranes.

  10. Initiation of rubber biosynthesis: in vitro comparisons of benzophenone-modified diphosphate analogue structure in three natural rubber-producing species

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Natural rubber is synthesized by initiation with one allylic pyrophosphate (APPs) molecule followed by elongation with thousands of isopentenyl pyrophosphate (IPP) molecules by the enzyme rubber transferase (a cis-prenyl transferase). To better understand how rubber transferase initiates and binds A...

  11. Iodine and selenium in natural water, their fixation on geochemical barriers in soils and rocks and explanation of I and Se behavior in water-solid phase system using thermodynamic modeling

    NASA Astrophysics Data System (ADS)

    Korobova, Elena; Ryzhenko, Boris; Cherkasova, Elena; Sedykh, Ivelina; Korsakova, Nadezhda; Berezkin, Victor; Kolmykova, Lyudmila; Danilova, Valentina; Khushvakhtova, Sabzbakhor

    2014-05-01

    Iodine and selenium are essential for normal functioning of thyroid gland. Their natural deficiency in areas subjected to radioiodine contamination during nuclear tests and accidents may increase the risk of thyroid cancer among the most sensitive groups of population. Deficiency is caused by both the low abundance of microelements in the environmental components of the local food chain and their fixation on geochemical barriers due to such processes as chemical transformation, sorption, chemisorption, complexing. The studies of iodine and selenium distribution in soils, herbs and drinking water in rural settlements of the Bryansk oblast' confirmed low level of iodine and selenium content in local soils, plants and water and revealed different character of their distribution in soils and waters formed in geochemically different conditions of water migration in areas of fluvioglacial, moraine and loess-like soil forming rocks (the polesje, moraine and opolje landscapes correspondingly). Iodine content in top horizons of the soils developed on loess-like sediments and rich in organic matter was considerably higher as compared to those formed on sandy moraine or fluvioglacial sediments. For selenium the difference was not pronounced. Iodine was noted for positive correlation with Corg and fixation in the soil profile on carbonate barrier. A negative correlation was found between selenium content in grasses and in topsoil of subordinated elementary landscapes characterized by waterlogged and reduction conditions in soils. Thermodynamic modeling performed for 47 water samples on the basis of their chemical composition helped to explain the established patterns of iodine and selenium behavior in soil-water system. It demonstrated the possibility of existence of CaI+ and MgI+ complexes in water and sedimentation of FeSe(cr) in presence of a considerable amount of Fe2+. Iodine complexation with Ca and Mg ions may explain its further fixation on carbonate barrier in soils

  12. Thermodynamic Data for Geochemical Modeling of Carbonate Reactions Associated with CO2 Sequestration – Literature Review

    SciTech Connect

    Krupka, Kenneth M.; Cantrell, Kirk J.; McGrail, B. Peter

    2010-09-01

    Permanent storage of anthropogenic CO2 in deep geologic formations is being considered as a means to reduce the concentration of atmospheric CO2 and thus its contribution to global climate change. To ensure safe and effective geologic sequestration, numerous studies have been completed of the extent to which the CO2 migrates within geologic formations and what physical and geochemical changes occur in these formations when CO2 is injected. Sophisticated, computerized reservoir simulations are used as part of field site and laboratory CO2 sequestration studies. These simulations use coupled multiphase flow-reactive chemical transport models and/or standalone (i.e., no coupled fluid transport) geochemical models to calculate gas solubility, aqueous complexation, reduction/oxidation (redox), and/or mineral solubility reactions related to CO2 injection and sequestration. Thermodynamic data are critical inputs to modeling geochemical processes. The adequacy of thermodynamic data for carbonate compounds has been identified as an important data requirement for the successful application of these geochemical reaction models to CO2 sequestration. A review of thermodynamic data for CO2 gas and carbonate aqueous species and minerals present in published data compilations and databases used in geochemical reaction models was therefore completed. Published studies that describe mineralogical analyses from CO2 sequestration field and natural analogue sites and laboratory studies were also reviewed to identify specific carbonate minerals that are important to CO2 sequestration reactions and therefore require thermodynamic data. The results of the literature review indicated that an extensive thermodynamic database exists for CO2 and CH4 gases, carbonate aqueous species, and carbonate minerals. Values of ΔfG298° and/or log Kr,298° are available for essentially all of these compounds. However, log Kr,T° or heat capacity values at temperatures above 298 K exist for less than

  13. Geochemical Trends and Natural Attenuation of RDX, Nitrate, and Perchlorate in the Hazardous Test Area Fractured-Granite Aquifer, White Sands Missile Range, New Mexico, 1996-2006

    USGS Publications Warehouse

    Langman, Jeff B.; Robertson, Andrew J.; Bynum, Jamar; Gebhardt, Fredrick E.

    2008-01-01

    A fractured-granite aquifer at White Sands Missile Range is contaminated with the explosive compound RDX, nitrate, and perchlorate (oxidizer associated with rocket propellant) from the previous use of the Open Burn/Open Detonation site at the Hazardous Test Area. RDX, nitrate, and perchlorate ground-water concentrations were analyzed to examine source characteristics, spatial and temporal variability, and the influence of the natural attenuation processes of dilution and degradation in the Hazardous Test Area fractured-granite aquifer. Two transects of ground-water wells from the existing monitoring-site network - one perpendicular to ground-water flow (transect A-A') and another parallel to ground-water flow (transect B-B') - were selected to examine source characteristics and the spatial and temporal variability of the contaminant concentrations. Ground-water samples collected in 2005 from a larger sampling of monitoring sites than the two transects were analyzed for various tracers including major ions, trace elements, RDX degradates, dissolved gases, water isotopes, nitrate isotopes, and sulfate isotopes to examine the natural attenuation processes of dilution and degradation. Recharge entrains contaminants at the site and transports them downgradient towards the Tularosa Basin floor through a poorly connected fracture system(s). From 1996 to 2006, RDX, nitrate, and perchlorate concentrations in ground water downgradient from the Open Burn/Open Detonation site have been relatively stable. RDX, nitrate, and perchlorate in ground water from wells near the site indicate dispersed contaminant sources in and near the Open Burn/Open Detonation pits. The sources of RDX and nitrate in the pit area have shifted with time, and the shift correlates with the regrading of the south and east berms of each pit in 2002 and 2003 following closure of the site. The largest RDX concentrations were in ground water about 0.1 mile downgradient from the pits, the largest perchlorate

  14. Anorogenic nature of magmatism in the Northern Baikal volcanic belt: Evidence from geochemical, geochronological (U-Pb), and isotopic (Pb, Nd) data

    USGS Publications Warehouse

    Neymark, L.A.; Larin, A.M.; Nemchin, A.A.; Ovchinnikova, G.V.; Rytsk, E. Yu

    1998-01-01

    The Northern Baikal volcanic belt has an age of 1.82-1.87 Ga and extends along the boundary between the Siberian Platform and the Baikal foldbelt. The volcanic belt is composed of volcanics of the Akitkan Group and granitic rocks of the Irel and Primorsk complexes. The geochemistry of the rocks points to the intraplate anorogenic nature of the belt. U-Pb zircon dating of the Chuya granitoids revealed that they are older (2020-2060 Ma) than the Northern Baikal volcanic belt and, thus, cannot be regarded as its component. Data on the Pb isotopic system of feldspars from the granitoids confirm the contemporaneity of all volcanic rocks of the belt except the volcanics of the upper portion of the Akitkan Group (Chaya Formation). Our data suggest its possibly younger (???1.3 Ga) age. The isotopic Nd and Pb compositions of the acid volcanic rocks provide evidence of the heterogeneity of their crustal protoliths. The volcanics of the Malaya Kosa Formation have ??Nd(T) = -6.1, ??2 = 9.36, and were most probably produced with the participation of the U-depleted lower continental crust of Archean age. Other rocks of the complex show ??Nd(T) from -0.1 to -2.4, ??2 = 9.78, and could have been formed by the recycling of the juvenile crust. The depletion of the Malaya Kosa volcanics in most LILEs and HFSEs compared with other acid igneous rocks of the belt possibly reflects compositional differences between the Late Archean and Early Proterozoic crustal sources. The basaltic rocks of the Malaya Kosa Formation (??Nd varies from -4.6 to -5.4) were produced by either the melting of the enriched lithospheric mantle or the contamination of derivatives of the depleted mantle by Early Archean lower crustal rocks, which are not exposed within the area. Copyright ?? 1998 by MAEe Cyrillic signK Hay??a/Interperiodica Publishing.

  15. Geochemical assessment of nuclear waste isolation. Report of activities during fiscal year 1982

    SciTech Connect

    Not Available

    1983-07-01

    The status of the following investigations is reported: canister/overpack-backfill chemical interactions and mechanisms; backfill and near-field host rock chemical interactions mechanisms; far-field host rock geochemical interactions; verification and improvement of predictive algorithms for radionuclide migration; and geologic systems as analogues for long-term radioactive waste isolation.

  16. Geochemical modeling: a review

    SciTech Connect

    Jenne, E.A.

    1981-06-01

    Two general families of geochemical models presently exist. The ion speciation-solubility group of geochemical models contain submodels to first calculate a distribution of aqueous species and to secondly test the hypothesis that the water is near equilibrium with particular solid phases. These models may or may not calculate the adsorption of dissolved constituents and simulate the dissolution and precipitation (mass transfer) of solid phases. Another family of geochemical models, the reaction path models, simulates the stepwise precipitation of solid phases as a result of reacting specified amounts of water and rock. Reaction path models first perform an aqueous speciation of the dissolved constituents of the water, test solubility hypotheses, then perform the reaction path modeling. Certain improvements in the present versions of these models would enhance their value and usefulness to applications in nuclear-waste isolation, etc. Mass-transfer calculations of limited extent are certainly within the capabilities of state-of-the-art models. However, the reaction path models require an expansion of their thermodynamic data bases and systematic validation before they are generally accepted.

  17. Synthesis of Natural O-Linked Carba-Disaccharides, (+)- and (−)-Pericosine E, and Their Analogues as α-Glucosidase Inhibitors

    PubMed Central

    Usami, Yoshihide; Mizuki, Koji; Kawahata, Rikiya; Shibano, Makio; Sekine, Atsuko; Yoneyama, Hiroki; Harusawa, Shinya

    2017-01-01

    Pericosine E (6), a metabolite of Periconia byssoides OUPS-N133 was originally isolated from the sea hare Aplysia kurodai, which exists as an enantiomeric mixture in nature. The enantiospecific syntheses of both enantiomers of Periconia byssoides OUPS-N133 has been achieved, along with six stereoisomers, using a common simple synthetic strategy. For these efficient syntheses, highly regio- and steroselective processes for the preparation of bromohydrin and anti-epoxide intermediates were applied. In order to access the unique O-linked carbadisaccharide structure, coupling of chlorohydrin as a donor and anti-epoxide as an acceptor was achieved using catalytic BF3·Et2O. Most of the synthesized compounds exhibited selectively significant inhibitory activity against α-glycosidase derived from yeast. The strongest analog showed almost 50 times the activity of the positive control, deoxynojirimycin. PMID:28124983

  18. Hot isostatically-pressed aluminosilicate glass-ceramic with natural crystalline analogues for immobilizing the calcined high-level nuclear waste at the Idaho Chemical Processing Plant

    SciTech Connect

    Raman, S.

    1993-12-01

    The additives Si, Al, MgO, P{sub 2}O{sub 5} were mechanically blended with fluorinelsodium calcine in varying proportions. The batches were vacuum sealed in stainless steel canisters and hot isostatically pressed at 20,000 PSI and 1000 C for 4 hours. The resulting suite of glass-ceramic waste forms parallels the natural rocks in microstructural and compositional heterogeneity. Several crystalline phases ar analogous in composition and structure to naturally occurring minerals. Additional crystalline phases are zirconia and Ca-Mg borate. The glasses are enriched in silica and alumina. Approximately 7% calcine elements occur dissolved in this glass and the total glass content in the waste forms averages 20 wt%. The remainder of the calcine elements are partitioned into crystalline phases at 75 wt% calcine waste loading. The waste forms were tested for chemical durability in accordance with the MCC1-test procedure. The leach rates are a function of the relative proportions of additives and calcine, which in turn influence the composition and abundances of the glass and crystalline phases. The DOE leach rate criterion of less than 1 g/m{sup 2}-day is met by all the elements B, Cs and Na are increased by lowering the melt viscosity. This is related to increased crystallization or devitrification with increases in MgO addition. This exploratory work has shown that the increases in waste loading occur by preferred partitioning of the calcine components among crystalline and glass phases. The determination of optimum processing parameters in the form of additive concentration levels, homogeneous blending among the components, and pressure-temperature stabilities of phases must be continued to eliminate undesirable effects of chemical composition, microstructure and glass devitrification.

  19. Confocal {mu}-XRF, {mu}-XAFS, and {mu}-XRD Studies of Sediment from a Nuclear Waste Disposal Natural Analogue Site and Fractured Granite Following a Radiotracer Migration Experiment

    SciTech Connect

    Denecke, Melissa A.; Brendebach, Boris; Rothe, Joerg; Simon, Rolf; Janssens, Koen; Nolf, Wout de; Vekemans, Bart; Falkenberg, Gerald; Somogyi, Andrea; Noseck, Ulrich

    2007-02-02

    Combined {mu}-XRF, {mu}-XAFS, and {mu}-XRD investigations of a uranium-rich tertiary sediment, from a nuclear repository natural analogue site, and a fractured granite bore core section after a column tracer experiment using a Np(V) containing cocktail have been performed. Most {mu}-XRF/{mu}-XAFS measurements are recorded in a confocal geometry to provide added depth information. The U-rich sediment results show uranium to be present as a tetravalent phosphate and that U(IV) is associated with As(V). Arsenic present is either As(V) or As(0). The As(0) forms thin coatings on the surface of pyrite nodules. A hypothesis for the mechanism of uranium immobilization is proposed, where arsenopyrite acted as reductant of ground water dissolved U(VI) leading to precipitation of less soluble U(IV) and thereby forming As(V). Results for the granite sample show the immobilized Np to be tetravalent and associated with facture material.

  20. New synthetic routes to chain-extended selenium, sulfur, and nitrogen analogues of the naturally occurring glucosidase inhibitor salacinol and their inhibitory activities against recombinant human maltase glucoamylase.

    PubMed

    Liu, Hui; Nasi, Ravindranath; Jayakanthan, Kumarasamy; Sim, Lyann; Heipel, Heather; Rose, David R; Pinto, B Mario

    2007-08-17

    Six heteroanalogues (X = S, Se, NH) of the naturally occurring glucosidase inhibitor salacinol, containing polyhydroxylated, acyclic chains of 6-carbons, were synthesized for structure-activity studies with different glycosidase enzymes. The target zwitterionic compounds were synthesized by means of nucleophilic attack of the PMB-protected 1,4-anhydro-4-seleno-, 1,4-anhydro-4-thio-, and 1,4-anhydro-4-imino-D-arabinitols at the least hindered carbon atom of 1,3-cyclic sulfates. These 1,3-cyclic sulfates were derived from D-glucose and D-galactose, and significantly, they utilized butane diacetal as the protecting groups for the trans 2,3-diequatorial positions. Deprotection of the coupled products proceeded smoothly, unlike in previous attempts with different protecting groups, and afforded the target selenonium, sulfonium, and ammonium sulfates with different stereochemistry at the stereogenic centers. The four new heterosubstituted compounds (X = Se, NH) inhibited recombinant human maltase glucoamylase (MGA), one of the key intestinal enzymes involved in the breakdown of glucose oligosaccharides in the small intestine. The two selenium derivatives each had Ki values of 0.10 microM, giving the most active compounds to date in this general series of zwitterionic glycosidase inhibitors. The two nitrogen compounds also inhibited MGA but were less active, with Ki values of 0.8 and 35 microM. The compounds in which X = S showed Ki values of 0.25 and 0.17 microM. Comparison of these data with those reported previously for related compounds reinforces the requirements for an effective inhibitor of MGA. With respect to chain extension, the configurations at C-2' and C-4' are critical for activity, the configuration at C-3', bearing the sulfate moiety, being unimportant. It would also appear that the configuration at C-5' is important but the relationship is dependent on the heteroatom.

  1. Heteroatom-Containing Porphyrin Analogues.

    PubMed

    Chatterjee, Tamal; Shetti, Vijayendra S; Sharma, Ritambhara; Ravikanth, Mangalampalli

    2017-02-22

    The heteroatom-containing porphyrin analogues or core-modified porphyrins that resulted from the replacement of one or two pyrrole rings with other five-membered heterocycles such as furan, thiophene, selenophene, tellurophene, indene, phosphole, and silole are highly promising macrocycles and exhibit quite different physicochemical properties compared to regular azaporphyrins. The properties of heteroporphyrins depend on the nature and number of different heterocycle(s) present in place of pyrrole ring(s). The heteroporphyrins provide unique and unprecedented coordination environments for metals. Unlike regular porphyrins, the monoheteroporphyrins are known to stabilize metals in unusual oxidation states such as Cu and Ni in +1 oxidation states. The diheteroporphyrins, which are neutral macrocycles without ionizable protons, also showed interesting coordination chemistry. Thus, significant progress has been made in last few decades on core-modified porphyrins in terms of their synthesis, their use in building multiporphyrin arrays for light-harvesting applications, their use as ligands to form interesting metal complexes, and also their use for several other studies. The synthetic methods available in the literature allow one to prepare mono- and diheteroporphyrins and their functionalized derivatives, which were used extensively to prepare several covalent and noncovalent heteroporphyrin-based multiporphyrin arrays. The methods are also developed to synthesize different hetero analogues of porphyrin derivatives such as heterocorroles, heterochlorins, heterocarbaporphyrinoids, heteroatom-substituted confused porphyrins, and so on. This Review summarizes the key developments that have occurred in heteroporphyrin chemistry over the last four decades.

  2. The IUGS/IAGC Task Group on Global Geochemical Baselines

    USGS Publications Warehouse

    Smith, David B.; Wang, Xueqiu; Reeder, Shaun; Demetriades, Alecos

    2012-01-01

    The Task Group on Global Geochemical Baselines, operating under the auspices of both the International Union of Geological Sciences (IUGS) and the International Association of Geochemistry (IAGC), has the long-term goal of establishing a global geochemical database to document the concentration and distribution of chemical elements in the Earth’s surface or near-surface environment. The database and accompanying element distribution maps represent a geochemical baseline against which future human-induced or natural changes to the chemistry of the land surface may be recognized and quantified. In order to accomplish this long-term goal, the activities of the Task Group include: (1) developing partnerships with countries conducting broad-scale geochemical mapping studies; (2) providing consultation and training in the form of workshops and short courses; (3) organizing periodic international symposia to foster communication among the geochemical mapping community; (4) developing criteria for certifying those projects whose data are acceptable in a global geochemical database; (5) acting as a repository for data collected by those projects meeting the criteria for standardization; (6) preparing complete metadata for the certified projects; and (7) preparing, ultimately, a global geochemical database. This paper summarizes the history and accomplishments of the Task Group since its first predecessor project was established in 1988.

  3. Aspartame and Its Analogues

    NASA Astrophysics Data System (ADS)

    Pavlova, L. A.; Komarova, T. V.; Davidovich, Yurii A.; Rogozhin, S. V.

    1981-04-01

    The results of studies on the biochemistry of the sweet taste are briefly reviewed. The methods of synthesis of "aspartame" — a sweet dipeptide — are considered, its structural analogues are described, and quantitative estimates are made of the degree of sweetness relative to sucrose. Attention is concentrated mainly on problems of the relation between the structure of the substance and its taste in the series of aspartyl derivatives. The bibliography includes 118 references.

  4. Quantum analogue computing.

    PubMed

    Kendon, Vivien M; Nemoto, Kae; Munro, William J

    2010-08-13

    We briefly review what a quantum computer is, what it promises to do for us and why it is so hard to build one. Among the first applications anticipated to bear fruit is the quantum simulation of quantum systems. While most quantum computation is an extension of classical digital computation, quantum simulation differs fundamentally in how the data are encoded in the quantum computer. To perform a quantum simulation, the Hilbert space of the system to be simulated is mapped directly onto the Hilbert space of the (logical) qubits in the quantum computer. This type of direct correspondence is how data are encoded in a classical analogue computer. There is no binary encoding, and increasing precision becomes exponentially costly: an extra bit of precision doubles the size of the computer. This has important consequences for both the precision and error-correction requirements of quantum simulation, and significant open questions remain about its practicality. It also means that the quantum version of analogue computers, continuous-variable quantum computers, becomes an equally efficient architecture for quantum simulation. Lessons from past use of classical analogue computers can help us to build better quantum simulators in future.

  5. Concerning evaluation of eco-geochemical background in remediation strategy

    NASA Astrophysics Data System (ADS)

    Korobova, Elena; Romanov, Sergey

    2015-04-01

    The geochemical concept of biosphere developed by V.I. Vernadsky states the geological role of the living organisms in the course of their active chemical interaction with the inert matter (Vernadsky, 1926, 1960). Basing on this theory it is reasonable to suggest that coevolution of living organisms and their environment led to development of the dynamically stable biogeocenoses precisely adequate to their geochemical environment. Soil cover was treated by V.I. Vernadsky as a balanced bio-inert matter resulting from this interaction. Appearance of human mind and then a civilization led to global expansion of human beings, first able to survive in unfavorable geochemical conditions and then starting chemical transformation of the environment to satisfy the growing demands of mankind in food and energy. The residence in unfavorable environment and local contamination was followed by appearance of endemic diseases of plants, animals and man. Therefore zonal, regional and local chemical composition of the soil cover formed in natural conditions may be used for estimation of the optimum geochemical background, most adequate for the corresponding zonal biogeocenoses and species. Moreover, the natural geochemical background and technogenic fields have unequal spatial structure and this facilitates their identification that may be relatively easy realized in remediation strategy. On the assumption of the foregoing, the adequate methodical approach to remediation of technogenically affected areas should account of the interaction of the existing natural and the newly formed technogenic geochemical fields and include the following steps: 1) the study and mapping of geochemical structure of the natural geochemical background basing on soil maps; 2) the study of contaminants and mapping spatial distribution of technogenic releases; 3) construction of risk maps for the target risk groups with due regard to natural ecological threshold concentration in context of risk degree for

  6. Crystal chemistry of a Ba-dominant analogue of hydrodelhayelite and natural ion-exchange transformations in double- and triple-layer phyllosilicates in post-volcanic systems of the Eifel region, Germany

    NASA Astrophysics Data System (ADS)

    Zubkova, N. V.; Chukanov, N. V.; Pekov, I. V.; Turchkova, A. G.; Lykova, I. S.; Schüller, W.; Ternes, B.; Pushcharovsky, D. Yu.

    2016-12-01

    A Ba-dominant (Ba > K) analogue of hydrodelhayelite (BDAH) from Löhley (Eifel Mts., Rhineland-Palatinate, Germany) and Ba-enriched varieties of related double- and triple-layer phyllosilicates from Eifel are studied. The crystal structure of BDAH was solved by direct methods and refined to R = 0.0698 [1483 unique reflections with I > 2σ( I)]. It is orthorhombic, Pmmn, a = 23.9532(9), b = 7.0522(3), c = 6.6064(3) Å, V = 1115.97(8) Å3, Z = 2. The structure is based upon delhayelite-type double-layer tetrahedral blocks [(Al,Si)4Si12O34(OH,O)4] connected by chains of (Ca,Fe)-centered octahedra. Ba2+ and subordinate K+ occur at partially vacant sites in zeolitic channels within the tetrahedral blocks. The crystal-chemical formula of BDAH is: (Ba0.42K0.34□0.24)(Ca0.88Fe0.12)2(□0.90Mg0.10)2[Si6(Al0.5Si0.5)2O17(OH0.71O0.29)2]ṡ6H2O. The formation of BDAH and Ba-rich varieties of altered delhayelite/fivegite, günterblassite and hillesheimite is considered as a result of leaching of Na, Cl, F and, partially, K and Ca accompanied with hydration and the capture of Ba as a result of natural ion exchange. These minerals are structurally a "bridge" between single-layer phyllosilicates and zeolites having the open three-dimensional tetrahedral Al-Si-O frameworks.

  7. Global geochemical problems

    NASA Technical Reports Server (NTRS)

    Harriss, R. C.

    1980-01-01

    Application of remote sensing techniques to the solution of geochemical problems is considered with emphasis on the 'carbon-cycle'. The problem of carbon dioxide sinks and the areal extent of coral reefs are treated. In order to assess the problems cited it is suggested that remote sensing techniques be utilized to: (1)monitor globally the carbonate and bicarbonate concentrations in surface waters of the world ocean; (2)monitor the freshwater and oceanic biomass and associated dissolved organic carbon; (3) inventory the coral reef areas and types and the associated oceanographic climatic conditions; and (4)measure the heavy metal fluxes from forested and vegetated areas, from volcanos, from different types of crustal rocks, from soils, and from sea surfaces.

  8. [Microbial geochemical calcium cycle].

    PubMed

    Zavarzin, G A

    2002-01-01

    The participation of microorganisms in the geochemical calcium cycle is the most important factor maintaining neutral conditions on the Earth. This cycle has profound influence on the fate of inorganic carbon, and, thereby, on the removal of CO2 from the atmosphere. The major part of calcium deposits was formed in the Precambrian, when prokaryotic biosphere predominated. After that, calcium recycling based on biogenic deposition by skeletal organisms became the main process. Among prokaryotes, only a few representatives, e.g., cyanobacteria, exhibit a special calcium function. The geochemical calcium cycle is made possible by the universal features of bacteria involved in biologically mediated reactions and is determined by the activities of microbial communities. In the prokaryotic system, the calcium cycle begins with the leaching of igneous rock predominantly through the action of the community of organotrophic organisms. The release of carbon dioxide to the soil air by organotrophic aerobes leads to leaching with carbonic acid and soda salinization. Under anoxic conditions, of major importance is the organic acid production by primary anaerobes (fermentative microorganisms). Calcium carbonate is precipitated by secondary anaerobes (sulfate reducers) and to a smaller degree by methanogens. The role of the cyanobacterial community in carbonate deposition is exposed by stromatolites, which are the most common organo-sedimentary Precambrian structures. Deposition of carbonates in cyanobacterial mats as a consequence of photoassimilation of CO2 does not appear to be a significant process. It is argued that carbonates were deposited at the boundary between the "soda continent", which emerged as a result of subaerial leaching with carbonic acid, and the ocean containing Ca2+. Such ecotones provided favorable conditions for the development of the benthic cyanobacterial community, which was a precursor of stromatolites.

  9. Geochemical Speciation Mass Transfer

    SciTech Connect

    1985-12-01

    PHREEQC is designed to model geochemical reactions. Based on an ion association aqueous model, PHREEQC can calculate pH, redox potential, and mass transfer as a function of reaction progress. It can be used to describe geochemical processes for both far-field and near-field performance assessment and to evaluate data acquisition needs and test data. It can also calculate the composition of solutions in equilibrium with multiple phases. The data base, including elements, aqueous species, and mineral phases, is independent of the program and is completely user-definable. PHREEQC requires thermodynamic data for each solid, gaseous, or dissolved chemical species being modeled. The two data bases, PREPHR and DEQPAK7, supplied with PHREEQC are for testing purposes only and should not be applied to real problems without first being carefully examined. The conceptual model embodied in PHREEQC is the ion-association model of Pearson and Noronha. In this model a set of mass action equations are established for each ion pair (and controlling solid phases when making mass transfer calculations) along with a set of mass balance equations for each element considered. These sets of equations are coupled using activity coefficient values for each aqueous species and solved using a continued fraction approach for the mass balances combined with a modified Newton-Raphson technique for all other equations. The activity coefficient expressions in PHREEQC include the extended Debye-Huckel, WATEQ Debye-Huckel, and Davies equations from the original United States Geological Survey version of the program. The auxiliary preprocessor program PHTL, which is derived from EQTL, converts EQ3/6 thermodynamic data to PHREEQC format so that the two programs can be compared. PHREEQC can be used to determine solubility limits on the radionuclides present in the waste form. These solubility constraints may be input to the WAPPA leach model.

  10. Collected radiochemical and geochemical procedures

    SciTech Connect

    Kleinberg, J

    1990-05-01

    This revision of LA-1721, 4th Ed., Collected Radiochemical Procedures, reflects the activities of two groups in the Isotope and Nuclear Chemistry Division of the Los Alamos National Laboratory: INC-11, Nuclear and radiochemistry; and INC-7, Isotope Geochemistry. The procedures fall into five categories: I. Separation of Radionuclides from Uranium, Fission-Product Solutions, and Nuclear Debris; II. Separation of Products from Irradiated Targets; III. Preparation of Samples for Mass Spectrometric Analysis; IV. Dissolution Procedures; and V. Geochemical Procedures. With one exception, the first category of procedures is ordered by the positions of the elements in the Periodic Table, with separate parts on the Representative Elements (the A groups); the d-Transition Elements (the B groups and the Transition Triads); and the Lanthanides (Rare Earths) and Actinides (the 4f- and 5f-Transition Elements). The members of Group IIIB-- scandium, yttrium, and lanthanum--are included with the lanthanides, elements they resemble closely in chemistry and with which they occur in nature. The procedures dealing with the isolation of products from irradiated targets are arranged by target element.

  11. Environmental Applications of Geochemical Modeling

    NASA Astrophysics Data System (ADS)

    Zhu, Chen; Anderson, Greg

    2002-05-01

    This book discusses the application of geochemical models to environmental practice and studies, through the use of numerous case studies of real-world environmental problems, such as acid mine drainage, pit lake chemistry, nuclear waste disposal, and landfill leachates. In each example the authors clearly define the environmental threat in question; explain how geochemical modeling may help solve the problem posed; and advise the reader how to prepare input files for geochemical modeling codes and interpret the results in terms of meeting regulatory requirements.

  12. Catalytic antioxidants: regenerable tellurium analogues of vitamin E.

    PubMed

    Singh, Vijay P; Poon, Jia-fei; Engman, Lars

    2013-12-20

    In an effort to improve the chain-breaking capacity of the natural antioxidants, an octyltelluro group was introduced next to the phenolic moiety in β- and δ-tocopherol. The new vitamin E analogues quenched peroxyl radicals more efficiently than α-tocopherol and were readily regenerable by aqueous N-acetylcysteine in a simple membrane model composed of a stirring chlorobenzene/water two-phase system. The novel tocopherol analogues could also mimic the action of the glutathione peroxidase enzymes.

  13. Geochemical processes at mineral surfaces

    SciTech Connect

    Davis, J.A.; Hayes, K.F.

    1986-01-01

    This volume includes 32 papers which were presented at a symposium on geochemical processes at mineral-water interfaces in 1985 and which bring to bear on this area a very wide range of expertise. The discontinuities in properties which occur at the mineral-water interface have profound effects on the movement of naturally occurring ions. Weathering and precipitation processes control the concentrations and speciation of ions in natural waters and the movements of these within the hydrosphere; both classes of processes take place at mineral-water interfaces. After an introductory overview, the book is divided into seven major sections, each dealing with one of the aspects of the processes occurring at the mineral-water interface. Five papers deal with the physical properties of the mineral-water interface; these represent a well-balanced mix of experimental and theoretical (mathematical modeling) work. Adsorption phenomena are dealt with in another five papers; these are largely experimental in character. Ion-exchange processes are discussed in four papers, one of which addresses the use of relaxation methods to study ion exchange kinetics at the microscopic level. Spectroscopic techniques (including electron-spin resonance and Moessbauer spectroscopy) are utilized in four papers. Chemical reactions, mainly redox processes, at mineral-water interfaces are treated in four papers, one of which deals with non-biological organic reactions. Solid-solution formation and equilibria are the subjects of another set of four articles, and the last group of papers deals with the processes involved in precipitation and dissolution, including weathering.

  14. Radionuclide migration at the Koongarra uranium deposit, Northern Australia Lessons from the Alligator Rivers analogue project

    NASA Astrophysics Data System (ADS)

    Payne, Timothy E.; Airey, Peter L.

    The Koongarra uranium deposit in Northern Australia provides a ‘natural analogue’ for processes that are of relevance for assessing the safety of radioactive waste disposal. In an international project extending over two decades, the Koongarra ore body was studied to increase the understanding of radionuclide migration and retention mechanisms that might occur in the vicinity of a geological repository. The research effort included extensive characterisation of the geological, hydrological and geochemical conditions at the site. Patterns of the distribution of radionuclides (predominantly members of the 238U decay chain, but also the rare isotopes 239Pu, 99Tc and 129I) were studied in both solid and groundwater phases. The project included detailed studies of uranium adsorption on mineral surfaces, and of subsequent processes that may lead to long-term uranium immobilisation. Numerous models for uranium migration were developed during the project. This paper provides a comprehensive review of the research at Koongarra, and assesses the value of the site for integrating the results of a complex series of laboratory, modelling and field studies. The insights gained from this review of the Koongarra project may assist in maximising the potential scientific benefit of future natural analogue studies.

  15. Analogue-to-Digital and Digital-to-Analogue Conversion.

    ERIC Educational Resources Information Center

    Gregory, Martin

    1997-01-01

    Discusses circuits for three-bit and four-bit analogue digital converters and digital analogue converters. These circuits feature slow operating speeds that enable the circuitry to be used to demonstrate the mode of operation using oscilloscopes and signal generators. (DDR)

  16. Mammary Analogue Secretory Carcinoma.

    PubMed

    Stevens, Todd M; Parekh, Vishwas

    2016-09-01

    Mammary analogue secretory carcinoma (MASC) is a recently described salivary gland tumor that shares the same histologic appearance and ETV6 gene (12p13) rearrangement as secretory carcinoma of the breast. Prior to its recognition, MASC cases were commonly labeled acinic cell carcinoma and adenocarcinoma, not otherwise specified. Despite distinctive histologic features, MASC may be difficult to distinguish from other salivary gland tumors, in particular zymogen-poor acinic cell carcinoma and low-grade salivary duct carcinoma. Although characteristic morphologic and immunohistochemical features form the basis of a diagnosis of MASC, the presence of an ETV6-NTRK3 gene fusion is confirmatory. Given its recent recognition the true prognostic import of MASC is not yet clearly defined.

  17. Benchmarking analogue models of brittle thrust wedges

    NASA Astrophysics Data System (ADS)

    Schreurs, Guido; Buiter, Susanne J. H.; Boutelier, Jennifer; Burberry, Caroline; Callot, Jean-Paul; Cavozzi, Cristian; Cerca, Mariano; Chen, Jian-Hong; Cristallini, Ernesto; Cruden, Alexander R.; Cruz, Leonardo; Daniel, Jean-Marc; Da Poian, Gabriela; Garcia, Victor H.; Gomes, Caroline J. S.; Grall, Céline; Guillot, Yannick; Guzmán, Cecilia; Hidayah, Triyani Nur; Hilley, George; Klinkmüller, Matthias; Koyi, Hemin A.; Lu, Chia-Yu; Maillot, Bertrand; Meriaux, Catherine; Nilfouroushan, Faramarz; Pan, Chang-Chih; Pillot, Daniel; Portillo, Rodrigo; Rosenau, Matthias; Schellart, Wouter P.; Schlische, Roy W.; Take, Andy; Vendeville, Bruno; Vergnaud, Marine; Vettori, Matteo; Wang, Shih-Hsien; Withjack, Martha O.; Yagupsky, Daniel; Yamada, Yasuhiro

    2016-11-01

    We performed a quantitative comparison of brittle thrust wedge experiments to evaluate the variability among analogue models and to appraise the reproducibility and limits of model interpretation. Fifteen analogue modeling laboratories participated in this benchmark initiative. Each laboratory received a shipment of the same type of quartz and corundum sand and all laboratories adhered to a stringent model building protocol and used the same type of foil to cover base and sidewalls of the sandbox. Sieve structure, sifting height, filling rate, and details on off-scraping of excess sand followed prescribed procedures. Our analogue benchmark shows that even for simple plane-strain experiments with prescribed stringent model construction techniques, quantitative model results show variability, most notably for surface slope, thrust spacing and number of forward and backthrusts. One of the sources of the variability in model results is related to slight variations in how sand is deposited in the sandbox. Small changes in sifting height, sifting rate, and scraping will result in slightly heterogeneous material bulk densities, which will affect the mechanical properties of the sand, and will result in lateral and vertical differences in peak and boundary friction angles, as well as cohesion values once the model is constructed. Initial variations in basal friction are inferred to play the most important role in causing model variability. Our comparison shows that the human factor plays a decisive role, and even when one modeler repeats the same experiment, quantitative model results still show variability. Our observations highlight the limits of up-scaling quantitative analogue model results to nature or for making comparisons with numerical models. The frictional behavior of sand is highly sensitive to small variations in material state or experimental set-up, and hence, it will remain difficult to scale quantitative results such as number of thrusts, thrust spacing

  18. Analogue Missions on Earth, a New Approach to Prepare Future Missions on the Moon

    NASA Astrophysics Data System (ADS)

    Lebeuf, Martin

    Human exploration of the Moon is a target by 2020 with an initial lunar outpost planned in polar regions. Current architectures maintain a capability for sorties to other latitudes for science activities. In the early stages of design of lunar outpost infrastructure and science activity planning, it has been recognized that analogue missions could play a major role in Moon mission design. Analogue missions, as high fidelity simulations of human and robotic surface operations, can help field scientists and engineers develop and test strategies as well as user requirements, as they provide opportunities to groundtruth measurements, and for the team to share understanding of key science needs and key engineering trades. These types of missions also provide direct training in planning science operations, and in team building and communication. The Canadian Space Agency's Exploration Core Program targets the development of technology infrastructure elements in key areas of science, technology and robotics in preparation for its role in the future exploration of the Moon and Mars. Within this Program, Analogue Missions specifically target the operations requirements and lessons learned that will reduce costs and lower the risk of planetary surface missions. Analogue missions are simulations of planetary surface operations that take place at analogue sites on Earth. A terrestrial analogue site resembles in some key way: eg. geomorphologically or geochemically, a surface environment of another planet. An analogue mission can, therefore, be defined as an integrated set of activities that represent (or simulate) entire mission designs or narrowly focus on specific aspects of planned or potential future planetary exploration missions. Within the CSA's Exploration Core Program, Analogue Missions facilitate the maturation of science instruments and mission concepts by integrating ongoing space instrument and technology development programs with science and analogue elements. As

  19. Ranking Geochemical Energy Availability in Hydrothermal Ecosystems

    NASA Astrophysics Data System (ADS)

    Holland, M. E.; Shock, E. L.; Meyer-Dombard, D.; Amend, J. P.

    2004-12-01

    The energy available to hyperthermophilic microorganisms in hot springs can be theoretically estimated using thermodynamic calculations based on geochemical measurements. The relative abundance of different geochemical energy sources (the "ranking" of these reactions) in particular hot springs may provide one explanation for the differences in hot spring microbial communities and also facilitate the culture of ecologically-relevant microorganisms. Geochemical sampling of seven Yellowstone National Park hot springs was repeated five times from 1999 to 2004 with the intent to compare the geochemistry and geochemical energy available to microorganisms. These seven hot springs were located in three separate regions of Yellowstone National Park: three hot springs, including Obsidian Pool, were sampled in the Mud Volcano area; two in the Sylvan Springs area (Gibbon Meadows); and one each in Imperial Meadows and Sentinel Meadows (Lower Geyser Basin). The hot springs were 75 to 93° C (with one 65° C exception) and spanned the bulk of the pH range at Yellowstone (pH 1.8 to 7.6). Geochemical measurements made on hot springs included redox-active species containing C, N, O, H, S, and Fe; these species were measured by field spectrophotometry and ion chromatography of fluid samples and gas chromatographic analysis of gas samples. From these measurements chemical affinities were calculated for 179 inorganic reactions which encompass the suite of autotrophic energy sources potentially available in each pool. Composite affinities for each reaction were compiled for each of the seven primary pools. The composite for each pool was assembled from repeat measurements from the primary pool as well as nearby pools with similar geochemistry. Calculations show that over half of these inorganic reactions could provide enough energy for a microorganism to survive, based on the threshold value of energy required by {it E. coli} (20 kJ per mole of electron pairs). Some microorganisms

  20. Geochemical data for Colorado soils-Results from the 2006 state-scale geochemical survey

    USGS Publications Warehouse

    Smith, David B.; Ellefsen, Karl J.; Kilburn, James E.

    2010-01-01

    In 2006, soil samples were collected at 960 sites (1 site per 280 square kilometers) throughout the state of Colorado. These samples were collected from a depth of 0-15 centimeters and, following a near-total multi-acid digestion, were analyzed for a suite of more than 40 major and trace elements. The resulting data set provides a baseline for the natural variation in soil geochemistry for Colorado and forms the basis for detecting changes in soil composition that might result from natural processes or anthropogenic activities. This report describes the sampling and analytical protocols used and makes available all the soil geochemical data generated in the study.

  1. NASA/ESMD Analogue Mission Plans

    NASA Technical Reports Server (NTRS)

    Hoffman, Stephen J.

    2007-01-01

    A viewgraph presentation exploring Earth and its analogues is shown. The topics include: 1) ESMD Goals for the Use of Earth Analogues; 2) Stakeholders Summary; 3) Issues with Current Analogue Situation; 4) Current state of Analogues; 5) External Implementation Plan (Second Step); 6) Recent Progress in Utilizing Analogues; 7) Website Layout Example-Home Page; 8) Website Layout Example-Analogue Site; 9) Website Layout Example-Analogue Mission; 10) Objectives of ARDIG Analog Initiatives; 11) Future Plans; 12) Example: Cold-Trap Sample Return; 13) Example: Site Characterization Matrix; 14) Integrated Analogue Studies-Prerequisites for Human Exploration; and 15) Rating Scale Definitions.

  2. Modeling Low-temperature Geochemical Processes

    NASA Astrophysics Data System (ADS)

    Nordstrom, D. K.

    2003-12-01

    Geochemical modeling has become a popular and useful tool for a wide number of applications from research on the fundamental processes of water-rock interactions to regulatory requirements and decisions regarding permits for industrial and hazardous wastes. In low-temperature environments, generally thought of as those in the temperature range of 0-100 °C and close to atmospheric pressure (1 atm=1.01325 bar=101,325 Pa), complex hydrobiogeochemical reactions participate in an array of interconnected processes that affect us, and that, in turn, we affect. Understanding these complex processes often requires tools that are sufficiently sophisticated to portray multicomponent, multiphase chemical reactions yet transparent enough to reveal the main driving forces. Geochemical models are such tools. The major processes that they are required to model include mineral dissolution and precipitation; aqueous inorganic speciation and complexation; solute adsorption and desorption; ion exchange; oxidation-reduction; or redox; transformations; gas uptake or production; organic matter speciation and complexation; evaporation; dilution; water mixing; reaction during fluid flow; reaction involving biotic interactions; and photoreaction. These processes occur in rain, snow, fog, dry atmosphere, soils, bedrock weathering, streams, rivers, lakes, groundwaters, estuaries, brines, and diagenetic environments. Geochemical modeling attempts to understand the redistribution of elements and compounds, through anthropogenic and natural means, for a large range of scale from nanometer to global. "Aqueous geochemistry" and "environmental geochemistry" are often used interchangeably with "low-temperature geochemistry" to emphasize hydrologic or environmental objectives.Recognition of the strategy or philosophy behind the use of geochemical modeling is not often discussed or explicitly described. Plummer (1984, 1992) and Parkhurst and Plummer (1993) compare and contrast two approaches for

  3. Geochemical Origin of Biological Molecules

    NASA Astrophysics Data System (ADS)

    Bassez, Marie-Paule

    2013-04-01

    Conference and abstract in OLEB, 2008, 39 (3-4) 223. BASSEZ M.P. 2009 Prebiotic synthesis under hydothermal conditions, C. R. Chimie, Académie des Sciences, Paris 12 (6-7) : 801-807. BASSEZ M.P. 2012 A model for a geochemical origin of life in preparation BASSEZ M.P., TAKANO Y., OHKOUCHI N. 2009a Organic analysis of peridotite rocks from Ashadze and Logatchev hydrothermal sites, Int. J. Mol. Sci. 10(7): 2986-2998. BASSEZ M.P., TAKANO Y., OHKOUCHI N. 2009b Organic analysis of peridotite rocks from the MAR, AGU fall meeting, P43C-1441, San Francisco, 14-18/12/2009. BASSEZ M.P., TAKANO Y. 2010a Prebiotic organic globules, Nature Precedings: Posted 21 Jul http://hdl:10101/npre.2010.4694.1. BASSEZ M.P., TAKANO Y., OHKOUCHI N. 2010b Organic analysis of peridotite rocks, First chemical steps towards the Origin of Life colloquium, Turin 16-17/09/2010. BASSEZ M.P., TAKANO Y., OHKOUCHI N. 2011a A search for prebiotic molecular signatures inside rocks, Geobiology in Space exploration workshop, P sans n°, Marrakech 07-14/02/2011. BASSEZ M.P., TAKANO Y., OHKOUCHI N. 2011b Detection of molecular biosignatures inside rocks, Origins 2011 ISSOL and Bioastronomy conference, P2-17, Montpellier, 04-08/07/2011. BASSEZ M.P., TAKANO Y., 2011c Organic microstructures, Origins 2011 ISSOL and Bioastronomy conference, P2-34, Montpellier, 04-08/07/2011. BASSEZ M.P., TAKANO Y. KOBAYASHI K. 2011d Prebiotic organic microstructures, Nature Precedings: Posted 14 Nov. http://hdl.handle.net/10101/npre.2011.4694.2 BASSEZ M.P., TAKANO Y., KOBAYASHI K. 2012a Prebiotic organic microstructures, Origin of Life Gordon Research Conference P4, Galveston, 08-13/01/2012. BASSEZ M.P., TAKANO Y., KOBAYASHI K. 2012b Prebiotic organic microstructures, Orig. Life Evol. Biosph. 42 (4) : 307-316.

  4. The relevance of analogue studies for understanding obsessions and compulsions.

    PubMed

    Abramowitz, Jonathan S; Fabricant, Laura E; Taylor, Steven; Deacon, Brett J; McKay, Dean; Storch, Eric A

    2014-04-01

    Analogue samples are often used to study obsessive-compulsive (OC) symptoms and related phenomena. This approach is based on the hypothesis that results derived from such samples are relevant to understanding OC symptoms in individuals with a diagnosis of obsessive-compulsive disorder (OCD). Two decades ago, Gibbs (1996) reviewed the available literature and found initial support for this hypothesis. Since then there have been many important advances addressing this issue. The purpose of the present review was to synthesize various lines of research examining the assumptions of using analogue samples to draw inferences about people with OCD. We reviewed research on the prevalence of OC symptoms in non-clinical populations, the dimensional (vs. categorical) nature of these symptoms, phenomenology, etiology, and studies on developmental and maintenance factors in clinical and analogue samples. We also considered the relevance of analogue samples in OCD treatment research. The available evidence suggests research with analogue samples is highly relevant for understanding OC symptoms. Guidelines for the appropriate use of analogue designs and samples are suggested.

  5. Forensic Analysis using Geological and Geochemical Techniques

    NASA Astrophysics Data System (ADS)

    Hoogewerff, J.

    2009-04-01

    Due to the globalisation of legal (and illegal) trade there is an increasing demand for techniques which can verify the geographical origin and transfer routes of many legal and illegal commodities and products. Although geological techniques have been used in forensic investigations since the emergence of forensics as a science in the late eighteen hundreds, the last decade has seen a marked increase in geo-scientists initiating concept studies using the latest analytical techniques, including studying natural abundance isotope variations, micro analysis with laser ablation ICPMS and geochemical mapping. Most of the concept studies have shown a good potential but uptake by the law enforcement and legal community has been limited due to concerns about the admissibility of the new methods. As an introduction to the UGU2009 session "Forensic Provenancing using Geological and Geochemical Techniques" I will give an overview of the state of the art of forensic geology and the issues that concern the admissibility of geological forensic evidence. I will use examples from the NITECRIME and FIRMS networks, the EU TRACE project and other projects and literature to illustrate the important issues at hand.

  6. Analogues of uracil nucleosides with intrinsic fluorescence (NIF-analogues): synthesis and photophysical properties.

    PubMed

    Segal, Meirav; Fischer, Bilha

    2012-02-28

    Uridine cannot be utilized as fluorescent probe due to its extremely low quantum yield. For improving the uracil fluorescence characteristics we extended the natural chromophore at the C5 position by coupling substituted aromatic rings directly or via an alkenyl or alkynyl linker to create fluorophores. Extension of the uracil base was achieved by treating 5-I-uridine with the appropriate boronic acid under the Suzuki coupling conditions. Analogues containing an alkynyl linker were obtained from 5-I-uridine and the suitable boronic acid in a Sonogashira coupling reaction. The uracil fluorescent analogues proposed here were designed to satisfy the following requirements: a minimal chemical modification at a position not involved in base-pairing, resulting in relatively long absorption and emission wavelengths and high quantum yield. 5-((4-Methoxy-phenyl)-trans-vinyl)-2'-deoxy-uridine, 6b, was found to be a promising fluorescent probe. Probe 6b exhibits a quantum yield that is 3000-fold larger than that of the natural chromophore (Φ 0.12), maximum emission (478 nm) which is 170 nm red shifted as compared to uridine, and a Stokes shift of 143 nm. In addition, since probe 6b adopts the anti conformation and S sugar puckering favored by B-DNA, it makes a promising nucleoside analogue to be incorporated in an oligonucleotide probe for detection of genetic material.

  7. Condensed matter analogues of cosmology

    NASA Astrophysics Data System (ADS)

    Kibble, Tom; Srivastava, Ajit

    2013-10-01

    liveliest. A number of new experiments are reported here studying the dynamical evolution of domains and defects. Another phenomenon that played a key early role was the formation of vortices in the normal-to-superfluid transition in liquid helium-3. The complicated nature of the order parameter energy surface gives rise to a variety of intriguing effects. This too is still a vigorous field. Superconductivity is a special case because the symmetry that is broken is a gauge symmetry. This is also true in fundamental particle physics theories of relevance to cosmology, and for that reason experiments on superconductors are of particular interest to cosmologists. The situation in this case is more complicated because there are competing mechanisms of defect formation. Experiments in the field have not proved easy, either to perform or to interpret, but the papers in this collection show that good progress has been made of late. In recent years a new type of system has proved immensely fruitful, namely atomic Bose-Einstein or Fermi-gas condensates. Experiments on condensates with tunable parameters have in general provided broad support for the theory, and have also revealed a wide range of interesting and novel features, with intriguing possible analogues in cosmology (e.g. causal horizons and particle creation). The basic idea of the Kibble-Zurek mechanism has been shown to be relevant in this whole range of systems. But numerous complexities have also emerged, concerned for example with the role of inhomogeneity or the existence of composite defects. The field is still developing rapidly. Acknowledgments Finally, we would like to thank all the authors who have contributed to this issue, and the staff of Journal of Physics: Condensed Matter who have made it possible. Condensed matter analogues of cosmology contents Condensed matter analogues of cosmologyTom Kibble and Ajit Srivastava Symmetry breaking in nematic liquid crystals: analogy with cosmology and magnetismR Repnik, A

  8. IRETHERM: Developing a Strategic and Holistic Understanding of Ireland's Geothermal Energy Potential through Integrated Modelling of New and Existing Geophysical, Geochemical and Geological Data

    NASA Astrophysics Data System (ADS)

    Jones, Alan G.; Daly, Stephen; Vozar, Jan; Rath, Volker; Campanya, Joan; Blake, Sarah; Delhaye, Robert; Fritschle, Tobias; Willmot Noller, Nicola; Long, Mike; Waters, Tim

    2015-04-01

    The Science Foundation Ireland funded academia-government-industry collaborative IRETHERM project (www.iretherm.ie), initiated in 2011, is developing a strategic understanding of Ireland's (all-island) deep geothermal energy potential through integrated modelling of new and existing geophysical, geochemical and geological data. Potential applications include both low enthalpy district space heating of large urban centres and electricity generation from intermediate-temperature waters. IRETHERM comprises three broad geothermal target types; 1) Assessment of the geothermal energy potential of Ireland's radiogenic granites (EGS), (2) Assessment of the geothermal energy potential of Ireland's deep sedimentary basins (HSA), and, (3) Assessment of the geothermal energy potential of warm springs. The geophysical subsurface imaging techniques of choice are controlled-source (CSEM) and natural-source (magnetotellurics, MT) electromagnetic methods. Electrical conductivity, being a transport property, is a proxy for permeability, and appropriate porosity-permeability relations are being developed. To date, MT measurements have been made at 466 sites over sedimentary basins (190 sites), granites (156 sites) and warm springs (120 sites), with CSEM across one warm spring. An ongoing continuous geochemical (temperature and electrical conductivity every 15 mins) and time-lapse seasonal hydrochemical sampling programmes are in progress at six warm spring sites. A database on heat production in Irish rocks has been compiled, of more than 3,300 geochemical sample measurements, with 3,000 retrieved from various archives and over 300 new analyses. Geochemistry, geochronology and isotopic analyses have been conducted on subsurface granites and exposed analogues astride the Iapetus Suture Zone in order to understand the underlying reasons for their radiogenic heat production. Finally, thermal conductivity measurements have been made on borehole samples from representative lithologies

  9. Paired Magmatic-Metallogenic Belts in Myanmar - an Andean Analogue?

    NASA Astrophysics Data System (ADS)

    Gardiner, Nicholas; Robb, Laurence; Searle, Michael; Morley, Christopher

    2015-04-01

    Myanmar (Burma) is richly endowed in precious and base metals, having one of the most diverse collections of natural resources in SE Asia. Its geological history is dominated by the staged closing of Tethys and the suturing of Gondwana-derived continental fragments onto the South China craton during the Mesozoic-Cenozoic. The country is located at a crucial geologic juncture where the main convergent Tethyan collision zone swings south around the Namche Barwa Eastern Himalayan syntaxis. However, despite recent work, the geological and geodynamic history of Myanmar remains enigmatic. Plate margin processes, magmatism, metasomatism and the genesis of mineral deposits are intricately linked, and there has long been recognized a relationship between the distribution of certain mineral deposit types, and the tectonic settings which favour their genesis. A better knowledge of the regional tectonic evolution of a potential exploration jurisdiction is therefore crucial to understanding its minerals prospectivity. This strong association between tectonics and mineralization can equally be applied in reverse. By mapping out the spatial, and temporal, distribution of presumed co-genetic mineral deposits, coupled with an understanding of their collective metallogenetic origin, a better appreciation of the tectonic evolution of a terrane may be elucidated. Identification and categorization of metallotects within a geodynamically-evolving terrane thus provides a complimentary tool to other methodologies (e.g. geochemical, geochronological, structural, geophysical, stratigraphical), for determining the tectonic history and inferred geodynamic setting of that terrane through time. Myanmar is one such study area where this approach can be undertaken. Here are found two near-parallel magmatic belts, which together contain a significant proportion of that country's mineral wealth of tin, tungsten, copper, gold and silver. Although only a few 100 km's apart, these belts exhibit a

  10. Geochemical cycles of atmospheric gases

    NASA Technical Reports Server (NTRS)

    Walker, J. C. G.; Drever, J. I.

    1988-01-01

    The processes that control the atmosphere and atmospheric changes are reviewed. The geochemical cycles of water vapor, nitrogen, carbon dioxide, oxygen, and minor atmospheric constituents are examined. Changes in atmospheric chemistry with time are discussed using evidence from the rock record and analysis of the present atmosphere. The role of biological evolution in the history of the atmosphere and projected changes in the future atmosphere are considered.

  11. Derivatisable Cyanobactin Analogues: A Semisynthetic Approach

    PubMed Central

    Oueis, Emilia; Adamson, Catherine; Mann, Greg; Ludewig, Hannes; Redpath, Philip; Migaud, Marie

    2015-01-01

    Abstract Many natural cyclic peptides have potent and potentially useful biological activities. Their use as therapeutic starting points is often limited by the quantities available, the lack of known biological targets and the practical limits on diversification to fine‐tune their properties. We report the use of enzymes from the cyanobactin family to heterocyclise and macrocyclise chemically synthesised substrates so as to allow larger‐scale syntheses and better control over derivatisation. We have made cyclic peptides containing orthogonal reactive groups, azide or dehydroalanine, that allow chemical diversification, including the use of fluorescent labels that can help in target identification. We show that the enzymes are compatible and efficient with such unnatural substrates. The combination of chemical synthesis and enzymatic transformation could help renew interest in investigating natural cyclic peptides with biological activity, as well as their unnatural analogues, as therapeutics. PMID:26507241

  12. New rubrolide analogues as inhibitors of photosynthesis light reactions.

    PubMed

    Varejão, Jodieh O S; Barbosa, Luiz C A; Ramos, Gabriela Álvarez; Varejão, Eduardo V V; King-Díaz, Beatriz; Lotina-Hennsen, Blas

    2015-04-01

    Natural products called rubrolides have been investigated as a model for the development of new herbicides that act on the photosynthesis apparatus. This study comprises a comprehensive analysis of the photosynthesis inhibitory ability of 27 new structurally diverse rubrolide analogues. In general, the results revealed that the compounds exhibited efficient inhibition of the photosynthetic process, but in some cases low water solubility may be a limiting factor. To elucidate their mode of action, the effects of the compounds on PSII and PSI, as well as their partial reaction on chloroplasts and the chlorophyll a fluorescence transients were measured. Our results showed that some of the most active rubrolide analogues act as a Hill reaction inhibitors at the QB level by interacting with the D1 protein at the reducing side of PSII. All of the active analogues follow Tice's rule of 5, which indicates that these compounds present physicochemical properties suitable for herbicides.

  13. Synthesis and antioxidant activity of a procyanidin B3 analogue.

    PubMed

    Mizuno, Mirei; Nakanishi, Ikuo; Matsubayashi, Satoko; Imai, Kohei; Arai, Takuya; Matsumoto, Ken-Ichiro; Fukuhara, Kiyoshi

    2017-02-15

    Proanthocyanidin, an oligomer of catechin, is a natural antioxidant and a potent inhibitor of lectin-like oxidized LDL receptor-1, which is involved in the pathogenesis of arteriosclerosis. We synthesized proanthocyanidin analogue 1, in which the geometry of one catechin molecule in procyanidin B3, a dimer of (+)-catechin, is constrained to be planar. The antioxidant activities of the compounds were evaluated in terms of their capacities to scavenge galvinoxyl radicals, and results demonstrate that while procyanidin was 3.8 times more potent than (+)-catechin, the radical scavenging activity of proanthocyanidin analogue 1 was further increased to 1.9 times that of procyanidin B3. This newly designed proanthocyanidin analogue 1 may be a promising lead compound for the treatment of arteriosclerosis and related cerebrovascular diseases.

  14. Migrastatin analogues target fascin to block tumour metastasis.

    PubMed

    Chen, Lin; Yang, Shengyu; Jakoncic, Jean; Zhang, J Jillian; Huang, Xin-Yun

    2010-04-15

    Tumour metastasis is the primary cause of death of cancer patients. Development of new therapeutics preventing tumour metastasis is urgently needed. Migrastatin is a natural product secreted by Streptomyces, and synthesized migrastatin analogues such as macroketone are potent inhibitors of metastatic tumour cell migration, invasion and metastasis. Here we show that these migrastatin analogues target the actin-bundling protein fascin to inhibit its activity. X-ray crystal structural studies reveal that migrastatin analogues bind to one of the actin-binding sites on fascin. Our data demonstrate that actin cytoskeletal proteins such as fascin can be explored as new molecular targets for cancer treatment, in a similar manner to the microtubule protein tubulin.

  15. Mineralogical and geochemical consequences of the long-term presence of CO2 in natural reservoirs: An example from the Springerville-St. Johns Field, Arizona, and New Mexico, U.S.A

    USGS Publications Warehouse

    Moore, J.; Adams, M.; Allis, R.; Lutz, S.; Rauzi, S.

    2005-01-01

    The Springerville-St. Johns CO2 field in eastern Arizona and western New Mexico is one of more than a dozen gas fields developed within the Colorado Plateau and Southern Rocky Mountain region. Extensive travertine (CaCO3) deposits record a long history of CO2 migration and leakage to the atmosphere. The oldest travertine deposits may have formed during the initial filling of the CO2 reservoir when groundwaters exsolved CO2 upon reaching the surface. The youngest travertine deposits are associated with springs on the floor of the Little Colorado River valley, but travertine deposition appears to be insignificant today. Older deposits occur up to 325 m above the valley floor. Geologic relationships suggest travertine deposition began in the late Pleistocene after volcanic activity ended at ???0.3 Ma. Most of the CaCO3 could have been derived from dissolution of the underlying limestones and dolomites. Interactions between the reservoir fluids and rocks were observed in core samples from one of the intervals that produced dry gas. These reactions resulted in the dissolution of carbonate cements and detrital feldspars and the formation of dawsonite and kaolinite. Geochemical simulations suggest that the dawsonite could have been deposited when the CO2 fugacity reached 20 bars and that the kaolinite formed as the CO2 fugacity decreased. Corrosion of drill pipe by acidic waters and a pronounced HCO3 anomaly above the CO2 reservoir provide evidence of a continuing flux of CO2 from depth. CO2 storage occurs primarily as dissolved carbonate species and as gas accumulations. Only a small percentage of the CO2 was sequestered in secondary minerals. ?? 2005 Elsevier B.V. All rights reserved.

  16. Theoretical study on absorption and emission spectra of adenine analogues.

    PubMed

    Liu, Hongxia; Song, Qixia; Yang, Yan; Li, Yan; Wang, Haijun

    2014-04-01

    Fluorescent nucleoside analogues have attracted much attention in studying the structure and dynamics of nucleic acids in recent years. In the present work, we use theoretical calculations to investigate the structural and optical properties of four adenine analogues (termed as A1, A2, A3, and A4), and also consider the effects of aqueous solution and base pairing. The results show that the fluorescent adenine analogues can pair with thymine to form stable H-bonded WC base pairs. The excited geometries of both adenine analogues and WC base pairs are similar to the ground geometries. The absorption and emission maxima of adenine analogues are greatly red shifted compared with nature adenine, the oscillator strengths of A1 and A2 are stronger than A3 and A4 in both absorption and emission spectra. The calculated low-energy peaks in the absorption spectra are in good agreement with the experimental data. In general, the aqueous solution and base pairing can slightly red-shift both the absorption and emission maxima, and can increase the oscillator strengths of absorption spectra, but significantly decrease the oscillator strengths of A3 in emission spectra.

  17. Fetal bovine serum influences the stability and bioactivity of resveratrol analogues: A polyphenol-protein interaction approach.

    PubMed

    Tang, Fen; Xie, Yixi; Cao, Hui; Yang, Hua; Chen, Xiaoqing; Xiao, Jianbo

    2017-03-15

    Fetal bovine serum (FBS) is a universal growth supplement of cell and tissue culture media. Herein, the influences of FBS on the stability and antioxidant activity of 21 resveratrol analogues were investigated using a polyphenol-protein interaction approach. The structure-stability relationships of resveratrol analogues in FBS showed a clear decrease in the stability of hydroxylated resveratrol analogues in the order: resorcinol-type>pyrogallol-type>catechol-type. The glycosylation and methoxylation of resveratrol analogues enhanced their stability. A linear relationship between the stability of resveratrol analogues in FBS and the affinity of resveratrol analogues-FBS interaction was found. The oxidation process is not the only factor governing the stability of resveratrol analogues in FBS. These results facilitated the insightful investigation of the role of polyphenol-protein interactions in serum, thereby providing some fundamental clues for future clinical research and pharmacological studies on natural small molecules.

  18. Missions to Mars: Characterisation of Mars analogue rocks for the International Space Analogue Rockstore (ISAR)

    NASA Astrophysics Data System (ADS)

    Bost, Nicolas; Westall, Frances; Ramboz, Claire; Foucher, Frédéric; Pullan, Derek; Meunier, Alain; Petit, Sabine; Fleischer, Iris; Klingelhöfer, Göstar; Vago, Jorge L.

    2013-07-01

    Instruments for surface missions to extraterrestrial bodies should be cross-calibrated using a common suite of relevant materials. Such work is necessary to improve instrument performance and aids in the interpretation of in-situ measurements. At the CNRS campus in Orléans, the Observatoire des Sciences de l'Univers en région Centre (OSUC) has created a collection of well-characterised rocks and minerals for testing and calibrating instruments to be flown in space missions. The characteristics of the analogue materials are documented in an accompanying online database. In view of the recent and upcoming rover missions to Mars (NASA's 2011 Mars Science Laboratory (MSL) and ESA/Roscosmos' 2018 ExoMars), we are concentrating initially on materials of direct relevance to the red planet. The initial collection consists of 15 well-studied rock and mineral samples, including a variety of basalts (ultramafic, weathered, silicified, primitive), sediments (volcanic sands, chert, and a banded iron formation -BIF-), and the phyllosilicate nontronite (a clay). All the samples were characterised petrographically, petrologically, and geochemically using the types of analyses likely to be performed during in-situ missions, in particular ExoMars: hand specimen description; optical microscopy; mineralogical analysis by XRD, Raman and IR spectrometry; iron phase analysis by Mössbauer spectroscopy (MBS), elemental analysis by Energy-Dispersive X-ray spectroscopy (EDX), microprobe, Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) and Mass Spectrometry (ICP-MS); and reduced carbon analysis by Raman spectrometry.

  19. Geochemical barriers for environment protection and recovery of nonferrous metals.

    PubMed

    Chanturiya, Valentine; Masloboev, Vladimir; Makarov, Dmitriy; Nesterov, Dmitriy; Bajurova, Julia; Svetlov, Anton; Men'shikov, Yuriy

    2014-01-01

    A study of natural minerals, ore tailings and their products as materials for artificial geochemical barriers is presented. In particular, it focuses on interaction between calcite and dolomite and sulfate solutions containing nickel, copper and iron under static conditions. Calcite of -0.1 mm fraction has been shown to perform well as a barrier when added to water phases of tailing dumps and natural reservoirs. Experiments under dynamic conditions have revealed a high potential of thermally activated copper-nickel tailings as barriers. After a 500-day precipitating period on a geochemical barrier, the contents of nickel and copper in ore dressing tailings were found to increase 12- and 28-fold, respectively. An effective sorbent of copper, iron and nickel ions is a brucite-based product of hydrochloric acid treatment of vermiculite ore tailings. Its sorption capacity can be essentially increased through thermal activation.

  20. Composition of natural gas and crude oil produced from 14 wells in the Lower Silurian "Clinton" Sandstone and Medina Group Sandstones, northeastern Ohio and northwestern Pennsylvania: Chapter G.6 in Coal and petroleum resources in the Appalachian basin: distribution, geologic framework, and geochemical character

    USGS Publications Warehouse

    Burruss, Robert A.; Ryder, Robert T.; Ruppert, Leslie F.; Ryder, Robert T.

    2014-01-01

    The geochemical processes that control the distribution of hydrocarbons in the regional accumulation of natural gas and crude oil in reservoirs of Early Silurian age in the central Appalachian basin are not well understood. Gas and oil samples from 14 wells along a down-dip transect through the accumulation in northeastern Ohio and northwestern Pennsylvania were analyzed for molecular and stable isotopic compositions to look for evidence of hydrocarbon source, thermal maturation, migration, and alteration parameters. The correlation of carbon and hydrogen stable isotopic composition of methane with thermal maturation indicates that the deepest gases are more thermally mature than independent estimates of thermal maturity of the reservoir horizon based on the conodont alteration index. This correlation indicates that the natural gas charge in the deepest parts of the regional accumulation sampled in this study originated in deeper parts of the Appalachian basin and migrated into place. Other processes, including mixing and late-stage alteration of hydrocarbons, may also impact the observed compositions of natural gases and crude oils.

  1. Nanochannels: biological channel analogues.

    PubMed

    Pradeep, H; Rajanikant, G K

    2012-06-01

    The flux of ions across the biological membrane is a central activity to many cellular processes, from conduction of nerve impulse to the apoptosis. Traffic of ions or molecules across the membrane and organelles is governed by natural machines of great precision; ion channels, a special class of proteins, reside in the biological membranes. Recent studies in the field of nanoscience have concentrated on to precisely mimic the physical and chemical properties of these pores that make them increasingly attractive in this field. Synthetic nanoporous materials have a great deal of medical applications, including biosensing, biosorting, immune-isolation and drug delivery. In this review, the authors briefly describe the interesting synthetic channels that are extensively studied, and also attempt to furnish a precise overview of recent advances in this arena.

  2. Geochemical Arrays at Woolsey Mound Seafloor Observatory

    NASA Astrophysics Data System (ADS)

    Sleeper, K.; Wilson, R. M.; Chanton, J.; Lapham, L.; Farr, N.; Camilli, R.; Martens, C. S.; Pontbriand, C.

    2011-12-01

    incorporated into the Benthic Boundary Layer Array for high-speed, wireless data transmission. Combining this system with a cabled observatory will allow real-time monitoring of gas hydrates in the natural environment. The arrays have each been deployed at the Woolsey Mound Seafloor Observatory for extended durations. Woolsey Mound is at a depth of approximately 900m on the continental slope of the northern Gulf of Mexico in Mississippi Canyon Federal Lease Block 118. The Observatory is a multi-component facility that will have geophysical and microbial components in addition to the geochemical arrays described here. The goal of the Observatory is to develop a facility to evaluate the formation and stability of gas hydrates in a natural system. Specific areas of interest include geohazards, alternative energy resources, climate change and unique, deep- marine habitats. The poster presents the major geochemical arrays at Woolsey Mound Seafloor Observatory, including their design, sensor specifications, deployment and installation platforms, and scientific relevance.

  3. Summary geochemical maps of the Harrison 1° x 2° quadrangle, Arkansas and Missouri

    USGS Publications Warehouse

    Erickson, R.L.; Chazin, Barbara; Erickson, M.S.

    1989-01-01

    Geochemical studies of the Harrison lo x 2° quadrangle, Arkansas and Missouri, are part of a joint multidisciplinary study by the U.S. Geological Survey; the Division of Geology and Land Survey, Missouri Department of Natural Resources; and the Arkansas Geological Commission. The objective of the joint study is to assess the mineral-resource potential of the area by integrated geologic, geochemical, and geophysical investigations.

  4. Validation of the WATEQ4 geochemical model for uranium

    SciTech Connect

    Krupka, K.M.; Jenne, E.A.; Deutsch, W.J.

    1983-09-01

    As part of the Geochemical Modeling and Nuclide/Rock/Groundwater Interactions Studies Program, a study was conducted to partially validate the WATEQ4 aqueous speciation-solubility geochemical model for uranium. The solubility controls determined with the WATEQ4 geochemical model were in excellent agreement with those laboratory studies in which the solids schoepite (UO/sub 2/(OH)/sub 2/ . H/sub 2/O), UO/sub 2/(OH)/sub 2/, and rutherfordine ((UO/sub 2/CO/sub 3/) were identified as actual solubility controls for uranium. The results of modeling solution analyses from laboratory studies of uranyl phosphate solids, however, identified possible errors in the characterization of solids in the original solubility experiments. As part of this study, significant deficiencies in the WATEQ4 thermodynamic data base for uranium solutes and solids were corrected. Revisions included recalculation of selected uranium reactions. Additionally, thermodynamic data for the hydroxyl complexes of U(VI), including anionic (VI) species, were evaluated (to the extent permitted by the available data). Vanadium reactions were also added to the thermodynamic data base because uranium-vanadium solids can exist in natural ground-water systems. This study is only a partial validation of the WATEQ4 geochemical model because the available laboratory solubility studies do not cover the range of solid phases, alkaline pH values, and concentrations of inorganic complexing ligands needed to evaluate the potential solubility of uranium in ground waters associated with various proposed nuclear waste repositories. Further validation of this or other geochemical models for uranium will require careful determinations of uraninite solubility over the pH range of 7 to 10 under highly reducing conditions and of uranyl hydroxide and phosphate solubilities over the pH range of 7 to 10 under oxygenated conditions.

  5. Geochemical Characteristics of Typhoon - and Tsunami - Induced Deposits from Western Kyushu Islands

    NASA Astrophysics Data System (ADS)

    Kanamaru, K.; Woodruff, J. D.; Kundu, S.; Cook, T.

    2014-12-01

    Western Kyushu Island is a region of Japan frequently impacted by typhoon landfalls. This region is relatively tectonically stable with few active faults and therefore known for far fewer great earthquakes when compared to the Nankai Trough region. Only a few studies have examined the history of tsunamis impacting the region. Hence, studies from western Kyushu provide a unique opportunity to study tsunami deposits in a broader geographic context in order to delineate regional typhoon impacts. This study presents results from both modern analogue from Typhoon Neoguri in 2014 and legendary Kamikaze Typhoons from 13th century. The initial coring was conducted in 2010. Total of 9 sediment cores were collected from two natural freshwater lakes along the western coast of Kyushu: Lake Daija (32.248°N, 129.985°E) and Lake Kawahara (32.624°N, 129.831°E). In order to further understand the characteristics of typhoon deposits, we collected 4 additional sediment cores from Kawahara in July of 2014, approximately one week after landfall of Typhoon Neoguri. We use a multi-proxy approach to identify event deposits. These approaches include loss on ignition, X-Ray fluorescence, X-radiograph, grain size, magnetic susceptibility, and SEM/EDS analyses. Initial results yielded commonalities between the two lakes. Linear interpolation of the most prominent event deposits within multiple cores, presenting highs in Sr and Ca intensities, constrain the dates of deposits of interest to the late 13th century—consistent with the Mongol invasions. Here we present preliminary geochemical results from Lake Kawahara, which further constrain the typhoon deposits, and use this as a reference event for comparison to tsunami deposits found in other regions.

  6. Comparative studies of the antioxidant effects of a naturally occurring resveratrol analogue -- trans-3,3',5,5'-tetrahydroxy-4'-methoxystilbene and resveratrol -- against oxidation and nitration of biomolecules in blood platelets.

    PubMed

    Olas, Beata; Wachowicz, Barbara; Nowak, Pawel; Stochmal, Anna; Oleszek, Wieslaw; Glowacki, Rafal; Bald, Edward

    2008-08-01

    The action of two phenolic compounds isolated from the bark of Yucca schidigera: trans-3,3',5,5'-tetrahydroxy-4'-methoxystilbene and its analogue -- resveratrol (trans-3,4',5-trihydroxystilbene, present also in grapes and wine) on oxidative/nitrative stress induced by peroxynitrite (ONOO(-), which is strong physiological oxidant and inflammatory mediator) in human blood platelets was compared. The trans-3,3',5,5'-tetrahydroxy-4'-methoxystilbene, like resveratrol, significantly inhibited protein carbonylation and nitration (measured by enzyme-linked immunosorbent assay method) in the blood platelets treated with peroxynitrite (0.1 mM) and markedly reduced an oxidation of thiol groups of proteins (estimated with 5,5'-dithio-bis(2-nitro-benzoic acid)] or glutathione (measured by high performance liquid chromatography method) in these cells. The trans-3,3',5,5'-tetrahydroxy-4'-methoxystilbene, like resveratrol, also caused a distinct reduction of platelet lipid peroxidation induced by peroxynitrite. The obtained results indicate that in vitro trans-3,3',5,5'-tetrahydroxy-4'-methoxystilbene and resveratrol have very similar protective effects against peroxynitrite-induced oxidative/nitrative damage to the human platelet proteins and lipids. Moreover, trans-3,3',5,5'-tetrahydroxy-4'-methoxystilbene proved to be even more potent than resveratrol in antioxidative tests. We conclude that the novel tested phenolic compound -- trans-3,3',5,5'-tetrahydroxy-4'-methoxystilbene isolated from Y. schidigera bark possessing Generally Recognized As Safe label given by the Food and Drug Administration and allows their human dietary use -- seems to be a promising candidate for future evaluations of its antioxidative activity and may be a good candidate for scavenging peroxynitrite.

  7. Synthetic isoprenoid analogues for the study of prenylated proteins: Fluorescent imaging and proteomic applications.

    PubMed

    Wang, Yen-Chih; Distefano, Mark D

    2016-02-01

    Protein prenylation is a posttranslational modification catalyzed by prenyltransferases involving the attachment of farnesyl or geranylgeranyl groups to residues near the C-termini of proteins. This irreversible covalent modification is important for membrane localization and proper signal transduction. Here, the use of isoprenoid analogues for studying prenylated proteins is reviewed. First, experiments with analogues containing small fluorophores that are alternative substrates for prenyltransferases are described. Those analogues have been useful for quantifying binding affinity and for the production of fluorescently labeled proteins. Next, the use of analogues that incorporate biotin, bioorthogonal groups or antigenic moieties is described. Such probes have been particularly useful for identifying proteins that are naturally prenylated within mammalian cells. Overall, the use of isoprenoid analogues has contributed significantly to the understanding of protein prenlation.

  8. Long-Lived, Sub-Surface Layers of Toxic Oil in the Deep-Sea: A Molecular Organic and Isotopic Geochemical Approach to Understanding their Nature, Molecular Distribution, Origin and Impact to the Northern Gulf of Mexico

    NASA Astrophysics Data System (ADS)

    Hollander, D. J.; Freeman, K. H.; Ellis, G.; Diefendorf, A. F.; Peebles, E. B.; Paul, J.

    2010-12-01

    Here we present the results from two research cruises to the Northern Gulf of Mexico (GoM) during May and August 2010, after the April 20th blowout of BP’s Deepwater Horizon (DWH) drilling rig. Not only was the DWH tragedy the largest oil spill to have ever occurred in the United States but it was also the first blowout of a deep-sea oil exploration well. The BP oil spill presents the scientific community with a critically important and unique opportunity: i) to characterize the occurrence, molecular distribution and abundance of the hydrocarbons in the sub-surface, ii) to identify the source of the oil in the environment and, iii) to study how the distribution and chemistry of the hydrocarbons change over time and space and whether the sub-surface hydrocarbons are toxic to marine plankton and bacteria. Using sonar, fluorometry and backscatter, we were able to trace the occurrence of layers of sub-surface oil. These oil layers were found suspended at depths of 400 m and 1000-1400 m in the form of small microdroplets that were not visible to the naked eye. Both the 400 and the 1000 m layers were traced for more than 20 miles in length and 4 miles in width. Molecular organic geochemical analyses determined that petroleum hydrocarbons were the dominant components of the 400 and 1000 m layers. Interesting, the distribution of compounds was extremely consistent among all the samples with n-alkanes ranging from C24 to C37 with a maximum at C28. The loss of the lower molecular weight components of the crude oil is attributed to biodegradation. This distribution of n-alkanes was the same regardless of whether the samples were from 400 or 1000 m, whether the sites were 25 or 45 miles from the DWH site or whether the samples were collected in May or August. These observations strongly suggest that the bacteria are not able to consume all of the oil, and that these higher molecular weight compounds may persist in the environment for extended lengths of time, at least months

  9. Landscape and bio- geochemical strategy for monitoring transformation and reclamation of the soil mining sites

    NASA Astrophysics Data System (ADS)

    Korobova, Elena

    2010-05-01

    Sites of active or abandoned mining represent areas of considerable technogenic impact and need scientifically ground organization of their monitoring and reclamation. The strategy of monitoring and reclamation depends on the scale and character of the physical, chemical and biological consequences of the disturbances. The geochemical studies for monitoring and rehabilitation of the career-dump complexes should methodically account of formation of the particular new landforms and the changes in circulation of the remobilized elements of the soil cover. However, the general strategy should account of both the initial and transformed landscape geochemical structure of the area with due regard to the natural and new content of chemical elements in the environmental components. For example the tailings and waste rocks present new geochemical fields with specifically different concentration of chemical elements that cause formation of new geochemical barriers and landscapes. The way of colonization of the newly formed landscapes depends upon the new geochemical features of the technogenic environment and the adaptive ability of local and intrusive flora. The newly formed biogeochemical anomalies need organization of permanent monitoring not only within the anomaly itself but also of its impact zones. Spatial landscape geochemical monitoring combined with bio-geochemical criteria of threshold concentrations seems to be a helpful tool for decision making on reclamation and operation of the soil mining sites to provide a long-term ecologically sustainable development of the impact zone as a whole.

  10. Neuronal Analogues of Conditioning Paradigms

    DTIC Science & Technology

    1984-04-24

    Although the mechanisms of interneuronal communication have been well established, the changes underlying most forms of learning have thus far eluded...stimulating electrodes on one of the connectives was adjusted so as to produce a small excitatory postsynaptic potential ( EPSP ) in the impaled cell...two stimuli would constitute a neuronal analogue of conditioning by producing an increased EPSP in response to the test stimulus alone. If so, then

  11. Substrate analogues for isoprenoid enzymes

    SciTech Connect

    Stremler, K.E.

    1987-01-01

    Diphosphonate analogues of geranyl diphosphate, resistant to degradation by phosphatases, were found to be alternate substrates for the reaction with farnesyl diphosphate synthetase isolated from avian liver. The difluoromethane analogue was shown to be the better alternate substrate, in agreement with solvolysis results which indicate that the electronegativity of the difluoromethylene unit more closely approximates that of the normal bridging oxygen. The usefulness of the C/sub 10/ difluoro analogue, for detecting low levels of isoprenoid enzymes in the presence of high levels of phosphatase activity, was demonstrated with a cell-free preparation from lemon peel. A series of C/sub 5/ through C/sub 15/ homoallylic and allylic diphosphonates, as well as two 5'-nucleotide diphosphonates, was prepared in high overall yield using the activation-displacement sequence. Radiolabeled samples of several of the allylic diphosphonates were prepared with tritium located at C1. A series of geraniols, stereospecifically deuterated at C1, was prepared. The enantiomeric purities and absolute configurations were determined by derivatization as the mandelate esters for analysis by /sup 1/H NMR. The stereochemistry of the activation-displacement sequence was examined using C1-deuterated substrates.

  12. Proceedings of the workshop on geochemical modeling

    SciTech Connect

    Not Available

    1986-01-01

    The following collection of papers was presented at a workshop on geochemical modeling that was sponsored by the Office of Civilian Radioactive Waste Management Program at the Lawrence Livermore National Laboratory (LLNL). The LLNL Waste Management Program sponsored this conference based on their belief that geochemical modeling is particularly important to the radioactive waste disposal project because of the need to predict the consequences of long-term water-rock interactions at the proposed repository site. The papers included in this volume represent a subset of the papers presented at the Fallen Leaf Lake Conference and cover a broad spectrum of detail and breadth in a subject that reflects the diverse research interests of the conference participants. These papers provide an insightful look into the current status of geochemical modeling and illustrate how various geochemical modeling codes have been applied to problems of geochemical interest. The emphasis of these papers includes traditional geochemical modeling studies of individual geochemical systems, the mathematical and theoretical development and refinement of new modeling capabilities, and enhancements of data bases on which the computations are based. The papers in this proceedings volume have been organized into the following four areas: Geochemical Model Development, Hydrothermal and Geothermal Systems, Sedimentary and Low Temperature Environments, and Data Base Development. The participants of this symposium and a complete list of the talks presented are listed in the appendices.

  13. Detection of organometallic and radical intermediates in the catalytic mechanism of methyl-coenzyme M reductase using the natural substrate methyl-coenzyme M and a coenzyme B substrate analogue.

    PubMed

    Dey, Mishtu; Li, Xianghui; Kunz, Ryan C; Ragsdale, Stephen W

    2010-12-28

    Methyl-coenzyme M reductase (MCR) from methanogenic archaea catalyzes the terminal step in methanogenesis using coenzyme B (CoBSH) as the two-electron donor to reduce methyl-coenzyme M (methyl-SCoM) to form methane and the heterodisulfide, CoBS-SCoM. The active site of MCR contains an essential redox-active nickel tetrapyrrole cofactor, coenzyme F(430), which is active in the Ni(I) state (MCR(red1)). Several catalytic mechanisms have been proposed for methane synthesis that mainly differ in whether an organometallic methyl-Ni(III) or a methyl radical is the first catalytic intermediate. A mechanism was recently proposed in which methyl-Ni(III) undergoes homolysis to generate a methyl radical (Li, X., Telser, J., Kunz, R. C., Hoffman, B. M., Gerfen, G., and Ragsdale, S. W. (2010) Biochemistry 49, 6866-6876). Discrimination among these mechanisms requires identification of the proposed intermediates, none of which have been observed with native substrates. Apparently, intermediates form and decay too rapidly to accumulate to detectible amounts during the reaction between methyl-SCoM and CoBSH. Here, we describe the reaction of methyl-SCoM with a substrate analogue (CoB(6)SH) in which the seven-carbon heptanoyl moiety of CoBSH has been replaced with a hexanoyl group. When MCR(red1) is reacted with methyl-SCoM and CoB(6)SH, methanogenesis occurs 1000-fold more slowly than with CoBSH. By transient kinetic methods, we observe decay of the active Ni(I) state coupled to formation and subsequent decay of alkyl-Ni(III) and organic radical intermediates at catalytically competent rates. The kinetic data also revealed substrate-triggered conformational changes in active Ni(I)-MCR(red1). Electron paramagnetic resonance (EPR) studies coupled with isotope labeling experiments demonstrate that the radical intermediate is not tyrosine-based. These observations provide support for a mechanism for MCR that involves methyl-Ni(III) and an organic radical as catalytic intermediates

  14. Geochemical study of Palong Pluton at Negeri Sembilan-Pahang border

    NASA Astrophysics Data System (ADS)

    Selamat Din, Khairil Izam Bin; Umor, Mohd Rozi

    2013-11-01

    The geochemical studies are carried out for igneous rocks from Palong Pluton at the border area of Negeri Sembilan and Pahang. The study area is about 250 km2, covering the area of Kemayan, Pasoh and Serting. The purposes of the geochemical study are to classify and determine the chemical characteristic of the granitic rocks, to correlate and interpret the crystallization history of igneous rocks, to determine the rock genesis and to determine the origin of magma. The Palong Pluton is divided into three groups, namely the Kemayan Granite, Serting Granite and Lui Granite. The geochemical data are presented by TAS and Harker Diagrams. The geochemical results show that Kemayan Granite, Serting Granite and Lui Granite are naturally originated from a single magma source. The magma evolution started from Kemayan Granite to Lui Granite and Serting Granite by differentiation proceses.

  15. Alligator rivers analogue project an OECD/NEA international project

    SciTech Connect

    Duerden, P.; Airey, P.; Pescatore, C.

    1994-12-31

    The Koongarra uranium deposit in the Alligator Rivers Region of the Northern Territory of Australia was studied as a natural analogue of the far field behaviour of high level waste repositories following groundwater ingress. A number of mathematical modelling approaches were developed for processes as diverse as groundwater transport, host rock weathering, radionuclide sorption, evolution of the uranium dispersion fan and the distribution of uranium series nuclides between mineral assemblages in weathered host rock. Some of these models are relevant to performance assessment at the level of individual processes and subsystem performance. Through the project, new insights into the application of the natural analogue approach to the assessment of potential waste repository sites were obtained.

  16. Geochemical data synthesis and analysis

    NASA Technical Reports Server (NTRS)

    Philpotts, J. A.

    1979-01-01

    Data obtained at the Goddard Flight Center were collected for the purpose of completing analyses started at Goddard in order to maximize the scientific yield of the geochemistry program which was terminated in 1977. The major analytical task undertaken was to complete Gd analyses on a large number of samples already analyzed by mass spectrometry for other rare earth element abundances at Goddard. Gd values are important for pinning down the central part of the geochemically significant rare earth abundance pattern and are especially useful in the high precision definition of the utilitarian Eu anomaly. Isotope-dilution Gd abundances were obtained for 39 samples. The data are for 27 partition-coefficient samples, six Apollo 15 and 16 breccia samples, four terrestrial impactities, and associated rock standards.

  17. Geochemical challenge to earthquake prediction.

    PubMed

    Wakita, H

    1996-04-30

    The current status of geochemical and groundwater observations for earthquake prediction in Japan is described. The development of the observations is discussed in relation to the progress of the earthquake prediction program in Japan. Three major findings obtained from our recent studies are outlined. (i) Long-term radon observation data over 18 years at the SKE (Suikoen) well indicate that the anomalous radon change before the 1978 Izu-Oshima-kinkai earthquake can with high probability be attributed to precursory changes. (ii) It is proposed that certain sensitive wells exist which have the potential to detect precursory changes. (iii) The appearance and nonappearance of coseismic radon drops at the KSM (Kashima) well reflect changes in the regional stress state of an observation area. In addition, some preliminary results of chemical changes of groundwater prior to the 1995 Kobe (Hyogo-ken nanbu) earthquake are presented.

  18. PHREEQC. Geochemical Speciation Mass Transfer

    SciTech Connect

    Parkhurst, D.L.

    1995-01-01

    PHREEQC is designed to model geochemical reactions. Based on an ion association aqueous model, PHREEQC can calculate pH, redox potential, and mass transfer as a function of reaction progress. It can be used to describe geochemical processes for both far-field and near-field performance assessment and to evaluate data acquisition needs and test data. It can also calculate the composition of solutions in equilibrium with multiple phases. The data base, including elements, aqueous species, and mineral phases, is independent of the program and is completely user-definable. PHREEQC requires thermodynamic data for each solid, gaseous, or dissolved chemical species being modeled. The two data bases, PREPHR and DEQPAK7, supplied with PHREEQC are for testing purposes only and should not be applied to real problems without first being carefully examined. The conceptual model embodied in PHREEQC is the ion-association model of Pearson and Noronha. In this model a set of mass action equations are established for each ion pair (and controlling solid phases when making mass transfer calculations) along with a set of mass balance equations for each element considered. These sets of equations are coupled using activity coefficient values for each aqueous species and solved using a continued fraction approach for the mass balances combined with a modified Newton-Raphson technique for all other equations. The activity coefficient expressions in PHREEQC include the extended Debye-Huckel, WATEQ Debye-Huckel, and Davies equations from the original United States Geological Survey version of the program. The auxiliary preprocessor program PHTL, which is derived from EQTL, converts EQ3/6 thermodynamic data to PHREEQC format so that the two programs can be compared. PHREEQC can be used to determine solubility limits on the radionuclides present in the waste form. These solubility constraints may be input to the WAPPA leach model.

  19. Synthesis of a Functionalized Benzofuran as a Synthon for Salvianolic Acid C Analogues as Potential LDL Antioxidants.

    PubMed

    López-Frías, Gabriela; Camacho-Dávila, Alejandro A; Chávez-Flores, David; Zaragoza-Galán, Gerardo; Ramos-Sánchez, Víctor H

    2015-05-14

    A palladium mediated synthesis of a common synthon for the syntheses of antioxidant analogues of naturally occurring salvianolic acids is presented. The synthetic route may be used to obtain analogues with a balanced lipophilicity/hydrophilicity which may result in potentially interesting LDL antioxidants for the prevention of cardiovascular diseases.

  20. Synthesis and bioactivity of analogues of the marine antibiotic tropodithietic acid

    PubMed Central

    Rabe, Patrick; Klapschinski, Tim A; Brock, Nelson L; Citron, Christian A; D’Alvise, Paul; Gram, Lone

    2014-01-01

    Summary Tropodithietic acid (TDA) is a structurally unique sulfur-containing antibiotic from the Roseobacter clade bacterium Phaeobacter inhibens DSM 17395 and a few other related species. We have synthesised several structural analogues of TDA and used them in bioactivity tests against Staphylococcus aureus and Vibrio anguillarum for a structure–activity relationship (SAR) study, revealing that the sulfur-free analogue of TDA, tropone-2-carboxylic acid, has an antibiotic activity that is even stronger than the bioactivity of the natural product. The synthesis of this compound and of several analogues is presented and the bioactivity of the synthetic compounds is discussed. PMID:25161739

  1. The role of the "Casimir force analogue" at the microscopic processes of crystallization and melting

    NASA Astrophysics Data System (ADS)

    Chuvildeev, V. N.; Semenycheva, A. V.

    2016-10-01

    Melting (crystallization), a phase transition from a crystalline solid to a liquid state, is a common phenomenon in nature. We suggest a new factor, "the Casimir force analogue", to describe mechanisms of melting and crystallization. The Casimir force analogue is a force occurring between the surfaces of solid and liquid phases of metals caused by different energy density of phonons of these phases. It explains abrupt changes in geometry and thermodynamic parameters at a melting point. "The Casimir force analogue" helps to estimate latent melting heat and to gain an insight into a solid-liquid transition problem.

  2. FUNCTION GENERATOR FOR ANALOGUE COMPUTERS

    DOEpatents

    Skramstad, H.K.; Wright, J.H.; Taback, L.

    1961-12-12

    An improved analogue computer is designed which can be used to determine the final ground position of radioactive fallout particles in an atomic cloud. The computer determines the fallout pattern on the basis of known wind velocity and direction at various altitudes, and intensity of radioactivity in the mushroom cloud as a function of particle size and initial height in the cloud. The output is then displayed on a cathode-ray tube so that the average or total luminance of the tube screen at any point represents the intensity of radioactive fallout at the geographical location represented by that point. (AEC)

  3. Choline Analogues in Malaria Chemotherapy

    PubMed Central

    Peyrottes, Suzanne; Caldarelli, Sergio; Wein, Sharon; Périgaud, Christian; Pellet, Alain; Vial, Henri

    2012-01-01

    Emerging resistance against well-established anti-malaria drugs warrants the introduction of new therapeutic agents with original mechanisms of action. Inhibition of membrane-based phospholipid biosynthesis, which is crucial for the parasite, has thus been proposed as a novel and promising therapeutic strategy. This review compiles literature concerning the design and study of choline analogues and related cation derivatives as potential anti-malarials. It covers advances achieved over the last two decades and describes: the concept validation, the design and selection of a clinical candidate (Albitiazolium), back-up derivatives while also providing insight into the development of prodrug approaches. PMID:22607139

  4. Synthesis of the Insecticide Prothrin and Its Analogues from Biomass-Derived 5-(Cloromethyl)furfural

    DTIC Science & Technology

    2013-12-19

    insecticide prothrin (4) alongside five-step routes to analogues 5 and 6. The naturally occurring insecticide pyrethrum, isolated from flowers of...Synthesis of the Insecticide Prothrin and Its Analogues from Biomass-Derived 5‑(Chloromethyl)furfural Fei Chang,† Saikat Dutta,† James J. Becnel...Jacksonville, Florida 32212, United States *S Supporting Information ABSTRACT: Prothrin, a synthetic pyrethroid insecticide , was synthesized from the biomass

  5. Appalachian basin oil and natural gas: stratigraphic framework, total petroleum systems, and estimated ultimate recovery: Chapter C.1 in Coal and petroleum resources in the Appalachian basin: distribution, geologic framework, and geochemical character

    USGS Publications Warehouse

    Ryder, Robert T.; Milici, Robert C.; Swezey, Christopher S.; Trippi, Michael H.; Ruppert, Leslie F.; Ryder, Robert T.

    2014-01-01

    The most recent U.S. Geological Survey (USGS) assessment of undiscovered oil and gas resources of the Appalachian basin was completed in 2002 (Milici and others, 2003). This assessment was based on the total petroleum system (TPS), a concept introduced by Magoon and Dow (1994) and developed during subsequent studies such as those by the U.S. Geological Survey World Energy Assessment Team (2000) and by Biteau and others (2003a,b). Each TPS is based on specific geologic elements that include source rocks, traps and seals, reservoir rocks, and the generation and migration of hydrocarbons. This chapter identifies the TPSs defined in the 2002 Appalachian basin oil and gas assessment and places them in the context of the stratigraphic framework associated with regional geologic cross sections D–D′ (Ryder and others, 2009, which was re-released in this volume, chap. E.4.1) and E–E′ (Ryder and others, 2008, which was re-released in this volume, chap. E.4.2). Furthermore, the chapter presents a recent estimate of the ultimate recoverable oil and natural gas in the basin.

  6. Predictive Radiological Background Distributions from Geochemical Data

    NASA Astrophysics Data System (ADS)

    Haber, D.; Burnley, P. C.; Marsac, K.; Malchow, R.

    2014-12-01

    Gamma ray surveys are an important tool for both national security interests as well as industry in determininglocations of both anthropogenic radiological sources and natural occurrences of radiologic material. The purpose ofthis project is to predict the radiologic exposure rate of geologic materials by creating a model using publishedgeochemical data, geologic data, GIS software, and freely available remote sensing data sets. If K, U, and Thabundance values are known for a given geologic unit, the expected radiation exposure rate can be calculated. Oneof the primary challenges surrounding this project is that alluvial units are classified by age rather than rock type. Itis therefore important to determine sediment sources and estimate their relative contribution to alluvial units.ASTER data from the Terra satellite can differentiate between surface mineralogies and can aid us in calculating therelative percentage of sediment from each source and by extension the geochemical concentrations of challengingsurfaces such as alluvium. An additional problem is that U and Th do not directly contribute to the measuredradiation exposure rate. Instead, daughter isotopes of these radioelements emit detectable gamma rays and may nothave reached equilibrium in younger surfaces. U can take up to 1.5 Ma to come to equilibrium with its daughterisotopes while Th takes only about 40 years. Further modeling with software such as Monte Carlo N-ParticleTransport from Los Alamos National Laboratory, will help us correct for this disequilibrium in our models. Once the predicted exposure rate is calculated for a geologic unit, it can then be assigned to a geographic area basedon geologic and geomorphic trends. This prediction will be subtracted from data collected through aerial surveys,effectively ignoring geology, and allowing areas of interest to be narrowed down considerably. The study areasinclude the alluvium on the west shore of Lake Mohave and Government Wash north of Lake Mead

  7. Deep-fault connection characterization from combined field and geochemical methodology; examples from Green River and Haiti fault systems

    NASA Astrophysics Data System (ADS)

    Nadine, E. Z.; Frery, E.; Leroy, S.; Mercier De Lepinay, B. F.; Momplaisir, R.

    2011-12-01

    widening of the impacted zones indicating a strong partitioning of the deformation. The resulting stress re-location is well expressed by (1) the dispersion of the aftershocks, essentially North of the strike-slip fault, (2) a progressive local uplift on the hanging wall, and (3) by along-fault fluid flow variation (leaking segments) either along the EPGF recently active segments but also around the Cul-de-Sac plain. As a first approach, we focus our attention on fault-related fluid leakage distribution, located at intersection points between strike-slip and compressive faults. Using this combined approach, mixing structural and geochemical analytical work, we will hopefully be able (i) to identify the transient and permanent fault activity, and (ii) to characterize the time recurrence (if any) and (iii) the location of the seismic activity during the Quaternary in this two natural analogues.

  8. Electrostatic evaluation of isosteric analogues

    NASA Astrophysics Data System (ADS)

    Sayle, Roger; Nicholls, Anthony

    2006-04-01

    A method is presented for enumerating a large number of isosteric analogues of a ligand from a known protein-ligand complex structure and then rapidly calculating an estimate of their binding energies. This approach takes full advantage of the observed crystal structure, by reusing the atomic co-ordinates determined experimentally for one ligand, to approximate those of similar compounds that have approximately the same shape. By assuming that compounds with similar shapes adopt similar binding poses, and that entropic and protein flexibility effects are approximately constant across such an isosteric series ("the frozen ligand approximation"), it is possible to order their binding affinities relatively accurately. Additionally, the constraint that the atomic coordinates are invariant allows for a dramatic simplification in the Poisson-Boltzmann method used to calculation the electrostatic component of the binding energy. This algorithmic improvement allows for the calculation of tens of thousands of binding energies per second for drug-like molecules, enabling this technique to be used in screening large virtual libraries of isosteric analogues. Most significantly, this procedure is shown to be able to reproduce SAR effects of subtle medicinal chemistry substitutions. Finally, this paper reports the results of the proposed methodology on␣seven model systems; dihydrofolate reductase, Lck␣kinase, ribosome inactivating protein, l-arabinose binding protein, neuraminidase, HIV-1 reverse transcriptase and COX-2.

  9. Sulphamoylated 2-Methoxyestradiol Analogues Induce Apoptosis in Adenocarcinoma Cell Lines

    PubMed Central

    Visagie, Michelle; Theron, Anne; Mqoco, Thandi; Vieira, Warren; Prudent, Renaud; Martinez, Anne; Lafanechère, Laurence; Joubert, Annie

    2013-01-01

    2-Methoxyestradiol (2ME2) is a naturally occurring estradiol metabolite which possesses antiproliferative, antiangiogenic and antitumor properties. However, due to its limited biological accessibility, synthetic analogues have been synthesized and tested in attempt to develop drugs with improved oral bioavailability and efficacy. The aim of this study was to evaluate the antiproliferative effects of three novel in silico-designed sulphamoylated 2ME2 analogues on the HeLa cervical adenocarcinoma cell line and estrogen receptor-negative breast adenocarcinoma MDA-MB-231 cells. A dose-dependent study (0.1–25 μM) was conducted with an exposure time of 24 hours. Results obtained from crystal violet staining indicated that 0.5 μM of all 3 compounds reduced the number of cells to 50%. Lactate dehydrogenase assay was used to assess cytotoxicity, while the mitotracker mitochondrial assay and caspase-6 and -8 activity assays were used to investigate the possible occurrence of apoptosis. Tubulin polymerization assays were conducted to evaluate the influence of these sulphamoylated 2ME2 analogues on tubulin dynamics. Double immunofluorescence microscopy using labeled antibodies specific to tyrosinate and detyrosinated tubulin was conducted to assess the effect of the 2ME2 analogues on tubulin dynamics. An insignificant increase in the level of lactate dehydrogenase release was observed in the compounds-treated cells. These sulphamoylated compounds caused a reduction in mitochondrial membrane potential, cytochrome c release and caspase 3 activation indicating apoptosis induction by means of the intrinsic pathway in HeLa and MDA-MB-231 cells. Microtubule depolymerization was observed after exposure to these three sulphamoylated analogues. PMID:24039728

  10. Singularity analysis based on wavelet transform of fractal measures for identifying geochemical anomaly in mineral exploration

    NASA Astrophysics Data System (ADS)

    Chen, Guoxiong; Cheng, Qiuming

    2016-02-01

    Multi-resolution and scale-invariance have been increasingly recognized as two closely related intrinsic properties endowed in geofields such as geochemical and geophysical anomalies, and they are commonly investigated by using multiscale- and scaling-analysis methods. In this paper, the wavelet-based multiscale decomposition (WMD) method was proposed to investigate the multiscale natures of geochemical pattern from large scale to small scale. In the light of the wavelet transformation of fractal measures, we demonstrated that the wavelet approximation operator provides a generalization of box-counting method for scaling analysis of geochemical patterns. Specifically, the approximation coefficient acts as the generalized density-value in density-area fractal modeling of singular geochemical distributions. Accordingly, we presented a novel local singularity analysis (LSA) using the WMD algorithm which extends the conventional moving averaging to a kernel-based operator for implementing LSA. Finally, the novel LSA was validated using a case study dealing with geochemical data (Fe2O3) in stream sediments for mineral exploration in Inner Mongolia, China. In comparison with the LSA implemented using the moving averaging method the novel LSA using WMD identified improved weak geochemical anomalies associated with mineralization in covered area.

  11. Geochemical methods of prospecting for hydrocarbons

    SciTech Connect

    Duchscherer, W. Jr.

    1980-12-01

    Because the commonly used reflection-seismograph exploration technique misses many marginal low-relief structural prospects and regardless of its electronic computer sophistication, overlooks almost all stratigraphic traps, the hydrocarbon exploration industry should take a look at geochemical prospecting methods, which detect geochemical anomalies in the near-surface soils by measuring the thermal dissociation of the soil carbonates that are found overlying hydrocarbon accumulations. To promote understanding of such prospecting techniques, Geochemical Surveys reviews the methods used, the soil-alteration patterns, the lateral and vertical migration of hydrocarbon gases, the halo phenomenon (a ring or annual anomaly), the geochemical modification of sediments, and the data-interpretation and exploration procedures involved in a carbonate ..delta.. C analysis, which measures the residual, stable, cumulative effect of hydrocarbon migration.

  12. Biological activity of silylated amino acid containing substance P analogues.

    PubMed

    Cavelier, F; Marchand, D; Martinez, J; Sagan, S

    2004-03-01

    The need to replace natural amino acids in peptides with nonproteinogenic counterparts to obtain new medicinal agents has stimulated a great deal of innovation on synthetic methods. Here, we report the incorporation of non-natural silylated amino acids in substance P (SP), the binding affinity for the two hNK-1 binding sites and, the potency to stimulate phospholipase C (PLC) and adenylate cyclase of the resulting peptide. We also assess the improvement of their stability towards enzyme degradation. Altogether, we found that replacing glycine with silaproline (Sip) in position 9 of SP leads to a potent analogue exhibiting an increased resistance to angiotensin-converting enzyme hydrolysis.

  13. Principles of landscape-geochemical studies in the zones contaminated by technogenical radionuclides for ecological and geochemical mapping

    NASA Astrophysics Data System (ADS)

    Korobova, Elena; Romanov, Sergey

    2013-04-01

    Efficiency of landscape-geochemical approach was proved to be helpful in spatial and temporal evaluation of the Chernobyl radionuclide distribution in the environment. The peculiarity of such approach is in hierarchical consideration of factors responsible for radionuclide redistribution and behavior in a system of inter-incorporated landscape-geochemical structures of the local and regional scales with due regard to the density of the initial fallout and patterns of radionuclide migration in soil-water-plant systems. The approach has been applied in the studies of distribution of Cs-137, Sr-90 and some other radionuclides in soils and vegetation cover and in evaluation of contribution of the stable iodine supply in soils to spatial variation of risk of thyroid cancer in areas subjected to radioiodine contamination after the Chernobyl accident. The main feature of the proposed approach is simultaneous consideration of two types of spatial heterogeneities: firstly, the inhomogeneity of external radiation exposure due to a complex structure of the contamination field, and, secondly, the landscape geochemical heterogeneity of the affected area, so that the resultant effect of radionuclide impact could significantly vary in space. The main idea of risk assessment in this respect was to reproduce as accurately as possible the result of interference of two surfaces in the form of risk map. The approach, although it demands to overcome a number of methodological difficulties, allows to solve the problems associated with spatially adequate protection of the affected population and optimization of the use of contaminated areas. In general it can serve the basis for development of the idea of the two-level structure of modern radiobiogeochemical provinces formed by superposition of the natural geochemical structures and the fields of technogenic contamination accompanied by the corresponding peculiar and integral biological reactions.

  14. Noble gas encapsulation: clathrate hydrates and their HF doped analogues.

    PubMed

    Mondal, Sukanta; Chattaraj, Pratim Kumar

    2014-09-07

    The significance of clathrate hydrates lies in their ability to encapsulate a vast range of inert gases. Although the natural abundance of a few noble gases (Kr and Xe) is poor their hydrates are generally abundant. It has already been reported that HF doping enhances the stability of hydrogen hydrates and methane hydrates, which prompted us to perform a model study on helium, neon and argon hydrates with their HF doped analogues. For this purpose 5(12), 5(12)6(8) and their HF doped analogues are taken as the model clathrate hydrates, which are among the building blocks of sI, sII and sH types of clathrate hydrate crystals. We use the dispersion corrected and gradient corrected hybrid density functional theory for the calculation of thermodynamic parameters as well as conceptual density functional theory based reactivity descriptors. The method of the ab initio molecular dynamics (AIMD) simulation is used through atom centered density matrix propagation (ADMP) techniques to envisage the structural behaviour of different noble gas hydrates on a 500 fs timescale. Electron density analysis is carried out to understand the nature of Ng-OH2, Ng-FH and Ng-Ng interactions. The current results noticeably demonstrate that the noble gas (He, Ne, and Ar) encapsulation ability of 5(12), 5(12)6(8) and their HF doped analogues is thermodynamically favourable.

  15. The National Geochemical Survey; database and documentation

    USGS Publications Warehouse

    ,

    2004-01-01

    The USGS, in collaboration with other federal and state government agencies, industry, and academia, is conducting the National Geochemical Survey (NGS) to produce a body of geochemical data for the United States based primarily on stream sediments, analyzed using a consistent set of methods. These data will compose a complete, national-scale geochemical coverage of the US, and will enable construction of geochemical maps, refine estimates of baseline concentrations of chemical elements in the sampled media, and provide context for a wide variety of studies in the geological and environmental sciences. The goal of the NGS is to analyze at least one stream-sediment sample in every 289 km2 area by a single set of analytical methods across the entire nation, with other solid sample media substituted where necessary. The NGS incorporates geochemical data from a variety of sources, including existing analyses in USGS databases, reanalyses of samples in USGS archives, and analyses of newly collected samples. At the present time, the NGS includes data covering ~71% of the land area of the US, including samples in all 50 states. This version of the online report provides complete access to NGS data, describes the history of the project, the methodology used, and presents preliminary geochemical maps for all analyzed elements. Future editions of this and other related reports will include the results of analysis of variance studies, as well as interpretive products related to the NGS data.

  16. CO2 Capture with Enzyme Synthetic Analogue

    SciTech Connect

    Cordatos, Harry

    2010-11-08

    Overview of an ongoing, 2 year research project partially funded by APRA-E to create a novel, synthetic analogue of carbonic anhydrase and incorporate it into a membrane for removal of CO2 from flue gas in coal power plants. Mechanism background, preliminary feasibility study results, molecular modeling of analogue-CO2 interaction, and program timeline are provided.

  17. Synthetic silvestrol analogues as potent and selective protein synthesis inhibitors.

    PubMed

    Liu, Tao; Nair, Somarajan J; Lescarbeau, André; Belani, Jitendra; Peluso, Stéphane; Conley, James; Tillotson, Bonnie; O'Hearn, Patrick; Smith, Sherri; Slocum, Kelly; West, Kip; Helble, Joseph; Douglas, Mark; Bahadoor, Adilah; Ali, Janid; McGovern, Karen; Fritz, Christian; Palombella, Vito J; Wylie, Andrew; Castro, Alfredo C; Tremblay, Martin R

    2012-10-25

    Misregulation of protein translation plays a critical role in human cancer pathogenesis at many levels. Silvestrol, a cyclopenta[b]benzofuran natural product, blocks translation at the initiation step by interfering with assembly of the eIF4F translation complex. Silvestrol has a complex chemical structure whose functional group requirements have not been systematically investigated. Moreover, silvestrol has limited development potential due to poor druglike properties. Herein, we sought to develop a practical synthesis of key intermediates of silvestrol and explore structure-activity relationships around the C6 position. The ability of silvestrol and analogues to selectively inhibit the translation of proteins with high requirement on the translation-initiation machinery (i.e., complex 5'-untranslated region UTR) relative to simple 5'UTR was determined by a cellular reporter assay. Simplified analogues of silvestrol such as compounds 74 and 76 were shown to have similar cytotoxic potency and better ADME characteristics relative to those of silvestrol.

  18. New homoisoflavonoid analogues protect cells by regulating autophagy.

    PubMed

    Gan, Li-She; Zeng, Lin-Wei; Li, Xiang-Rong; Zhou, Chang-Xin; Li, Jie

    2017-03-15

    As a special group of naturally occurring flavonoids, homoisoflavonoids have been discovered as active components of several traditional Chinese medicines for nourishing heart and mind. In this study, twenty homoisoflavonoid analogues, including different substitution groups on rings A and B, as well as heteroaromatic B ring, were synthesized and evaluated for their cardioprotective and neuroprotective activities. In a H2O2-induced H9c2 cardiomyocytes injury assay, nine homoisoflavonoid analogues showed promising activities in the same level as the positive control, diazoxide. Six cardioprotective compounds with representative structure diversities were then evaluated for their neuroprotective effects on MPP+ induced SH-SY5Y cell injury model. Furthermore, autophagy inducing monodansylcadaverine (MDC) fluorescence staining methods and molecular docking studies indicated the action mechanism of these compounds may involve autophagy regulating via class I PI3K signaling pathway.

  19. Analogue Transformations in Physics and their Application to Acoustics

    PubMed Central

    García-Meca, C.; Carloni, S.; Barceló, C.; Jannes, G.; Sánchez-Dehesa, J.; Martínez, A.

    2013-01-01

    Transformation optics has shaped up a revolutionary electromagnetic design paradigm, enabling scientists to build astonishing devices such as invisibility cloaks. Unfortunately, the application of transformation techniques to other branches of physics is often constrained by the structure of the field equations. We develop here a complete transformation method using the idea of analogue spacetimes. The method is general and could be considered as a new paradigm for controlling waves in different branches of physics, from acoustics in quantum fluids to graphene electronics. As an application, we derive an “analogue transformation acoustics” formalism that naturally allows the use of transformations mixing space and time or involving moving fluids, both of which were impossible with the standard approach. To demonstrate the power of our method, we give explicit designs of a dynamic compressor, a spacetime cloak for acoustic waves and a carpet cloak for a moving aircraft. PMID:23774575

  20. New Immunosuppressive Sphingoid Base and Ceramide Analogues in Wild Cordyceps

    PubMed Central

    Mi, Jia-Ning; Han, Yuwei; Xu, Yingqiong; Kou, Junping; Wang, Jing-Rong; Jiang, Zhi-Hong

    2016-01-01

    A comprehensive identification of sphingoid bases and ceramides in wild Cordyceps was performed by integrating a sequential chromatographic enrichment procedure and an UHPLC-ultrahigh definition-Q-TOF-MS based sphingolipidomic approach. A total of 43 sphingoid bases and 303 ceramides were identified from wild Cordyceps, including 12 new sphingoid base analogues and 159 new ceramide analogues based on high-resolution MS and MS/MS data, isotope distribution, matching with the comprehensive personal sphingolipid database, confirmation by sphingolipid standards and chromatographic retention time rule. The immunosuppressive bioassay results demonstrated that Cordyceps sphingoid base fraction exhibits more potent immunosuppressive activity than ceramide fraction, elucidating the immunosuppressive ingredients of wild Cordyceps. This study represented the most comprehensive identification of sphingoid bases and ceramides from a natural source. The findings of this study provided an insight into therapeutic application of wild Cordyceps. PMID:27966660

  1. New Immunosuppressive Sphingoid Base and Ceramide Analogues in Wild Cordyceps.

    PubMed

    Mi, Jia-Ning; Han, Yuwei; Xu, Yingqiong; Kou, Junping; Wang, Jing-Rong; Jiang, Zhi-Hong

    2016-12-14

    A comprehensive identification of sphingoid bases and ceramides in wild Cordyceps was performed by integrating a sequential chromatographic enrichment procedure and an UHPLC-ultrahigh definition-Q-TOF-MS based sphingolipidomic approach. A total of 43 sphingoid bases and 303 ceramides were identified from wild Cordyceps, including 12 new sphingoid base analogues and 159 new ceramide analogues based on high-resolution MS and MS/MS data, isotope distribution, matching with the comprehensive personal sphingolipid database, confirmation by sphingolipid standards and chromatographic retention time rule. The immunosuppressive bioassay results demonstrated that Cordyceps sphingoid base fraction exhibits more potent immunosuppressive activity than ceramide fraction, elucidating the immunosuppressive ingredients of wild Cordyceps. This study represented the most comprehensive identification of sphingoid bases and ceramides from a natural source. The findings of this study provided an insight into therapeutic application of wild Cordyceps.

  2. High-resolution mass spectrometry analysis of tetrodotoxin (TTX) and its analogues in puffer fish and shellfish.

    PubMed

    Bane, Vaishali; Brosnan, Brid; Barnes, Paul; Lehane, Mary; Furey, Ambrose

    2016-09-01

    Tetrodotoxin (TTX) is an emerging toxin in the European marine environment. It has various known structural analogues. It acts as a sodium channel blocker; the ability of each analogue to bind to the sodium channel varies with the particular structure of each analogue. Thus, each analogue will vary in its toxic potential. TTX analogues co-occur in food samples at variable concentrations. An LC-MS method was developed for the identification and quantitation of several analogues of TTX using an LTQ-Orbitrap XL mass spectrometer. The LTQ-Orbitrap XL mass spectrometer facilitates high mass accuracy measurement up to 100,000 full width at half maximum (FWHM). Using high resolution at 100,000 FWHM allows for the identification of TTX and its analogues in various matrices, including puffer fish and molluscan shellfish samples (Δ ppm = 0.28-3.38). The confirmation of characteristic fragment ions of TTX and its analogues was achieved by determining their elemental formulae via high mass accuracy. A quantitative method was then developed and optimised using these characteristic fragment ions. The limit of quantitation (LOQ) of the method was 0.136 µg g(-1) (S/N = 10) and the limit of detection (LOD) was 0.041 µg g(-1) (S/N = 3) spiking TTX standard into TTX-free mackerel fish extracts. The method was applied to naturally contaminated puffer fish and molluscan shellfish samples to confirm the presence of TTX and its analogues.

  3. The future of somatostatin analogue therapy.

    PubMed

    Stewart, P M; James, R A

    1999-10-01

    Since its discovery almost 30 years ago, the mode of action and therapeutic applications of somatostatin have been defined. In particular the cloning and characterization of somatostatin receptor subtypes has facilitated the development of high affinity analogues. In the context of pituitary disease, long-acting somatostatin analogues (octreotide, lanreotide) have been used to treat a variety of pituitary tumours but are most efficacious for the treatment of GH and TSH-secreting adenomas. In patients with acromegaly, depot preparations of these analogues are administered intramuscularly every 10-28 days and provide consistent suppression of GH levels to < 5 mU/l in approximately 50-65% of all cases. Even more specific somatostatin receptor analogues are under development. Finally, radiolabelled somatostatin analogue scintigraphy and, in larger doses, therapy, are now established tools in the evaluation and treatment of neuroendocrine tumours.

  4. Continuous analogues of matrix factorizations

    PubMed Central

    Townsend, Alex; Trefethen, Lloyd N.

    2015-01-01

    Analogues of singular value decomposition (SVD), QR, LU and Cholesky factorizations are presented for problems in which the usual discrete matrix is replaced by a ‘quasimatrix’, continuous in one dimension, or a ‘cmatrix’, continuous in both dimensions. Two challenges arise: the generalization of the notions of triangular structure and row and column pivoting to continuous variables (required in all cases except the SVD, and far from obvious), and the convergence of the infinite series that define the cmatrix factorizations. Our generalizations of triangularity and pivoting are based on a new notion of a ‘triangular quasimatrix’. Concerning convergence of the series, we prove theorems asserting convergence provided the functions involved are sufficiently smooth. PMID:25568618

  5. Fully analogue photonic reservoir computer.

    PubMed

    Duport, François; Smerieri, Anteo; Akrout, Akram; Haelterman, Marc; Massar, Serge

    2016-03-03

    Introduced a decade ago, reservoir computing is an efficient approach for signal processing. State of the art capabilities have already been demonstrated with both computer simulations and physical implementations. If photonic reservoir computing appears to be promising a solution for ultrafast nontrivial computing, all the implementations presented up to now require digital pre or post processing, which prevents them from exploiting their full potential, in particular in terms of processing speed. We address here the possibility to get rid simultaneously of both digital pre and post processing. The standalone fully analogue reservoir computer resulting from our endeavour is compared to previous experiments and only exhibits rather limited degradation of performances. Our experiment constitutes a proof of concept for standalone physical reservoir computers.

  6. Fully analogue photonic reservoir computer

    PubMed Central

    Duport, François; Smerieri, Anteo; Akrout, Akram; Haelterman, Marc; Massar, Serge

    2016-01-01

    Introduced a decade ago, reservoir computing is an efficient approach for signal processing. State of the art capabilities have already been demonstrated with both computer simulations and physical implementations. If photonic reservoir computing appears to be promising a solution for ultrafast nontrivial computing, all the implementations presented up to now require digital pre or post processing, which prevents them from exploiting their full potential, in particular in terms of processing speed. We address here the possibility to get rid simultaneously of both digital pre and post processing. The standalone fully analogue reservoir computer resulting from our endeavour is compared to previous experiments and only exhibits rather limited degradation of performances. Our experiment constitutes a proof of concept for standalone physical reservoir computers. PMID:26935166

  7. Habitability & Astrobiology Research in Mars Terrestrial Analogues

    NASA Astrophysics Data System (ADS)

    Foing, Bernard

    2014-05-01

    We performed a series of field research campaigns (ILEWG EuroMoonMars) in the extreme Utah desert relevant to Mars environments, and in order to help in the interpretation of Mars missions measurements from orbit (MEX, MRO) or from the surface (MER, MSL), or Moon geochemistry (SMART-1, LRO). We shall give an update on the sample analysis in the context of habitability and astrobiology. Methods & Results: In the frame of ILEWG EuroMoonMars campaigns (2009 to 2013) we deployed at Mars Desert Research station, near Hanksville Utah, a suite of instruments and techniques [A, 1, 2, 9-11] including sample collection, context imaging from remote to local and microscale, drilling, spectrometers and life sensors. We analyzed how geological and geochemical evolution affected local parameters (mineralogy, organics content, environment variations) and the habitability and signature of organics and biota. Among the important findings are the diversity in the composition of soil samples even when collected in close proximity, the low abundances of detectable PAHs and amino acids and the presence of biota of all three domains of life with significant heterogeneity. An extraordinary variety of putative extremophiles was observed [3,4,9]. A dominant factor seems to be soil porosity and lower clay-sized particle content [6-8]. A protocol was developed for sterile sampling, contamination issues, and the diagnostics of biodiversity via PCR and DGGE analysis in soils and rocks samples [10, 11]. We compare the 2009 campaign results [1-9] to new measurements from 2010-2013 campaigns [10-12] relevant to: comparison between remote sensing and in-situ measurements; the study of minerals; the detection of organics and signs of life. Keywords: field analogue research, astrobiology, habitability, life detection, Earth-Moon-Mars, organics References [A] Foing, Stoker & Ehrenfreund (Editors, 2011) "Astrobiology field Research in Moon/Mars Analogue Environments", Special Issue of International

  8. Organic geochemical constraints on paleoelevation

    NASA Astrophysics Data System (ADS)

    Polissar, P. J.; Rowley, D. B.; Currie, B. S.; Freeman, K. H.

    2012-12-01

    The elevation history of the land surface is an important factor in the interpretation of past tectonic, climate and ecological processes. However, quantitative estimates of paleoelevation are difficult to produce and new techniques are needed. Organic geochemical approaches to quantifying paleoelevations provide a new perspective on this difficult task. The hydrogen isotopic composition of organic biomarker molecules synthesized by plants and algae is systematically related to the water used for growth. Organic molecules in ancient sediments can provide values for the isotopic composition of this water and thus elevation, provided the relationship between elevation and isotopic values is known. Molecular hydrogen isotope ratios from Cenozoic lake sediments on the Tibetan Plateau demonstrate the utility of a biomarker approach. Terrestrial plant-wax D/H values on Neogene sediments from the Namling-Oiyug Basin provide new paleoelevation estimates that compare well with previous studies. Plant wax D/H ratios paired with lacustrine carbonate oxygen isotope values from the Lunpola and Hoh-Xil basins illustrate how paired isotope systems can unravel the isotopic composition of precipitation from evaporative enrichment of lake waters. A potentially fruitful avenue for future research is illustrated by D/H analyses on older sediments from the Namling-Oiyug Basin. These sediments—like many that could be useful for paleoaltimetry—have experienced significant burial and heating. As temperatures approach the oil window it becomes possible to exchange hydrogen in both the extractable organic molecules (bitumen) and the insoluble organic residue (kerogen). The extent to which this exchange alters the original isotopic composition will determine the usefulness of D/H analyses on thermally mature organic matter. The potential payoff and pitfalls of D/H analyses on heated sediments is illustrated with thermally immature and mature samples from the Namling-Oiyug Basin.

  9. Synthesis of structurally simplified analogues of pancratistatin: truncation of the cyclitol ring.

    PubMed

    Manpadi, Madhuri; Kireev, Artem S; Magedov, Igor V; Altig, Jeff; Tongwa, Paul; Antipin, Mikhail Yu; Evidente, Antonio; van Otterlo, Willem A L; Kornienko, Alexander

    2009-09-18

    Pancratistatin is a phenanthridone-type natural product isolated from several plants of the Amaryllidaceae family. Its potent antiproliferative, antivascular, antiviral, and antiparasitic properties have attracted the attention of synthetic, biological, and medicinal chemists. Pancratistatin's low natural availability and complex structure have steered many of these research projects toward the preparation of its simplified synthetic analogues with useful levels of activity. In this work we have developed synthetic chemistry aimed at the preparation of pancratistatin analogues with a truncated cyclitol portion of the molecule. The described synthetic pathways are based on a highly anti-diastereoselective arylcuprate conjugate addition to gamma-alkoxy-alpha,beta-enoates and syn-selective azidation at the alpha-position of ester enolates. Analogues with the formally cleaved C3-C4 bond, and thus containing an open ring C, as well as a compound containing a truncated lactol moiety in lieu of the cyclitol, were prepared. Several of the analogues exhibited weak antiproliferative activity, with the highest potency observed in the case of the lactol analogue. From these results implications for the design of future pancratistatin analogues are discussed. Furthermore, the synthetic pathways can be used to construct pancratistatin-mimetic libraries, in which the cyclitol moiety is replaced by other cyclic motifs.

  10. Some biochemical properties of an acyclic oligonucleotide analogue. A plausible ancestor of the DNA?

    NASA Astrophysics Data System (ADS)

    Merle, Liliane; Spach, Gérard; Merle, Yves; Sági, János; Szemzö, Attila

    1993-04-01

    As acyclic oligonucleotides have been suggested as a primitive model of DNA or RNA in prebiotic times, we compared some biochemical properties of these analogues to that of natural ones. Firstly, an acyclic analogue of deoxyribonucleoside triphosphates was tested as a potential substrate of enzymes intervening in nucleic acids synthesis. GlyTTP, a dTTP analogue with a missing 2'-methylene group is notaccepted as a substrate by either DNA polymerase or deoxynucleotidyl terminal transferase (TdT). Secondly, themodified dodecathymidylate (GlyT)12, the racemic acyclic sugar analogue of (dT)12, proved to be anefficient primer for DNA polymerase and TdT, though the associative properties of (GlyT)12 are very weak as shown by UV spectroscopy in phosphate buffer without magnesium chloride. But (GlyT)12 has the advantage to be 500-times more stable against hydrolysis by snake venom phosphodiesterase than the corresponding oligothymidylate.

  11. Emulating exhalative chemistry: synthesis and structural characterization of ilinskite, Na[Cu5O2](SeO3)2Cl3, and its K-analogue

    NASA Astrophysics Data System (ADS)

    Kovrugin, Vadim M.; Siidra, Oleg I.; Colmont, Marie; Mentré, Olivier; Krivovichev, Sergey V.

    2015-08-01

    The K- and Na-synthetic analogues of the fumarolic mineral ilinskite have been synthesized by the chemical vapor transport (CVT) reactions method. The A[Cu5O2](SeO3)2Cl3 ( A + = K+, Na+) compounds crystallize in the orthorhombic space group Pnma: a = 18.1691(6) Å, b = 6.4483(2) Å, c = 10.5684(4) Å, V = 1238.19(7) Å3, R 1 = 0.018 for 1957 unique reflections with F > 4σ F for K[Cu5O2](SeO3)2Cl3 ( KI), and a = 17.7489(18) Å, b = 6.4412(6) Å, c = 10.4880(12) Å, V = 1199.0(2) Å3, R 1 = 0.049 for 1300 unique reflections with F > 4σ F for Na[Cu5O2](SeO3)2Cl3 ( NaI). The crystal structures of KI and NaI are based upon the [O2Cu5]6+ sheets consisting of corner-sharing (OCu4)6+ tetrahedra. The Na-for-K substitution results in the significant expansion of the interlayer space and changes in local coordination of some of the Cu2+ cations. The A + cation coordination changes from fivefold (for Na+) to ninefold (for K+). The CVT reactions method provides a unique opportunity to model physicochemical conditions existing in fumarolic environments and may be used not only to model exhalative processes, but also to predict possible mineral phases that may form in fumaroles. In particular, the K analogue of ilinskite is not known in nature, whereas it may well form from volcanic gases in a K-rich local geochemical environment.

  12. Geochemical Interactions and Viral-Prokaryote Relationships in Freshwater Environments

    NASA Astrophysics Data System (ADS)

    Kyle, J. E.; Ferris, G.

    2009-05-01

    Viral and prokaryotic abundances were surveyed throughout southern Ontario aquatic habitats to determine relationships with geochemical parameters in the natural environment. Surface water samples were collected from acid mine drainage in summer of 2007 and 2008 and from circum-neutral pH environments in October to November 2008. Site determination was based on collecting samples from various aquatic habitats (acid mine drainage, lakes, rivers, tributaries, wetlands) with differing bedrock geology (limestone and shale dominated vs granitic Canadian Shield) to obtain a range of geochemical conditions. At each site, measurements of temperature, pH, and Eh were conducted. Samples collected for microbial counts and electron imaging were preserved to a final concentration of 2.5 % (v/v) glutaraldehyde. Additional sample were filtered into 60 mL nalgene bottles and amber EPA certified 40 mL glass vials to determine chemical constituents and dissolved organic carbon (DOC), respectively. Water was also collected to determine additional physiochemical parameters (dissolved total iron, ferric iron, nitrate, sulfate, phosphate, alkalinity, and turbidity). All samples were stored at 4 °C until analysis. Viral and prokaryotic abundance was determined by staining samples with SYBR Green I and examining with a epifluorescence microscope under blue excitation. Multiple regression analysis using stepwise backwards regression and general linear models revealed that viral abundance was the most influential predictor of prokaryotic abundance. Additional predictors include pH, sulfate, phosphate, and magnesium. The strength of the model was very strong with 90 % of the variability explained (R2 = 0.90, p < 0.007). This is the first report, to our knowledge, of viruses exhibiting such strong controls over prokaryotic abundance in the natural environment. All relationships are positively correlated with the exception of Mg, which is negatively correlated. Iron was also noted as a

  13. Low-density geochemical mapping and the robustness of geochemical patterns

    USGS Publications Warehouse

    Smith, D.B.; Reimann, C.

    2008-01-01

    Geochemical mapping of entire continents and, ultimately, the world is still a challenge for applied geochemists. At sample densities traditionally used for geochemical exploration (1 site per 1-25 km2), geochemical mapping of whole continents is logistically extremely demanding and tremendously expensive. The first low-density geochemical surveys (1 site per 200 km2) were carried out during the late 1960s in Africa. Later surveys conducted in various parts of the world had sample densities ranging from 1 site per 300 km2 to 1 site per 18 000 km2. Although these surveys were deemed successful by the investigators in defining variations in background element content on a regional scale, the scientific community was sceptical that low-density geochemical mapping was possible and would provide useful information. The main area of criticism centred around the concern that at such low sample densities the resulting maps would not be robust, i.e. if the same area were resampled and remapped, different geochemical patterns would emerge. Different examples from the USA, Europe, China and Africa demonstrate that low-density geochemical mapping will result in stable and robust geochemical patterns at the continental scale. Such maps are urgently needed for a wide variety of applications. ?? 2008 AAG/ Geological Society of London.

  14. Nano-FTIR for Geochemical Sample Analysis

    NASA Astrophysics Data System (ADS)

    Dominguez, G.; McCleod, A.; Gainsforth, Z.; Keilmann, F.; Westphal, A.; Thiemens, M. H.; Basov, D.

    2014-12-01

    Infrared (IR) spectroscopy is considered by many to be the "gold standard" for chemical identification, providing a direct connection between chemical compounds found in the laboratory and those found in natural samples including remote astrophysical environments. However, a well known limitation of using conventional IR spectroscopy is its spatial resolution determined by the wavelength of IR photons. Thus, while other techniques such as XANES and micro-Raman are capable of limited functional group mapping at tens to hundreds of nanometers, their use is limited by accessibility (the need for synchrotron beamlines) or the need for intense irradiation conditions (Raman) that can lead to sample alteration. These limitations and the wealth of information that can be extracted from detailed studies of unique micron-sized samples brought back by recent sample return missions such as NASA's Stardust mission, have motivated the development of a novel infrared mapping technique that is capable of mapping the chemical functional properties of geochemical samples with submicron resolutions. Here we describe our nano-FTIR imaging and analysis technique that allows us to bypass diffraction limited sample imaging in the infrared. Here we show, for the first time, that 1) the combination of an atomic-force microscope (AFM) and laser can be used to obtain the FTIR-equivalent spectra on spatial scales that are much smaller than the wavelength of IR radiation used 2) this technique responds to subtle shifts in cation concentrations as evidenced by changes in the frequencies of phonons at sub-micron scales 3) this technique can be used to identify regions of crystalline and semi-crystalline materials as demonstrated in our analysis of a cometary dust grain Iris. This work has clear implications for interpretations of astronomical observations and adds a new technique for the non-destructive characterization of terrestrial and extraterrestrial samples.

  15. Geologic and geochemical studies of the New Albany Shale Group (Devonian-Mississippian) in Illinois. Final report

    SciTech Connect

    Bergstrom, R.E.; Shimp, N.F.

    1980-06-30

    The Illinois State Geological Survey is conducting geological and geochemical investigations to evaluate the potential of New Albany Group shales as a source of hydrocarbons, particularly natural gas. Geological studies include stratigraphy and structure, mineralogic and petrographic characterization; analyses of physical properties; and development of a computer-based resources evaluation system. Geochemical studies include organic carbon content and trace elements; hydrocarbon content and composition; and adsorption/desorption studies of gas through shales. Separate abstracts have been prepared for each task reported.

  16. Geochemical and spectral characterization of naturally altered rock surfaces

    NASA Technical Reports Server (NTRS)

    Chang, L. L. Y.; Sommer, S. E.; Buckingham, W. F.

    1981-01-01

    The possibility of using the visible-near infrared region for compositional analysis of remotely sensed rock surfaces is studied. This would allow mapping rock type both on the Earth's surface and on other planetary surfaces. Reflectance spectroscopy, economic geology, optical depth determination, and X-ray diffraction mineralogy are discussed.

  17. Fluorescent polyene ceramide analogues as membrane probes.

    PubMed

    Nieves, Ingrid; Artetxe, Ibai; Abad, José Luis; Alonso, Alicia; Busto, Jon V; Fajarí, Lluís; Montes, L Ruth; Sot, Jesús; Delgado, Antonio; Goñi, Félix M

    2015-03-03

    Three ceramide analogues have been synthesized, with sphingosine-like chains containing five conjugated double bonds. Pentaene I has an N-palmitoyl acyl chain, while the other two pentaenes contain also a doxyl radical, respectively, at C5 (Penta5dox) and at C16 (Penta16dox) positions of the N-acyl chain. Pentaene I maximum excitation and emission wavelengths in a phospholipid bilayer are 353 and 478 nm, respectively. Pentaene I does not segregate from the other lipids in the way natural ceramide does, but rather mixes with them in a selective way according to the lipid phases involved. Fluorescence confocal microscopy studies show that when lipid domains in different physical states coexist, Pentaene I emission is higher in gel than in fluid domains, and in liquid-ordered than in liquid-disordered areas. Electron paramagnetic resonance of the pentaene doxyl probes confirms that these molecules are sensitive to the physical state of the bilayer. Calorimetric and fluorescence quenching experiments suggest that the lipids under study orient themselves in lipid bilayers with their polar moieties located at the lipid-water interface. The doxyl radical in the N-acyl chain quenches the fluorescence of the pentaene group when in close proximity. Because of this property, Penta16dox can detect gel-fluid transitions in phospholipids. The availability of probes for lipids in the gel phase is important in view of novel evidence for the existence of gel microdomains in cell membranes.

  18. Synthesis and antioxidant activity of peptide-based ebselen analogues.

    PubMed

    Satheeshkumar, Kandhan; Mugesh, Govindasamy

    2011-04-18

    A series of di- and tripeptide-based ebselen analogues has been synthesized. The compounds were characterized by (1)H, (13)C, and (77)Se NMR spectroscopy and mass spectral techniques. The glutathione peroxidase (GPx)-like antioxidant activity has been studied by using H(2)O(2) , tert-butyl hydroperoxide (tBuOOH), and cumene hydroperoxide (Cum-OOH) as substrates, and glutathione (GSH) as a cosubstrate. Although all the peptide-based compounds have a selenazole ring similar to that of ebselen, the GPx activity of these compounds highly depends on the nature of the peptide moiety attached to the nitrogen atom of the selenazole ring. It was observed that the introduction of a phenylalanine (Phe) amino acid residue in the N-terminal reduces the activity in all three peroxide systems. On the other hand, the introduction of aliphatic amino acid residues such as valine (Val) significantly enhances the GPx activity of the ebselen analogues. The difference in the catalytic activity of dipeptide-based ebselen derivatives can be ascribed mainly to the change in the reactivity of these compounds toward GSH and peroxide. Although the presence of the Val-Ala-CO(2) Me moiety facilitates the formation of a catalytically active selenol species, the reaction of ebselen analogues that has a Phe-Ile-CO(2) Me residue with GSH does not generate the corresponding selenol. To understand the antioxidant activity of the peptide-based ebselen analogues in the absence of GSH, these compounds were studied for their ability to inhibit peroxynitrite (PN)-mediated nitration of bovine serum albumin (BSA) and oxidation of dihydrorhodamine 123. In contrast to the GPx activity, the PN-scavenging activity of the Phe-based peptide analogues was found to be comparable to that of the Val-based compounds. However, the introduction of an additional Phe residue to the ebselen analogue that had a Val-Ala dipeptide significantly reduced the potency of the parent compound in PN-mediated nitration.

  19. Hawai'i and Gale Crater: A Mars Analogue Study of Igneous, Sedimentary, Weathering, and Alteration Trends in Geochemistry

    NASA Technical Reports Server (NTRS)

    Berger, J. A.; Flemming, R. L.; Schmidt, M. E.; Gellert, R.; Morris, R. V.; Ming, D. W.

    2017-01-01

    Sedimentary rocks in Gale Crater on Mars indicate a varied provenance with a range of alteration and weathering [1, 2]. Geochemical trends identified in basaltic and alkalic sedimentary rocks by the Alpha Particle X-ray Spectrometer (APXS) on the Mars rover Curiosity represent a complex interplay of igneous, sedimentary, weathering, and alteration processes. Assessing the relative importance of these processes is challenging with unknown compositions for parent sediment sources and with the constraints provided by Curiosity's instruments. We therefore look to Mars analogues on Earth where higher-resolution analyses and geologic context can constrain interpretations of Gale Crater geochemical observations. We selected Maunakea (AKA Mauna Kea) and Kohala volcanoes, Hawai'i, for an analogue study because they are capped by post-shield transitional basalts and alkalic lavas (hawaiites, mugearites) with compositions similar to Gale Crater [1, 3]. Our aim was to characterize Hawaiian geochemical trends associated with igneous processes, sediment transport, weathering, and alteration. Here, we present initial results and discuss implications for selected trends observed by APXS in Gale Crater.

  20. Plant Volatile Analogues Strengthen Attractiveness to Insect

    PubMed Central

    Sun, Yufeng; Yu, Hao; Zhou, Jing-Jiang; Pickett, John A.; Wu, Kongming

    2014-01-01

    Green leaf bug Apolygus lucorum (Meyer-Dür) is one of the major pests in agriculture. Management of A. lucorum was largely achieved by using pesticides. However, the increasing population of A. lucorum since growing Bt cotton widely and the increased awareness of ecoenvironment and agricultural product safety makes their population-control very challenging. Therefore this study was conducted to explore a novel ecological approach, synthetic plant volatile analogues, to manage the pest. Here, plant volatile analogues were first designed and synthesized by combining the bioactive components of β-ionone and benzaldehyde. The stabilities of β-ionone, benzaldehyde and analogue 3 g were tested. The electroantennogram (EAG) responses of A. lucorum adult antennae to the analogues were recorded. And the behavior assay and filed experiment were also conducted. In this study, thirteen analogues were acquired. The analogue 3 g was demonstrated to be more stable than β-ionone and benzaldehyde in the environment. Many of the analogues elicited EAG responses, and the EAG response values to 3 g remained unchanged during seven-day period. 3 g was also demonstrated to be attractive to A. lucorum adults in the laboratory behavior experiment and in the field. Its attractiveness persisted longer than β-ionone and benzaldehyde. This indicated that 3 g can strengthen attractiveness to insect and has potential as an attractant. Our results suggest that synthetic plant volatile analogues can strengthen attractiveness to insect. This is the first published study about synthetic plant volatile analogues that have the potential to be used in pest control. Our results will support a new ecological approach to pest control and it will be helpful to ecoenvironment and agricultural product safety. PMID:24911460

  1. Stereochemical Assignment of Strigolactone Analogues Confirms Their Selective Biological Activity.

    PubMed

    Artuso, Emma; Ghibaudi, Elena; Lace, Beatrice; Marabello, Domenica; Vinciguerra, Daniele; Lombardi, Chiara; Koltai, Hinanit; Kapulnik, Yoram; Novero, Mara; Occhiato, Ernesto G; Scarpi, Dina; Parisotto, Stefano; Deagostino, Annamaria; Venturello, Paolo; Mayzlish-Gati, Einav; Bier, Ariel; Prandi, Cristina

    2015-11-25

    Strigolactones (SLs) are new plant hormones with various developmental functions. They are also soil signaling chemicals that are required for establishing beneficial mycorrhizal plant/fungus symbiosis. In addition, SLs play an essential role in inducing seed germination in root-parasitic weeds, which are one of the seven most serious biological threats to food security. There are around 20 natural SLs that are produced by plants in very low quantities. Therefore, most of the knowledge on SL signal transduction and associated molecular events is based on the application of synthetic analogues. Stereochemistry plays a crucial role in the structure-activity relationship of SLs, as compounds with an unnatural D-ring configuration may induce biological effects that are unrelated to SLs. We have synthesized a series of strigolactone analogues, whose absolute configuration has been elucidated and related with their biological activity, thus confirming the high specificity of the response. Analogues bearing the R-configured butenolide moiety showed enhanced biological activity, which highlights the importance of this stereochemical motif.

  2. Do film soundtracks contain nonlinear analogues to influence emotion?

    PubMed Central

    Blumstein, Daniel T.; Davitian, Richard; Kaye, Peter D.

    2010-01-01

    A variety of vertebrates produce nonlinear vocalizations when they are under duress. By their very nature, vocalizations containing nonlinearities may sound harsh and are somewhat unpredictable; observations that are consistent with them being particularly evocative to those hearing them. We tested the hypothesis that humans capitalize on this seemingly widespread vertebrate response by creating nonlinear analogues in film soundtracks to evoke particular emotions. We used lists of highly regarded films to generate a set of highly ranked action/adventure, dramatic, horror and war films. We then scored the presence of a variety of nonlinear analogues in these film soundtracks. Dramatic films suppressed noise of all types, contained more abrupt frequency transitions and musical sidebands, and fewer noisy screams than expected. Horror films suppressed abrupt frequency transitions and musical sidebands, but had more non-musical sidebands, and noisy screams than expected. Adventure films had more male screams than expected. Together, our results suggest that film-makers manipulate sounds to create nonlinear analogues in order to manipulate our emotional responses. PMID:20504815

  3. Do film soundtracks contain nonlinear analogues to influence emotion?

    PubMed

    Blumstein, Daniel T; Davitian, Richard; Kaye, Peter D

    2010-12-23

    A variety of vertebrates produce nonlinear vocalizations when they are under duress. By their very nature, vocalizations containing nonlinearities may sound harsh and are somewhat unpredictable; observations that are consistent with them being particularly evocative to those hearing them. We tested the hypothesis that humans capitalize on this seemingly widespread vertebrate response by creating nonlinear analogues in film soundtracks to evoke particular emotions. We used lists of highly regarded films to generate a set of highly ranked action/adventure, dramatic, horror and war films. We then scored the presence of a variety of nonlinear analogues in these film soundtracks. Dramatic films suppressed noise of all types, contained more abrupt frequency transitions and musical sidebands, and fewer noisy screams than expected. Horror films suppressed abrupt frequency transitions and musical sidebands, but had more non-musical sidebands, and noisy screams than expected. Adventure films had more male screams than expected. Together, our results suggest that film-makers manipulate sounds to create nonlinear analogues in order to manipulate our emotional responses.

  4. Bilateral Choroidal Metastases from Endobronchial Carcinoid Treated with Somatostatin Analogues

    PubMed Central

    De Bruyn, Deborah; Lamont, Jan; Vanderstraeten, Erik; Van Belle, Simon; Platteau, Elise; De Zaeytijd, Julie; Hoornaert, Kristien P.

    2016-01-01

    Objective: To describe a patient with bilateral multifocal choroidal metastases from an endobronchial carcinoid treated with a somatostatin analogue. Method: A 60-year-old woman presenting with photopsia in the left eye underwent an extensive ophthalmic examination, including fluorescein angiography, OCT and ultrasound. Results: Fundoscopy revealed a small retinal tear in the left eye, for which she received laser treatment. In addition, choroidal masses were detected in both eyes. Her medical history of a pneumectomy for a bronchial carcinoid six years earlier together with recent elevated chromogranin A blood levels prompted a diagnosis of choroidal metastases. Subsequently, a Gallium-68 DOTANOC positron emitting tomography/computer tomography scan revealed a spinal cord metastasis and mediastinal as well as mesenterial lymph node invasion. Systemic treatment with Sandostatin®, a somatostatin analogue was started. Up until two years after the initial presentation and treatment, these choroidal lesions remained stable without any signs of growth. Conclusion: Endobronchial carcinoid tumors have an indolent nature and long-term follow-up is recommended for early detection of metastases. Although treatment with somatostatin analogues rarely induces complete tumor regression, tumor stabilization and prevention of symptoms related to hormone secretion is achieved. This well-tolerated systemic treatment provides a worthy alternative treatment for choroidal metastasis compared to classic radiotherapy without any risk of radiation or laser-related visual loss. PMID:27843513

  5. Space analogue studies in Antarctica

    NASA Astrophysics Data System (ADS)

    Lugg, D.; Shepanek, M.

    1999-09-01

    Medical research has been carried out on the Australian National Antarctic Research Expeditions (ANARE) for 50 years. As an extension of this program collaborative Australian/United States research on immunology, microbiology, psychology and remote medicine has produced important data and insight on how humans adapt to the stress of extreme isolation, confinement and the harsh environment of Antarctica. An outstanding analogue for the isolation and confinement of space missions (especially planetary outposts), ANARE has been used as an international research platform by Australia and the United States since 1993. Collaborative research has demonstrated a lowered responsiveness of the immune system under the isolation and confinement of Antarctic winter-over; a reduction of almost 50% in T cell proliferation to mltogen phytohaemogglutinin, as well as changes in latent herpesvirus states and the expansion of the polyclonal latent Epstein-Barr virus infected B cell populations. Although no clinically significant disease has been found to result from these immune changes, research is currently assessing the effects of psychological factors on the immune system. This and associated research performed to date and its relevance to both organisations is discussed, and comment made on possible extensions to the program in both medical and other fields.

  6. Space analogue studies in Antarctica.

    PubMed

    Lugg, D; Shepanek, M

    1999-01-01

    Medical research has been carried out on the Australian National Antarctic Research Expeditions (ANARE) for 50 years. As an extension of this program collaborative Australian/United States research on immunology, microbiology, psychology and remote medicine has produced important data and insight on how humans adapt to the stress of extreme isolation, confinement and the harsh environment of Antarctica. An outstanding analogue for the isolation and confinement of space missions (especially planetary outposts), ANARE has been used as an international research platform by Australia and the United States since 1993. Collaborative research has demonstrated a lowered responsiveness of the immune system under the isolation and confinement of Antarctic winter-over; a reduction of almost 50% in T cell proliferation to mitogen phytohaemogglutinin, as well as changes in latent herpesvirus states and the expansion of the polyclonal latent Epstein-Barr virus infected B cell populations. Although no clinically significant disease has been found to result from these immune changes, research is currently assessing the effects of psychological factors on the immune system. This and associated research performed to date and its relevance to both organisations is discussed, and comment made on possible extensions to the program in both medical and other fields.

  7. Space analogue studies in Antarctica

    NASA Technical Reports Server (NTRS)

    Lugg, D.; Shepanek, M.

    1999-01-01

    Medical research has been carried out on the Australian National Antarctic Research Expeditions (ANARE) for 50 years. As an extension of this program collaborative Australian/United States research on immunology, microbiology, psychology and remote medicine has produced important data and insight on how humans adapt to the stress of extreme isolation, confinement and the harsh environment of Antarctica. An outstanding analogue for the isolation and confinement of space missions (especially planetary outposts), ANARE has been used as an international research platform by Australia and the United States since 1993. Collaborative research has demonstrated a lowered responsiveness of the immune system under the isolation and confinement of Antarctic winter-over; a reduction of almost 50% in T cell proliferation to mitogen phytohaemogglutinin, as well as changes in latent herpesvirus states and the expansion of the polyclonal latent Epstein-Barr virus infected B cell populations. Although no clinically significant disease has been found to result from these immune changes, research is currently assessing the effects of psychological factors on the immune system. This and associated research performed to date and its relevance to both organisations is discussed, and comment made on possible extensions to the program in both medical and other fields.

  8. Dimerization and DNA recognition rules of mithramycin and its analogues

    PubMed Central

    Weidenbach, Stevi; Hou, Caixia; Chen, Jhong-Min; Tsodikov, Oleg V.; Rohr, Jürgen

    2016-01-01

    The antineoplastic and antibiotic natural product mithramycin (MTM) is used against cancer-related hypercalcemia and, experimentally, against Ewing sarcoma and lung cancers. MTM exerts its cytotoxic effect by binding DNA as a divalent metal ion (Me2+)-coordinated dimer and disrupting the function of transcription factors. A precise molecular mechanism of action of MTM, needed to develop MTM analogues selective against desired transcription factors, is lacking. Although it is known that MTM binds G/C-rich DNA, the exact DNA recognition rules that would allow one to map MTM binding sites remain incompletely understood. Towards this goal, we quantitatively investigated dimerization of MTM and several of its analogues, MTM SDK (for Short side chain, DiKeto), MTM SA-Trp (for Short side chain and Acid), MTM SA-Ala, and a biosynthetic precursor premithramycin B (PreMTM B), and measured the binding affinities of these molecules to DNA oligomers of different sequences and structural forms at physiological salt concentrations. We show that MTM and its analogues form stable dimers even in the absence of DNA. All molecules, except for PreMTM B, can bind DNA with the following rank order of affinities (strong to weak): MTM = MTM SDK > MTM SA-Trp > MTM SA-Ala. An X(G/C)(G/C)X motif, where X is any base, is necessary and sufficient for MTM binding to DNA, without a strong dependence on DNA conformation. These recognition rules will aid in mapping MTM sites across different promoters towards development of MTM analogues as useful anticancer agents. PMID:26760230

  9. Evaluation of Anti-HIV-1 Mutagenic Nucleoside Analogues*

    PubMed Central

    Vivet-Boudou, Valérie; Isel, Catherine; El Safadi, Yazan; Smyth, Redmond P.; Laumond, Géraldine; Moog, Christiane; Paillart, Jean-Christophe; Marquet, Roland

    2015-01-01

    Because of their high mutation rates, RNA viruses and retroviruses replicate close to the threshold of viability. Their existence as quasi-species has pioneered the concept of “lethal mutagenesis” that prompted us to synthesize pyrimidine nucleoside analogues with antiviral activity in cell culture consistent with an accumulation of deleterious mutations in the HIV-1 genome. However, testing all potentially mutagenic compounds in cell-based assays is tedious and costly. Here, we describe two simple in vitro biophysical/biochemical assays that allow prediction of the mutagenic potential of deoxyribonucleoside analogues. The first assay compares the thermal stabilities of matched and mismatched base pairs in DNA duplexes containing or not the nucleoside analogues as follows. A promising candidate should display a small destabilization of the matched base pair compared with the natural nucleoside and the smallest gap possible between the stabilities of the matched and mismatched base pairs. From this assay, we predicted that two of our compounds, 5-hydroxymethyl-2′-deoxyuridine and 5-hydroxymethyl-2′-deoxycytidine, should be mutagenic. The second in vitro reverse transcription assay assesses DNA synthesis opposite nucleoside analogues inserted into a template strand and subsequent extension of the newly synthesized base pairs. Once again, only 5-hydroxymethyl-2′-deoxyuridine and 5-hydroxymethyl-2′-deoxycytidine are predicted to be efficient mutagens. The predictive potential of our fast and easy first line screens was confirmed by detailed analysis of the mutation spectrum induced by the compounds in cell culture because only compounds 5-hydroxymethyl-2′-deoxyuridine and 5-hydroxymethyl-2′-deoxycytidine were found to increase the mutation frequency by 3.1- and 3.4-fold, respectively. PMID:25398876

  10. Upscaling Geochemical and Hydrologic Parameters using a Novel Depth Fragmented Approach

    NASA Astrophysics Data System (ADS)

    Arora, B.; Mohanty, B. P.; McGuire, J. T.

    2012-12-01

    Knowledge about effective hydrologic and geochemical properties at field scales is pertinent in predicting and managing the fate and transport of reactive contaminants from landfill and waste management sites. A significant challenge in predicting these reactive contaminant concentrations at large scales is the lack of an efficient upscaling methodology that serves as a link between process understanding gained at the laboratory scale and application needed at the field scale. Here, we explore the concept of a new depth-wise upscaling framework, which addresses the effect of structural heterogeneity on developing scale-appropriate hydrologic and geochemical parameters. A Markov chain Monte Carlo algorithm (MCMC) is used to derive these upscaling parameters, which are tested for variations across heterogeneous systems (layers and lenses) at the Norman landfill site. The Norman landfill is a closed municipal landfill with prevalent organic contamination. The results of the MCMC simulations indicate that the use of a heterogeneity formulation in the likelihood function significantly improves the prediction of geochemical concentrations at the landfill site. The results also indicate that geochemical scaling coefficients based on dominant biogeochemical processes (sulfate and iron reduction) are reproducible for conservative (such as bromide) and other redox-sensitive concentrations (such as nitrate) at the Norman landfill. These geochemical scaling coefficients derived through the upscaling algorithm demonstrate unimodal characteristics in the posterior distribution while the hydrologic scaling coefficient is multimodal in nature. The multi-modality is again suggestive of the effect of heterogeneity and lithologic variability on redox processes at the Norman landfill site.

  11. Characterization of Synthetic and Natural Manganese Oxides as Martian Analogues

    NASA Technical Reports Server (NTRS)

    Fox, V. K.; Arvidson, R. E.; Jolliff, B. L.; Carpenter, P. K.; Catalano, J. G.; Hinkle, M. A. G.; Morris, R. V.

    2015-01-01

    Recent discoveries of highly concentrated manganese oxides in Gale Crater and on the rim of Endeavour Crater by the Mars Science Laboratory Curiosity and Mars Exploration Rover Opportunity, respectively, imply more highly oxidizing aqueous conditions than previously recognized. Manganese oxides are a significant environmental indicator about ancient aqueous conditions, provided the phases can be characterized reliably. Manganese oxides are typically fine-grained and poorly crystalline, making the mineral structures difficult to determine, and they generally have very low visible reflectance with few distinctive spectral features in the visible to near infrared, making them a challenge for interpretation from remote sensing data. Therefore, these recent discoveries motivate better characterization using methods available on Mars, particularly visible to near infrared (VNIR) spectroscopy, X-ray diffractometry (XRD), and compositional measurements. Both rovers have complementary instruments in this regard. Opportunity is equipped with its multispectral visible imager, Pancam, and an Alpha Particle X-ray Spectrometer (APXS), and Curiosity has the multispectral Mastcam, ChemCam (laser-induced breakdown spectroscopy and passive spectroscopy), and APXS for in situ characterization, and ChemMin (XRD) for collected samples.

  12. Antarctica natural laboratory and space analogue for psychological research.

    PubMed

    Suedfeld, P; Weiss, K

    2000-01-01

    This introduction to the special issue traces the history of psychosocial concerns related to Antarctic exploration, from the heroic age of early explorers through the International Geophysical Year (IGY) of 1957 to 1958 to recent and current systematic research projects. The introduction discusses the organization and topics of international psychological investigations in polar stations and summarizes the articles that follow. Living in Antarctica imposes some unusual restrictions as well as opportunities, and it requires psychological adaptation to extreme environmental circumstances. The thrust of previous scientific and popular literature has been to focus on the negative effects of the situation and ignore the positive ones; however, ongoing studies are bringing about a more balanced view. Having an accurate understanding is important not only intrinsically and for appropriate application in the Antarctic itself but also in analogous extreme and unusual environments. These include extended space flight and space habitation, such as the projected voyage to Mars.

  13. A Novel Field Apparatus for Conducting Linked Geochemical-Microbiological Experiments in Shallow Sediments

    NASA Astrophysics Data System (ADS)

    Smith, E. W.; Voytek, M. A.; McGuire, J. T.; Cozzarelli, I. M.; Kneeshaw, T. A.; Baez-Cazull, S. E.

    2008-12-01

    Collecting in-situ experimental data for microbially mediated geochemical reactions is complex because it is difficult to assess the impact of the heterogeneity of natural systems. Specifically it is often difficult to constrain the degree of interaction between the pore water collected for geochemical analysis and a sampled microbial population. The newly developed apparatus, called a Native Organism Geochemical Experimentation Enclosure (NOGEE), provides the means to measure changes in well defined geochemical solutions that have been in direct contact with a known in-situ microbial population. The sampling apparatus is similar to a drive-point well. A short screened chamber (~60 ml) at the tip houses a polycarbonate sponge, which serves as a substrate for colonization by native microorganisms when it is open to the surrounding sediment. Following a colonization period dependent on season and temperature, the sponge chamber is closed to the surrounding environment by lowering an inner pipe and amended test solutions are introduced from the surface via tubing. An advantage to this method over laboratory microcosms is that the in-situ setting provides a natural, intrinsic control over environmental variables and minimizes disturbance to the system. To date, NOGEE's have been used to evaluate kinetic controls on sulfate reduction. Experimental results showed changing rates of sulfate reduction coincident with changes in microbial population and demonstrate the utility of using NOGEEs to quantify linkages between geochemistry and microbiology in complex natural environments.

  14. Isobrassinin and its analogues: novel types of antiproliferative agents.

    PubMed

    Csomós, Péter; Zupkó, István; Réthy, Borbála; Fodor, Lajos; Falkay, George; Bernáth, Gábor

    2006-12-15

    Isobrassinin (2-(S-methyldithiocarbamoylaminomethyl)indole (7a), a regioisomer of the cruciferous phytoalexin brassinin (1), exerted marked antiproliferative effects on the HeLa, A431 and MCF7 cell lines (>78.6% inhibition at 30muM). For structure-activity relationships, further analogues were synthesized. The highest cytotoxic effect was displayed by 2-phenylimino-1,3-thiazino[5,6-b]indole (10) (10 microM, 76.8%-HeLa and 46.3%-MCF7). The effect of the natural phytoalexin brassinin was also determined.

  15. Laboratory simulation of organic geochemical processes.

    NASA Technical Reports Server (NTRS)

    Eglinton, G.

    1972-01-01

    Discussion of laboratory simulations that are important to organic geochemistry in that they provide direct evidence relating to geochemical cycles involving carbon. Reviewed processes and experiments include reactions occurring in the geosphere, particularly, short-term diagenesis of biolipids and organochlorine pesticides in estuarine muds, as well as maturation of organic matter in ancient sediments.

  16. Geochemical Reaction Mechanism Discovery from Molecular Simulation

    DOE PAGES

    Stack, Andrew G.; Kent, Paul R. C.

    2014-11-10

    Methods to explore reactions using computer simulation are becoming increasingly quantitative, versatile, and robust. In this review, a rationale for how molecular simulation can help build better geochemical kinetics models is first given. We summarize some common methods that geochemists use to simulate reaction mechanisms, specifically classical molecular dynamics and quantum chemical methods and discuss their strengths and weaknesses. Useful tools such as umbrella sampling and metadynamics that enable one to explore reactions are discussed. Several case studies wherein geochemists have used these tools to understand reaction mechanisms are presented, including water exchange and sorption on aqueous species and mineralmore » surfaces, surface charging, crystal growth and dissolution, and electron transfer. The impact that molecular simulation has had on our understanding of geochemical reactivity are highlighted in each case. In the future, it is anticipated that molecular simulation of geochemical reaction mechanisms will become more commonplace as a tool to validate and interpret experimental data, and provide a check on the plausibility of geochemical kinetic models.« less

  17. Geochemical Reaction Mechanism Discovery from Molecular Simulation

    SciTech Connect

    Stack, Andrew G.; Kent, Paul R. C.

    2014-11-10

    Methods to explore reactions using computer simulation are becoming increasingly quantitative, versatile, and robust. In this review, a rationale for how molecular simulation can help build better geochemical kinetics models is first given. We summarize some common methods that geochemists use to simulate reaction mechanisms, specifically classical molecular dynamics and quantum chemical methods and discuss their strengths and weaknesses. Useful tools such as umbrella sampling and metadynamics that enable one to explore reactions are discussed. Several case studies wherein geochemists have used these tools to understand reaction mechanisms are presented, including water exchange and sorption on aqueous species and mineral surfaces, surface charging, crystal growth and dissolution, and electron transfer. The impact that molecular simulation has had on our understanding of geochemical reactivity are highlighted in each case. In the future, it is anticipated that molecular simulation of geochemical reaction mechanisms will become more commonplace as a tool to validate and interpret experimental data, and provide a check on the plausibility of geochemical kinetic models.

  18. Geochemical Mapping of 4 Vesta Begins

    NASA Technical Reports Server (NTRS)

    Prettyman, Thomas H.; Feldman, William C.; Forni, Olivier; Joy, Steven P.; Lawrence, David J.; LeCorre, Lucille; Mafi, Joseph N.; McCord, Thomas B.; McCoy, Timothy J.; McSween, Harry Y.; Middlefehldt, David W.; Polanskey, Carol; Rayman, Marc; Raymond, Carol A.; Reddy, Vishnu; Reedy, Robert C.; Russell, Christopher T.; Titus, Timothy N.; Toplis, Mike J.

    2011-01-01

    By December, the NASA Dawn spacecraft will have descended to a low altitude mapping orbit (LAMO), where the Gamma Ray and Neutron Detector (GRaND) will acquire global mapping data for up to four months. Measurements by GRaND will help answer elusive questions about how Vesta differentiated and the nature of processes that shaped Vesta s surface. The data will be analyzed to determine the abundances of Mg, Si, Fe, K, Th, and H at a spatial resolution of roughly 300 km full-width-at-half-maximum from a 465 km radius orbit. Thermal and fast neutron counting data will be analyzed to determine the neutron macroscopic absorption cross section and average atomic mass, providing constraints on additional elements, such as Ca and Al. GRaND will quantify the elemental composition of coarse spatial units identified by Dawn s Framing Camera (FC) and the Visible & Infrared Spectrometer (VIR). In addition, GRaND will map the mixing ratio of compositional end members selected from the howardite, eucrite and diogenite (HED) meteorites, determine the relative proportions of plagioclase and mafic minerals, and search for compositions that are absent or under-represented in the meteorite collection. While it is generally thought that Vesta s crust on a regional scale should be well-represented by linear mixing of HED whole-rock compositions, there are hints that Vesta may be more diverse than implied by this model. For example, the discovery of K-rich impact glasses in howardites suggests that K-rich rocks may be present on a portion of Vesta s surface, and the analysis of diogenites indicates considerable variability in the magmatic processes that formed them. The chemical composition of materials within Vesta s south polar structure may provide further clues to how it formed. An impact might have exposed mantle and lower crustal materials, which should have a distinctive compositional signature. We present the analysis of data acquired by GRaND from cruise through the descent to

  19. Alaska Geochemical Database (AGDB)-Geochemical data for rock, sediment, soil, mineral, and concentrate sample media

    USGS Publications Warehouse

    Granitto, Matthew; Bailey, Elizabeth A.; Schmidt, Jeanine M.; Shew, Nora B.; Gamble, Bruce M.; Labay, Keith A.

    2011-01-01

    The Alaska Geochemical Database (AGDB) was created and designed to compile and integrate geochemical data from Alaska in order to facilitate geologic mapping, petrologic studies, mineral resource assessments, definition of geochemical baseline values and statistics, environmental impact assessments, and studies in medical geology. This Microsoft Access database serves as a data archive in support of present and future Alaskan geologic and geochemical projects, and contains data tables describing historical and new quantitative and qualitative geochemical analyses. The analytical results were determined by 85 laboratory and field analytical methods on 264,095 rock, sediment, soil, mineral and heavy-mineral concentrate samples. Most samples were collected by U.S. Geological Survey (USGS) personnel and analyzed in USGS laboratories or, under contracts, in commercial analytical laboratories. These data represent analyses of samples collected as part of various USGS programs and projects from 1962 to 2009. In addition, mineralogical data from 18,138 nonmagnetic heavy mineral concentrate samples are included in this database. The AGDB includes historical geochemical data originally archived in the USGS Rock Analysis Storage System (RASS) database, used from the mid-1960s through the late 1980s and the USGS PLUTO database used from the mid-1970s through the mid-1990s. All of these data are currently maintained in the Oracle-based National Geochemical Database (NGDB). Retrievals from the NGDB were used to generate most of the AGDB data set. These data were checked for accuracy regarding sample location, sample media type, and analytical methods used. This arduous process of reviewing, verifying and, where necessary, editing all USGS geochemical data resulted in a significantly improved Alaska geochemical dataset. USGS data that were not previously in the NGDB because the data predate the earliest USGS geochemical databases, or were once excluded for programmatic reasons

  20. Soil Lysimeter Excavation for Coupled Hydrological, Geochemical, and Microbiological Investigations.

    PubMed

    Sengupta, Aditi; Wang, Yadi; Meira Neto, Antonio A; Matos, Katarena A; Dontsova, Katerina; Root, Rob; Neilson, Julie W; Maier, Raina M; Chorover, Jon; Troch, Peter A

    2016-09-11

    Studying co-evolution of hydrological and biogeochemical processes in the subsurface of natural landscapes can enhance the understanding of coupled Earth-system processes. Such knowledge is imperative in improving predictions of hydro-biogeochemical cycles, especially under climate change scenarios. We present an experimental method, designed to capture sub-surface heterogeneity of an initially homogeneous soil system. This method is based on destructive sampling of a soil lysimeter designed to simulate a small-scale hillslope. A weighing lysimeter of one cubic meter capacity was divided into sections (voxels) and was excavated layer-by-layer, with sub samples being collected from each voxel. The excavation procedure was aimed at detecting the incipient heterogeneity of the system by focusing on the spatial assessment of hydrological, geochemical, and microbiological properties of the soil. Representative results of a few physicochemical variables tested show the development of heterogeneity. Additional work to test interactions between hydrological, geochemical, and microbiological signatures is planned to interpret the observed patterns. Our study also demonstrates the possibility of carrying out similar excavations in order to observe and quantify different aspects of soil-development under varying environmental conditions and scale.

  1. Geochemical patterns in soils of the karst region, Croatia

    USGS Publications Warehouse

    Prohic, E.; Hausberger, G.; Davis, J.C.

    1997-01-01

    Soil samples were collected at 420 locations in a 5-km grid pattern in the Istria and Gorski Kotar areas of Croatia, and on the Croatian islands of Cres, Rab and Krk, in order to relate geochemical variation in the soils to underlying differences in geology, bedrock lithology, soil type, environment and natural versus anthropogenic influences. Specific objectives included assessment of possible agricultural and industrial sources of contamination, especially from airborne effluent emitted by a local power plant. The study also tested the adequacy of a fixed-depth soil sampling procedure developed for meager karstic soils. Although 40 geochemical variables were analyzed, only 15 elements and 5 radionuclides are common to all the sample locations. These elements can be divided into three groups: (1) those of mostly anthropogenic origin -Pb, V, Cu and Cr; (2) those of mixed origin - radionuclides and Zn; and (3) those of mostly geogene origin -Ba, Sr, Ti, Al, Na, Ca, Mg, Fe, Mn, Ni and Co. Variation in Pb shows a strong correlation with the pattern of road traffic in Istria. The distributions of Ca, Na and Mg in the flysch basins of southern Istria and Slovenia are clearly distinguishable from the distributions of these elements in the surrounding carbonate terrains, a consequence of differences in bedrock permeability, type of drainage and pH. The spatial pattern of Cs from the Chernobyl nuclear power plant accident reflects almost exclusively the precipitation in Istria during the days immediately after the explosion. ?? 1997 Elsevier Science B.V.

  2. Geobiochemistry: Placing Biochemistry in Its Geochemical Context

    NASA Astrophysics Data System (ADS)

    Shock, E.; Boyer, G. M.; Canovas, P. A., III; Prasad, A.; Dick, J. M.

    2014-12-01

    Goals of geobiochemistry include simultaneously evaluating the relative stabilities of microbial cells and minerals, and predicting how the composition of biomolecules can change in response to the progress of geochemical reactions. Recent developments in theoretical geochemistry make it possible to predict standard thermodynamic properties of proteins, nucleotides, lipids, and many metabolites including the constituents of the citric acid cycle, at all temperatures and pressures where life is known to occur, and beyond. Combining these predictions with constraints from geochemical data makes it possible to assess the relative stabilities of biomolecules. Resulting independent predictions of the environmental occurrence of homologous proteins and lipid side-chains can be compared with observations from metagenomic and metalipidomic data to quantify geochemical driving forces that shape the composition of biomolecules. In addition, the energetic costs of generating biomolecules from within a diverse range of habitable environments can be evaluated in terms of prevailing geochemical variables. Comparisons of geochemical bioenergetic calculations across habitats leads to the generalization that the availability of H2 determines the cost of autotrophic biosynthesis relative to the aquatic environment external to microbial cells, and that pH, temperature, pressure, and availability of C, N, P, and S are typically secondary. Increasingly reduced conditions, which are determined by reactions of water with mineral surfaces and mineral assemblages, allow many biosynthetic reactions to shift from costing energy to releasing energy. Protein and lipid synthesis, as well as the reverse citric acid cycle, become energy-releasing processes under these conditions. The resulting energy balances that determine habitability contrast dramatically with assumptions derived from oxic surface conditions, such as those where human biochemistry operates.

  3. Past and present of analogue modelling, and its future trend

    NASA Astrophysics Data System (ADS)

    Koyi, Hemin

    2015-04-01

    Since Hull (1815) published his article on modelling, analogue modelling has expanded to simulate both a wider range of tectonic regimes and target more challenging set-ups, and has become an integrated part of the fields of tectonics and structural geology. Establishment of new laboratories testifies for the increased attention the technique receives. The ties between modellers and field geoscientists have become stronger with the focus being on understanding the parameters that govern the evolution of a tectonic regime and the processes that dominate it. Since the first sand castle was built with damp sand on a beach, sand has proven to be an appropriate material analogue. Even though granular materials is the most widely used analogue material, new materials are also (re)introduced as rock analogues. Emphasis has been on more precise measurements of the mechanical properties of the materials and on minimizing the preparation effects, which have a great impact on scaling, interpretations and benchmarking. The analytical technique used to quantify model results has also seen a great deal of improvement. In addition to X-ray tomography used to visualise internal structures of models, new techniques (e.g. PIV, high-resolution laser scanning, and interferometry) have enabled monitoring kinematics with a higher precision. Benchmarking exercises have given modelling an additional checking tool by outlining, in addition to the rheology of the modelling materials, the impact of different preparation approaches, the effect of boundary conditions, and the human factor on model results. However, despite the different approaches and deformation rigs, results of models of different tectonic laboratories have shown a great deal of similarities. Even with the introduction of more sophisticated numerical codes and usage of more powerful computers which enable the simulation of more challenging material properties and combinations of those, and 3D model set-up, analogue modelling

  4. Glucagonlike Peptide 2 Analogue Teduglutide

    PubMed Central

    Chaturvedi, Lakshmi S.; Basson, Marc D.

    2015-01-01

    IMPORTANCE Short bowel syndrome occurs when a shortened intestine cannot absorb sufficient nutrients or fluids. Teduglutide is a recombinant analogue of human glucagonlike peptide 2 that reduces dependence on parenteral nutrition in patients with short bowel syndrome by promoting enterocytic proliferation, increasing the absorptive surface area. However, enterocyte function depends not only on the number of cells that are present but also on differentiated features that facilitate nutrient absorption and digestion. OBJECTIVE To test the hypothesis that teduglutide impairs human intestinal epithelial differentiation. DESIGN AND SETTING We investigated the effects of teduglutide in the modulation of proliferation and differentiation in human Caco-2 intestinal epithelial cells at a basic science laboratory. This was an in vitro study using Caco-2 cells, a human-derived intestinal epithelial cell line commonly used to model enterocytic biology. EXPOSURE Cells were exposed to teduglutide or vehicle control. MAINOUTCOMESAND MEASURES We analyzed the cell cycle by bromodeoxyuridine incorporation or propidium iodide staining and flow cytometry and measured cell proliferation by 3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium (MTS) assay. We used quantitative reverse transcription–polymerase chain reaction to assay the expression of the enterocytic differentiation markers villin, sucrase-isomaltase, glucose transporter 2 (GLUT2), and dipeptidyl peptidase 4 (DPP-4), as well as that of the putative differentiation signals schlafen 12 (SLFN12) and caudal-related homeobox intestine-specific transcription factor (Cdx2). Villin promoter activity was measured by a luciferase-based assay. RESULTS The MTS assay demonstrated that teduglutide increased cell numbers by a mean (SD) of 10% (2%) over untreated controls at a maximal 500nM (n = 6, P < .05). Teduglutide increased bromodeoxyuridine-positive cells vs untreated controls by a mean (SD

  5. Geochemical Characterization Using Geophysical Data and Markov Chain Monte Carlo Methods

    NASA Astrophysics Data System (ADS)

    Chen, J.; Hubbard, S.; Rubin, Y.; Murray, C.; Roden, E.; Majer, E.

    2002-12-01

    Although the spatial distribution of geochemical parameters is extremely important for many subsurface remediation approaches, traditional characterization of those parameters is invasive and laborious, and thus is rarely performed sufficiently to describe natural hydrogeological variability at the field-scale. This study is an effort to jointly use multiple sources of information, including noninvasive geophysical data, for geochemical characterization of the saturated and anaerobic portion of the DOE South Oyster Bacterial Transport Site in Virginia. Our data set includes hydrogeological and geochemical measurements from five boreholes and ground-penetrating radar (GPR) and seismic tomographic data along two profiles that traverse the boreholes. The primary geochemical parameters are the concentrations of extractable ferrous iron Fe(II) and ferric iron Fe(III). Since iron-reducing bacteria can reduce Fe(III) to Fe(II) under certain conditions, information about the spatial distributions of Fe(II) and Fe(III) may indicate both where microbial iron reduction has occurred and in which zone it is likely to occur in the future. In addition, as geochemical heterogeneity influences bacterial transport and activity, estimates of the geochemical parameters provide important input to numerical flow and contaminant transport models geared toward bioremediation. Motivated by our previous research, which demonstrated that crosshole geophysical data could be very useful for estimating hydrogeological parameters, we hypothesize in this study that geochemical and geophysical parameters may be linked through their mutual dependence on hydrogeological parameters such as lithofacies. We attempt to estimate geochemical parameters using both hydrogeological and geophysical measurements in a Bayesian framework. Within the two-dimensional study domain (12m x 6m vertical cross section divided into 0.25m x 0.25m pixels), geochemical and hydrogeological parameters were considered as data

  6. On the mechanical analogue of DNA.

    PubMed

    Yakushevich, Ludmila

    2017-03-01

    The creation of mechanical analogues of biological systems is known as a useful instrument that helps to understand better the dynamical mechanisms of the functioning of living organisms. Mechanical analogues of biomolecules are usually constructed for imitation of their internal mobility, which is one of the most important properties of the molecules. Among the different types of internal motions, angular oscillations of nitrous bases are of special interest because they make a substantial contribution to the base pairs opening that in turn is an important element of the process of the DNA-protein recognition. In this paper, we investigate the possibility to construct a mechanical analogue for imitation of angular oscillations of nitrous bases in inhomogeneous DNA. It is shown that the analogue has the form of a mechanical chain of non-identical pendulums that oscillate in the gravitational field of the Earth and coupled by identical springs. The masses and lengths of pendulums, as well as the distances between neighboring pendulums and the rigidity of springs are calculated. To illustrate the approach, we present the result of construction of the mechanical analogue of the fragment of the sequence of bacteriophage T7D.

  7. Analogue Downscaling of Seasonal Rainfall Forecasts

    NASA Astrophysics Data System (ADS)

    Charles, A. N.; Timbal, B.; Hendon, H.

    2010-12-01

    We have taken an existing statistical downscaling model (SDM), based on meteorological analogues that was developed for downscaling climate change projections (Timbal et al 2009), and applied it in the seasonal forecasting context to produce downscaled rainfall hindcasts from a coupled model seasonal forecast system (POAMA). Downscaling of POAMA forecasts is required to provide seasonal climate information at local scales of interest. Analogue downscaling is a simple technique to generate rainfall forecasts appropriate to the local scale by conditioning on the large scale predicted GCM circulation and the local topography and climate. Analogue methods are flexible and have been shown to produce good results when downscaling 20th century South Eastern Australian rainfall output from climate models. A set of re-forecasts for three month rainfall at 170 observing stations in the South Murray Darling region of Australia were generated using predictors from the POAMA re-forecasts as input for the analogue SDM. The predictors were optimised over a number of different GCMS in previous climate change downscaling studies. Downscaling with the analogue SDM results in predicted rainfall with realistic variance while maintaining the modest predictive skill of the dynamical model. Evaluation of the consistency between the large scale mean of downscaled and direct GCM output precipitation is encouraging.

  8. Characterization of CO2-induced (?) bleaching phenomena in German red bed sediments by combined geochemical and evolved gas analysis

    NASA Astrophysics Data System (ADS)

    Hilse, Ulrike; Goepel, Andreas; Pudlo, Dieter; Heide, Klaus; Gaupp, Reinhard

    2010-05-01

    We investigated varied coloured Buntsandstein and Rotliegend sandstones in Central Germany (Thuringian Vorderrhön, Altmark) by thermogravimetric/pyrolytic (DEGAS- directly coupled evolved gas analysis) and geochemical (ICP-MS/OES) means to evaluate geochemical/mineralogical characteristics of red bed rocks and their presumably altered, bleached modifications. Commonly bleaching of primary red bed sediments is regarded as a result of fluid-rock reactions by the participation of CO2. This study is performed in the framework of the special research program 'GEOTECHNOLOGIEN' (funded by the German Ministry of Education and Research - BMBF) and is part of two BMBF sponsored projects - 'COMICOR', an analogue study on potential effects of CO2-bearing fluids on Buntsandstein and Rotliegend deposits in Hesse and Thuringia and 'CLEAN', an enhanced gas recovery (EGR) pilot project in cooperation with GDF SUEZ E&P Deutschland GmbH. The intention of CLEAN is to evaluate the feasibility of EGR techniques and the suitability of depleted natural gas reservoirs for potential industrial CO2 sequestration projects. According to rock colour variations two slices of handspecimens (M49, A1) were split into 12 and 15 equally sized samples for analytical work. The medium grained Lower Buntsandstein sample M49 from Thuringia is of fluvial origin and partially bleached with transitions from red (unbleached) to light colours (bleached). Bulk rock geochemistry of red bed and bleached subsamples of M49 are almost similar, including rare earth element (REE) content. Only the content of iron and related metals is depleted in bleached samples compared to the red bed types. All PAAS normalized pattern of M49 show positive Eu and slightly negative Ce anomalies, most likely caused by the presence of apatite and illite in the rocks. The degassing behavior observed by DEGAS of M49 subsamples is mainly controlled by the breakdown of sheet silicates, hydroxides and hydrates, as well as of carbonates and

  9. Significance of targeting polyamine metabolism as an antineoplastic strategy: unique targets for polyamine analogues.

    PubMed

    Casero, Robert A; Frydman, Benjamin; Stewart, Tracy Murray; Woster, Patrick M

    2005-01-01

    The polyamines, putrescine, spermidine, and spermine, are naturally occurring polycationic alkylamines that are absolutely required for eukaryotic cell growth. Importantly, the polyamine metabolic pathway, as well as the requirement of polyamines for cell growth, is frequently dysregulated in cancer cells, thus providing a unique set of targets for therapeutic intervention. Ornithine decarboxylase (ODC), a rate-limiting enzyme in polyamine biosynthesis, is frequently up-regulated in preneoplastic cells, and has been implicated as an oncogene in multiple tumor types. Several model systems have demonstrated that inhibition of ODC's enzymatic activity and down-regulation of its expression are rational strategies for both chemotherapy and chemoprevention. Specific inhibitors of ODC, most notably 2-difluoromethylornithine (DFMO), have been used experimentally to validate polyamine metabolism as an antineoplastic strategy. However, multiple biochemical and clinical limitations to these ODC-targeting strategies minimize their value as therapeutic tools. Included among these limitations are poor bioavailability of the inhibitor, and the compensatory up-regulation of polyamine metabolism and transport that allow tumor cells to escape the growth inhibitory effects of blockers specifically targeting ODC. As a strategy to overcome the limitations of direct enzyme inhibition, several groups have pursued the design of polyamine analogues that specifically target the dysregulated polyamine metabolism found in tumors. These analogues have been developed specifically to target the specific polyamine transporter, thus competing with circulating natural polyamines. Additionally, most of the analogues examined thus far maintain the regulatory function of the natural polyamines, but are unable to functionally substitute for them in promoting growth. Specifically, individual analogues have demonstrated the ability to down-regulate each of the biosynthetic enzymes without causing

  10. Pharmacologic profiles of investigational kisspeptin/metastin analogues, TAK-448 and TAK-683, in adult male rats in comparison to the GnRH analogue leuprolide.

    PubMed

    Matsui, Hisanori; Masaki, Tsuneo; Akinaga, Yumiko; Kiba, Atsushi; Takatsu, Yoshihiro; Nakata, Daisuke; Tanaka, Akira; Ban, Junko; Matsumoto, Shin-ichi; Kumano, Satoshi; Suzuki, Atsuko; Ikeda, Yukihiro; Yamaguchi, Masashi; Watanabe, Tatsuya; Ohtaki, Tetsuya; Kusaka, Masami

    2014-07-15

    Kisspeptin/metastin, a hypothalamic peptide, plays a pivotal role in controlling gonadotropin-releasing hormone (GnRH) neurons, and we have shown that continuous subcutaneous administration of kisspeptin analogues suppresses plasma testosterone in male rats. This study examined pharmacologic profiles of investigational kisspeptin analogues, TAK-448 and TAK-683, in male rats. Both analogues showed high receptor-binding affinity and potent and full agonistic activity for rat KISS1R, which were comparable to natural peptide Kp-10. A daily subcutaneous injection of TAK-448 and TAK-683 (0.008-8μmol/kg) for consecutive 7 days initially induced an increase in plasma luteinizing hormone and testosterone levels; however, after day 7, plasma hormone levels and genital organ weights were reduced. Continuous subcutaneous administrations of TAK-448 (≥10pmol/h, ca. 0.7nmol/kg/day) and TAK-683 (≥30pmol/h, ca. 2.1nmol/kg/day) induced a transient increase in plasma testosterone, followed by abrupt reduction of plasma testosterone to castrate levels within 3-7 days. This profound testosterone-lowering effect was sustained throughout 4-week dosing periods. At those dose levels, the weights of the prostate and seminal vesicles were reduced to castrate levels. These suppressive effects of kisspeptin analogues were more rapid and profound than those induced by the GnRH agonist analogue leuprolide treatment. In addition, TAK-683 reduced plasma prostate specific antigen (PSA) in the JDCaP androgen-dependent prostate cancer rat model. Thus, chronic administration of kisspeptin analogues may hold promise as a novel therapeutic approach for suppressing reproductive functions and hormone-related diseases such as prostate cancer. Further studies are warranted to elucidate clinical significance of TAK-448 and TAK-683.

  11. GABAA Receptor Modulation by Etomidate Analogues

    PubMed Central

    Pejo, Ervin; Santer, Peter; Wang, Lei; Dershwitz, Philip; Husain, S. Shaukat; Raines, Douglas E.

    2015-01-01

    Background Etomidate is a highly potent anesthetic agent that is believed to produce hypnosis by enhancing γ-aminobutyric acid type A (GABAA) receptor function. We characterized the GABAA receptor and hypnotic potencies of etomidate analogues. We then used computational techniques to build statistical and graphical models that relate the potencies of these etomidate analogues to their structures in order to identify the specific molecular determinants of potency. Methods GABAA receptor potencies were defined with voltage-clamp electrophysiology using α1β3γ2 receptors harboring a channel mutation (α1(L264T)) that enhances anesthetic sensitivity (n = 36 – 60 measurements per concentration-response curve). The hypnotic potencies of etomidate analogues were defined using a loss of righting reflexes assay in Sprague Dawley rats (n = 9 – 21 measurements per dose-response curve). Three-dimensional quantitative structure-activity relationships were determined in silico using comparative molecular field analysis. Results The GABAA receptor and hypnotic potencies of etomidate and the etomidate analogues ranged by 91-fold and 53-fold, respectively. These potency measurements were significantly correlated (r2 = 0.72), but neither measurement correlated with drug hydrophobicity (r2 = 0.019 and 0.005, respectively). Statistically significant and predictive comparative molecular field analysis models were generated and a pharmacophore model was built that revealed both the structural elements in etomidate analogues associated with high potency and the interactions that these elements make with the etomidate binding site. Conclusion There are multiple specific structural elements in etomidate and etomidate analogues that mediate GABAA receptor modulation. Modifying any one element can alter receptor potency by an order of magnitude or more. PMID:26691905

  12. Geochemical surveys in the United States in relation to health.

    USGS Publications Warehouse

    Tourtelot, H.A.

    1979-01-01

    Geochemical surveys in relation to health may be classified as having one, two or three dimensions. One-dimensional surveys examine relations between concentrations of elements such as Pb in soils and other media and burdens of the same elements in humans, at a given time. The spatial distributions of element concentrations are not investigated. The primary objective of two-dimensional surveys is to map the distributions of element concentrations, commonly according to stratified random sampling designs based on either conceptual landscape units or artificial sampling strata, but systematic sampling intervals have also been used. Political units have defined sample areas that coincide with the units used to accumulate epidemiological data. Element concentrations affected by point sources have also been mapped. Background values, location of natural or technological anomalies and the geographic scale of variation for several elements often are determined. Three-dimensional surveys result when two-dimensional surveys are repeated to detect environmental changes. -Author

  13. New optimized piperamide analogues with potent in vivo hypotensive properties.

    PubMed

    de Mattos Duarte, Carolina; Verli, Hugo; de Araújo-Júnior, João Xavier; de Medeiros, Isac Almeida; Barreiro, Eliezer J; Fraga, Carlos Alberto Manssour

    2004-12-01

    We describe herein the structural optimization of new piperamide analogues, designed from two natural prototypes, piperine 1 and piperdardine 2, obtained from Piper tuberculatum Jacq. (Piperaceae). Molecular modeling studies using semiempirical AM1 method were made in order to establish rational modifications to optimize them by molecular simplification. The targeted compounds (10) and (11) were respectively obtained using benzaldehyde (12) and para-anisaldehyde (13) as starting materials. 1H NMR spectra showed that the target compounds were diastereoselectively obtained as the (E)-isomer, the same geometry of the natural prototypes. These new synthetic amides presented significant hypotensive effects in cardiovascular essays using in vivo methodologies. Compound 11 (N-[5-(4'-methoxyphenyl)-2(E)-pentenoyl]thiomorpholine) showed a potency 10,000 times greater than its prototype 5, evidencing an optimization of the molecular architecture for this class of hypotensive drug candidates.

  14. Total Synthesis and Evaluation of Phostriecin and Key Structural Analogues

    PubMed Central

    Burke, Christopher P.; Swingle, Mark R.; Honkanen, Richard E.; Boger, Dale L.

    2010-01-01

    Full details of the total synthesis of phostriecin (2), the assignment of its relative and absolute stereochemistry, and the resultant structural reassignment of the natural product previously represented as sultriecin (1), a phosphate versus sulfate monoester, are detailed. Studies with authentic material confirmed that phostriecin, but not sultriecin, is an effective and selective inhibitor of protein phosphatase 2A (PP2A) defining a mechanism of action responsible for its antitumor activity. The extension of the studies to the synthesis and evaluation of a series of key synthetic analogues is disclosed that highlights the importance of the natural product phosphate monoester (vs sulfate or free alcohol, inactive and >250-fold), the α,β-unsaturated lactone (12-fold), and the hydrophobic Z,Z,E-triene tail (C12–C22, ca. 200-fold) including the unique importance of its unsaturation (50-fold, and no longer PP2A selective). PMID:20669916

  15. Classical Simulated Annealing Using Quantum Analogues

    NASA Astrophysics Data System (ADS)

    La Cour, Brian R.; Troupe, James E.; Mark, Hans M.

    2016-08-01

    In this paper we consider the use of certain classical analogues to quantum tunneling behavior to improve the performance of simulated annealing on a discrete spin system of the general Ising form. Specifically, we consider the use of multiple simultaneous spin flips at each annealing step as an analogue to quantum spin coherence as well as modifications of the Boltzmann acceptance probability to mimic quantum tunneling. We find that the use of multiple spin flips can indeed be advantageous under certain annealing schedules, but only for long anneal times.

  16. Insulin analogues: action profiles beyond glycaemic control.

    PubMed

    Eckardt, Kristin; Eckel, Jürgen

    2008-02-01

    A variety of studies have documented significant improvements in the treatment of type 1 and 2 diabetes after the introduction of artificial insulins. This review gives an overview of insulin analogues which are currently approved for therapeutical use. Clinical data regarding the efficiency to control blood glucose level as well as improving HbA1c level in comparison to conventional insulin preparations in type 1 and 2 diabetic patients are summarized. Furthermore, special features of insulin analogues regarding their signalling properties are discussed with focus on the proliferative effects of insulin glargine as well as some recent data of insulin detemir.

  17. Seeking a geochemical identifier for authigenic carbonate

    PubMed Central

    Zhao, Ming-Yu; Zheng, Yong-Fei; Zhao, Yan-Yan

    2016-01-01

    Authigenic carbonate was recently invoked as a third major global carbon sink in addition to primary marine carbonate and organic carbon. Distinguishing the two carbonate sinks is fundamental to our understanding of Earth's carbon cycle and its role in regulating the evolution of atmospheric oxygen. Here, using microscale geochemical measurements of carbonates in Early Triassic strata, we show that the growth of authigenic carbonate follows a different trajectory from primary marine carbonate in a cross-plot of uranium concentration and carbon isotope composition. Thus, a combination of the two geochemical variables is able to distinguish between the two carbonate sinks. The temporal distribution of authigenic carbonates in the Early Triassic strata suggests that the increase in the extent of carbonate authigenesis acted as a negative feedback to the elevated atmospheric CO2 concentration. PMID:26947562

  18. Dicentrine Analogue-Induced G2/M Arrest and Apoptosis through Inhibition of Topoisomerase II Activity in Human Cancer Cells.

    PubMed

    Lin, Huei-Fang; Huang, Huey-Lan; Liao, Jyh-Fei; Shen, Chien-Chang; Huang, Ray-Ling

    2015-07-01

    Lindera megaphylla has been traditionally used as an antineoplastic and wound healing remedy. We previously demonstrated the antitumor effects of D-dicentrine, a natural aporphine alkaloid from the root of L. megaphylla. To generate analogues, series of phenanthrene alkaloids from D-dicentrine were synthesized by degradation with ethyl chloroformate in pyridine, base hydrolysis, and N-alkylation. In this study, we demonstrated that one of the synthesized D-dicentrine analogues (here after designated as analogue 1) exhibited more potent cytotoxic effects than D-dicentrine in colon adenocarcinoma, hepatoma, leukemia, and epidermoid carcinoma cells. We performed cell cycle and apoptotic analysis by flow cytometry, an apoptotic DNA detection ELISA assay, and topoisomerase II activity by the kinetoplast DNA concatenation assay for studying their cytotoxic mechanisms. We found that both D-dicentrine and analogue 1 induced apoptosis and G2/M arrest in HL-60 leukemia cells. The percentage of apoptotic cells induced by analogue 1 was 4.5-fold higher than that induced by D-dicentrine as evident from measuring the amount of histone-bound DNA fragments. Moreover, we found that analogue 1 was 28-fold more potent than D-dicentrine for inhibition of topoisomerase II activity by the kinetoplast DNA concatenation assay. Our findings indicate that D-dicentrine analogue 1 is very promising as a potential antitumor agent for future study.

  19. Geochemical engineering and materials program plan

    SciTech Connect

    1982-08-01

    The Department of Energy (DOE) was designated as lead agency in discharging the overall legislative mandate for federal R&D to assist the private sector in developing appropriate technology for exploiting geothermal energy resources. The Geochemical Engineering and Materials (GEM) Program was conceived, as part of DOE'S overall strategy, to address specific and plant-wide problems and uncertainties in the use of materials and in geochemical engineering. This program assists industry in the conduct of long-term,high-risk R&D needed to overcome the significant technical and economic GEM-related obstacles faced by developers and potential developers of this alternative energy source. The program focuses on: (1) Increasing the knowledge about the properties of materials and their performance under geothermal energy system conditions; (2) Developing and utilizing more reliable and/or cost-effective materials than previously available; and (3) Developing a greater understanding of and control over geochemical processes during fluid production and transport, energy conversion, and waste management. As a stand-alone program and as support to other DOE geothermal technology development programs, the GEM Program contributes to the feasibility of designing and operating efficient, reliable, and safe fluid handling and energy conversion systems.

  20. Design of novel analogues of short antimicrobial peptide anoplin with improved antimicrobial activity.

    PubMed

    Wang, Yang; Chen, Jianbo; Zheng, Xin; Yang, Xiaoli; Ma, Panpan; Cai, Ying; Zhang, Bangzhi; Chen, Yuan

    2014-12-01

    Currently, novel antibiotics are urgently required to combat the emergence of drug-resistant bacteria. Antimicrobial peptides with membrane-lytic mechanism of action have attracted considerable interest. Anoplin, a natural α-helical amphiphilic antimicrobial peptide, is an ideal research template because of its short sequence. In this study, we designed and synthesized a group of analogues of anoplin. Among these analogues, anoplin-4 composed of D-amino acids displayed the highest antimicrobial activity due to increased charge, hydrophobicity and amphiphilicity. Gratifyingly, anoplin-4 showed low toxicity to host cells, indicating high bacterial selectivity. Furthermore, the mortality rate of mice infected with Escherichia coli was significantly reduced by anoplin-4 treatment relative to anoplin. In conclusion, anoplin-4 is a novel anoplin analogue with high antimicrobial activity and enzymatic stability, which may represent a potent agent for the treatment of infection.

  1. Synthesis and conformational analysis of 17alpha,21-cyclo-22-unsaturated analogues of calcitriol.

    PubMed

    Riveiros, Ricardo; Rumbo, Antonio; Sarandeses, Luis A; Mouriño, Antonio

    2007-07-20

    Six new calcitriol analogues, conformationally restricted at their side chain by the introduction of both a cyclopropane ring at C17-C20 and a double or triple bond at C22, were synthesized using the Wittig-Horner approach to construct the triene system. The six CD-ring and side-chain bearing fragments were prepared from ketone 14 by a divergent route to generate both series of epimers at C20, followed by stereoselective cyclopropanation. The (E)-alkenyl side chain was synthesized by means of a Wittig reaction. The alkynyl side chain was prepared by Corey-Fuchs homologation, followed by alkylation. The (Z)-alkenyl side chain was prepared from the previous alkyne by partial hydrogenation. The 20-epi analogues bind more strongly to VDR than the corresponding analogues with the C20 natural stereochemistry. These results can be reasoned by conformational analysis and hydrophobic interactions with the VDR ligand-binding domain.

  2. Component-based syntheses of trioxacarcin A, DC-45-A1 and structural analogues

    NASA Astrophysics Data System (ADS)

    Magauer, Thomas; Smaltz, Daniel J.; Myers, Andrew G.

    2013-10-01

    The trioxacarcins are polyoxygenated, structurally complex natural products that potently inhibit the growth of cultured human cancer cells. Here we describe syntheses of trioxacarcin A, DC-45-A1 and structural analogues by late-stage stereoselective glycosylation reactions of fully functionalized, differentially protected aglycon substrates. Key issues addressed in this work include the identification of an appropriate means to activate and protect each of the two 2-deoxysugar components, trioxacarcinose A and trioxacarcinose B, as well as a viable sequencing of the glycosidic couplings. The convergent, component-based sequence we present allows for rapid construction of structurally diverse, synthetic analogues that would be inaccessible by any other means, in amounts required to support biological evaluation. Analogues that arise from the modification of four of five modular components are assembled in 11 steps or fewer. The majority of these are found to be active in antiproliferative assays using cultured human cancer cells.

  3. Synthesis and Structure activity relationships of EGCG Analogues, A Recently Identified Hsp90 Inhibitor

    PubMed Central

    Khandelwal, Anuj; Hall, Jessica

    2014-01-01

    Epigallocatechin-3-gallate (EGCG), the principal polyphenol isolated from green tea, was recently shown to inhibit Hsp90, however structure-activity relationships for this natural product have not yet been produced. Herein, we report the synthesis and biological evaluation of EGCG analogues to establish structure-activity relationships between EGCG and Hsp90. All four rings as well as the linker connecting the C- and the D-rings were systematically investigated, which led to the discovery of compounds that inhibit Hs90 and display improvement in efficacy over EGCG. Anti-proliferative activity of all the analogues was determined against MCF-7 and SKBr3 cell lines and Hsp90 inhibitory activity of four most potent analogues was further evaluated by western blot analyses and degradation of Hsp90-dependent client proteins. Prenyl substituted aryl ester of 3,5-dihydroxychroman-3-ol ring system was identified as novel scaffold that exhibit Hsp90 inhibitory activity. PMID:23834230

  4. Design, synthesis and cytotoxic evaluation of o-carboxamido stilbene analogues.

    PubMed

    Azmi, Mohamad Nurul; Din, Mohd Fadzli Md; Kee, Chin Hui; Suhaimi, Munirah; Ping, Ang Kheng; Ahmad, Kartini; Nafiah, Mohd Azlan; Thomas, Noel F; Mohamad, Khalit; Hoong, Leong Kok; Awang, Khalijah

    2013-11-27

    Resveratrol, a natural stilbene found in grapes and wines exhibits a wide range of pharmacological properties. Resveratrol is also known as a good chemopreventive agent for inhibiting carcinogenesis processes that target kinases, cyclooxygenases, ribonucleotide reductase and DNA polymerases. A total of 19 analogues with an amide moiety were synthesized and the cytotoxic effects of the analogues on a series of human cancer cell lines are reported. Three compounds 6d, 6i and 6n showed potent cytotoxicity against prostate cancer DU-145 (IC50=16.68 µM), colon cancer HT-29 (IC50=7.51 µM) and breast cancer MCF-7 (IC50=21.24 µM), respectively, which are comparable with vinblastine. The resveratrol analogues were synthesized using the Heck method.

  5. Geochemical and isotopic constraints on the tectonic setting of Serra dos Carajas belt, eastern Para, Brazil

    NASA Technical Reports Server (NTRS)

    Olszewski, W. J., Jr.; Gibbs, A. K.; Wirth, K. R.

    1986-01-01

    The lower part of the Serra dos Carajas belt is the metavolcanic and metasedimentary Grao para Group (GPG). The GPG is thought to unconformably overlie the older (but undated) Xingu Complex, composed of medium and high-grade gneisses and amphibolite and greenstone belts. The geochemical data indicate that the GPG has many features in common with ancient and modern volcanic suites erupted through continental crust. The mafic rocks clearly differ from those of most Archean greenstone belts, and modern MORB, IAB, and hot-spot basalts. The geological, geochemical, and isotopic data are all consistent with deposition on continental crust, presumably in a marine basin formed by crustal extension. The isotopic data also suggest the existence of depleted mantle as a source for the parent magmas of the GPG. The overall results suggest a tectonic environment, igneous sources, and petrogenesis similar to many modern continental extensional basins, in contrast to most Archean greenstone belts. The Hammersley basin in Australia and the circum-Superior belts in Canada may be suitable Archean and Proterozoic analogues, respectively.

  6. Synthesis, DNA Binding and Antitumor Evaluation of Styelsamine and Cystodytin Analogues

    PubMed Central

    Fong, Hugo K. H.; Copp, Brent R.

    2013-01-01

    A series of N-14 sidechain substituted analogues of styelsamine (pyrido[4,3,2-mn]acridine) and cystodytin (pyrido[4,3,2-mn]acridin-4-one) alkaloids have been prepared and evaluated for their DNA binding affinity and antiproliferative activity towards a panel of human tumor cell lines. Overall it was found that styelsamine analogues were stronger DNA binders, with the natural products styelsamines B and D having particularly high affinity (Kapp 5.33 × 106 and 3.64 × 106 M−1, respectively). In comparison, the cystodytin iminoquinone alkaloids showed lower affinity for DNA, but were typically just as active as styelsamine analogues at inhibiting proliferation of tumor cells in vitro. Sub-panel selectivity towards non-small cell lung, melanoma and renal cancer cell lines were observed for a number of the analogues. Correlation was observed between whole cell activity and clogP, with the most potent antiproliferative activity being observed for 3-phenylpropanamide analogues 37 and 41 (NCI panel average GI50 0.4 μM and 0.32 μM, respectively) with clogP ~4.0–4.5. PMID:23358307

  7. Synthesis and Evaluation of Novel Triterpene Analogues of Ursolic Acid as Potential Antidiabetic Agent

    PubMed Central

    Wu, Panpan; Zheng, Jie; Huang, Tianming; Li, Dianmeng; Hu, Qingqing; Cheng, Anming; Jiang, Zhengyun; Jiao, Luoying; Zhao, Suqing; Zhang, Kun

    2015-01-01

    Ursolic acid (UA) is a naturally bioactive compound that possesses potential anti-diabetic activity. The relatively safe and effective molecule intrigued us to further explore and to improve its anti-diabetic activity. In the present study, a series of novel UA analogues was synthesized and their structures were characterized. Their bioactivities against the α-glucosidase from baker's yeast were determined in vitro. The results suggested that most of the analogues exhibited significant inhibitory activity, especially analogues 8b and 9b with the IC50 values of 1.27 ± 0.27 μM (8b) and 1.28 ± 0.27 μM (9b), which were lower than the other analogues and the positive control. The molecular docking and 2D-QSAR studies were carried out to prove that the C-3 hydroxyl could interact with the hydrophobic region of the active pocket and form hydrogen bonds to increase the binding affinity of ligand and the homology modelling protein. Thus, these results will be helpful for understanding the relationship between binding mode and bioactivity and for designing better inhibitors from UA analogues. PMID:26406581

  8. VNIR spectral modeling of Mars analogue rocks: first results

    NASA Astrophysics Data System (ADS)

    Pompilio, L.; Roush, T.; Pedrazzi, G.; Sgavetti, M.

    Knowledge regarding the surface composition of Mars and other bodies of the inner solar system is fundamental to understanding of their origin, evolution, and internal structures. Technological improvements of remote sensors and associated implications for planetary studies have encouraged increased laboratory and field spectroscopy research to model the spectral behavior of terrestrial analogues for planetary surfaces. This approach has proven useful during Martian surface and orbital missions, and petrologic studies of Martian SNC meteorites. Thermal emission data were used to suggest two lithologies occurring on Mars surface: basalt with abundant plagioclase and clinopyroxene and andesite, dominated by plagioclase and volcanic glass [1,2]. Weathered basalt has been suggested as an alternative to the andesite interpretation [3,4]. Orbital VNIR spectral imaging data also suggest the crust is dominantly basaltic, chiefly feldspar and pyroxene [5,6]. A few outcrops of ancient crust have higher concentrations of olivine and low-Ca pyroxene, and have been interpreted as cumulates [6]. Based upon these orbital observations future lander/rover missions can be expected to encounter particulate soils, rocks, and rock outcrops. Approaches to qualitative and quantitative analysis of remotely-acquired spectra have been successfully used to infer the presence and abundance of minerals and to discover compositionally associated spectral trends [7-9]. Both empirical [10] and mathematical [e.g. 11-13] methods have been applied, typically with full compositional knowledge, to chiefly particulate samples and as a result cannot be considered as objective techniques for predicting the compositional information, especially for understanding the spectral behavior of rocks. Extending the compositional modeling efforts to include more rocks and developing objective criteria in the modeling are the next required steps. This is the focus of the present investigation. We present results of

  9. Controls on OIB and MORB Geochemical Variabilty

    NASA Astrophysics Data System (ADS)

    Shorttle, O.; Maclennan, J.

    2014-12-01

    The geochemical variability preserved in Ocean Island and Mid-ocean ridge basalt (MORB) is a key tracer of the magmatic storage and transport processes they experience during their ascent through the mantle and crust. The effect of these processes is to collapse the huge diversity of melt compositions predicted to form during polybaric fractional melting of a lithologically heterogeneous mantle, into the narrow range we see expressed in most ocean island and mid-ocean ridge settings. Magma mixing can therefore be seen as contaminating the variance structure of primitive mantle melts, akin to the way in which wall-rock assimilation contaminates melts by chemical addition. The key observation from the melt inclusion and whole-rock records from ocean islands such as Iceland, is that as crystallisation proceeds mixing in magma chambers progressively reduces geochemical variability, until by ~5wt% MgO almost all primary chemical diversity has been lost. These chemical systematics allow us to extend the observations made at ocean islands to make predictions about how mixing processes should operate in MORB generally and the key factors controlling mixing efficiency: melt flow out of the mantle, crustal thickness, magma supply rate, and by extension spreading rate, and mantle potential temperature. However, with its low sampling density, the global MORB database does not easily allow testing of these hypotheses. We have developed a novel geospatial statistical analysis to bridge the gap between observations made on a small scale - at single ocean islands and ridge segments - to the entire global dataset of MORB chemistry. By analysing the geochemical variance in MORB over a range of bandwidths we have captured the ~200km lengthscale at which the simple relationships between geochemical variability and MgO appear. Our results demonstrate that on short lengthscales mantle chemical structure and magmatic processes operate coherently in destruction of geochemical variability

  10. A geochemical sampling technique for use in areas of active alpine glaciation: an application from the central Alaska Range

    USGS Publications Warehouse

    Stephens, G.C.; Evenson, E.B.; Detra, D.E.

    1990-01-01

    In mountainous regions containing extensive glacier systems there is a lack of suitable material for conventional geochemical sampling. As a result, in most geochemical sampling programs a few stream-sediment samples collected at, or near, the terminus of valley glaciers are used to evaluate the mineral potential of the glaciated area. We have developed and tested a technique which utilizes the medial moraines of valley glaciers for systematic geochemical exploration of the glacial catchment area. Moraine sampling provides geochemical information that is site-specific in that geochemical anomalies can be traced directly up-ice to bedrock sources. Traverses were made across the Trident and Susitna glaciers in the central Alaska Range where fine-grained (clay to sand size) samples were collected from each medial moraine. These samples were prepared and chemically analyzed to determine the concentration of specific elements. Fifty pebbles were collected at each moraine for archival purposes and for subsequent lithologic identification. Additionally, fifty cobbles and fifty boulders were examined and described at each sample site to determine the nature and abundance of lithologies present in the catchment area, the extent and nature of visible mineralization, the presence and intensity of hydrothermal alteration and the existence of veins, dikes and other minor structural features. Results from the central Alaska Range have delineated four distinct multi-element anomalies which are a response to potential mineralization up-ice from the medial moraine traverse. By integrating the lithologic, mineralogical and geochemical data the probable geological setting of the geochemical anomalies is determined. ?? 1990.

  11. Dumb holes: analogues for black holes.

    PubMed

    Unruh, W G

    2008-08-28

    The use of sonic analogues to black and white holes, called dumb or deaf holes, to understand the particle production by black holes is reviewed. The results suggest that the black hole particle production is a low-frequency and low-wavenumber process.

  12. CO2 Capture with Enzyme Synthetic Analogue

    SciTech Connect

    Cordatos, Harry

    2010-03-01

    Project overview provides background on carbonic anhydrase transport mechanism for CO2 in the human body and proposed approach for ARPA-E project to create a synthetic enzyme analogue and utilize it in a membrane for CO2 capture from flue gas.

  13. Solanapyrone analogues from a Hawaiian fungicolous fungus

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Four new solanayrone analogues (solanapyrones J-M; 1-4) have been isolated from an unidentified fungicolous fungus collected in Hawaii. The structures and relative configurations of these compounds were determined by analysis of ID NMR, 2D NMR, and MS data. Solanapyrone J(1) showed antifungal acti...

  14. Geochemical characteristics of an urban river: Geochemical contamination and urban stream syndrome

    NASA Astrophysics Data System (ADS)

    MacAvoy, S. E.; Connor, N.; Sarraino, S.; Frantz, D.; Bushaw-Newton, K. L.

    2013-12-01

    The Anacostia River in Washington, D.C. is among the 10 most contaminated rivers in the USA, containing sewage, metals, PAHs, and PCBs. The biogeochemical characteristics of urban rivers, including the Anacostia, remain largely unstudied. Here we examine the base-flow geochemistry of the tidal freshwater Anacostia over a two-year period (April 2010- April 2012), concentrating on water chemistry (pH, hardness, SAR, alkalinity, Ca, Mg, Na, K, Fe, Mn, Zn, Al, Ba, Ni, P, S, Sr, NO3, NH4, PO4) at 3 locations in the stream. Mean NO3was generally between 1.1 and 1.3 mg/L, although occasionally concentrations increased to 3-4 mg/L at all sites. NH4 was very low generally (0.0 to 0.3 mg/L) with occasional peaks of 1.5-3.9 mg/L downstream. A Principle Components Analysis of stream chemistry showed that the upstream site had two components that explained 34.2 and 29.2% of the data variance; PC1 was most strongly negatively correlated with Ca (-.896), Mg (-.585) and hardness (-.823), and was positively correlated with Ba (which is sometimes associated with disturbance), B, NO3, P, PO4, Sr and Al. PC2 was strongly correlated with Mg, K, S, Ni and NH4. Na was positively and significantly correlated with both components, but more so with PC1. At the middle and downstream sites, two components explained 41 to 44% (PC1) and 22 to 28% (PC2) of the data set variance respectively. The components were essentially the same as the upstream site, with the dominance switched. PC1 was positively and highly correlated with ions associated with bedrock components (Ca, Mg, K, Na, and pH but also S and NH4). PC2 was not positively correlated with any of the dominant geochemical variables, but was negatively correlated with Ca and K and positively correlated with NO3, Ba and Mn. The principle components analysis suggests that there is a strong geochemical component and weaker anion/nitrate component contributing to the ion distribution, and their relative dominance changes moving downstream

  15. [Dmt(1)]DALDA analogues modified with tyrosine analogues at position 1.

    PubMed

    Cai, Yunxin; Lu, Dandan; Chen, Zhen; Ding, Yi; Chung, Nga N; Li, Tingyou; Schiller, Peter W

    2016-08-01

    Analogues of [Dmt(1)]DALDA (H-Dmt-d-Arg-Phe-Lys-NH2; Dmt=2',6'-dimethyltyrosine), a potent μ opioid agonist peptide with mitochondria-targeted antioxidant activity were prepared by replacing Dmt with various 2',6'-dialkylated Tyr analogues, including 2',4',6'-trimethyltyrosine (Tmt), 2'-ethyl-6'-methyltyrosine (Emt), 2'-isopropyl-6'-methyltyrosine (Imt) and 2',6'-diethyltyrosine (Det). All compounds were selective μ opioid agonists and the Tmt(1)-, Emt(1) and Det(1)-analogues showed subnanomolar μ opioid receptor binding affinities. The Tmt(1)- and Emt(1)-analogues showed improved antioxidant activity compared to the Dmt(1)-parent peptide in the DPPH radical-scavenging capacity assay, and thus are of interest as drug candidates for neuropathic pain treatment.

  16. Electromagnetic induction in New Zealand: analogue model and field results

    NASA Astrophysics Data System (ADS)

    Chen, J.; Dosso, H. W.; Ingham, M.

    The behaviour of electric and magnetic variations over North Island (New Zealand) is studied with the aid of a laboratory analogue model. The source field frequencies used in the analogue modelling simulate naturally occurring geomagnetic variations of 5-120 min periods. In-phase and quadrature magnetic and electric fields for a selection of traverses for the modelled region of North Island are presented. Since North Island is of a relatively narrow cross-section, the field responses, even for inland locations, are expected to show strongly the effects of the surrounding ocean. The irregular coastlines, as well as the strait between North and South Islands, lead to coastal and inland field anomalies due to induced currents being deflected and channelled to produce localized current densities. The comparison of model results with field station measurements obtained earlier individually by Ingham and by Midha for sites in the northeastern, central, and southern (near Cook Strait) regions of North Island demonstrates the large role the ocean has in the observed field responses. Differences in the model and field results at some sites are expected and should reflect the effects of the local geology and the conductive substructure related to the complex tectonics of the region not simulated in the model.

  17. A new antiproliferative noscapine analogue: chemical synthesis and biological evaluation.

    PubMed

    Ghaly, Peter E; Abou El-Magd, Rabab M; Churchill, Cassandra D M; Tuszynski, Jack A; West, F G

    2016-06-28

    Noscapine, a naturally occurring opium alkaloid, is a widely used antitussive medication. Noscapine has low toxicity and recently it was also found to possess cytotoxic activity which led to the development of many noscapine analogues. In this paper we report on the synthesis and testing of a novel noscapine analogue. Cytotoxicity was assessed by MTT colorimetric assay using SKBR-3 and paclitaxel-resistant SKBR-3 breast cancer cell lines using different concentrations for both noscapine and the novel compound. Microtubule polymerization assay was used to determine the effect of the new compound on microtubules. To compare the binding affinity of noscapine and the novel compound to tubulin, we have done a fluorescence quenching assay. Finally, in silico methods using docking calculations were used to illustrate the binding mode of the new compound to α,β-tubulin. Our cytotoxicity results show that the new compound is more cytotoxic than noscapine on both SKBR-3 cell lines. This was confirmed by the stronger binding affinity of the new compound, compared to noscapine, to tubulin. Surprisingly, our new compound was found to have strong microtubule-destabilizing properties, while noscapine is shown to slightly stabilize microtubules. Our calculation indicated that the new compound has more binding affinity to the colchicine-binding site than to the noscapine site. This novel compound has a more potent cytotoxic effect on cancer cell lines than its parent, noscapine, and hence should be of interest as a potential anti-cancer drug.

  18. A new antiproliferative noscapine analogue: chemical synthesis and biological evaluation

    PubMed Central

    Ghaly, Peter E.; Abou El-Magd, Rabab M.; Churchill, Cassandra D. M.; Tuszynski, Jack A.; West, F. G.

    2016-01-01

    Noscapine, a naturally occurring opium alkaloid, is a widely used antitussive medication. Noscapine has low toxicity and recently it was also found to possess cytotoxic activity which led to the development of many noscapine analogues. In this paper we report on the synthesis and testing of a novel noscapine analogue. Cytotoxicity was assessed by MTT colorimetric assay using SKBR-3 and paclitaxel-resistant SKBR-3 breast cancer cell lines using different concentrations for both noscapine and the novel compound. Microtubule polymerization assay was used to determine the effect of the new compound on microtubules. To compare the binding affinity of noscapine and the novel compound to tubulin, we have done a fluorescence quenching assay. Finally, in silico methods using docking calculations were used to illustrate the binding mode of the new compound to α,β-tubulin. Our cytotoxicity results show that the new compound is more cytotoxic than noscapine on both SKBR-3 cell lines. This was confirmed by the stronger binding affinity of the new compound, compared to noscapine, to tubulin. Surprisingly, our new compound was found to have strong microtubule-destabilizing properties, while noscapine is shown to slightly stabilize microtubules. Our calculation indicated that the new compound has more binding affinity to the colchicine-binding site than to the noscapine site. This novel compound has a more potent cytotoxic effect on cancer cell lines than its parent, noscapine, and hence should be of interest as a potential anti-cancer drug. PMID:27777381

  19. A new antiproliferative noscapine analogue: chemical synthesis and biological evaluation.

    PubMed

    Ghaly, Peter E; El-Magd, Rabab M Abou; Churchill, Cassandra D M; Tuszynski, Jack A; West, F G

    2016-05-26

    Noscapine, a naturally occurring opium alkaloid, is a widely used antitussive medication. Noscapine has low toxicity and recently it was also found to possess cytotoxic activity which led to the development of many noscapine analogues. In this paper we report on the synthesis and testing of a novel noscapine analogue. Cytotoxicity was assessed by MTT colorimetric assay using SKBR-3 and paclitaxel-resistant SKBR-3 breast cancer cell lines using different concentrations for both noscapine and the novel compound. Microtubule polymerization assay was used to determine the effect of the new compound on microtubules. To compare the binding affinity of noscapine and the novel compound to tubulin, we have done a fluorescence quenching assay. Finally, in silico methods using docking calculations were used to illustrate the binding mode of the new compound to α,β-tubulin. Our cytotoxicity results show that the new compound is more cytotoxic than noscapine on both SKBR-3 cell lines. This was confirmed by the stronger binding affinity of the new compound, compared to noscapine, to tubulin. Surprisingly, our new compound was found to have strong microtubule-destabilizing properties, while noscapine is shown to slightly stabilize microtubules. Our calculation indicated that the new compound has more binding affinity to the colchicine-binding site than to the noscapine site. This novel compound has a more potent cytotoxic effect on cancer cell lines than its parent, noscapine, and hence should be of interest as a potential anti-cancer drug.

  20. A geochemical atlas of South Carolina--an example using data from the National Geochemical Survey

    USGS Publications Warehouse

    Sutphin, David M.

    2005-01-01

    National Geochemical Survey data from stream-sediment and soil samples, which have been analyzed using consistent methods, were used to create maps, graphs, and tables that were assembled in a consistent atlas format that characterizes the distribution of major and trace chemical elements in South Carolina. Distribution patterns of the elements in South Carolina may assist mineral exploration, agriculture, waste-disposal-siting issues, health, environmental, and other studies. This atlas is an example of how data from the National Geochemical Survey may be used to identify general or regional patterns of elemental occurrences and to provide a snapshot of element concentration in smaller areas.

  1. A geochemical perspective of Red Mountain: an unmined volcanogenic massive sulfide deposit in the Alaska Range

    USGS Publications Warehouse

    Giles, Stuart A.; Eppinger, Robert G.

    2014-01-01

    The U.S. Geological Survey (USGS) has investigated the environmental geochemistry of a group of unmined volcanogenic massive sulfide (VMS) deposits in the Bonnifield mining district, Alaska Range, east-central Alaska. The spectacularly colored Red Mountain deposit is the best exposed of these and provides excellent baseline geochemical data for natural environmental impacts of acidic rock drainage, metal dissolution and transport, and acidic salt and metal precipitation from an exposed and undisturbed VMS deposit.

  2. Quantitative comparisons of analogue models of brittle wedge dynamics

    NASA Astrophysics Data System (ADS)

    Schreurs, Guido

    2010-05-01

    Analogue model experiments are widely used to gain insights into the evolution of geological structures. In this study, we present a direct comparison of experimental results of 14 analogue modelling laboratories using prescribed set-ups. A quantitative analysis of the results will document the variability among models and will allow an appraisal of reproducibility and limits of interpretation. This has direct implications for comparisons between structures in analogue models and natural field examples. All laboratories used the same frictional analogue materials (quartz and corundum sand) and prescribed model-building techniques (sieving and levelling). Although each laboratory used its own experimental apparatus, the same type of self-adhesive foil was used to cover the base and all the walls of the experimental apparatus in order to guarantee identical boundary conditions (i.e. identical shear stresses at the base and walls). Three experimental set-ups using only brittle frictional materials were examined. In each of the three set-ups the model was shortened by a vertical wall, which moved with respect to the fixed base and the three remaining sidewalls. The minimum width of the model (dimension parallel to mobile wall) was also prescribed. In the first experimental set-up, a quartz sand wedge with a surface slope of ˜20° was pushed by a mobile wall. All models conformed to the critical taper theory, maintained a stable surface slope and did not show internal deformation. In the next two experimental set-ups, a horizontal sand pack consisting of alternating quartz sand and corundum sand layers was shortened from one side by the mobile wall. In one of the set-ups a thin rigid sheet covered part of the model base and was attached to the mobile wall (i.e. a basal velocity discontinuity distant from the mobile wall). In the other set-up a basal rigid sheet was absent and the basal velocity discontinuity was located at the mobile wall. In both types of experiments

  3. Geochemical analysis of layered outcrops using laser-induced breakdown spectroscopy (LIBS) - Implications for Mars exploration

    NASA Astrophysics Data System (ADS)

    Sobron, P.; Lefebvre, C.; Leveille, R. J.; Koujelev, A.; Haltigin, T.; Hongwei, D.; Wang, A.; Cabrol, N. A.; Zacny, K.; Craft, J.

    2012-12-01

    The chemistry and the stratigraphy of sedimentary, evaporative, and other types of deposits are indicators of their depositional environment and climate, and the evolution of these over time. Over the past eight years, the Mars Exploration Rovers (MER) have investigated several outcrops at Meridiani Planum and Gusev Crater. Compared to the MER, the capabilities of Curiosity to investigate outcrops and other deposits are enhanced because the rover incorporates a stand-off laser-induced breakdown spectroscopy (LIBS) instrument within the ChemCam suite. ChemCam's LIBS instrument has the capability to obtain chemical information from a large variety of targets at various distances, up to 7 m, including targets at a distance within stratigraphic layers non-accessible to other payload elements. In this work we demonstrate that semi-quantitative chemical stratigraphy can be very rapidly obtained by performing LIBS measurements on visually distinct layers within an outcrop at a terrestrial Mars analogue: the Atacama Desert, Chile. Such semi-quantitative chemical stratigraphy provides very valuable information on the distribution of elements within the analyzed layers, which can be used for tactical mission planning purposes. We performed laboratory laser-induced breakdown spectroscopy (LIBS) and laser Raman spectroscopy measurement on field samples from a layered outcrop from the Atacama Desert, Chile. This layered outcrop is a good terrestrial morphological analogue for similar formations that will likely be investigated by the Mars Science Laboratory on Gale crater. Our results demonstrate that LIBS can generate semi-quantitative chemical profiles in less than 1 min using automated data processing tools, and therefore the LIBS instrument can become an invaluable tactical tool on MSL for rapid geochemical survey of layered outcrops. The derived chemical profile at the terrestrial analogue is consistent with the range of minerals identified by Raman spectroscopy. In the

  4. Tryptophan analogues. 1. Synthesis and antihypertensive activity of positional isomers.

    PubMed

    Safdy, M E; Kurchacova, E; Schut, R N; Vidrio, H; Hong, E

    1982-06-01

    A series of tryptophan analogues having the carboxyl function at the beta-position was synthesized and tested for antihypertensive activity. The 5-methoxy analogue 46 exhibited antihypertensive activity in the rat via the oral route and was much more potent than the normal tryptophan analogue. The methyl ester was found to be a critical structural feature for activity.

  5. Antimicrobial and antibiofilm activity of quorum sensing peptides and Peptide analogues against oral biofilm bacteria.

    PubMed

    LoVetri, Karen; Madhyastha, Srinivasa

    2010-01-01

    Widespread antibiotic resistance is a major incentive for the investigation of novel ways to treat or prevent infections. Much effort has been put into the discovery of peptides in nature accompanied by manipulation of natural peptides to improve activity and decrease toxicity. The ever increasing knowledge about bacteria and the discovery of quorum sensing have presented itself as another mechanism to disrupt the infection process. We have shown that the natural quorum sensing (QS) peptide, competence-stimulating peptide (CSP), used by the caries causing bacteria Streptococcus mutans when used in higher than normally present concentrations can actually contribute to cell death in S. mutans. Using an analogue of this quorum sensing peptide (KBI-3221), we have shown it to be beneficial at decreasing biofilm of various Streptococcus species. This chapter looks at a number of assay methods to test the inhibitory effects of quorum sensing peptides and their analogues on the growth and biofilm formation of oral bacteria.

  6. In pursuit of natural product leads: synthesis and biological evaluation of 2-[3-hydroxy-2-[(3-hydroxypyridine-2-carbonyl)amino]phenyl]benzoxazole-4-carboxylic acid (A-33853) and its analogues: discovery of N-(2-benzoxazol-2-ylphenyl)benzamides as novel antileishmanial chemotypes.

    PubMed

    Tipparaju, Suresh K; Joyasawal, Sipak; Pieroni, Marco; Kaiser, Marcel; Brun, Reto; Kozikowski, Alan P

    2008-12-11

    The first synthesis and biological evaluation of antibiotic 31 (A-33853) and its analogues are reported. Initial screening for inhibition of L. donovani, T. b. rhodesiense, T. cruzi, and P. falciparum cultures followed by determination of IC(50) in L. donovani and cytotoxicity on L6 cells revealed 31 to be 3-fold more active than miltefosine, a known antileishmanial drug. Compounds 14, 15, and 25 selectively inhibited L. donovani at nanomolar concentrations and showed much lower cytotoxicity.

  7. Using Geochemical Indicators to Distinguish High Biogeochemical Activity in Sediments

    NASA Astrophysics Data System (ADS)

    Kenwell, A. M.; Navarre-Sitchler, A.; Prugue, R.; Spear, J. R.; Williams, K. H.; Maxwell, R. M.

    2014-12-01

    A better understanding of how microbial communities interact with their surroundings in physically and chemically heterogeneous subsurface environments will lead to improved quantification of biogeochemical reactions and associated nutrient cycling. This study develops a methodology to predict elevated rates of biogeochemical activity (microbial "hotspots") in subsurface environments by correlating microbial community structure with the spatial distribution of geochemical indicators in subsurface sediments. Statistical hierarchical cluster analyses (HCA) of X-ray fluorescence (XRF), simulated precipitation leachate, bioavailable Fe and Mn, total organic carbon (TOC), microbial community structure, grain size, bulk density and moisture content data were used to identify regions of the subsurface characterized by biogeochemical hotspots and sample characteristics indicative of these hotspots within fluvially-derived aquifer sediments. The methodology has been applied to (a) alluvial materials collected at a former uranium mill site near Rifle, Colorado and (b) relatively undisturbed floodplain deposits (soils and sediments) collected along the East River near Crested Butte, Colorado. At Rifle, 33 sediment samples were taken from 8 sediment cores and at the East River 33 soil/sediment samples were collected across and perpendicular to 3 active meanders. The East River watershed exhibits characteristic fluvial progression and serves as a representative example of many headwater catchments with the upper Colorado River basin. Initial clustering revealed that operationally defined hotspots were characterized by high organic carbon, bioavailable iron and dark colors but not necessarily low hydraulic conductivity. Applying the method to identify hotspots in both contaminated and natural floodplain deposits and their associated alluvial aquifers demonstrates the broad applicability of a geochemical indicator based approach.

  8. The Orléans-Lithothèque - an analogue rockstore for in situ missions

    NASA Astrophysics Data System (ADS)

    Bost, Nicolas; Westall, Frances; Ramboz, Claire

    2010-05-01

    The Orléans-Lithothèque - an analogue rockstore for in situ missions Nicolas Bost, Frances Westall, Claire Ramboz, Axelle Hubert, Derek Pullan, Beda Hofmann, Elisabeth Vergès, Michel Viso, Jorge Vago, Christelle Briois, Bruno Scaillet, Michel Tagger Instruments for in-situ missions to extraterrestrial bodies should ideally be cross calibrated using a common suite of relevant materials. Such multi-instrument calibration would enable a better comparison of instrument performances during the mission, as well as aid in the interpretation of the in-situ measurements. At the CNRS in Orléans, the Observatoire des Sciences de l'Univers de la region Centre is creating a collection of well-characterised rocks that will be available for testing and calibrating instruments to be flown on space missions. The characteristics of the collection's analogue materials will be described in an online database. In view of the upcoming 2018 ExoMars rover mission, we are concentrating initially on materials of direct relevance to Mars. The initial collection includes basalts (ultramafic, weathered, andesitic, hydrothermally-silicified); sediments (volcanic, biolaminated, banded iron formation); and minerals (silica, evaporites, clays, Fe oxides). This set of samples will be augmented with time. All samples will be characterised petrographically, petrologically, and geochemically using the types of analyses likely to be performed during an in-situ mission: hand specimen description, optical microscopy, mineralogical analysis (XRD, Raman and IR spectrometry), elemental analysis (EDX, microprobe, ICP) and organics analysis (Raman, pyr-GCMS).

  9. The International Space Analogue Rock Store (ISAR): A key tool for future planetary exploration.

    NASA Astrophysics Data System (ADS)

    Bost, N.; Westall, F.; Ramboz, C.; Foucher, F.

    2012-04-01

    In order to prepare the next in situ space missions we have created a « lithothèque » of analogue rocks for calibrating and testing future (and existing) space flight instruments. This rock collection is called the International Space Analogue Rockstore (ISAR) and is hosted in the CNRS and the Observatoire des Sciences de l'Univers en Region Centre (OSUC) in Orléans. For maximum science return, all instruments on a single mission should ideally be tested with the same suite of relevant analogue materials. The ISAR lithothéque aims to fulfill this role by providing suitable materials to instrument teams [1]. The lithothèque is accompanied by an online database of all relevant structural, textural, and geochemical data (www.isar.cnrs-orleans.fr).The data base will also be available during missions to aid interpretation of data obtained in situ. Mars is the immediate goal for MSL-2011 and the new international Mars 2018 mission. The lithothèque thus presently contains relevant Mars-analogue rock and mineral samples, a preliminary range of which is now available to the scientific community for instrument testing [2]. The preliminary group of samples covers a range of lithologies to be found on Mars, especially those in Noachain/Hesperian terrains where MSL will land (Gale Crater) and where the 2018 landing site will most likely be located. It includes a variety of basalts (tephrite, primitive basalt, silicified basalt; plus cumulates), komatiites, artificially synthesized martian basalts [3], volcanic sands, a banded iron formation, carbonates associated with volcanic lithologies and hydrothermalism, the clay Nontronite, and hydrothermal cherts. Some of the silicified volcanic sands contain traces of early life that are good analogues for potential martian life [4]. [1] Westall F. et al., LPI contribution 1608, 1346, 42nd LPSC, 2011; [2] Bost N. et al., in review (Icarus); [3] Bost N. et al., in review (Meteoritics); [4] Westall et al., 2011, Planetary and Space

  10. DNA-based methods of geochemical prospecting

    DOEpatents

    Ashby, Matthew [Mill Valley, CA

    2011-12-06

    The present invention relates to methods for performing surveys of the genetic diversity of a population. The invention also relates to methods for performing genetic analyses of a population. The invention further relates to methods for the creation of databases comprising the survey information and the databases created by these methods. The invention also relates to methods for analyzing the information to correlate the presence of nucleic acid markers with desired parameters in a sample. These methods have application in the fields of geochemical exploration, agriculture, bioremediation, environmental analysis, clinical microbiology, forensic science and medicine.

  11. DNA interaction with antitumor polyamine analogues: a comparison with biogenic polyamines.

    PubMed

    N'soukpoé-Kossi, C N; Ouameur, A Ahmed; Thomas, T; Shirahata, A; Thomas, T J; Tajmir-Riahi, H A

    2008-10-01

    Biogenic polyamines, putrescine, spermidine, and spermine, are ubiquitous cellular cations and exert multiple biological functions. Polyamine analogues mimic biogenic polyamines at macromolecular level but are unable to substitute for natural polyamines and maintain cell proliferation, indicating biomedical applications. The mechanistic differences in DNA binding mode between natural and synthetic polyamines have not been explored. The aim of this study was to examine the interaction of calf thymus DNA with three polyamine analogues, 1,11-diamino-4,8-diazaundecane (333), 3,7,11,15-tetrazaheptadecane x 4 HCl (BE-333), and 3,7,11,15,19-pentazahenicosane x 5 HCl (BE-3333), using FTIR, UV-visible, and CD spectroscopy. Polyamine analogues bind with guanine and backbone PO2 group as major targets in DNA, whereas biogenic polyamines bind to major and minor grooves as well as to phosphate groups. Weaker interaction with DNA was observed for analogues with respect to biogenic polyamines, with K(333) = 1.90 (+/-0.5) x 10(4) M(-1), K(BE-333) = 6.4 (+/-1.7) x 10(4) M(-1), K(BE-3333) = 4.7 (+/-1.4) x 10(4) M(-1) compared to K(Spm) = 2.3 (+/-1.1) x 10(5) M(-1), K(Spd) = 1.4 (+/-0.6) x 10(5) M(-1), and K(Put) = 1.02 (+/-0.5) x 10(5) M(-1). A partial B- to A-DNA transition was also provoked by analogues. These data suggest distinct differences in the binding of natural and synthetic polyamines with DNA.

  12. Evaluation of Geochemical Fracture Conductivity Alterations in Shale under Laboratory Conditions

    NASA Astrophysics Data System (ADS)

    Radonjic, M.; Olabode, A.

    2015-12-01

    . The result indicated that rock-fluid geochemical interactions can constrict natural fracture conductivity under CO2 sequestration conditions. This diagenetic accretions can lead to significant improvement in the seal integrity of shaly caprocks.

  13. Geochemical baseline distribution of harmful elements in the surface soils of Campania region.

    NASA Astrophysics Data System (ADS)

    Albanese, Stefano; Lima, Annamaria; Qu, Chengkai; Cicchella, Domenico; Buccianti, Antonella; De Vivo, Benedetto

    2015-04-01

    Environmental geochemical mapping has assumed an increasing relevance and the separation of values to discriminate between anthropogenic pollution and natural (geogenic) sources has become crucial to address environmental problems affecting the quality of life of human beings. In the last decade, a number of geochemical prospecting projects, mostly focused on surface soils (topsoils), were carried out at different scales (from regional to local) across the whole Campania region (Italy) to characterize the distribution of both harmful elements and persistent organic pollutants (POP) in the environment and to generating a valuable database to serve as reference in developing geomedical studies. During the 2014, a database reporting the distribution of 53 chemical elements in 3536 topsoil samples, collected across the whole region, was completed. The geochemical data, after necessary quality controls, were georeferenced and processed in a geochemistry dedicated GIS software named GEODAS. For each considered element a complete set of maps was generated to depict both the discrete and the spatially continuous (interpolated) distribution of elemental concentrations across the region. The interpolated maps were generated using the Multifractal Inverse Distance eighted (MIDW) algorithm. Subsequently, the S-A method, also implemented in GEODAS, was applied to MIDW maps to eliminate spatially limited anomalies from the original grid and to generate the distribution patterns of geochemical baselines for each element. For a selected group of elements geochemical data were also treated by means of a Compositional Data Analysis (CoDA) aiming at investigating the regionalised structure of the data by considering the joint behaviour of several elements constituting for each sample its whole composition. A regional environmental risk assessment was run on the basis of the regional distribution of heavy metals in soil, land use types and population. The risk assessment produced a

  14. Measurement of stimulated Hawking emission in an analogue system.

    PubMed

    Weinfurtner, Silke; Tedford, Edmund W; Penrice, Matthew C J; Unruh, William G; Lawrence, Gregory A

    2011-01-14

    Hawking argued that black holes emit thermal radiation via a quantum spontaneous emission. To address this issue experimentally, we utilize the analogy between the propagation of fields around black holes and surface waves on moving water. By placing a streamlined obstacle into an open channel flow we create a region of high velocity over the obstacle that can include surface wave horizons. Long waves propagating upstream towards this region are blocked and converted into short (deep-water) waves. This is the analogue of the stimulated emission by a white hole (the time inverse of a black hole), and our measurements of the amplitudes of the converted waves demonstrate the thermal nature of the conversion process for this system. Given the close relationship between stimulated and spontaneous emission, our findings attest to the generality of the Hawking process.

  15. Analogue of Cosmological Particle Creation in an Ion Trap

    SciTech Connect

    Schuetzhold, Ralf; Uhlmann, Michael; Petersen, Lutz; Schmitz, Hector; Friedenauer, Axel; Schaetz, Tobias

    2007-11-16

    We study phonons in a dynamical chain of ions confined by a trap with a time-dependent (axial) potential strength and demonstrate that they behave in the same way as quantum fields in an expanding or contracting Universe. Based on this analogy, we present a scheme for the detection of the analogue of cosmological particle creation which should be feasible with present day technology. In order to test the quantum nature of the particle creation mechanism and to distinguish it from classical effects such as heating, we propose to measure the two-phonon amplitude via the 2nd red sideband transition and to compare it with the one-phonon amplitude (1st red sideband)

  16. Geochemical orientation for mineral exploration in the Hashemite Kingdom of Jordan

    USGS Publications Warehouse

    Overstreet, W.C.; Grimes, D.J.; Seitz, J.F.

    1982-01-01

    This report is a supplement to previous accounts of geochemical exploration conducted in the Hashemite Kingdom of Jordan by the Natural Resources Authority of the Royal Government of Jordan and the U.S. Geological Survey. The field work on which this report is based was sponsored by the U.S. Agency for International Development, U.S. Department of State. Procedures used in collecting various kinds of rocks, ores, slags, eluvial and alluvial sediments, heavy-mineral concentrates, and organic materials for use as geochemical sample media are summarized, as are the laboratory procedures followed for the analysis of these sample materials by semiquantitative spectrographic, atomic absorption, fluorometric, and X-ray diffraction methods. Geochemical evaluations of the possibilities for economic mineral deposits in certain areas are presented. The results of these preliminary investigations open concepts for further use in geochemical exploration in the search for metallic mineral deposits in Jordan. Perhaps the most desirable new activity would be hydrogeochemical exploration for uranium and base metals, accompanied by interpretation of such remote-sensing data as results of airborne radiometric surveys and computer-enhanced LANDSAT imagery. For more conventional approaches to geochemical exploration, however, several fundamental problems regarding proper choice of geochemical sample media for different geologic and geographic parts of the Country must be solved before effective surveys can be made. The present results also show that such common geochemical exploration techniques as the determination of the trace-element contents of soils, plant ash, and slags have direct application also toward the resolution of several archaeological problems in Jordan. These include the relation of trace-elements chemistry of local soils to the composition of botanic remains, the trace-elements composition of slags to the technological development of the extractive metallurgy of

  17. Optimization of propafenone analogues as antimalarial leads.

    PubMed

    Lowes, David J; Guiguemde, W Armand; Connelly, Michele C; Zhu, Fangyi; Sigal, Martina S; Clark, Julie A; Lemoff, Andrew S; Derisi, Joseph L; Wilson, Emily B; Guy, R Kiplin

    2011-11-10

    Propafenone, a class Ic antiarrythmic drug, inhibits growth of cultured Plasmodium falciparum. While the drug's potency is significant, further development of propafenone as an antimalarial would require divorcing the antimalarial and cardiac activities as well as improving the pharmacokinetic profile of the drug. A small array of propafenone analogues was designed and synthesized to address the cardiac ion channel and PK liabilities. Testing of this array revealed potent inhibitors of the 3D7 (drug sensitive) and K1 (drug resistant) strains of P. falciparum that possessed significantly reduced ion channel effects and improved metabolic stability. Propafenone analogues are unusual among antimalarial leads in that they are more potent against the multidrug resistant K1 strain of P. falciparum compared to the 3D7 strain.

  18. Enzymatic synthesis of lipid II and analogues.

    PubMed

    Huang, Lin-Ya; Huang, Shih-Hsien; Chang, Ya-Chih; Cheng, Wei-Chieh; Cheng, Ting-Jen R; Wong, Chi-Huey

    2014-07-28

    The emergence of antibiotic resistance has prompted active research in the development of antibiotics with new modes of action. Among all essential bacterial proteins, transglycosylase polymerizes lipid II into peptidoglycan and is one of the most favorable targets because of its vital role in peptidoglycan synthesis. Described in this study is a practical enzymatic method for the synthesis of lipid II, coupled with cofactor regeneration, to give the product in a 50-70% yield. This development depends on two key steps: the overexpression of MraY for the synthesis of lipid I and the use of undecaprenol kinase for the preparation of polyprenol phosphates. This method was further applied to the synthesis of lipid II analogues. It was found that MraY and undecaprenol kinase can accept a wide range of lipids containing various lengths and configurations. The activity of lipid II analogues for bacterial transglycolase was also evaluated.

  19. Analogue modeling of instabilities in crater lake hydrothermal systems

    NASA Astrophysics Data System (ADS)

    Vandemeulebrouck, Jean; Stemmelen, Didier; Hurst, Tony; Grangeon, Jacques

    2005-02-01

    We carried out analogue experiments on two-phase boiling systems, using a porous vertical cylinder, saturated with water. The base of the cylinder was heated, and the top was cooled, as in a natural hydrothermal system. Previous work had shown that once the two-phase zone reached a certain level, thermal instabilities would develop. We made measurements of the acoustic energy related to boiling, and we found that high levels of acoustic noise were associated with the part of the cycle in which there was upward water movement. We repeated our experiments with a cooling water tank at the top of the system, representing a crater lake. This showed that periodic thermal instabilities still developed in this situation. We then compared our analogue measurements to two natural systems known to exhibit periodic behavior. There is good agreement between the thermal and acoustic cycling seen in our model and the observations made at Inferno Crater Lake in the Waimangu Geothermal area, New Zealand, whose level cycles by nearly 10 m, with a typical period of 38 days. Particularly notable is how in both systems high levels of acoustic noise are associated with rising water level. The much larger Ruapehu Crater Lake, also in New Zealand, cycled with a period of several months to a year for over a decade prior to the 1995 eruption. Strong acoustic and seismic energy usually occurred just before the lake temperature started to rise. This suggests a slightly different model, in which the increasing two-phase flow zone triggers more general convection once it reaches the base of the lake.

  20. Polyamine analogues targeting epigenetic gene regulation.

    PubMed

    Huang, Yi; Marton, Laurence J; Woster, Patrick M; Casero, Robert A

    2009-11-04

    Over the past three decades the metabolism and functions of the polyamines have been actively pursued as targets for antineoplastic therapy. Interactions between cationic polyamines and negatively charged nucleic acids play a pivotal role in DNA stabilization and RNA processing that may affect gene expression, translation and protein activity. Our growing understanding of the unique roles that the polyamines play in chromatin regulation, and the discovery of novel proteins homologous with specific regulatory enzymes in polyamine metabolism, have led to our interest in exploring chromatin remodelling enzymes as potential therapeutic targets for specific polyamine analogues. One of our initial efforts focused on utilizing the strong affinity that the polyamines have for chromatin to create a backbone structure, which could be combined with active-site-directed inhibitor moieties of HDACs (histone deacetylases). Specific PAHAs (polyaminohydroxamic acids) and PABAs (polyaminobenzamides) polyamine analogues have demonstrated potent inhibition of the HDACs, re-expression of p21 and significant inhibition of tumour growth. A second means of targeting the chromatin-remodelling enzymes with polyamine analogues was facilitated by the recent identification of flavin-dependent LSD1 (lysine-specific demethylase 1). The existence of this enzyme demonstrated that histone lysine methylation is a dynamic process similar to other histone post-translational modifications. LSD1 specifically catalyses demethylation of mono- and di-methyl Lys4 of histone 3, key positive chromatin marks associated with transcriptional activation. Structural and catalytic similarities between LSD1 and polyamine oxidases facilitated the identification of biguanide, bisguanidine and oligoamine polyamine analogues that are potent inhibitors of LSD1. Cellular inhibition of LSD1 by these unique compounds led to the re-activation of multiple epigenetically silenced genes important in tumorigenesis. The use of

  1. Antitumoral cyclic peptide analogues of chlamydocin.

    PubMed

    Bernardi, E; Fauchere, J L; Atassi, G; Viallefont, P; Lazaro, R

    1993-01-01

    A series of cyclic tetrapeptides bearing the bioactive alkylating group on an epsilon-amino-lysyl function have been examined for their antitumoral activity on L1210 and P388 murine leukemia cell lines. One analogue belonging to the chlamydocin family and bearing a beta-chloroethylnitrosourea group was found to be potent at inhibiting L1210 cell proliferation and had a higher therapeutic index than the reference compound bis-beta-chloroethylnitrosourea (BCNU) on the in vivo P388-induced leukemia model.

  2. Synthesis of constrained analogues of tryptophan

    PubMed Central

    Negrato, Marco; Abbiati, Giorgio; Dell’Acqua, Monica

    2015-01-01

    Summary A Lewis acid-catalysed diastereoselective [4 + 2] cycloaddition of vinylindoles and methyl 2-acetamidoacrylate, leading to methyl 3-acetamido-1,2,3,4-tetrahydrocarbazole-3-carboxylate derivatives, is described. Treatment of the obtained cycloadducts under hydrolytic conditions results in the preparation of a small library of compounds bearing the free amino acid function at C-3 and pertaining to the class of constrained tryptophan analogues. PMID:26664620

  3. The Brookhaven electron analogue, 1953--1957

    SciTech Connect

    Plotkin, M.

    1991-12-18

    The following topics are discussed on the Brookhaven electron analogue: L.J. Haworth and E.L. VanHorn letters; Original G.K. Green outline for report; General description; Parameter list; Mechanical Assembly; Alignment; Degaussing; Vacuum System; Injection System; The pulsed inflector; RF System; Ferrite Cavity; Pick-up electrodes and preamplifiers; Radio Frequency power amplifier; Lens supply; Controls and Power; and RF acceleration summary.

  4. Is formamide a geochemically plausible prebiotic solvent?

    PubMed

    Bada, Jeffrey L; Chalmers, John H; Cleaves, H James

    2016-07-27

    From a geochemical perspective, significant amounts of pure formamide (HCONH2) would have likely been rare on the early Earth. There may have been mixed formamide-water solutions, but even in the presence of catalyst, solutions with >20 weight% water in formamide would not have produced significant amounts of prebiotic compounds. It might be feasible to produce relatively pure formamide by a rare occurrence of freezing formamide/water mixtures at temperatures lower than formamide's freezing point (2.55 °C) but greater than the freezing point of water. Because of the high density of formamide ice it would have sunk and accumulated at the bottom of the solution. If the remaining water froze on the surface of this ice, and was then removed by a sublimation-ablation process, a small amount of pure formamide ice might have been produced. In addition a recent report suggested that ∼85 weight% formamide could be prepared by a geochemical type of fractional distillation process, offering another possible route for prebiotic formamide production.

  5. Geochemical controls on groundwater chemistry in shales

    SciTech Connect

    Von Damm, K.L.

    1989-01-01

    The chemistry of groundwaters is one of the most important parameters in determining the mobility of species within a rock formation. A three pronged approach was used to determine the composition of, and geochemical controls, on groundwaters specifically within shale formations: (1) available data were collected from the literature, the US Geological Survey WATSTORE data base, and field sampling, (2) the geochemical modeling code EQ3/6 was used to simulate interaction of various shales and groundwaters, and (3) several types of shale were reacted with synthetic groundwaters in the laboratory. The comparison of model results to field and laboratory data provide a means of validating the models, as well as a means of deconvoluting complex field interactions. Results suggest that groundwaters in shales have a wide range in composition and are primarily of the Na-Cl-HCO/sub 3/- type. The constancy of the Na:Cl (molar) ratio at 1:1 and the Ca:Mg ratio from 3:1 to 1:1 suggests the importance of halite and carbonates in controlling groundwater compositions. In agreement with the reaction path modeling, most of the groundwaters are neutral to slightly alkaline at low temperatures. Model and experimental results suggest that reaction (1) at elevated temperatures, or (2) in the presence of oxygen will lead to more acidic conditions. Some acetate was found to be produced in the experiments; depending on the constraints applied, large amounts of acetate were produced in the model results. 13 refs., 1 tab.

  6. Archean crust-mantle geochemical differentiation

    NASA Technical Reports Server (NTRS)

    Tilton, G. R.

    1983-01-01

    Isotope measurements on carbonatite complexes and komatiites can provide information on the geochemical character and geochemical evolution of the mantle, including the sub-continental mantle. Measurements on young samples establish the validity of the method. These are based on Sr, Nd and Pb data from the Tertiary-Mesozoic Gorgona komatiite and Sr and Pb data from the Cretaceous Oka carbonatite complex. In both cases the data describe a LIL element-depleted source similar to that observed presently in MORB. Carbonatite data have been used to study the mantle beneath the Superior Province of the Canadian Shield one billion years (1 AE) ago. The framework for this investigation was established by Bell et al., who showed that large areas of the province appear to be underlain by LIL element-depleted mantle (Sr-85/Sr-86=0.7028) at 1 AE ago. Additionally Bell et al. found four complexes to have higher initial Sr ratios (Sr-87/Sr-86=0.7038), which they correlated with less depleted (bulk earth?) mantle sources, or possibly crustal contamination. Pb isotope relationships in four of the complexes have been studied by Bell et al.

  7. Thymidine analogues for tracking DNA synthesis.

    PubMed

    Cavanagh, Brenton L; Walker, Tom; Norazit, Anwar; Meedeniya, Adrian C B

    2011-09-15

    Replicating cells undergo DNA synthesis in the highly regulated, S-phase of the cell cycle. Analogues of the pyrimidine deoxynucleoside thymidine may be inserted into replicating DNA, effectively tagging dividing cells allowing their characterisation. Tritiated thymidine, targeted using autoradiography was technically demanding and superseded by 5-bromo-2-deoxyuridine (BrdU) and related halogenated analogues, detected using antibodies. Their detection required the denaturation of DNA, often constraining the outcome of investigations. Despite these limitations BrdU alone has been used to target newly synthesised DNA in over 20,000 reviewed biomedical studies. A recent breakthrough in "tagging DNA synthesis" is the thymidine analogue 5-ethynyl-2'-deoxyuridine (EdU). The alkyne group in EdU is readily detected using a fluorescent azide probe and copper catalysis using 'Huisgen's reaction' (1,3-dipolar cycloaddition or 'click chemistry'). This rapid, two-step biolabelling approach allows the tagging and imaging of DNA within cells whilst preserving the structural and molecular integrity of the cells. The bio-orthogonal detection of EdU allows its application in more experimental assays than previously possible with other "unnatural bases". These include physiological, anatomical and molecular biological experimentation in multiple fields including, stem cell research, cancer biology, and parasitology. The full potential of EdU and related molecules in biomedical research remains to be explored.

  8. Blood Loss Estimation Using Gauze Visual Analogue

    PubMed Central

    Ali Algadiem, Emran; Aleisa, Abdulmohsen Ali; Alsubaie, Huda Ibrahim; Buhlaiqah, Noora Radhi; Algadeeb, Jihad Bagir; Alsneini, Hussain Ali

    2016-01-01

    Background Estimating intraoperative blood loss can be a difficult task, especially when blood is mostly absorbed by gauze. In this study, we have provided an improved method for estimating blood absorbed by gauze. Objectives To develop a guide to estimate blood absorbed by surgical gauze. Materials and Methods A clinical experiment was conducted using aspirated blood and common surgical gauze to create a realistic amount of absorbed blood in the gauze. Different percentages of staining were photographed to create an analogue for the amount of blood absorbed by the gauze. Results A visual analogue scale was created to aid the estimation of blood absorbed by the gauze. The absorptive capacity of different gauze sizes was determined when the gauze was dripping with blood. The amount of reduction in absorption was also determined when the gauze was wetted with normal saline before use. Conclusions The use of a visual analogue may increase the accuracy of blood loss estimation and decrease the consequences related to over or underestimation of blood loss. PMID:27626017

  9. A geochemical atlas of North Carolina, USA

    USGS Publications Warehouse

    Reid, J.C.

    1993-01-01

    A geochemical atlas of North Carolina, U.S.A., was prepared using National Uranium Resource Evaluation (NURE) stream-sediment data. Before termination of the NURE program, sampling of nearly the entire state (48,666 square miles of land area) was completed and geochemical analyses were obtained. The NURE data are applicable to mineral exploration, agriculture, waste disposal siting issues, health, and environmental studies. Applications in state government include resource surveys to assist mineral exploration by identifying geochemical anomalies and areas of mineralization. Agriculture seeks to identify areas with favorable (or unfavorable) conditions for plant growth, disease, and crop productivity. Trace elements such as cobalt, copper, chromium, iron, manganese, zinc, and molybdenum must be present within narrow ranges in soils for optimum growth and productivity. Trace elements as a contributing factor to disease are of concern to health professionals. Industry can use pH and conductivity data for water samples to site facilities which require specific water quality. The North Carolina NURE database consists of stream-sediment samples, groundwater samples, and stream-water analyses. The statewide database consists of 6,744 stream-sediment sites, 5,778 groundwater sample sites, and 295 stream-water sites. Neutron activation analyses were provided for U, Br, Cl, F, Mn, Na, Al, V, Dy in groundwater and stream water, and for U, Th, Hf, Ce, Fe, Mn, Na, Sc, Ti, V, Al, Dy, Eu, La, Sm, Yb, and Lu in stream sediments. Supplemental analyses by other techniques were reported on U (extractable), Ag, As, Ba, Be, Ca, Co, Cr, Cu, K, Li, Mg, Mo, Nb, Ni, P, Pb, Se, Sn, Sr, W, Y, and Zn for 4,619 stream-sediment samples. A small subset of 334 stream samples was analyzed for gold. The goal of the atlas was to make available the statewide NURE data with minimal interpretation to enable prospective users to modify and manipulate the data for their end use. The atlas provides only

  10. The effect of scale on the interpretation of geochemical anomalies

    USGS Publications Warehouse

    Theobald, P.K.; Eppinger, R.G.; Turner, R.L.; Shiquan, S.

    1991-01-01

    The purpose of geochemical surveys changes with scale. Regional surveys identify areas where mineral deposits are most likely to occur, whereas intermediate surveys identify and prioritize specific targets. At detailed scales specific deposit models may be applied and deposits delineated. The interpretation of regional geochemical surveys must take into account scale-dependent difference in the nature and objectives of this type of survey. Overinterpretation of regional data should be resisted, as should recommendations to restrict intermediate or detailed follow-up surveys to the search for specific deposit types or to a too limited suite of elements. Regional surveys identify metallogenic provinces within which a variety of deposit types and metals are most likely to be found. At intermediate scale, these regional provinces often dissipate into discrete clusters of anomalous areas. At detailed scale, individual anomalous areas reflect local conditions of mineralization and may seem unrelated to each other. Four examples from arid environments illustrate the dramatic change in patterns of anomalies between regional and more detailed surveys. On the Arabian Shield, a broad regional anomaly reflects the distribution of highly differentiated anorogenic granites. A particularly prominent part of the regional anomaly includes, in addition to the usual elements related to the granites, the assemblage of Mo, W and Sn. Initial interpretation suggested potential for granite-related, stockwork Mo deposits. Detailed work identified three separate sources for the anomaly: a metal-rich granite, a silicified and stockwork-veined area with scheelite and molybdenite, and scheelite/powellite concentrations in skarn deposits adjacent to a ring-dike complex. Regional geochemical, geophysical and remote-sensing data in the Sonoran Desert, Mexico, define a series of linear features interpreted to reflect fundamental, northeast-trending fractures in the crust that served as the prime

  11. A microenvironment-sensitive fluorescent pyrimidine ribonucleoside analogue: synthesis, enzymatic incorporation, and fluorescence detection of a DNA abasic site.

    PubMed

    Tanpure, Arun A; Srivatsan, Seergazhi G

    2011-11-04

    Base-modified fluorescent ribonucleoside-analogue probes are valuable tools in monitoring RNA structure and function because they closely resemble the structure of natural nucleobases. Especially, 2-aminopurine, a highly environment-sensitive adenosine analogue, is the most extensively utilized fluorescent nucleoside analogue. However, only a few isosteric pyrimidine ribonucleoside analogues that are suitable for probing the structure and recognition properties of RNA molecules are available. Herein, we describe the synthesis and photophysical characterization of a small series of base-modified pyrimidine ribonucleoside analogues derived from tagging indole, N-methylindole, and benzofuran onto the 5-position of uracil. One of the analogues, based on a 5-(benzofuran-2-yl)pyrimidine core, shows emission in the visible region with a reasonable quantum yield and, importantly, displays excellent solvatochromism. The corresponding triphosphate substrate is effectively incorporated into oligoribonucleotides by T7 RNA polymerase to produce fluorescent oligoribonucleotide constructs. Steady-state and time-resolved spectroscopic studies with fluorescent oligoribonucleotide constructs demonstrate that the fluorescent ribonucleoside photophysically responds to subtle changes in its environment brought about by the interaction of the chromophore with neighboring bases. In particular, the emissive ribonucleoside, if incorporated into an oligoribonucleotide, positively reports the presence of a DNA abasic site with an appreciable enhancement in fluorescence intensity. The straightforward synthesis, amicability to enzymatic incorporation, and sensitivity to changes in the microenvironment highlight the potential of the benzofuran-conjugated pyrimidine ribonucleoside as an efficient fluorescent probe to investigate nucleic acid structure, dynamics, and recognition events.

  12. Seasonal distribution and geochemical fractionation of heavy metals from surface sediment in a tropical estuary of Jeneberang River, Indonesia.

    PubMed

    Najamuddin; Prartono, Tri; Sanusi, Harpasis S; Nurjaya, I Wayan

    2016-10-15

    Lead (Pb) and zinc (Zn) concentrations from surface sediments were determined at 17 stations in riverine, estuarine, and marine environments during the wet and dry seasons. The geochemical fractionations were obtained by a sequential extraction procedure in five geochemical forms: exchangeable, bound to carbonate, iron-manganese oxide, organic, and residual fractions. The concentrations of Pb and Zn in the water were higher during the wet season than the dry season and higher in the riverine and marine samples than the estuarine samples. Following geochemical fractionation, the metals were found mainly in the residual fraction. The results indicated that the concentrations were influenced by season, with the sources of Pb and Zn derived mainly from rivers and natural sources. The contamination status in the estuary of the Jeneberang River was classified as weak to moderate pollution and the risk level to aquatic biota attributed was no risk to low risk.

  13. The costal landslide from analogue experiments: perspectives and limitation

    NASA Astrophysics Data System (ADS)

    Del Ventisette, C.; Nolesini, T.; Moretti, S.; Fanti, R.

    2010-12-01

    Understanding the triggering mechanism of coastal landslides (triggered and/or developed at air-water interface) and their evolution is fundamental to evaluate their hazard and, predicting the energy, the associated tsunami risk. The aim of this work is to verify the suitability of analogue modelling to understand the triggering mechanism and the evolution of landslide along the costal line. As a starting case study the Sciara del Fuoco (SdF), northwest flank of the volcanic island of Stromboli (Italy), was chosen. The analogue modelling technique has been proven to represent an useful tool to understand many geological processes, as it allows studying the progressive deformation, providing also useful indications about the role of distinct factors controlling the final deformation pattern. The models simulated at a first approximation the geological geometries observed at Stromboli, a composite volcano forming the northernmost island of the Aeolian Archipelago (Tyrrhenian Sea). The activity of Stromboli volcano is characterized by a persistent mild explosive activity at the summit craters sporadically interrupted by episodes of lava effusion and violent paroxysmal explosions as in 2002-2003 and in 2007. During the 2002 effusion a large landslide occurred on the SdF. The landslide caused a tsunami, which produced severe damages along the island shores. A series of analogue models was performed to investigate the influence of two different types of triggering mechanism and the behaviour of landslides both in air and air-water interface: 1) surface bulging due to the intrusion of a dike; 2) accumulation of material due to an uppermost landslide or due to opening of a new vent. The models, constructed in a Plexiglas tank, were scaled to the natural prototype following the geometrical, rheological, kinematical and dynamical similarities (e.g. Hubbert, 1937; Ramberg, 1981). The modelling material (Fontainbleau sand and rice) was sieved on a slope, inclination of which

  14. Identification and Separation of Geochemical Distribution Patterns using Fractal/Multifractal Methods

    NASA Astrophysics Data System (ADS)

    Liu, Yue; Cheng, Qiuming

    2015-04-01

    Identification and separation of anomalies from background for mineral exploration or environmental assessment is a fundamental issue in the field of exploration geochemistry. Traditionally, geochemical data are usually considered to follow normal or lognormal distributions, this scenario might lead to the extreme values cannot be detected by ordinary statistic methods, because the data of interest cannot meet the prerequisites of some typical statistic methods, and usually it is hard to separate geochemical anomalies from background, especially when weak anomalies are hidden in high background or the difference between anomaly and background is feeble. Cheng (2000) demonstrated that background values of geochemical data typically followed normal or lognormal distributions, and and anomalous values usually followed fractal/multifractal distributions. West and Shlesinger (1990) investigated the relationships of normal/lognormal distributions with Pareto distributions, the results indicated that the natural system was gradually tend to complexity from normal distributions to lognormal distributions, and then to Pareto distributions. Pareto distributions describe the most complex natural system, showing stronger fractal/multifractal characteristics. From the perspective of ore-forming processes, ore formation is the result of complex physical and chemical processes, there are considerable overlaps between igneous and hydrothermal and between sedimentary and hydrothermal, as a result, complex ore-forming processes might result in fractal/multifractal pattern. In the present study, a case study of anomaly identification of REE mineralization- related La and Y concentration values from 1617 stream sediment samples in the Nanling belt, South China, is used to demonstrate the application of two fractal/multifractal methods, singularity analysis and concentration-area (C-A) fractal method. First, singularity analysis is used to identify weak anomalies hidden within

  15. Selected Geochemical Data for Modeling Near-Surface Processes in Mineral Systems

    USGS Publications Warehouse

    Giles, Stuart A.; Granitto, Matthew; Eppinger, Robert G.

    2009-01-01

    The database herein was initiated, designed, and populated to collect and integrate geochemical, geologic, and mineral deposit data in an organized manner to facilitate geoenvironmental mineral deposit modeling. The Microsoft Access database contains data on a variety of mineral deposit types that have variable environmental effects when exposed at the ground surface by mining or natural processes. The data tables describe quantitative and qualitative geochemical analyses determined by 134 analytical laboratory and field methods for over 11,000 heavy-mineral concentrate, rock, sediment, soil, vegetation, and water samples. The database also provides geographic information on geology, climate, ecoregion, and site contamination levels for over 3,000 field sites in North America.

  16. Central Colorado Assessment Project - Application of integrated geologic, geochemical, biologic, and mineral resource studies

    USGS Publications Warehouse

    Klein, T.L.; Church, S.E.; Caine, J.S.; Schmidt, T.S.; deWitt, E.H.

    2008-01-01

    Cooperative studies by USDA Forest Service, National Park Service supported by the USGS Mineral Resources Program (MRP), and National Cooperative Geologic Mapping Programs (NCGMP) contributed to the mineral-resource assessment and included regional geologic mapping at the scale 1:100,000, collection and geochemical studies of stream sediments, surface water, and bedrock samples, macroinvertebrate and biofilm studies in the riparian environment, remote-sensing studies, and geochronology. Geoscience information available as GIS layers has improved understanding of the distribution of metallic, industrial, and aggregate resources, location of areas that have potential for their discovery or development, helped to understand the relation of tectonics, magmatism, and paleohydrology to the genesis of the metal deposits in the region, and provided insight on the geochemical and environmental effects that historical mining and natural, mineralized rock exposures have on surface water, ground water, and aquatic life.

  17. Geochemical Evidence for a Terrestrial Magma Ocean

    NASA Technical Reports Server (NTRS)

    Agee, Carl B.

    1999-01-01

    The aftermath of phase separation and crystal-liquid fractionation in a magma ocean should leave a planet geochemically differentiated. Subsequent convective and other mixing processes may operate over time to obscure geochemical evidence of magma ocean differentiation. On the other hand, core formation is probably the most permanent, irreversible part of planetary differentiation. Hence the geochemical traces of core separation should be the most distinct remnants left behind in the mantle and crust, In the case of the Earth, core formation apparently coincided with a magma ocean that extended to a depth of approximately 1000 km. Evidence for this is found in high pressure element partitioning behavior of Ni and Co between liquid silicate and liquid iron alloy, and with the Ni-Co ratio and the abundance of Ni and Co in the Earth's upper mantle. A terrestrial magma ocean with a depth of 1000 km will solidify from the bottom up and first crystallize in the perovskite stability field. The largest effect of perovskite fractionation on major element distribution is to decrease the Si-Mg ratio in the silicate liquid and increase the Si-Mg ratio in the crystalline cumulate. Therefore, if a magma ocean with perovskite fractionation existed, then one could expect to observe an upper mantle with a lower than chondritic Si-Mg ratio. This is indeed observed in modern upper mantle peridotites. Although more experimental work is needed to fully understand the high-pressure behavior of trace element partitioning, it is likely that Hf is more compatible than Lu in perovskite-silicate liquid pairs. Thus, perovskite fractionation produces a molten mantle with a higher than chondritic Lu-Hf ratio. Arndt and Blichert-Toft measured Hf isotope compositions of Barberton komatiites that seem to require a source region with a long-lived, high Lu-Hf ratio. It is plausible that that these Barberton komatiites were generated within the majorite stability field by remelting a perovskite

  18. Methodological approaches in estimating anomalous geochemical field structure

    NASA Astrophysics Data System (ADS)

    Gavrilov, R.; Rudmin, M.

    2015-02-01

    Mathematical statistic methods were applied to analyze the core samples from vertical expendable wells in Chertovo Koryto gold ore field. The following methods were used to analyse gold in samples: assay tests and atomic absorption method (AAS), while emission spectrum semiquantative method was applied to identify traces. The analysis of geochemical association distribution in one central profile demonstrated that bulk metasomatic aureoles are characteristic of concentric zonal structure. The distribution of geochemical associations is correlated to the hydrothermal stages of mineral formation identified in this deposit. It was proved that the processed geochemical data by factor and cluster analyses provided additional information on the anomalous geochemical field structure in gold- bearing black-shale strata. Such methods are effective tools in interpretating specific features of geochemical field structures in analogous potential ore-bearing areas.

  19. Urban geochemical mapping studies: how and why we do them.

    PubMed

    Johnson, Christopher C; Ander, E Louise

    2008-12-01

    Geochemical mapping is a technique rooted in mineral exploration but has now found worldwide application in studies of the urban environment. Such studies, involving multidisciplinary teams including geochemists, have to present their results in a way that nongeochemists can comprehend. A legislatively driven demand for urban geochemical data in connection with the need to identify contaminated land and subsequent health risk assessments has given rise to a greater worldwide interest in the urban geochemical environment. Herein, the aims and objectives of some urban studies are reviewed and commonly used terms such as baseline and background are defined. Geochemists need to better consider what is meant by the term urban. Whilst the unique make up of every city precludes a single recommended approach to a geochemical mapping strategy, more should be done to standardise the sampling and analytical methods. How (from a strategic and presentational point of view) and why we do geochemical mapping studies is discussed.

  20. Molecular docking and QSAR of aplyronine A and analogues: potent inhibitors of actin

    NASA Astrophysics Data System (ADS)

    Hussain, Abrar; Melville, James L.; Hirst, Jonathan D.

    2010-01-01

    Actin-binding natural products have been identified as a potential basis for the design of cancer therapeutic agents. We report flexible docking and QSAR studies on aplyronine A analogues. Our findings show the macrolide `tail' to be fundamental for the depolymerisation effect of actin-binding macrolides and that it is the tail which forms the initial interaction with the actin rather than the macrocycle, as previously believed. Docking energy scores for the compounds were highly correlated with actin depolymerisation activity. The 3D-QSAR models were predictive, with the best model giving a q 2 value of 0.85 and a r 2 of 0.94. Results from the docking simulations and the interpretation from QSAR "coeff*stdev" contour maps provide insight into the binding mechanism of each analogue and highlight key features that influence depolymerisation activity. The results herein may aid the design of a putative set of analogues that can help produce efficacious and tolerable anti-tumour agents. Finally, using the best QSAR model, we have also made genuine predictions for an independent set of recently reported aplyronine analogues.

  1. Synthesis of tyrocidine A and its analogues by spontaneous cyclization in aqueous solution.

    PubMed

    Bu, Xianzhang; Wu, Xiaoming; Xie, Guiyang; Guo, Zhihong

    2002-08-22

    [reaction: see text] Head-to-tail cyclization of peptides is a multistep process involving tedious C-terminal activation and side chain protection. Here we report a facile, quantitative cyclization method in aqueous ammonia solution for the total syntheses of the cyclic decapeptide antibiotic Tyrocidine A and its analogues from their fully deprotected linear thioester precursors on a solid support. This novel aqueous method is conformation-dependent and may be applicable to syntheses of other natural cyclic peptides.

  2. A geochemical basis for endomyocardial fibrosis.

    PubMed

    Valiathan, M S; Kartha, C C; Panday, V K; Dang, H S; Sunta, C M

    1986-09-01

    In a search for geochemical factors that could play a role in the pathogenesis of tropical endomyocardial fibrosis, endomyocardial tissue samples obtained from patients at necropsy or operation were analysed for major elements present in laterite and monazite, which are important soil constituents of Kerala State of India. Atomic absorption spectrophotometry was used for detecting iron, silicon, aluminium, zinc, magnesium, calcium, sodium, potassium, and manganese and neutron activation analysis for thorium. Compared with control samples from victims of fatal accidents, an excess of thorium, sodium, and calcium and a deficiency of magnesium were present in samples from patients. It has been shown earlier that the staple diets of people in Kerala have high concentrations of thorium, and these data show that thorium can become concentrated in cardiac tissues. It is speculated that thorium excess in conjunction with magnesium deficiency may play a role in the causation of tropical endomyocardial fibrosis.

  3. The geochemical record in rock glaciers

    USGS Publications Warehouse

    Steig, E.J.; Fitzpatrick, J.J.; Potter, N.; Clark, D.H.

    1998-01-01

    A 9.5 m ice core was extracted from beneath the surficial debris cover of a rock glacier at Galena Creek, northwestern Wyoming. The core contains clean, bubble-rich ice with silty debris layers spaced at roughly 20 cm intervals. The debris layers are similar in appearance to those in typical alpine glaciers, reflecting concentration of debris by melting at the surface during the summer ablation season. Profiles of stable isotope concentrations and electrical conductivity measurements provide independent evidence for melting in association with debris layers. These observations are consistent with a glacial origin for the ice, substantiating the glacigenic model for rock glacier formation. The deuterium excess profile in the ice indicates that the total depth of meltwater infiltration is less than the thickness of one annual layer, suggesting that isotope values and other geochemical signatures are preserved at annual resolution. This finding demonstrates the potential for obtaining useful paleoclimate information from rock glacier ice.

  4. A Farside Geochemical Window into the Moon

    NASA Astrophysics Data System (ADS)

    Martel, L. M. V.

    2008-04-01

    A low-albedo area on the lunar farside near Dewar crater has the geochemical characteristics of mare basalt despite the fact that no maria have ever been identified there. The area sits in the previously-mapped Feldspathic Highlands Terrane (FHT) that is characterized by very low thorium and iron oxide abundances. Yet further remote sensing studies show the featured area near Dewar has anomalously elevated thorium, samarium, iron oxide, and titanium oxide values compared to the FHT. Samuel Lawrence (formerly at the Hawaii Institute of Geophysics and Planetology and now at Arizona State University) and colleagues from Hawaii, Los Alamos National Lab, and USGS Flagstaff analyzed a suite of Lunar Prospector data, Clementine ultraviolet-visible (UVVIS) images, and Lunar Orbiter photographs to determine the composition and probable origin of the Dewar anomaly. The body of evidence points to excavated material from a farside buried mare basalt, or cryptomare, derived from a mag ma with enhanced thorium concentrations.

  5. Isolation, semisynthesis, covalent docking and transforming growth factor beta-activated kinase 1 (TAK1)-inhibitory activities of (5Z)-7-oxozeaenol analogues.

    PubMed

    Fakhouri, Lara; El-Elimat, Tamam; Hurst, Dow P; Reggio, Patricia H; Pearce, Cedric J; Oberlies, Nicholas H; Croatt, Mitchell P

    2015-11-01

    (5Z)-7-Oxozeanol and related analogues were isolated and screened to explore their activity as TAK1 inhibitors. Seven analogues were synthesized and more than a score of natural products isolated that examined the role that different areas of the molecule contribute to TAK1 inhibition. A novel nonaromatic difluoro-derivative was synthesized that had similar potency compared to the lead. This is the first example of a nonaromatic compound in this class to have TAK1 inhibition. Covalent docking for the isolated and synthesized analogues was carried out and found a strong correlation between the observed activities and the calculated binding.

  6. Code System to Model Aqueous Geochemical Equilibria.

    SciTech Connect

    PETERSON, S. R.

    2001-08-23

    Version: 00 MINTEQ is a geochemical program to model aqueous solutions and the interactions of aqueous solutions with hypothesized assemblages of solid phases. It was developed for the Environmental Protection Agency to perform the calculations necessary to simulate the contact of waste solutions with heterogeneous sediments or the interaction of ground water with solidified wastes. MINTEQ can calculate ion speciation/solubility, adsorption, oxidation-reduction, gas phase equilibria, and precipitation/dissolution ofsolid phases. MINTEQ can accept a finite mass for any solid considered for dissolution and will dissolve the specified solid phase only until its initial mass is exhausted. This ability enables MINTEQ to model flow-through systems. In these systems the masses of solid phases that precipitate at earlier pore volumes can be dissolved at later pore volumes according to thermodynamic constraints imposed by the solution composition and solid phases present. The ability to model these systems permits evaluation of the geochemistry of dissolved traced metals, such as low-level waste in shallow land burial sites. MINTEQ was designed to solve geochemical equilibria for systems composed of one kilogram of water, various amounts of material dissolved in solution, and any solid materials that are present. Systems modeled using MINTEQ can exchange energy and material (open systems) or just energy (closed systems) with the surrounding environment. Each system is composed of a number of phases. Every phase is a region with distinct composition and physically definable boundaries. All of the material in the aqueous solution forms one phase. The gas phase is composed of any gaseous material present, and each compositionally and structurally distinct solid forms a separate phase.

  7. New geochemical insights into volcanic degassing.

    PubMed

    Edmonds, Marie

    2008-12-28

    Magma degassing plays a fundamental role in controlling the style of volcanic eruptions. Whether a volcanic eruption is explosive, or effusive, is of crucial importance to approximately 500 million people living in the shadow of hazardous volcanoes worldwide. Studies of how gases exsolve and separate from magma prior to and during eruptions have been given new impetus by the emergence of more accurate and automated methods to measure volatile species both as volcanic gases and dissolved in the glasses of erupted products. The composition of volcanic gases is dependent on a number of factors, the most important being magma composition and the depth of gas-melt segregation prior to eruption; this latter parameter has proved difficult to constrain in the past, yet is arguably the most critical for controlling eruptive style. Spectroscopic techniques operating in the infrared have proved to be of great value in measuring the composition of gases at high temporal resolution. Such methods, when used in tandem with microanalytical geochemical investigations of erupted products, are leading to better constraints on the depth at which gases are generated and separated from magma. A number of recent studies have focused on transitions between explosive and effusive activity and have led to a better understanding of gas-melt segregation at basaltic volcanoes. Other studies have focused on degassing during intermediate and silicic eruptions. Important new results include the recognition of fluxing by deep-derived gases, which buffer the amount of dissolved volatiles in the melt at shallow depths, and the observation of gas flow up permeable conduit wall shear zones, which may be the primary mechanism for gas loss at the cusp of the most explosive and unpredictable volcanic eruptions. In this paper, I review current and future directions in the field of geochemical studies of volcanic degassing processes and illustrate how the new insights are beginning to change the way in

  8. The geochemical atlas of Italian soils

    NASA Astrophysics Data System (ADS)

    De Vivo, Benedetto; Cicchella, Domenico; Albanese, Stefano; Dinelli, Enrico; Giaccio, Lucia; Lima, Annamaria; Valera, Paolo

    2014-05-01

    The geochemical Atlas of Italian agricultural and grazing land soils was carried out as part of GEMAS project whose objective was to characterize soils of rural areas of the whole Europe. Soil samples were collected at an average sampling density of 1 site per 2500 km2. Two different sample types were collected: (1) 121 agricultural soils (Ap) on regularly ploughed land to a depth of 20 cm and (2) 121 grazing land soils (Gr) (land under permanent grass cover) to a depth of 10 cm. All soil samples were air dried, sieved to <2 mm, homogenised and finally split into 10 sub-samples. Both sample types (Ap and Gr) were analysed at the BGR for a suite of 41 elements by WD-XRFS. The same samples were also analysed after AR and MMI extractions by a combination of ICP-AES and ICP-MS for 53 elements. In addition, other parameters were determined: pH, TOC, total carbon and total sulphur, LOI, CEC, Sr-isotopes, Pb-isotopes, MIR-spectra. By means of a GIS software, georeferenced data of the Italian territory were used to produce the geochemical maps of all the analysed elements for both agricultural and grazing land soils. Specifically, for each element and sampling media a map reporting interpolated data and graduated dots was produced; univariate statistics and graphs were also associated to each map. The Atlas also contain: 5 maps for regional variability of factor scores of elemental associations resulting from R-mode factor analysis and 15 baseline and land use maps for some selected elements (As, Be, Cd, Co, Cr, Cu, Hg, Ni, Pb, Sb, Se, Sn, Tl, V, Zn) following the Italian intervention criteria.

  9. Geochemical microanalysis: The link between textural and geochemical characterization of igneous rocks

    NASA Astrophysics Data System (ADS)

    Kent, A. J.

    2003-12-01

    In this presentation I will review recent advances in microanalytical techniques that allow us to directly couple textural and geochemical information to the study of igneous rocks, particularly with respect to the analysis of silicate melt inclusions. Textural examination has long been a mainstay of the classification and petrologic study of igneous materials. The advent of the electron microprobe over 50 years ago allowed textural and geochemical observations to be coupled at small spatial scales and directly related to the physical and chemical conditions of formation and subsequent melt evolution. This resulted in a revolution in the petrological investigation and understanding of igneous rocks that continues today. Recent advances in geochemical microanalysis techniques are providing exciting access to new geochemical information at smaller and smaller spatial scales. These are enabling measurement of the abundances, and in some cases isotopic compositions, of a range of elements in correspondingly smaller sample volumes. A case in point is the study of silicate melt inclusions. Although melt inclusions have been recognized and studied for over a century, there has been a recent surge in interest directly tied to development of techniques capable of performing in-situ analysis of trace element and volatile components at small spatial scales. Melt inclusions allow direct sampling of melts present during crystal formation, and are particularly useful for relating crystal textures and compositions to those of their source melts. Chemical compositions of melt inclusions reveal the diversity of igneous compositions present in igneous systems, and may be combined with textural observations to constrain a wide range of igneous processes, including degassing, assimilation, fractional crystallization and mixing.

  10. Geochemical Fate and Transport of Diphenhydramine and Cetirizine in Soil

    NASA Astrophysics Data System (ADS)

    Wireman, R.; Rutherford, C. J.; Vulava, V. M.; Cory, W. C.

    2015-12-01

    Pharmaceuticals compounds presence in natural soils and water around the world has become a growing concern. These compounds are being discharged into the environment through treated wastewater or municipal sludge applications. The main goal of this study is determine their geochemical fate in natural soils. In this study we investigated sorption and transport behavior of diphenhydramine (DPH) and cetirizine (CTZ) in natural soils. These two commonly-used antihistamines are complex aromatic hydrocarbons with polar functional groups. Two clean acidic soils (pH~4.5) were used for these studies - an A-horizon soil that had higher organic matter content (OM, 7.6%) and a B-horizon soil that had lower OM (1.6%), but higher clay content (5.1%). Sorption isotherms were measured using batch reactor experiments. Data indicated that sorption was nonlinear and that it was stronger in clay-rich soils. The pKa's of DPH and CTZ are 8.98 and 8.27 respectively, i.e., these compounds are predominantly in cationic form at soil pH. In these forms, they preferentially sorb to negatively charged mineral surfaces (e.g., clay) present in the soils. Soil clay mineral characterization indicated that kaolinite was the dominant clay mineral present along with small amount of montmorillonite. The nonlinear sorption isotherms were fitted with Freundlich model. Transport behavior of both compounds was measured using glass chromatography columns. As expected both DPH and CTZ were strongly retained in the clay-rich soil as compared with OM-rich soil. The asymmetrical shape of the breakthrough curves indicated that there were likely two separate sorption sites in the soil, each with different reaction rates with each compound. A two-region advection-dispersion transport code was used to model the transport breakthrough curves. There was no evidence of transformation or degradation of the compounds during our sorption and transport studies.

  11. Polyamine analogues bind human serum albumin.

    PubMed

    Beauchemin, R; N'soukpoé-Kossi, C N; Thomas, T J; Thomas, T; Carpentier, R; Tajmir-Riahi, H A

    2007-10-01

    Polyamine analogues show antitumor activity in experimental models, and their ability to alter activity of cytotoxic chemotherapeutic agents in breast cancer is well documented. Association of polyamines with nucleic acids and protein is included in their mechanism of action. The aim of this study was to examine the interaction of human serum albumin (HSA) with several polyamine analogues, such as 1,11-diamino-4,8-diazaundecane (333), 3,7,11,15-tetrazaheptadecane.4HCl (BE-333), and 3,7,11,15,19-pentazahenicosane.5HCl (BE-3333), in aqueous solution at physiological conditions using a constant protein concentration and various polyamine contents (microM to mM). FTIR, UV-visible, and CD spectroscopic methods were used to determine the polyamine binding mode and the effects of polyamine complexation on protein stability and secondary structure. Structural analysis showed that polyamines bind nonspecifically (H-bonding) via polypeptide polar groups with binding constants of K333 = 9.30 x 10(3) M(-1), KBE-333 = 5.63 x 10(2) M(-1), and KBE-3333 = 3.66 x 10(2) M(-1). The protein secondary structure showed major alterations with a reduction of alpha-helix from 55% (free protein) to 43-50% and an increase of beta-sheet from 17% (free protein) to 29-36% in the 333, BE-333, and BE-3333 complexes, indicating partial protein unfolding upon polyamine interaction. HSA structure was less perturbed by polyamine analogues compared to those of the biogenic polyamines.

  12. New synthetic approaches towards analogues of bedaquiline.

    PubMed

    Priebbenow, Daniel L; Barbaro, Lisa; Baell, Jonathan B

    2016-10-12

    Multi-drug resistant tuberculosis (MDR-TB) is of growing global concern and threatens to undermine increasing efforts to control the worldwide spread of tuberculosis (TB). Bedaquiline has recently emerged as a new drug developed to specifically treat MDR-TB. Despite being highly effective as a result of its unique mode of action, bedaquiline has been associated with significant toxicities and as such, safety concerns are limiting its clinical use. In order to access pharmaceutical agents that exhibit an improved safety profile for the treatment of MDR-TB, new synthetic pathways to facilitate the preparation of bedaquiline and analogues thereof have been discovered.

  13. The Lehmer Matrix and Its Recursive Analogue

    DTIC Science & Technology

    2010-01-01

    for failing to comply with a collection of information if it does not display a currently valid OMB control number . 1. REPORT DATE 2010 2. REPORT...TYPE 3. DATES COVERED 00-00-2010 to 00-00-2010 4. TITLE AND SUBTITLE The Lehmer matrix and its recursive analogue 5a. CONTRACT NUMBER 5b...GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e. TASK NUMBER 5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND

  14. In search of future earths: assessing the possibility of finding Earth analogues in the later stages of their habitable lifetimes.

    PubMed

    O'Malley-James, Jack T; Greaves, Jane S; Raven, John A; Cockell, Charles S

    2015-05-01

    Earth will become uninhabitable within 2-3 Gyr as a result of the increasing luminosity of the Sun changing the boundaries of the habitable zone (HZ). Predictions about the future of habitable conditions on Earth include declining species diversity and habitat extent, ocean loss, and changes to geochemical cycles. Testing these predictions is difficult, but the discovery of a planet that is an analogue to future Earth could provide the means to test them. This planet would need to have an Earth-like biosphere history and to be approaching the inner edge of the HZ at present. Here, we assess the possibility of finding such a planet and discuss the benefits of analyzing older Earths. Finding an old-Earth analogue in nearby star systems would be ideal, because this would allow for atmospheric characterization. Hence, as an illustrative example, G stars within 10 pc of the Sun are assessed as potential old-Earth-analog hosts. Six of these represent good potential hosts. For each system, a hypothetical Earth analogue is placed at locations within the continuously habitable zone (CHZ) that would allow enough time for Earth-like biosphere development. Surface temperature evolution over the host star's main sequence lifetime (assessed by using a simple climate model) is used to determine whether the planet would be in the right stage of its late-habitable lifetime to exhibit detectable biosignatures. The best candidate, in terms of the chances of planet formation in the CHZ and of biosignature detection, is 61 Virginis. However, planet formation studies suggest that only a small fraction (0.36%) of G stars in the solar neighborhood could host an old-Earth analogue. If the development of Earth-like biospheres is rare, requiring a sequence of low-probability events to occur, biosphere evolution models suggest they are rarer still, with only thousands being present in the Galaxy as a whole.

  15. CO2 Removal using a Synthetic Analogue of Carbonic Anhydrase

    SciTech Connect

    Cordatos, Harry

    2010-09-14

    Project attempts to develop a synthetic analogue for carbonic anhydrase and incorporate it in a membrane for separation of CO2 from coal power plant flue gas. Conference poster presents result of first 9 months of project progress including concept, basic system architecture and membrane properties target, results of molecular modeling for analogue - CO2 interaction, and next steps of testing analogue resistance to flue gas contaminants.

  16. Synthesis of "neoprofen", a rigidified analogue of ibuprofen, exemplifying synthetic methodology for altering the 3-D topology of pharmaceutical substances.

    PubMed

    Ramsubhag, Ron R; Massaro, Chelsea L; Dadich, Christina M; Janeczek, Andrew J; Hoang, Tung T; Mazzio, Elizabeth A; Eyunni, Suresh; Soliman, Karam F A; Dudley, Gregory B

    2016-08-16

    3,3-Dimethylcyclopentanes (neopentylenes) are ubiquitous in Nature but largely absent from synthetic pharmaceutical libraries. Neopentylenes define a hydrophobic and rigid 3-D topology with distinct molecular pharmacology, as exemplified here with two neopentylene-fused analogues of the synthetic anti-inflammatory drug, ibuprofen.

  17. A bifunctional curcumin analogue for two-photon imaging and inhibiting crosslinking of amyloid beta in Alzheimer's disease.

    PubMed

    Zhang, Xueli; Tian, Yanli; Yuan, Peng; Li, Yuyan; Yaseen, Mohammad A; Grutzendler, Jaime; Moore, Anna; Ran, Chongzhao

    2014-10-09

    In this report, we designed a highly bright bifunctional curcumin analogue CRANAD-28. In vivo two-photon imaging suggested that CRANAD-28 could penetrate the blood brain barrier (BBB) and label plaques and cerebral amyloid angiopathies (CAAs). We also demonstrated that this imaging probe could inhibit the crosslinking of amyloid beta induced either by copper or by natural conditions.

  18. Geochemical and isotopic characterization of groundwater origins in a Mediterranean karst system (southern France)

    NASA Astrophysics Data System (ADS)

    Seidel, J. L.; Ladouche, B.; Batiot-Guilhe, C.

    2013-12-01

    Geochemical and isotopic ratio (11B/10B and 87Sr/86Sr) results are reported for better determining the groundwater origins in the Lez Karst system (southern France). The Lez spring is the main perennial outlet of the system and supplies with drinking water the metropolitan area of Montpellier. According to the hydrodynamic conditions, five water-types discharge at the Lez spring with important mineralization fluctuations (Caetano Bicalho et al., 2012). This geochemical response suggests that hydrodynamics targets groundwater circulation, resulting from different water end-member solicitation and mixing. Previous studies using conventional natural tracers do not succeed to identify all the water compartments supporting the flow during the hydrologic cycle (Marjolet & Salado, 1977; Joseph et al., 1988) and to explain the mineralization variation of the Lez spring. The present study combines a basic geochemical survey data with boron and strontium isotope ratio data for a better characterization of the Lez spring geochemical functioning. Groundwater samples were collected at the Lez spring and surrounding springs and wells under different hydrologic conditions from 2009 to 2011. Major, trace and rare earth elements were determined at AETE analytical platform (OREME, Univ. Montpellier 2) by ionic chromatography and Q-ICP-MS respectively. d11B and 87Sr/86Sr were determined at BRGM/MMA Orleans by TIMS. The geochemical survey has been extended at a larger scale by sampling the main geochemical end- members already identified to replace the Lez spring waters in the regional geochemical context. From this geochemical study, valuable informations have been provided on the reservoir types and water origins flowing in high and low stage periods. For the highly mineralized waters occurring in the fall first rainy events or severe low stages, a deep contribution is highlighted but B and Sr isotopic data do not ascertain the two Triassic end-members (halite or gypsum) as possible

  19. Synthesis of a cyanopeptide-analogue with trypsin activating properties.

    PubMed

    Radau, G; Rauh, D

    2000-04-17

    An efficient synthesis of a peptidic analogue of cyanobacterial metabolites with proposed serine protease inhibitory activity has been developed. Surprisingly, one trypsin activating compound was obtained.

  20. Modeling Background Radiation in our Environment Using Geochemical Data

    SciTech Connect

    Malchow, Russell L.; Marsac, Kara; Burnley, Pamela; Hausrath, Elisabeth; Haber, Daniel; Adcock, Christopher

    2015-02-01

    Radiation occurs naturally in bedrock and soil. Gamma rays are released from the decay of the radioactive isotopes K, U, and Th. Gamma rays observed at the surface come from the first 30 cm of rock and soil. The energy of gamma rays is specific to each isotope, allowing identification. For this research, data was collected from national databases, private companies, scientific literature, and field work. Data points were then evaluated for self-consistency. A model was created by converting concentrations of U, K, and Th for each rock and soil unit into a ground exposure rate using the following equation: D=1.32 K+ 0.548 U+ 0.272 Th. The first objective of this research was to compare the original Aerial Measurement System gamma ray survey to results produced by the model. The second objective was to improve the method and learn the constraints of the model. Future work will include sample data analysis from field work with a goal of improving the geochemical model.

  1. New geochemical investigations in Platanares and Azacualpa geothermal sites (Honduras)

    NASA Astrophysics Data System (ADS)

    Barberi, Franco; Carapezza, Maria Luisa; Cioni, Roberto; Lelli, Matteo; Menichini, Matia; Ranaldi, Massimo; Ricci, Tullio; Tarchini, Luca

    2013-05-01

    Platanares and Azacualpa geothermal sites of Honduras are located in an inner part of the Caribbean Plate far from the active volcanic front of Central America. Here geology indicates that there are not the conditions for the occurrence of shallow magmatic heat sources for high-enthalpy geothermal resources. Geothermal perspectives are related to the possibility of a deep circulation of meteoric water along faults and the storage of the heated fluid in fractured permeable reservoirs. Geochemical geothermometers indicate a temperature for the deeper part of the geothermal reservoir close to 200 °C for Platanares and of 150-170 °C for Azacualpa. Calcite scaling, with subordinate silica deposition has to be expected in both sites. CO2 soil flux investigations have been carried out in both areas and reveal the presence of positive anomalies likely corresponding to the presence at depth of fractured degassing geothermal reservoirs. Compared with the geothermal areas of Central Italy whose reservoirs are hosted in carbonate rocks, e.g. Latera (Chiodini et al., 2007), the CO2 soil flux measured in Honduras is significantly lower (mean of 17 g/m2day at Platanares and of 163 g/m2day at Azacualpa) probably because of the dominant silicate nature of the deep reservoirs.

  2. A model of isotope fractionation in reacting geochemical systems

    SciTech Connect

    Lee, Ming-Kuo; Bethke, C.M.

    1996-11-01

    The authors present a numerical technique that predicts how the stable isotopes {sup 2}H, {sup 13}C, {sup 18}O, and {sup 34}S fractionate among solvent, aqueous species, minerals, and gases over the course of a geochemical reaction process. This model is based on mass balance techniques similar to those already presented in the literature but differs from previous techniques in that it allows minerals to be segregated form isotopic exchange instead of remaining in isotopic equilibrium. Such an approach allows us to simulate the fractionation of isotopes between rock and fluid resulting solely from mineral dissolution and precipitation. The technique was tested by modeling isotopic fractionation during several reaction processes, including (1) dolomitization of limestone by a migrating pore fluid, (2) diagenetic alteration of the Permian Lyons sandstone in the Denver basin, and (3) hydrothermal alteration of the Okanagan Batholith in southern British Columbia. The results of calculations in which minerals are segregated from isotopic exchange compare well to isotopic trends observed in nature but differ markedly from calculations that assume isotopic equilibrium. 54 refs., 4 figs., 3 tabs.

  3. Practical aspects with multifractal simulation of a geochemical landscape

    NASA Astrophysics Data System (ADS)

    Yao, Lingqing

    2015-04-01

    Geochemical prospecting plays important role in mineral exploration and environmental risk monitoring. Either targeting a potential mineralized area or evaluating the environmental risk, has close relationship with identification of geochemical anomalies, which are featured by spatial patterns of geochemical elements. Simulation technique helps to mathematically capture the mechanism of formation of a geochemical landscape, and to reproduce the related spatial patterns. Traditionally, conditional simulations are used to reproduce the frequency distributions and spatial correlations of geochemical landscapes. The traditional approaches to conditional simulation assume wide sense stationary and Gaussian distribution, and thus have limitations with simulating the skewed distributions and reflecting singularity of geochemical anomalies. Multifractal simulation provides an alternative to generate the spatial patterns of the geochemical landscapes, and most importantly, to reproduce the singularity of geochemical concentrations. Multiplicative cascade process has been one most compelling method to implement multifractal simulation and there are several different ways to perform the simulation in the context of different disciplines or mechanisms, and thus the results can also be different. In the present work, moment method is used to find the scaling law and to analyze the multifractal spectra. A second-order spatial correlation as a power-law model is constructed from the scaling properties of the data, and conditional simulation is carried out with the correlation model. Moreover, multifractal simulations are generated from the multiplicative cascade models which are discrete-in-scale and continuous-in-scale, respectively. A specific data is used as an example to carry out the simulations with different methods, and some findings with respect to the practical aspects of multifractal simulations of a geochemical landscape are given from further analysis and comparison

  4. Self-Powered Analogue Smart Skin.

    PubMed

    Shi, Mayue; Zhang, Jinxin; Chen, Haotian; Han, Mengdi; Shankaregowda, Smitha A; Su, Zongming; Meng, Bo; Cheng, Xiaoliang; Zhang, Haixia

    2016-04-26

    The progress of smart skin technology presents unprecedented opportunities for artificial intelligence. Resolution enhancement and energy conservation are critical to improve the perception and standby time of robots. Here, we present a self-powered analogue smart skin for detecting contact location and velocity of the object, based on a single-electrode contact electrification effect and planar electrostatic induction. Using an analogue localizing method, the resolution of this two-dimensional smart skin can be achieved at 1.9 mm with only four terminals, which notably decreases the terminal number of smart skins. The sensitivity of this smart skin is remarkable, which can even perceive the perturbation of a honey bee. Meanwhile, benefiting from the triboelectric mechanism, extra power supply is unnecessary for this smart skin. Therefore, it solves the problems of batteries and connecting wires for smart skins. With microstructured poly(dimethylsiloxane) films and silver nanowire electrodes, it can be covered on the skin with transparency, flexibility, and high sensitivity.

  5. Analysis of Geochemical Element Behaviors in Soils by Multifractal Methods

    NASA Astrophysics Data System (ADS)

    Xie, S.; Cheng, Q.; Huang, K.; Bao, Z.

    2009-04-01

    Soils are not only one of crucial environmental media but also one of the most important objects for environmental geochemistry. Usually, soils are developed from various kinds of rocks. During the weathering of rocks, the issues, such as the evolution of geochemical elements and the different behaviors of geochemical elements in soils, have been gaining great concern. This paper will explore the geochemical distribution patterns by fractal and multifractal methods, and then use the soils with different periods in the Hainan Island, China, as the case study to analyze the behaviors of geochemical elements. The soils in the Hainan Island are strongly aluminized, and anthropological activities have little impacts on the zonal soils. Thus the dynamic evolutions of the geochemical elements in soils are relatively of their original characteristics. The TAS analysis based on the diagram of SiO2-Na2O+K2O is implemented and has shown that most of the soils are evolved from granodiorite rocks, and some from basalts. This analytical result is quite consistent to the regional rock sampling investigation. Spider diagrams of trace elements also present that the soils are mainly developed from basalts and granites. In terms of the multifractal parameters characterizing the distribution patterns of the geochemical elements in the soils evolved from seven geological systems, it is shown that in the surroundings the multifractal behaviors of the geochemical elements are strongly associated with their inner geochemical behaviors on one hand, and on the other hand, anthropological activities and weathering behaviors of the soils also have specific effects on the multifractal parameters. In the study, the right parts of the multifractal spectrum curves of the geochemical elements in soils evolved from the Changchengian system change significantly, which implies that there are much lower geochemical data for elements. But for the soils evolved from granites and basalts, the left parts

  6. Targeted Melanoma Imaging and Therapy with Radiolabeled Alpha-Melanocyte Stimulating Hormone Peptide Analogues

    PubMed Central

    Quinn, Thomas; Zhang, Xiuli; Miao, Yubin

    2010-01-01

    Radiolabeled alpha-melanocyte stimulating hormone (α-MSH) analogues have been used to define the expression, affinity and function of the melanocortin-1 receptor (MC1-R). The MC1-R is one of a family of five G-protein linker receptors, which is primarily involved in regulation of skin pigmentation. Over-expression of the MC1-R on melanoma tumor cells has made it an attractive target for the development of α-MSH peptide based imaging and therapeutic agents. Initially, the native α-MSH peptide was radiolabeled directly, but it suffered from low specific activity and poor stability. The addition of non-natural amino acids yielded α-MSH analogues with greater MC-1R affinity and stability. Furthermore, peptide cyclization via disulfide and lactam bond formation as well as site-specific metal coordination resulted in additional gains in receptor affinity and peptide stability in vitro and in vivo. Radiochemical stability of the α-MSH analogues was improved through the conjugation of metal chelators to the peptide’s N-terminus or lysine residues for radionuclide coordination. In vitro cell binding studies demonstrated that the radiolabeled α-MSH analogues had low to subnanomolar affinities for the MC1-R. Biodistribution and imaging studies in the B16 mouse melanoma modeled showed rapid tumor uptake of the radiolabeled peptides, with the cyclic peptides demonstrating prolonged tumor retention. Cyclic α-MSH analogues labeled with beta and alpha emitting radionuclides demonstrated melanoma therapeutic efficacy in the B16 melanoma mouse model. Strong pre-clinical imaging and therapy data highlight the clinical potential use of radiolabeled α-MSH peptides for melanoma imaging and treatment of disseminated disease. PMID:20467398

  7. Top Soils Geochemical and Radioactivity Survey of Naples (Italy) Metropolitan.

    NASA Astrophysics Data System (ADS)

    Somma, R.; De Vivo, B.; Cicchella, D.

    2001-05-01

    The metropolitan area of Naples due to intense human activities is an emblematic area affected by various environmental pollution of soils and waters in addition to hydrogeological volcanic, seismic and bradyseismic hazards. The geology of the area is prevailing represented by volcanics erupted, from the Upper Pleistocene to Recent by Mt. Somma-Vesuvius on the east and the Campi Flegrei fields on the west. The morphology of the metropolitan area of Naples city can be subdivided in flat areas, constituted by reworked pyroclastic terrains, and by hills originated by the overlapping of different welded pyroclastic flows (i.e.: Campanian Ignimbrite and Neapoletan Yellow Tuff) intercalated with pyroclastic deposits of different origins (i.e.: Campi Flegrei, Mt. Somma-Vesuvius, Ischia) and ages. In order to compile a multi-element baseline geochemical and radioactivity mapping of the metropolitan area of the Napoli we have sampled for this study, in situ top soil and imported filling material (mainly soil, volcanic ash, pumice and scoriae). The sampling and radioactivity survey has been carried out on about 200 sampling sites covering an area of about 150 Km2, with a grid of 0.5 x 0.5 km in the urbanised downtown and 1 km x 1 km in the sub urban areas. In each site has been determined a radioactivity by a Scintrex GRS-500 at different emission spectra as total radioactivity (> 0.08 MeV and > 0.40 MeV), 238U (at 1.76 MeV mostly from 214Bi), 232Th (at 2.6 MeV mostly from 208Tl) and 40K (at 1.46 MeV mostly for 40K). The range of values of in situ soils are as follow for the in situ soils (Total radioactivity: 1327- 360 and 114- 47; 238U: 2.6- 1.3; 40K: 8.1- 3.1; 232U: 0.5- 0.1). Analyses of major, metallic elements and pH of each soil sample are in progress, while Pb isotopes compositions, for a selected number of samples, will be determined to discriminate the natural (geogenic) from the anthropogenic components in the soils by versus the anthropogenetic origin. The data

  8. In Situ Rates of Sulfate Reduction in Response to Geochemical Perturbations

    USGS Publications Warehouse

    Kneeshaw, T.A.; McGuire, J.T.; Cozzarelli, I.M.; Smith, E.W.

    2011-01-01

    Rates of in situ microbial sulfate reduction in response to geochemical perturbations were determined using Native Organism Geochemical Experimentation Enclosures (NOGEEs), a new in situ technique developed to facilitate evaluation of controls on microbial reaction rates. NOGEEs function by first trapping a native microbial community in situ and then subjecting it to geochemical perturbations through the introduction of various test solutions. On three occasions, NOGEEs were used at the Norman Landfill research site in Norman, Oklahoma, to evaluate sulfate-reduction rates in wetland sediments impacted by landfill leachate. The initial experiment, in May 2007, consisted of five introductions of a sulfate test solution over 11 d. Each test stimulated sulfate reduction with rates increasing until an apparent maximum was achieved. Two subsequent experiments, conducted in October 2007 and February 2008, evaluated the effects of concentration on sulfate-reduction rates. Results from these experiments showed that faster sulfate-reduction rates were associated with increased sulfate concentrations. Understanding variability in sulfate-reduction rates in response to perturbations may be an important factor in predicting rates of natural attenuation and bioremediation of contaminants in systems not at biogeochemical equilibrium. Copyright ?? 2011 The Author(s). Journal compilation ?? 2011 National Ground Water Association.

  9. Geochemical heterogeneities within the Crozet hotspot

    NASA Astrophysics Data System (ADS)

    Breton, Thomas; Nauret, François; Pichat, Sylvain; Moine, Bertrand; Moreira, Manuel; Rose-Koga, Estelle F.; Auclair, Delphine; Bosq, Chantal; Wavrant, Laurène-Marie

    2013-08-01

    The Crozet Plateau is a 54 Ma-old volcanic plateau that supports five islands characterized by recent volcanic manifestations that are the surface expression of a deep-mantle plume. Due to their remote location and difficult access, the Crozet Islands are poorly sampled. Both the petrological descriptions and geochemical data are scarce. Thus, the sources of the Crozet plume are still under debate. Similarly, the interactions between the Southwest Indian Ridge (SWIR) and the Crozet plume remain questioned. Here, we present a new set of isotopes (Pb, Sr, Nd and He), major and trace elements data on basalts from three islands of the Crozet Archipelago: Penguins, East, and Possession Islands. Our main purpose is to characterize the sources of the Crozet plume and to test its influence at regional scale. Two groups of lavas can be distinguished based on the isotopic data: East and Possession lavas, and Penguins lavas. Principal component analyses on our high-precision Pb isotopes data and literature data show that two mantle sources can explain most of the geochemical variability measured in Crozet lavas. A third minor contribution is however needed to fully explain the data. The entire set of isotopic compositions (Pb, Sr, Nd and He) can be explained by a mixing between three mantle sources: (1) a FOZO (Focus Zone) component, with 206Pb/204Pb higher than 19.5 and high 207Pb/204Pb, 208Pb/204Pb 87Sr/86Sr, 143Nd/144Nd and R/Ra (R/Ra=(He3/He4)sample/(He3/He4)atmosphere) ratios, that is mainly sampled Penguins lavas, (2) a component called “East-Possession” that is mostly sampled by the East-Possession lava group and which presents Pb, Sr and Nd isotope signatures similar to those of the Reunion-Mauritius Islands, and (3) a third minor contribution of the local Depleted MORB Mantle (DMM). The new He isotopes data on the Crozet plume allow us to propose that Crozet plume material is present in the segment of the Southwest Indian Ridge located between the Indomed (ITF

  10. Geochemical surveys in the Lusi mud eruption

    NASA Astrophysics Data System (ADS)

    Sciarra, Alessandra; Mazzini, Adriano; Etiope, Giuseppe; Inguaggiato, Salvatore; Hussein, Alwi; Hadi J., Soffian

    2016-04-01

    The Lusi mud eruption started in May 2006 following to a 6.3 M earthquake striking the Java Island. In the framework of the Lusi Lab project (ERC grant n° 308126) we carried out geochemical surveys in the Sidoarjo district (Eastern Java Island, Indonesia) to investigate the gas bearing properties of the Watukosek fault system that crosses the Lusi mud eruption area. Soil gas (222Rn, CO2, CH4) concentration and flux measurements were performed 1) along two detailed profiles (~ 1km long), trending almost W-E direction, and 2) inside the Lusi embankment (about 7 km2) built to contain the erupted mud. Higher gas concentrations and fluxes were detected at the intersection with the Watukosek fault and the antithetic fault system. These zones characterized by the association of higher soil gas values constitute preferential migration pathways for fluids towards surface. The fractures release mainly CO2 (with peaks up to 400 g/m2day) and display higher temperatures (up to 41°C). The main shear zones are populated by numerous seeps that expel mostly CH4. Flux measurements in the seeping pools reveal that φCO2 is an order of magnitude higher than that measured in the fractures, and two orders of magnitude higher for φCH4. An additional geochemical profile was completed perpendicularly to the Watukosek fault escarpement (W-E direction) at the foots of the Penanngungang volcano. Results reveal CO2 and CH4 flux values significantly lower than those measured in the embankment, however an increase of radon and flux measurements is observed approaching the foots of the escarpment. These measurements are complemented with a database of ~350 CH4 and CO2 flux measurements and some soil gas concentrations (He, H2, CO2, CH4 and C2H6) and their isotopic analyses (δ13C-CH4, δD-CH4 and δ13C-CO2). Results show that the whole area is characterized by diffused gas release through seeps, fractures, microfractures and soil degassing. The collected results shed light on the origin of the

  11. Combined thermodynamic-geochemical modeling in metamorphic geology: Boron as tracer of fluid-rock interaction

    NASA Astrophysics Data System (ADS)

    Konrad-Schmolke, Matthias; Halama, Ralf

    2014-11-01

    Quantitative geochemical modeling is today applied in a variety of geological environments from the petrogenesis of igneous rocks to radioactive waste disposal. In addition, the development of thermodynamic databases and computer programs to calculate equilibrium phase diagrams has greatly advanced our ability to model geodynamic processes. Combined with experimental data on elemental partitioning and isotopic fractionation, thermodynamic forward modeling unfolds enormous capacities that are far from exhausted. In metamorphic petrology the combination of thermodynamic and trace element forward modeling can be used to study and to quantify processes at spatial scales from μm to km. The thermodynamic forward models utilize Gibbs energy minimization to quantify mineralogical changes along a reaction path of a chemically open fluid/rock system. These results are combined with mass balanced trace element calculations to determine the trace element distribution between rock and melt/fluid during the metamorphic evolution. Thus, effects of mineral reactions, fluid-rock interaction and element transport in metamorphic rocks on the trace element and isotopic composition of minerals, rocks and percolating fluids or melts can be predicted. Here we illustrate the capacities of combined thermodynamic-geochemical modeling based on two examples relevant to mass transfer during metamorphism. The first example focuses on fluid-rock interaction in and around a blueschist-facies shear zone in felsic gneisses, where fluid-induced mineral reactions and their effects on boron (B) concentrations and isotopic compositions in white mica are modeled. In the second example, fluid release from a subducted slab, the associated transport of B as well as variations in B concentrations and isotopic compositions in liberated fluids and residual rocks are modeled. We compare the modeled results of both examples to geochemical data of natural minerals and rocks and demonstrate that the combination

  12. Geochemical study of coral skeletons from the Puerto Morelos Reef, southeastern Mexico

    NASA Astrophysics Data System (ADS)

    Kasper-Zubillaga, Juan J.; Armstrong-Altrin, John S.; Rosales-Hoz, Leticia

    2014-12-01

    Geochemical analyses in coral skeletons have been used as a proxy of marine environmental conditions and to understand the mechanisms of adsorption of chemical elements into the coral skeletons and growth forms. However, little attention has been given to show the possible differences in the growth rates of corals based upon major, trace, rare earth element and microprobe analyses to examine the physical-chemical conditions influencing those differences. Our goal is to show how branch and fan corals incorporate elements into their skeletons comparing them with their coral growth rates. We determine the development of the skeletons of two branching (Acropora palmata, Acropora cervicornis) and one fan shaped (Gorgonia ventalina) colonies in the Puerto Morelos Reef, southeastern Mexico based upon geochemical data and the influence of terrigenous input into the species. Mg and Sr concentrations were the most statistically significant elements among the species studied suggesting that Mg concentration in Gorgonia ventalina is probably not linked to its growth rate. Mn content in the sea water is adsorbed by the three corals during past growth rates during high rainfall events. Sr concentration may be associated with the growth rate of Acropora palmata. Little differences in the growth rate in Acropora palmata may be associated with low rates of calcitization, negligible changes in the Sr concentration and little influence of temperature and water depth in its growth. Trace elements like Cr, Co, Ni and V adsorbed by the corals are influenced by natural concentration of these elements in the sea-water. Rare earth elements in the corals studied suggests abundant inorganic ions CO32- with variable pH in modern shallow well-oxygenated sea water. Lack of terrigenous input seawards is supported by geochemical, geomorphological and biological evidences. This study is an example of how geochemical data are useful to observe the differences in environmental conditions related to

  13. Geochemical Fate and Transport of Sildenafil and Vardenafil

    NASA Astrophysics Data System (ADS)

    Richter, L.; Boudinot, G.; Vulava, V. M.; Cory, W. C.

    2015-12-01

    The geochemical fate of pharmaceuticals and their degradation products is a developing environmental field. The geologic, chemical, and biological fate of these pollutants has become very relevant with the increase in human population and the resulting increase in pollutant concentrations in the environment. In this study, we focus on sildenafil (SDF) and vardenafil (VDF), active compounds in Viagra and Levitra, respectively, two commonly used erectile dysfunction drugs. The main objective is to determine the sorption potential and transport behavior of these two compounds in natural soils. Both SDF and VDF are complex organic molecules with multiple amine functional groups in their structures. Two types of natural acidic soils (pH≈4.5), an organic-rich soil (7.6% OM) and clay-rich soil (5.1% clay) were used in this study to determine which soil components influence sorption behavior of both compounds. Sorption isotherms measured using batch reactors were nearly linear, but sorption was stronger in soil that contained higher clay content. Both compounds have multiple pKas due to the amine functional groups, the relevant pKas of SDF are 5.97 and 7.27, and those of VDF's are 4.72 and 6.21. These values indicate that these compounds likely behave as cations in soil suspensions and hence were strongly sorbed to negatively-charged clay minerals present in both soils. The clay composition in both soils is predominantly kaolinite with smaller amount of montmorillonite, both of which have a predominantly negative surface charge. Transport experiments using glass chromatography columns indicated that both compounds were more strongly retarded in the clay-rich soils. Breakthrough curves from the transport experiments were modeled using convection-dispersion transport equations. The organic matter in the soil seemed to play a less dominant role in the geochemistry in this study, but is likely to transform both compounds into derivative compounds as seen in other studies.

  14. On the inference of hydrogeological and geochemical parameters from tracer tests

    NASA Astrophysics Data System (ADS)

    Bellin, A.; Rubin, Y.

    2003-04-01

    We present a new methodology for inference of spatial variability models of the aquifer's hydrogeological and geochemical parameters from the breakthrough curves of tracers, measured at samplers placed within monitoring wells. Hypotheses on scaling effects on both hydrogeological and geochemical parameters can be confirmed, or rejected, based on the inference conducted with subsets of the full data set. Natural and forced head tracer tests typically reveal a significant disparity in both the arrival time and the spreading of the BTCs collected at the monitoring points belonging to the same well. We can then surmise that statistics of the BTC, such as the mean concentration arrival time, t_m, and the peak concentration arrival time, t_p, vary between the samplers due to the heterogeneity of the medium. One may further assume that the solute spreading observed at any of the monitoring points is controlled by local dispersion, while the disparity between the arrival times at the different samplers is the result of large-scale heterogeneity. The methodology relies on matching analytical models for travel time moments with the corresponding moments obtained from BTCs analysis. Specifically, the average of t_m is matched with the analytical expression of the mean travel time, while the variance of t_m, augmented by the average of the BTC second moment, is matched with the analytical expression of the travel time variance. We show, through a numerical example, that the same equivalences hold when t_m is replaced with t_p, with the latter providing more reliable results in presence of BTC truncation. The methodology can be applied to both natural and forced head gradient tracer tests, provided that suitable analytical models of the travel time moments are available, as confirmed by our analysis of published data on a forced head tracer experiment conducted at Borden (Canada). Furthermore, geochemical parameters are obtained by matching analytical models of travel time

  15. Antidepressant-like effects and mechanisms of flavonoids and related analogues.

    PubMed

    Guan, Li-Ping; Liu, Bing-Yu

    2016-10-04

    Flavonoids, possessing a basic phenylbenzopyrone core, are important components of the human diet, and are found in many medicinal plants. Flavonoids include chalcones, flavanones and their derivatives. Synthetic and natural isolated flavonoids display an enormous number of biological activities such as antitumor, antiplatelet, anti-malarial, anti-inflammatory, antidepressant and anticonvulsant properties. This review article focuses on the antidepressant-like effect, structure-activity relationship and mechanism of action of total flavonoid extracts isolation from natural sources, flavonoid compounds and their related analogues.

  16. [Oligonucleotide analogues bearing an acyclonucleoside linked by an internucleotide amide bond].

    PubMed

    Kochetkova, S V; Fillipova, E A; Kolganova, N A; Timofeev, E N; Florent'ev, V L

    2008-01-01

    Oligonucleotide analogues bearing an acyclocytidine linked to thymidine by an amide (3'-O-CH2-CO-N-5') bond were synthesized. Melting curves of duplexes formed by modified oligonucleotides and complementary natural oligomers were obtained and thermodynamic parameters of their formation were measured. Replacement of dCpT by a modified dinucleotide only moderately decreased the melting temperature of these modified duplexes in comparison with unmodified duplexes containing complementary natural bases. CD spectra of modified duplexes were studied, and the duplex spatial structures are discussed. The English version of the paper: Russian Journal of Bioorganic Chemistry, 2008, vol. 34, no. 2; see also http://www.maik.ru.

  17. Starting a European Space Agency Sample Analogue Collection for Robotic Exploration Missions

    NASA Astrophysics Data System (ADS)

    Smith, C. L.; Mavris, C.; Michalski, J. R.; Rumsey, M. S.; Russell, S. S.; Jones, C.; Schroeven-Deceuninck, H.

    2015-12-01

    The Natural History Museum is working closely with the European Space Agency (ESA) and the UK Space Agency to develop a European collection of analogue materials with appropriate physical/mechanical and chemical (mineralogical) properties which can support the development and verification of both spacecraft and scientific systems for potential science and exploration missions to Phobos/Deimos, Mars, C-type asteroids and the Moon. As an ESA Collection it will be housed at the ESA Centre based at Harwell, UK. The "ESA Sample Analogues Collection" will be composed of both natural and artificial materials chosen to (as closely as possible) replicate the surfaces and near-surfaces of different Solar System target bodies of exploration interest. The analogue samples will be fully characterised in terms of both their physical/mechanical properties (compressive strength, bulk density, grain shape, grain size, cohesion and angle of internal friction) and their chemical/mineralogical properties (texture, modal mineralogy, bulk chemical composition - major, minor and trace elements and individual mineralogical compositions). The Collection will be fully curated to international standards including implementation of a user-friendly database and will be available for use by engineers and scientists across the UK and Europe. Enhancement of the initial Collection will be possible through collaborations with other ESA and UK Space Agency supported activities, such as the acquisition of new samples during field trials.

  18. Starting a European Space Agency Sample Analogue Collection for Robotic Exploration Missions

    NASA Astrophysics Data System (ADS)

    Sherwood Lollar, B.; Sutcliffe, C. N.; Ballentine, C. J.; Onstott, T. C.; Lau, C. Y. M.; Magnabosco, C.; Slater, G.; Moser, D. P.

    2014-12-01

    The Natural History Museum is working closely with the European Space Agency (ESA) and the UK Space Agency to develop a European collection of analogue materials with appropriate physical/mechanical and chemical (mineralogical) properties which can support the development and verification of both spacecraft and scientific systems for potential science and exploration missions to Phobos/Deimos, Mars, C-type asteroids and the Moon. As an ESA Collection it will be housed at the ESA Centre based at Harwell, UK. The "ESA Sample Analogues Collection" will be composed of both natural and artificial materials chosen to (as closely as possible) replicate the surfaces and near-surfaces of different Solar System target bodies of exploration interest. The analogue samples will be fully characterised in terms of both their physical/mechanical properties (compressive strength, bulk density, grain shape, grain size, cohesion and angle of internal friction) and their chemical/mineralogical properties (texture, modal mineralogy, bulk chemical composition - major, minor and trace elements and individual mineralogical compositions). The Collection will be fully curated to international standards including implementation of a user-friendly database and will be available for use by engineers and scientists across the UK and Europe. Enhancement of the initial Collection will be possible through collaborations with other ESA and UK Space Agency supported activities, such as the acquisition of new samples during field trials.

  19. Strigolactone Analogues with a D‐Ring Modified at C‐2

    PubMed Central

    Mwakaboko, Alinanuswe S.

    2016-01-01

    Strigolactones (SLs) are important new plant hormones that receive much attention in current plant science. SLs are produced by many plants and are exuded by the root system. SLs are, amongst others, germination stimulants for seed of parasitic weeds. Naturally occurring SLs invariably contain three annelated rings, the ABC‐scaffold, connected to a butenolide (the D‐ring) via an enol ether unit. The synthesis of natural SLs requires many steps, therefore there is a continuous search for SL analogues with a simpler structure but with retention of bioactivity. In this study modified D‐ring variants are investigated, especially analogues having a methyl group at C‐2 instead of a hydrogen. For these analogues the ABC‐scaffolds of GR24 and Nijmegen‐1 were used. The coupling reaction proceeds profoundly better with chlorobutenolides than with the corresponding bromides. Bioassays reveal that the introduction an extra methyl at C‐2 does not influence the germination activity, which is relevant for gaining insight in the mode of action of SLs. PMID:27840586

  20. Podoconiosis: non-infectious geochemical elephantiasis.

    PubMed

    Davey, Gail; Tekola, Fasil; Newport, Melanie J

    2007-12-01

    This article reviews peer-reviewed publications and book chapters on the history, epidemiology, genetics, ecology, pathogenesis, pathology and management of podoconiosis (endemic non-filarial elephantiasis). Podoconiosis is a non-infectious geochemical elephantiasis caused by exposure of bare feet to irritant alkalic clay soils. It is found in at least 10 countries in tropical Africa, Central America and northwest India, where such soils coexist with high altitude, high seasonal rainfall and low income. Podoconiosis develops in men and women working barefoot on irritant soils, with signs becoming apparent in most patients by the third decade of life. Colloid-sized silicate particles appear to enter through the skin, are taken up into macrophages in the lower limb lymphatics and cause endolymphangitis and obliteration of the lymphatic lumen. Genetic studies provide evidence for high heritability of susceptibility to podoconiosis. The economic burden is significant in affected areas dependent on subsistence farming. Podoconiosis is unique in being an entirely preventable non-communicable disease. Primary prevention entails promoting use of footwear in areas of irritant soil; early stages are reversible given good foot hygiene, but late stages result in considerable economic and social difficulties, and require extended periods of elevation and occasionally nodulectomy.

  1. Venus: Geochemical conclusions from the Magellan data

    NASA Technical Reports Server (NTRS)

    Wood, J. A.

    1992-01-01

    Though the Magellan mission was not designed to collect geochemical or petrological information, it has done so nonetheless. Since the time of the Pioneer Venus mission it has been known that high-altitude (greater than 2.5-5 km) mountainous areas on Venus exhibit anomalously low radiothermal emissivity (e less than 0.6). Magellan has greatly refined and extended these observations. The low emissivity requires surface material in the uplands to have a mineralogical composition that gives it a high bulk dielectric constant, greater than 20. The dielectric constant of dry terrestrial volcanic rocks seldom exceeds 7. The high-dielectric character of high-altitude surface material cannot be a primary property of the local volcanic rock, because there is no reason why rock having the required special mineralogy would erupt only at high altitudes. Therefore it is a secondary property; the primary Venus rock has reacted with the atmosphere to form a mineralogically different surface layer, and the secondary minerals formed are controlled by the ambient temperature, which decreases with altitude on Venus. A further investigation of venusian mineralogy is presented.

  2. The Geochemical Earth Reference Model (GERM)

    SciTech Connect

    Staudigel, H.; Albarede, F.; Shaw, H.; McDonough, B.; White, W.

    1996-12-01

    The Geochemical Earth Reference Model (GERM) initiative is a grass- roots effort with the goal of establishing a community consensus on a chemical characterization of the Earth, its major reservoirs, and the fluxes between them. Long term goal of GERM is a chemical reservoir characterization analogous to the geophysical effort of the Preliminary Reference Earth Model (PREM). Chemical fluxes between reservoirs are included into GERM to illuminate the long-term chemical evolution of the Earth and to characterize the Earth as a dynamic chemical system. In turn, these fluxes control geological processes and influence hydrosphere-atmosphere-climate dynamics. While these long-term goals are clearly the focus of GERM, the process of establishing GERM itself is just as important as its ultimate goal. The GERM initiative is developed in an open community discussion on the World Wide Web (GERM home page is at http://www-ep.es.llnl. gov/germ/germ-home.html) that is mediated by a series of editors with responsibilities for distinct reservoirs and fluxes. Beginning with the original workshop in Lyons (March 1996) GERM is continued to be developed on the Internet, punctuated by workshops and special sessions at professional meetings. It is planned to complete the first model by mid-1997, followed by a call for papers for a February 1998 GERM conference in La Jolla, California.

  3. Geochemical Anomalies and Rock Coatings on Mars: Significance to MSR

    NASA Astrophysics Data System (ADS)

    Clark, B. C.; Gellert, R.

    2016-08-01

    Mars rover missions [Spirit (MER-A), Opportunity (MER-B), Curiosity (MSL)] have discovered unexpected geochemical extremes from aqueous alteration. Coatings and certain trace elements show large enrichment's well beyond magmatic differentiation.

  4. Toxicity of major geochemical ions to freshwater species

    EPA Science Inventory

    Extensive testing regarding the toxicity of major geochemical ions to Ceriodaphnia dubia, Hyalella azteca, and Pimephales promelas will be presented. For C. dubia, tests of single salts and binary mixtures in various dilution waters demonstrated multiple mechanisms of toxicity an...

  5. Geochemical and isotopic water results, Barrow, Alaska, 2012-2013

    DOE Data Explorer

    Heikoop, Jeff; Wilson, Cathy; Newman, Brent

    2012-07-18

    Data include a large suite of analytes (geochemical and isotopic) for samples collected in Barrow, Alaska (2012-2013). Sample types are indicated, and include soil pore waters, drainage waters, snowmelt, precipitation, and permafrost samples.

  6. GEOCHEM-EZ: a chemical speciation program with greater power and flexibility

    Technology Transfer Automated Retrieval System (TEKTRAN)

    GEOCHEM –EZ is a multi-functional chemical speciation program, which was designed to replace the existing GEOCHEM-PC, a program that can only be used on DOS consoles. Chemical speciation programs, such as GEOCHEM (Sposito and Mattigod, 1980) and GEOCHEM-PC (Parker et al., 1995), have been excellent ...

  7. Structure-geochemical zoning of Topolninsk gold-ore field (Gorny Altai)

    NASA Astrophysics Data System (ADS)

    Timkin, T. V.; Lavrov, D. S.; Askanakova, O. Y.; Korotchenko, T. V.

    2014-08-01

    Geochemical zoning of prospective mineable gold-bearing skarns was carried out. The geochemical field abnormal structures of different hierarchy levels associated with gold- skarn formations were revealed. The interrelation between the structure of ore-geochemical fields and associated ring structures was studied. Complex structure-geochemical criteria for gold mineralization prospecting and evaluation were proposed.

  8. Space Analogue Environments: Are the Populations Comparable?

    NASA Astrophysics Data System (ADS)

    Sandal, G. M.

    Background: Much of our present understanding about psychology in space is based on studies of groups operating in so-called analogue environments where personnel are exposed to many of the same stressors as those experienced by astronauts in space. One possible problem with extrapolating results is that personnel operating in various hazardous and confined environments might differ in characteristics influencing coping, interaction, and performance. The object of this study was to compare the psychological similarity of these populations in order to get a better understanding of whether this extrapolation is justifiable. The samples investigated include polar crossings (N= 22), personnel on Antarctic research stations (N= 183), several military occupations (N= 187), and participants in space simulation studies (N=20). Methods: Personnel in each of these environments were assessed using the Personality Characteristic Inventory (PCI) and Utrecht Coping List (UCL). The PCI is a multidimensional trait assessment battery that measures various aspects of achievement orientation and social competence. The UCL is a questionnaire designed to assess habitual coping strategies when encountering stressful or demanding situations. Results: Only minor differences in use of habitual coping strategies were evident across the different samples. In relation to personality scores, the military subjects and participants in space simulation studies indicated higher competitiveness and negative instrumentality compared to both the personnel on Antarctic research stations and participants in polar expedition. Among the personnel on Antarctic research stations, significant gender differences were found with women scoring lower on competitiveness, negative instrumentality and impatience/irritability. Compared to the other samples, the participants in polar expeditions were found to be more homogeneous in personality and no significant gender differences were evident on the traits that

  9. A nonlinear dynamic analogue model of substorms

    NASA Astrophysics Data System (ADS)

    Klimas, A. J.; Baker, D. N.; Roberts, D. A.; Fairfield, D. H.; Büchner, J.

    Linear prediction filter studies have shown that the magnetospheric response to energy transfer from the solar wind contains both directly driven and unloading components. These studies have also shown that the magnetospheric response is significantly nonlinear and, thus, the linear prediction filtering technique and other correlative techniques which assume a linear magnetospheric response cannot give a complete deacription of that response. Here, the solar wind-magnetosphere interaction is discussed within the framework of deterministic nonlinear dynamics. An earlier dripping faucet mechanical analogue to the magnetosphere is first reviewed and then the plasma physical counterpart to the mechanical model is constructed. A Faraday loop in the magnetotail is considered and the relationship of electric potentials on the loop to changes in the magnetic flux threading the loop is developed. This approach leads to a model of geomagnetic activity which is similar to the earlier mechanical model but described in terms of the geometry and plasma contents of the magnetotail. This Faraday loop response model contains analogues to both the directly driven and the storage-release magnetospheric responses and it includes, in a fundamental way, the inherent nonlinearity of the solar wind-magnetosphere system. It can be chancterized as a nonlinear, damped harmonic oscillator that is driven by the loading-unloading substorm cycle. The model is able to explain many of the features of the linear prediction filter results. In particular, at low geomagnetic activity levels the model exbibits the "regular dripping" response which provides an explanation for the unloading component at 1 hour lag in the linear prediction filters. Further, the model suggests that the disappearance of the unloading component in the linear prediction filters at high geomagnetic activity levels is due to a chaotic transition beyond which the loading-unloading mechanism becomes aperiodic. The model predicts

  10. Design and synthesis of novel arctigenin analogues for the amelioration of metabolic disorders.

    PubMed

    Duan, Shudong; Huang, Suling; Gong, Jian; Shen, Yu; Zeng, Limin; Feng, Ying; Ren, Wenming; Leng, Ying; Hu, Youhong

    2015-04-09

    Analogues of the natural product (-)-arctigenin, an activator of adenosine monophosphate activated protein kinase, were prepared in order to evaluate their effects on 2-deoxyglucose uptake in L6 myotubes and possible use in ameliorating metabolic disorders. Racemic arctigenin 2a was found to display a similar uptake enhancement as does (-)-arctigenin. As a result, the SAR study was conducted utilizing racemic compounds. The structure-activity relationship study led to the discovery of key substitution patterns on the lactone motif that govern 2-deoxyglucose uptake activities. The results show that replacement of the para-hydroxyl group of the C-2 benzyl moiety of arctigenin by Cl has a pronounced effect on uptake activity. Specifically, analogue 2p, which contains the p-Cl substituent, stimulates glucose uptake and fatty acid oxidation in L6 myotubes.

  11. Amygdalin analogues inhibit IFN-γ signalling and reduce the inflammatory response in human epidermal keratinocytes.

    PubMed

    Paoletti, Iole; De Gregorio, Vincenza; Baroni, Adone; Tufano, Maria Antonietta; Donnarumma, Giovanna; Perez, Juan Jesus

    2013-12-01

    Peptide T (PT), an octapeptide fragment located in the V2 region of the HIV-1 gp120-coating protein, appears to be beneficial in the treatment of psoriasis. Our previous investigations suggest that keratinocytes play a key role in conditioning the therapeutic effects of PT in psoriasis. The aim of this study was to explore the effects of PT and the peptidomimetic natural products, Dhurrin and Prunasin, on the expression of the IL-6, IL-8, IL-23, HSP70 and ICAM-1 on IFN-γ and TNF-α-NHEK activated cells. Moreover, we analysed the interference of PT and its analogues through STAT-3 activation. Our results show that the analogues tested exhibit the beneficial biological effects of PT, suggesting the primary role of keratinocytes upon which PT and the peptidomimetics act directly, by reducing proinflammatory responses. Its reduction appears to be important for therapeutic approach in psoriasis pathogenesis.

  12. Structural Insights Lead to a Negamycin Analogue with Improved Antimicrobial Activity against Gram-Negative Pathogens

    PubMed Central

    2015-01-01

    Negamycin is a natural product with antibacterial activity against a broad range of Gram-negative pathogens. Recent revelation of its ribosomal binding site and mode of inhibition has reinvigorated efforts to identify improved analogues with clinical potential. Translation-inhibitory potency and antimicrobial activity upon modification of different moieties of negamycin were in line with its observed ribosomal binding conformation, reaffirming stringent structural requirements for activity. However, substitutions on the N6 amine were tolerated and led to N6-(3-aminopropyl)-negamycin (31f), an analogue showing 4-fold improvement in antibacterial activity against key bacterial pathogens. This represents the most potent negamycin derivative to date and may be a stepping stone toward clinical development of this novel antibacterial class. PMID:26288696

  13. Interrogating the Tailoring Steps of Pactamycin Biosynthesis and Accessing New Pactamycin Analogues.

    PubMed

    Abugrain, Mostafa E; Lu, Wanli; Li, Yuexin; Serrill, Jeffrey D; Brumsted, Corey J; Osborn, Andrew R; Alani, Adam; Ishmael, Jane E; Kelly, Jane X; Mahmud, Taifo

    2016-09-02

    Pactamycin is a bacteria-derived aminocyclitol antibiotic with a wide-range of biological activity. Its chemical structure and potent biological activities have made it an interesting lead compound for drug discovery and development. Despite its unusual chemical structure, many aspects of its formation in nature remain elusive. Using a combination of genetic inactivation and metabolic analysis, we investigated the tailoring processes of pactamycin biosynthesis in Streptomyces pactum. The results provide insights into the sequence of events during the tailoring steps of pactamycin biosynthesis and explain the unusual production of various pactamycin analogues by S. pactum mutants. We also identified two new pactamycin analogues that have better selectivity indexes than pactamycin against malarial parasites.

  14. Novel propanamide analogue and antiproliferative diketopiperazines from mangrove Streptomyces sp. Q24.

    PubMed

    Ye, Xuewei; Chai, Weiyun; Lian, Xiao-Yuan; Zhang, Zhizhen

    2017-06-01

    A new propanamide analogue (1), along with one known alkaloid (2) and four known diketopiperazines (3-6), was isolated from a cultured broth of the actinomycete Streptomyces sp. Q24 that was obtained from a sample of mangrove soil. The structures of these isolates were characterised as 3-acetylamino-N-2-thienyl-propanamide (1), N-acetyltryptamine (2), cyclo-(l-phenylalanine-l-4-hydroxyproline) (3), cyclo-(l-leucine-l-4-hydroxyproline) (4), cyclo-(l-phenylalanine-d-4-hydroxyproline) (5) and cyclo-(l-leucine-l-proline) (6) based on their NMR and HRESIMS data as well as optical rotation. Three diketopiperazines (3, 4, 6) showed activity in inhibiting the proliferation of human glioma U87-MG and U251 cells. This type of the new propanamide analogue (1) is first found from a nature source and the antiproliferative property of these three diketopiperazines against glioma cells is also reported herein for the first time.

  15. Structure-activity analysis of 2'-modified cinnamaldehyde analogues as potential anticancer agents.

    PubMed

    Gan, Fei Fei; Chua, Yee Shin; Scarmagnani, Silvia; Palaniappan, Puvithira; Franks, Mark; Poobalasingam, Thurka; Bradshaw, Tracey D; Westwell, Andrew D; Hagen, Thilo

    2009-10-02

    The natural product 2'-hydroxycinnamaldehyde (HCA) and its analogue, 2'-benzoyloxycinnamaldehyde (BCA), have been previously shown to have antiproliferative and proapoptotic effects in vitro and inhibit tumor growth in vivo. In this study, we use structure-activity analysis to define structural features that are important for the activity of cinnamaldehyde analogues. Our results emphasize an important role for both the propenal group as well as the modification at the 2'-position. Further studies were aimed to characterize the mechanism of action of BCA. Exposure to BCA induced cell death via caspase-dependent and -independent pathways. Cell death was not due to autophagy or necrosis as a result of energy depletion or induction of reactive oxygen species. Our findings have important implications for future drug design and highlight the importance of defining molecular drug targets for this promising class of potential anticancer agents.

  16. Carbon and silicate grains in the laboratory as analogues of cosmic dust.

    PubMed

    Mennella, V; Brucato, J R; Colangeli, L

    2001-03-15

    Carbon and silicate grains are the two main components of cosmic dust. There is increasing spectroscopic evidence that their composition varies according to the cosmic environment and the experienced processing. Irradiation from ultraviolet photons and cosmic rays, as well as chemical interactions with the interstellar gas play a crucial role for grain transformation. The study of 'laboratory analogues' represents a powerful tool to better understand the nature and evolution of cosmic materials. In particular, simulations of grain processing are fundamental to outline an evolutionary pathway for interstellar particles. In the present work, we discuss the ultraviolet and infrared spectral changes induced by thermal annealing, ultraviolet irradiation, ion irradiation and hydrogen atom bombardment in carbon and silicate analogue materials. The laboratory results give the opportunity to shed light on the long-standing problems of the attribution of ultraviolet and infrared interstellar spectral features.

  17. Theoretical Studies on 4-amino-3,5-dinitropyrazole and Its Analogues

    NASA Astrophysics Data System (ADS)

    Guozheng, Zhao; Ming, Lu

    2013-01-01

    Seven analogues of a new high-energetic material, 4-amino-3,5-dinitropyrazole (LLM-116), were designed through changing NH2 or NO2 groups on the pyrazole ring of LLM-116. Density functional theory studies on LLM-116 and its analogues were performed at the B3LYP/6-31G(d) level. The geometric and electronic structures, natural bond orbital, charge on the nitro group (-QNO2 ), density, detonation properties, and bond dissociation energies (BDEs) of these molecules were investigated and compared with LLM-116. The results showed that molecules E , F , and G had comparable performance with better insensitivity characteristics and might be potential candidates of powerful energetic materials.

  18. Are introspective reaction times affected by the method of time estimation? A comparison of visual analogue scales and reproduction.

    PubMed

    Bryce, Donna; Bratzke, Daniel

    2015-04-01

    In this study, we investigated whether the method of time estimation plays a role in the apparent limits of introspection in dual-task processing. Previous studies showed that when participants reported introspective reaction times after each trial of a dual task by clicking on a visual analogue scale, they appeared to be unaware of the dual-task costs in their performance. However, visual analogue scales have seldom been used in interval estimation, and they may be inappropriate. In the present study, after each dual-task trial, participants reported their introspective reaction times either via a visual analogue scale or via the method of reproduction. The results replicated the previous findings, irrespective of method. That is, even though responses to the second task slowed down with increasing task overlap, this slowing was only very weakly reflected in the introspective reaction times. Thus, the participants' failure to report the objective dual-task costs in their reaction times is a rather robust finding that cannot be attributed to the method employed. However, introspective reaction times reported via visual analogue scales were more closely related to the objective reaction times, suggesting that visual analogue scales are preferable to reproduction. We conclude that introspective reaction times represent the same information regardless of method, but whether that information is temporal in nature is as yet unsettled.

  19. A visual basic spreadsheet macro for geochemical background analysis.

    PubMed

    Nakić, Zoran; Posavec, Kristijan; Bacani, Andrea

    2007-01-01

    A Visual Basic macro entitled BACKGROUND calculates geochemical background values of chemical parameters and estimates threshold values separating background data from anomalies. The macro uses two statistical methods, the iterative 2-sigma technique and the calculated distribution function, and integrates these model-based objective methods into a widely accessible platform (i.e., MS Excel). The macro offers the possibility for automated processing of geochemical data and enables an automated generation of background range and threshold values for chemical parameters.

  20. Present-day serpentinization in the Tablelands, Gros Morne National Park, Newfoundland: a Mars Analogue Site

    NASA Astrophysics Data System (ADS)

    Szponar, N.; Morrill, P. L.; Brazelton, W. J.; Schrenk, M. O.; Bower, D. M.; Steele, A.

    2010-12-01

    Serpentinization - a reaction between water and ultramafic rock (derived from the mantle) - is suspected to be a source of hydrocarbons such as methane on Mars. Through the hydration of ultramafic rock, this reaction produces hydrogen (H2) gas and reducing conditions necessary for abiogenic hydrocarbon synthesis, while also producing conditions amendable for the production of methane through microbial chemoautotrophic pathways. Mars analogue sites of present-day serpentinization can be used to determine what geochemical measurements are required for determining the reactions responsible for the methane in the Martian atmosphere. On Earth few locations that are known to exhibit active serpentinization are easily accessible. One such location is found in the Tablelands at Gros Morne National Park, Newfoundland. Peridotite rocks similar to those found on Mars dominate the Tablelands thus making the Tablelands an important analogue site for potential ecosystems on Mars. Present-day serpentinization is evidenced by fluid seeps characterized by highly alkaline (pH 11 to 12) and highly reducing (as low as -820 mV) conditions, travertine and the presence of dissolved methane. These fluids contain high concentrations of Ca2+ (~5.00x104ppb) compared to freshwater inputs (~ 1.00x103) and react at the surface with atmospheric CO2 producing travertine deposits (as CaCO3 precipitate). Dissolved H2 gas produced abiogenically through the serpentinization reaction also provides copious geofuels, which can be used for chemosynthesis. Preliminary data has shown that microbial life lives in the high pH springs of the Tablelands. Ongoing studies of targeted compounds including phospholipid fatty acids and ether-linked lipids are being used to determine the microbial community compositions and verify the occurrence of Bacteria and Archaea in these fluids. An important question is also the source of the serpentinized fluid seeps. Hydrogen (δ2H) and oxygen (δ18O) isotopes of these

  1. Tren-based analogues of bacillibactin: structure and stability.

    PubMed

    Dertz, Emily A; Xu, Jide; Raymond, Kenneth N

    2006-07-10

    Synthetic analogues were designed to highlight the effect of the glycine moiety of bacillibactin on the overall stability of the ferric complex as compared to synthetic analogues of enterobactin. Insertion of a variety of amino acids to catecholamide analogues based on a Tren (tris(2-aminoethyl)amine) backbone increased the overall acidity of the ligands, causing an enhancement of the stability of the resulting ferric complex as compared to TRENCAM. Solution thermodynamic behavior of these siderophores and their synthetic analogues was investigated through potentiometric and spectrophotometric titrations. X-ray crystallography, circular dichroism, and molecular modeling were used to determine the chirality and geometry of the ferric complexes of bacillibactin and its analogues. In contrast to the Tren scaffold, addition of a glycine to the catechol chelating arms causes an inversion of the trilactone backbone, resulting in opposite chiralities of the two siderophores and a destabilization of the ferric complex of bacillibactin compared to ferric enterobactin.

  2. Analogue Divider by Averaging a Triangular Wave

    NASA Astrophysics Data System (ADS)

    Selvam, Krishnagiri Chinnathambi

    2017-03-01

    A new analogue divider circuit by averaging a triangular wave using operational amplifiers is explained in this paper. The triangle wave averaging analog divider using operational amplifiers is explained here. The reference triangular waveform is shifted from zero voltage level up towards positive power supply voltage level. Its positive portion is obtained by a positive rectifier and its average value is obtained by a low pass filter. The same triangular waveform is shifted from zero voltage level to down towards negative power supply voltage level. Its negative portion is obtained by a negative rectifier and its average value is obtained by another low pass filter. Both the averaged voltages are combined in a summing amplifier and the summed voltage is given to an op-amp as negative input. This op-amp is configured to work in a negative closed environment. The op-amp output is the divider output.

  3. A simple analogue of lung mechanics.

    PubMed

    Sherman, T F

    1993-12-01

    A model of the chest and lungs can be easily constructed from a bottle of water, a balloon, a syringe, a rubber stopper, glass and rubber tubing, and clamps. The model is a more exact analogue of the body than the classic apparatus of Hering in two respects: 1) the pleurae and intrapleural fluid are represented by water rather than air, and 2) the subatmospheric "intrapleural" pressure is created by the elasticity of the "lung" (balloon) rather than by a vacuum pump. With this model, students can readily see how the lung is inflated and deflated by movements of the "diaphragm and chest" (syringe plunger) and how intrapleural pressures change as this is accomplished.

  4. The prediction of aquatic sediment-associated trace element concentration using selected geochemical factors

    USGS Publications Warehouse

    Horowitz, A.J.; Elrick, K.A.; Hooper, R.P.

    1989-01-01

    Multiple linear regression models calculated from readily obtainable chemical and physical parameters can explain a high percentage (70 per cent or greater) of observed sediment-trace element variance for Cu, Zn, Pb, Cr, Ni, Co, As, Sb, Se, and Hg in a widely divergent suite of 60 sediment samples. The geochemical parameters included in the models were of physical (e.g. grain size, surface area) and a chemical (e.g. organic matter, amorphous iron oxides) nature. Comparison between actual and predicted trace element concentrations obtained from the models may provide a means of defining "average' sediment trace element concentrations. -from Authors

  5. Chain of custody; recommendations for acceptance and analysis of evidentiary geochemical samples

    USGS Publications Warehouse

    Murphy, Christine M.; Briggs, Paul H.; Adrian, Betty M.; Wilson, Steve A.; Hageman, Phil L.; Theodorakos, Pete M.

    1997-01-01

    Personnel from the Analytical Chemistry Services Group (ACSG), Mineral Resource Survey Program, formed a team to determine the policies for acceptance and analysis of geochemical samples. This team contacted law enforcement agencies that handle litigious samples, laboratories that work with samples of special nature, and the Solicitor General, Department of the Interior. Using the knowledge from these agencies as well as the expertise of ACSG personnel, sample control routine procedures, sample control evidentiary procedures, personnel policy governing chain-of-custody samples, and the general polices governing physical security of chain-of custody samples have been enacted.

  6. Predicting species’ tolerance to salinity and alkalinity using distribution data and geochemical modelling: a case study using Australian grasses

    PubMed Central

    Saslis-Lagoudakis, C. Haris; Hua, Xia; Bui, Elisabeth; Moray, Camile; Bromham, Lindell

    2015-01-01

    Background and Aims Salt tolerance has evolved many times independently in different plant groups. One possible explanation for this pattern is that it builds upon a general suite of stress-tolerance traits. If this is the case, then we might expect a correlation between salt tolerance and other tolerances to different environmental stresses. This association has been hypothesized for salt and alkalinity tolerance. However, a major limitation in investigating large-scale patterns of these tolerances is that lists of known tolerant species are incomplete. This study explores whether species’ salt and alkalinity tolerance can be predicted using geochemical modelling for Australian grasses. The correlation between taxa found in conditions of high predicted salinity and alkalinity is then assessed. Methods Extensive occurrence data for Australian grasses is used together with geochemical modelling to predict values of pH and electrical conductivity to which species are exposed in their natural distributions. Using parametric and phylogeny-corrected tests, the geochemical predictions are evaluated using a list of known halophytes as a control, and it is determined whether taxa that occur in conditions of high predicted salinity are also found in conditions of high predicted alkalinity. Key Results It is shown that genera containing known halophytes have higher predicted salinity conditions than those not containing known halophytes. Additionally, taxa occurring in high predicted salinity tend to also occur in high predicted alkalinity. Conclusions Geochemical modelling using species’ occurrence data is a potentially useful approach to predict species’ relative natural tolerance to challenging environmental conditions. The findings also demonstrate a correlation between salinity tolerance and alkalinity tolerance. Further investigations can consider the phylogenetic distribution of specific traits involved in these ecophysiological strategies, ideally by

  7. Terrestrial Analogues for Lunar Impact Melt Flows

    NASA Technical Reports Server (NTRS)

    Neish, C. D.; Hamilton, C. W.; Hughes, S. S.; Nawotniak, S. Kobs; Garry, W. B.; Skok, J. R.; Elphic, R. C.; Schaefer, E.; Carter, L. M.; Bandfield, J. L.; Osinski, G. R.; Lim, D.; Heldmann, J. L.

    2016-01-01

    Lunar impact melt deposits have unique physical properties. They have among the highest observed radar returns at S-Band (12.6 cm wavelength), implying that they are rough at the decimeter scale. However, they are also observed in high-resolution optical imagery to be quite smooth at the meter scale. These characteristics distinguish them from well-studied terrestrial analogues, such as Hawaiian pahoehoe and ?a ?a lava flows. The morphology of impact melt deposits can be related to their emplacement conditions, so understanding the origin of these unique surface properties will help to inform us as to the circumstances under which they were formed. In this work, we seek to find a terrestrial analogue for well-preserved lunar impact melt flows by examining fresh lava flows on Earth. We compare the radar return and high-resolution topographic variations of impact melt flows to terrestrial lava flows with a range of surface textures. The lava flows examined in this work range from smooth Hawaiian pahoehoe to transitional basaltic flows at Craters of the Moon (COTM) National Monument and Preserve in Idaho to rubbly and spiny pahoehoe-like flows at the recent eruption at Holuhraun in Iceland. The physical properties of lunar impact melt flows appear to differ from those of all the terrestrial lava flows studied in this work. This may be due to (a) differences in post-emplacement modification processes or (b) fundamental differences in the surface texture of the melt flows due to the melts' unique emplacement and/or cooling environment. Information about the surface properties of lunar impact melt deposits will be critical for future landed missions that wish to sample these materials.

  8. Terrestrial analogues for lunar impact melt flows

    NASA Astrophysics Data System (ADS)

    Neish, C. D.; Hamilton, C. W.; Hughes, S. S.; Nawotniak, S. Kobs; Garry, W. B.; Skok, J. R.; Elphic, R. C.; Schaefer, E.; Carter, L. M.; Bandfield, J. L.; Osinski, G. R.; Lim, D.; Heldmann, J. L.

    2017-01-01

    Lunar impact melt deposits have unique physical properties. They have among the highest observed radar returns at S-Band (12.6 cm wavelength), implying that they are rough at the decimeter scale. However, they are also observed in high-resolution optical imagery to be quite smooth at the meter scale. These characteristics distinguish them from well-studied terrestrial analogues, such as Hawaiian pāhoehoe and ´a´ā lava flows. The morphology of impact melt deposits can be related to their emplacement conditions, so understanding the origin of these unique surface properties will help to inform us as to the circumstances under which they were formed. In this work, we seek to find a terrestrial analogue for well-preserved lunar impact melt flows by examining fresh lava flows on Earth. We compare the radar return and high-resolution topographic variations of impact melt flows to terrestrial lava flows with a range of surface textures. The lava flows examined in this work range from smooth Hawaiian pāhoehoe to transitional basaltic flows at Craters of the Moon (COTM) National Monument and Preserve in Idaho to rubbly and spiny pāhoehoe-like flows at the recent eruption at Holuhraun in Iceland. The physical properties of lunar impact melt flows appear to differ from those of all the terrestrial lava flows studied in this work. This may be due to (a) differences in post-emplacement modification processes or (b) fundamental differences in the surface texture of the melt flows due to the melts' unique emplacement and/or cooling environment. Information about the surface properties of lunar impact melt deposits will be critical for future landed missions that wish to sample these materials.

  9. Current european regulatory perspectives on insulin analogues

    PubMed Central

    2011-01-01

    Insulin analogues are increasingly considered as an alternative to human insulin in the therapy of diabetes mellitus. Insulin analogues (IAs) are chemically different from human insulin and may have different pharmacokinetic or pharmacodynamic properties. The significance of the modifications of the insulin molecule for the safety profile of IAs must be considered. This review describes the regulatory procedure and the expectations for the scientific content of European marketing authorization applications for innovative IAs submitted to the European Medicines Agency. Particular consideration is given to a potential cancer hazard. Specific regulatory guidance on how to address a possible carcinogenic or tumor promoting effect of innovative IAs in non-clinical studies is available. After marketing authorization, the factual access of patients to the new product will be determined to great extent by health technology assessment bodies, reimbursement decisions and the price. Whereas the marketing authorization is a European decision, pricing and reimbursement are national or regional responsibilities. The assessment of benefit and risk by the European Medicines Agency is expected to influence future decisions on price and reimbursement on a national or regional level. Collaborations between regulatory agencies and health technology assessment bodies have been initiated on European and national level to facilitate the use of the European Medicines Agency's benefit risk assessment as basis on which to build the subsequent health technology assessment. The option for combined or joint scientific advice procedures with regulators and health technology assessment bodies on European level or on a national level in several European Member States may help applicants to optimize their development program and dossier preparation in regard of both European marketing authorization application and reimbursement decisions. PMID:21736748

  10. Geochemistry of a continental site of serpentinization, the Tablelands Ophiolite, Gros Morne National Park: A Mars analogue

    NASA Astrophysics Data System (ADS)

    Szponar, Natalie; Brazelton, William J.; Schrenk, Matthew O.; Bower, Dina M.; Steele, Andrew; Morrill, Penny L.

    2013-06-01

    The presence of aqueously altered, olivine-rich rocks along with carbonate on Mars suggest that serpentinization may have occurred in the past and may be occurring presently in the subsurface, and possibly contributing methane (CH4) to the martian atmosphere. Serpentinization, the hydration of olivine in ultramafic rocks, yields ultra-basic fluids (pH ⩾ 10) with unique chemistry (i.e. Ca2+-OH- waters) and hydrogen gas, which can support abiogenic production of hydrocarbons (i.e. Fischer-Tropsch Type synthesis) and subsurface chemosynthetic metabolisms. Mars analogue sites of present-day serpentinization can be used to determine what geochemical measurements are required for determining the source methane at sites of serpentinization on Earth and possibly on Mars. The Tablelands Ophiolite is a continental site of present-day serpentinization and a Mars analogue due to the presence of altered olivine-rich ultramafic rocks with both carbonate and serpentine signatures. This study describes the geochemical indicators of present-day serpentinization as evidenced by meteoric ultra-basic reducing groundwater discharging from ultramafic rocks, and travertine and calcium carbonate sediment, which form at the discharge points of the springs. Dissolved hydrogen concentrations (0.06-1.20 mg/L) and methane (0.04-0.30 mg/L) with δ13CCH4 values (-28.5‰ to -15.6‰) were measured in the spring fluids. Molecular and isotopic analyses of CH4, ethane, propane, butane, pentane and hexane suggest a non-microbial source of methane, and attribute the origin of methane and higher hydrocarbon gases to either thermogenic or abiogenic pathways.

  11. Analogues to features and processes of a high-level radioactive waste repository proposed for Yucca Mountain, Nevada

    USGS Publications Warehouse

    Simmons, Ardyth M.; Stuckless, John S.; with a Foreword by Abraham Van Luik, U.S. Department of Energy

    2010-01-01

    Natural analogues are defined for this report as naturally occurring or anthropogenic systems in which processes similar to those expected to occur in a nuclear waste repository are thought to have taken place over time periods of decades to millennia and on spatial scales as much as tens of kilometers. Analogues provide an important temporal and spatial dimension that cannot be tested by laboratory or field-scale experiments. Analogues provide one of the multiple lines of evidence intended to increase confidence in the safe geologic disposal of high-level radioactive waste. Although the work in this report was completed specifically for Yucca Mountain, Nevada, as the proposed geologic repository for high-level radioactive waste under the U.S. Nuclear Waste Policy Act, the applicability of the science, analyses, and interpretations is not limited to a specific site. Natural and anthropogenic analogues have provided and can continue to provide value in understanding features and processes of importance across a wide variety of topics in addressing the challenges of geologic isolation of radioactive waste and also as a contribution to scientific investigations unrelated to waste disposal. Isolation of radioactive waste at a mined geologic repository would be through a combination of natural features and engineered barriers. In this report we examine analogues to many of the various components of the Yucca Mountain system, including the preservation of materials in unsaturated environments, flow of water through unsaturated volcanic tuff, seepage into repository drifts, repository drift stability, stability and alteration of waste forms and components of the engineered barrier system, and transport of radionuclides through unsaturated and saturated rock zones.

  12. Chasing An Analogue For The Holocene : The Astronomical Forcing

    NASA Astrophysics Data System (ADS)

    Loutre, M.; Crucifix, M.; Berger, A.

    2008-12-01

    Astronomical theories of paleoclimate, e.g. the Milankovitch theory, explain the long-term variations of climate by the changes in the Earth orbit and position against the Sun, and consequently by the change in the distribution of the solar energy reaching the Earth. On the other hand, anthropogenic activities from early agricultural practices to more recent fossil fuel burning also impact climate change. Models, from conceptual ones to the most sophisticated general circulation models can be used to try to disentangle the contribution from human activity and the natural contribution in the record of climate change. Alternatively, a comparison of the climate records during past interglacials similar to the one we are living in can give some insight into the natural behaviour of the climate system during an interglacial. As far as the long-term climate change is mostly orbitally driven, we will search orbital and insolation time series for past analogues of the non-human perturbed Holocene. When doing so, some key questions must be answered. The first one is related to the time interval to be used as target. A previous study (Loutre and Berger, 2000) focused on the interglacial itself, assuming that the preceding deglaciation had a negligible impact on the interglacial. Rather we decided here to choose a target time interval that includes the deglaciation. Another question is related to the choice of the variable that will be used for correlation. It can be the orbital parameters themselves. It is also possible to use top-of-the-atmosphere insolation. If daily insolation is chosen, the latitude and time in the year for which it is computed are crucial; if a more time- integrated insolation is used (e.g. seasonal insolation), the time interval for the integration is an essential feature. Loutre and Berger (2000) used mid-June insolation at 65N and identified MIS11 as the most recent potential analogue for the future climate. A higher correlation of the insolation was

  13. Geochemical Behavior of Selenium in Igneous Systems

    NASA Astrophysics Data System (ADS)

    Jenner, F. E.; Mavrogenes, J. A.; Arculus, R. J.; O'Neill, H. S.

    2008-12-01

    Selenium (Se) is generally assumed to behave much like sulfur (S) in igneous systems. However, it is unclear how valid this assumption is considering that so little is known about the geochemical behaviour of Se. Constraining the range in Se and S concentrations of mantle-derived magmas is important to studies of: core segregation; the composition of late-accreted material; collisional erosion models; processes of mantle melting in various tectonic environments; and recycling of lithospheric components into the mantle, to mention only a few. Previous estimates of the S/Se of primitive and depleted mantle assume that S-Se are similar to Zr-Hf and Nb-Ta in their geochemical coherence, and that S/Se of the Earth's mantle is chondritic (Palme and O"Neill 2003 and references therein). Due to the low abundances of Se in mantle-derived rocks and the lack of calibration materials for routine analysis (i.e. NIST 612), this assumption remains unchallenged. Using a combination of SHRIMP, electron probe, and LA-ICP-MS techniques the concentration of Se in NIST 612 and BCR-2G was obtained to permit rapid in situ LA-ICP-MS analysis of Se concentrations in volcanic glasses. We have obtained Se, S, major and comprehensive trace element data for volcanic glasses from a global range of tectonic settings (mid-ocean ridges, ocean island, island arc and back-arc basins) to improve understanding of the behaviour of Se during igneous processes (e.g. partial melting, fractional crystallisation, and volatile phase separation). Analysis of a range of mid-ocean ridge glasses shows that Se behaves as an incompatible element, but is decoupled from S as the S/Se extends to values well in excess of the chondritic estimate (i.e. 2528; Palme and O"Neill 2003). During back-arc basin and island-arc magmatism, the abundance, systematics and S/Se are diverse. For example, at a specific MgO content, the absolute abundance of Se varies with depletion of the mantle source. Within back-arc suites derived

  14. Preliminary geochemical and physical testing of materials for plugging of man-made accesses to a repository in basalt

    SciTech Connect

    Taylor, C.L.; Anttonen, G.J.; O'Rourke, J.E.; Allirot, D.

    1980-04-01

    The available data on environmental conditions (both natural and man-made) at the Hanford Site are sufficient for preconceptual plug system design. Results of the geochemical testing program indicate that preferred candidate plug materials are chemically nonreactive during laboratory tests that simulated some of the expected environmental conditions. Agitated, crushed-basalt samples and mixtures containing basalt were found to be self-cementing under the hydrothermal conditions. Materials considered most suitable for consideration in future test programs and preconceptual plug design are mixtures of natural materials (basalt, clay, glaciofluvial sand, gravel, and zeolite) and processed natural materials (portland cement Type V and grouts plus additives).

  15. Surface geochemical survey for geothermal exploration in the south-east zone of Tenerife Island, Canary Islands

    NASA Astrophysics Data System (ADS)

    Diaz Requejo, M.; Marrero, R.; Padron, E.; Melian, G.; Guerrero, V.; Hernandez Perez, P. A.; Perez, N.; Hidalgo, R.

    2009-12-01

    Water and gas sampling of natural discharges are the most common type of geochemical surveys for geothermal exploration. However, these natural discharges are generally scarces at geothermal exploration areas where the extent of the field is not known. Therefore, soil-volatile (Hg, As, Sb, NH3 and B) and soil-gas surveys (222Rn, CO2, He, H2, CH4, O2, Ar) are becoming a useful geochemical tool to identify permeable areas and potential upflow or boiling zones. These surveys can also help to delineate the margins of a geothermal system, and therefore often complement geophysical surveys particularly where the interpretation of geophysical data shows some difficulties. During July and August, 2008, a surface geochemical survey was undertaken in a ~120 km2 area at the south-east slope of Tenerife Island, Spain. In order to obtain a representative distribution of the whole study area, during the field work a total of 577 sampling points were performed. In-situ measurement of radon (222Rn) and thoron (220Rn) activities together with Hg0 and H2S gas concentration and CO2 and H2S soil effluxes were performed at each sampling point. At the same time, gas samples were taken from the soil atmosphere at 40 cm depth for subsequent chemical analysis by means of micro-gas chromatography and quadrupole mass spectrometry (He, H2, Ne, N2, CO2, CH4, Ar and CO2). At least two geochemical anomalous zones have been identified in the present work: (A) one close to Siete Fuentes-Fasnia historical vents (1704-1705 AD) and (B) located on the southwestern limit of the study area. Relatively high concentrations of H2 and ΔHe as well as high H2/Ar and He/CO2 ratios were observed at both zones, indicating a clear evidence of the existence of an upflow zone with an important contribution of endogenous gases. The existence of a volcanic-hydrothermal system coupled with a vertical permeability structures in both zones could explain these geochemical anomalies observed in the surface environment

  16. Geochemical precursors for eruption repose length

    NASA Astrophysics Data System (ADS)

    Green, R. M.; Bebbington, M. S.; Cronin, S. J.; Jones, G.

    2013-05-01

    We demonstrate using a high-resolution Holocene volcanic event record from Mt Taranaki (New Zealand) how geochemical data can be used to modulate a renewal model for the estimated probability of a future eruption. The andesitic stratovolcano Mt Taranaki has an activity record punctuated by long periods of quiescence and subsequent re-awakening. Thus, the distribution of interonset times is bimodal, with the possibility of anomalously long reposes. However, we show that a bimodal renewal distribution is outperformed for eruption forecasting by a proportional hazards type model. The latter model uses the major-oxide chemistry of the ubiquitous phenocryst mineral phase titanomagnetite as a proxy for the state of the magmatic system. We find that the concentrations of TiO2 and Al2O3 (or MgO) are useful predictors of repose length. These are major substituting elements in the titanomagnetite structure, reflecting variations in magmatic pressure/temperature and oxidation-state history. Highly variable Al2O3 (or MgO) indicates mixing of different magma batches deep within the plumbing system before eruption, and correlates with longer repose times. In contrast, high variability in TiO2 results from solid-state exsolution processes in the shallow, near-surface conduit and is an indicator for shorter repose times. In the bimodal renewal model, the estimated hazard is only updated to reflect the likelihood of a long repose after the present repose-length exceeds the shorter mode. In the geochemistry modulated model, this predictive information is available at the beginning of the repose to be forecast.

  17. Geochemical Stratigraphy of Southern Parana' Lava Piles

    NASA Astrophysics Data System (ADS)

    Marzoli, A.; De Min, A.; Marques, L. S.; Nardy, A.; Chiaradia, M.

    2015-12-01

    Basaltic lava flows of the Paranà Large Igneous Province exhibit significant regional and stratigraphic geochemical variations. While the most notable difference concerns the dominance of low-Ti (TiO2 < 2.0 wt.%) and high-Ti types in the southern and northern part of the province, respectively, detailed analyses of lava flow sequences sampled mostly in drill cores allowed definition of six main groups of chemically distinct flow units. The chemical and possible age differences among these units were then used to define the global time-related evolution of Paranà basaltic magmatism and involvement of distinct mantle-source components. Newly sampled outcropping lava flow sequences from the southern Paranà do however only partially support this picture. Our new major and trace element and Sr-Nd-Pb isotopic data show that high- and low-Ti basaltic flows are interlayered. In particular, Pitanga type high-Ti basalts are interlayered with Gramado and Esmeralda low-Ti basalts (these latter being present both towards the base and the top of the sequence) in Paranà State, while in Santa Caterina State Gramado flows are interlayered with Urubici-type high-Ti basalts. The interlayering of distinct basaltic magma type requires near-synchronous eruption of chemically strongly different magma types generated from clearly heterogeneous mantle sources and erupted through separated magma plumbing systems, without apparent interaction (mixing) among the distinct basalts. In conclusion, the relative timing of low- and high-Ti magma types seems to be much more complicated than previously thought, as for example Esmeralda or Pitanga basalts, previously considered as quite late and postdating Gramado basalts, are indeed synchronous with them.

  18. Geochemical behaviour of rare earths in Vitis vinifera grafted onto different rootstocks and growing on several soils.

    PubMed

    Censi, P; Saiano, F; Pisciotta, A; Tuzzolino, N

    2014-03-01

    The geochemical behaviour of lanthanides and yttrium (Rare Earth Elements, REEs) has been investigated mainly in geological systems where these elements represent the best proxies of processes involving the occurrence of an interface between different media. This behaviour is assessed according to features recorded in sequences of REE concentrations along the REE series normalised with respect to a reference material. In this study, the geochemical behaviour of REE was investigated in different parts of Vitis vinifera specimens grown off-soil, on soils of different nature and grafted onto several rootstocks in order to evaluate effects induced by these changes. The results indicated that roots are the plant organs where REEs are preferentially concentrated, in particular elements from Sm to Ho (middle REE, MREE) whereas Eu enrichments occur in aerial parts. The geochemical behaviour of REE suggests that MREE enrichments in roots are due to preferential MREE interactions with biological membranes or to surface complexation with newly formed phosphates. Eu-positive anomalies suggest that Eu(3+) can form stable organic complexes in place of Ca(2+) in several biological processes in xylem fluids. The possibility that Eu mobility in these fluids can be enhanced by its reductive speciation as Eu(2+) cannot be ruled out. The assessment of the geochemical behaviour of REE according to the theory of the Tetrad Effect carried out confirms that REEs coming from soil are scavenged onto root tissues or mineral surfaces whereas their behaviour in aerial parts of V. vinifera is driven by dissolved complexation.

  19. Synthesis of a uranium(VI)-carbene: reductive formation of uranyl(V)-methanides, oxidative preparation of a [R2C═U═O]2+ analogue of the [O═U═O]2+ uranyl ion (R = Ph2PNSiMe3), and comparison of the nature of U(IV)═C, U(V)═C, and U(VI)═C double bonds.

    PubMed

    Mills, David P; Cooper, Oliver J; Tuna, Floriana; McInnes, Eric J L; Davies, E Stephen; McMaster, Jonathan; Moro, Fabrizio; Lewis, William; Blake, Alexander J; Liddle, Stephen T

    2012-06-20

    We report attempts to prepare uranyl(VI)- and uranium(VI) carbenes utilizing deprotonation and oxidation strategies. Treatment of the uranyl(VI)-methanide complex [(BIPMH)UO(2)Cl(THF)] [1, BIPMH = HC(PPh(2)NSiMe(3))(2)] with benzyl-sodium did not afford a uranyl(VI)-carbene via deprotonation. Instead, one-electron reduction and isolation of di- and trinuclear [UO(2)(BIPMH)(μ-Cl)UO(μ-O){BIPMH}] (2) and [UO(μ-O)(BIPMH)(μ(3)-Cl){UO(μ-O)(BIPMH)}(2)] (3), respectively, with concomitant elimination of dibenzyl, was observed. Complexes 2 and 3 represent the first examples of organometallic uranyl(V), and 3 is notable for exhibiting rare cation-cation interactions between uranyl(VI) and uranyl(V) groups. In contrast, two-electron oxidation of the uranium(IV)-carbene [(BIPM)UCl(3)Li(THF)(2)] (4) by 4-morpholine N-oxide afforded the first uranium(VI)-carbene [(BIPM)UOCl(2)] (6). Complex 6 exhibits a trans-CUO linkage that represents a [R(2)C═U═O](2+) analogue of the uranyl ion. Notably, treatment of 4 with other oxidants such as Me(3)NO, C(5)H(5)NO, and TEMPO afforded 1 as the only isolable product. Computational studies of 4, the uranium(V)-carbene [(BIPM)UCl(2)I] (5), and 6 reveal polarized covalent U═C double bonds in each case whose nature is significantly affected by the oxidation state of uranium. Natural Bond Order analyses indicate that upon oxidation from uranium(IV) to (V) to (VI) the uranium contribution to the U═C σ-bond can increase from ca. 18 to 32% and within this component the orbital composition is dominated by 5f character. For the corresponding U═C π-components, the uranium contribution increases from ca. 18 to 26% but then decreases to ca. 24% and is again dominated by 5f contributions. The calculations suggest that as a function of increasing oxidation state of uranium the radial contraction of the valence 5f and 6d orbitals of uranium may outweigh the increased polarizing power of uranium in 6 compared to 5.

  20. Nonlinear geochemical dynamics and petrography: Burial dolomitization (Invited)

    NASA Astrophysics Data System (ADS)

    Merino, E.

    2010-12-01

    Many geochemical self-patterned structures exist in nature [1]: pisolitic, liesegang, orbicular, and agate bandings [2]; igneous and metamorphic bandings [3]; displacive dolomitic and serpentine “zebra” veins [4]; sets of stylolites [5]; oscillatory zoning in single crystals [6]. Large-scale examples: weathering profiles [7], banded iron formations [8], burial dolomitization [9], karst sinkholes [7]; etc. All involve disequilibrium and feedback, the two necessary conditions for self-patterning, but each case is unique. A good model should incorporate force(s), feedbacks, reactions, and boundary and initial conditions that are likely to apply to the genesis of the phenomenon under study. Problems: to confuse mass balances for local mineral reactions; whether the mineral pattern is made at a moving reaction front (as in agates [2]) or throughout the system at once (as in stylolitization [5] and zebra veins [4]). Self-consistent scaling of variables and linear instability analysis may tell us for what ranges of dynamic parameter values the system oscillates. A model may seem to work well - yet this does not prove that the initial choices of forcing, feedback and reactions were correct. Model predictions should be tested against petrographic and field evidence not used in constructing the model in the first place [2]. Recent models of dolomitization [10] and weathering are inconsistent with field and petrographic evidence. (P. K. Weyl, the first geochemical modeler: “We are not interested in what [a rock] is now but in how it became that way … Instead of looking at a rock and asking for an explanation of its past …”, J. Geophys. Res. 1959, p. 2001). A new dynamic model of dolomitization [9] correctly predicts a multitude of petrographic and other properties of burial dolostones. According to the model, the self-accelerating dolomite-for-calcite replacement forces a seamless rheological transition from replacive to displacive dolomite growth which predicts

  1. GEOCHEMICAL MODELING OF F AREA SEEPAGE BASIN COMPOSITION AND VARIABILITY

    SciTech Connect

    Millings, M.; Denham, M.; Looney, B.

    2012-05-08

    From the 1950s through 1989, the F Area Seepage Basins at the Savannah River Site (SRS) received low level radioactive wastes resulting from processing nuclear materials. Discharges of process wastes to the F Area Seepage Basins followed by subsequent mixing processes within the basins and eventual infiltration into the subsurface resulted in contamination of the underlying vadose zone and downgradient groundwater. For simulating contaminant behavior and subsurface transport, a quantitative understanding of the interrelated discharge-mixing-infiltration system along with the resulting chemistry of fluids entering the subsurface is needed. An example of this need emerged as the F Area Seepage Basins was selected as a key case study demonstration site for the Advanced Simulation Capability for Environmental Management (ASCEM) Program. This modeling evaluation explored the importance of the wide variability in bulk wastewater chemistry as it propagated through the basins. The results are intended to generally improve and refine the conceptualization of infiltration of chemical wastes from seepage basins receiving variable waste streams and to specifically support the ASCEM case study model for the F Area Seepage Basins. Specific goals of this work included: (1) develop a technically-based 'charge-balanced' nominal source term chemistry for water infiltrating into the subsurface during basin operations, (2) estimate the nature of short term and long term variability in infiltrating water to support scenario development for uncertainty quantification (i.e., UQ analysis), (3) identify key geochemical factors that control overall basin water chemistry and the projected variability/stability, and (4) link wastewater chemistry to the subsurface based on monitoring well data. Results from this study provide data and understanding that can be used in further modeling efforts of the F Area groundwater plume. As identified in this study, key geochemical factors affecting basin

  2. History and evaluation of national-scale geochemical data sets for the United States

    USGS Publications Warehouse

    Smith, David B.; Smith, Steven M.; Horton, John D.

    2013-01-01

    Six national-scale, or near national-scale, geochemical data sets for soils or stream sediments exist for the United States. The earliest of these, here termed the ‘Shacklette’ data set, was generated by a U.S. Geological Survey (USGS) project conducted from 1961 to 1975. This project used soil collected from a depth of about 20 cm as the sampling medium at 1323 sites throughout the conterminous U.S. The National Uranium Resource Evaluation Hydrogeochemical and Stream Sediment Reconnaissance (NURE-HSSR) Program of the U.S. Department of Energy was conducted from 1975 to 1984 and collected either stream sediments, lake sediments, or soils at more than 378,000 sites in both the conterminous U.S. and Alaska. The sampled area represented about 65% of the nation. The Natural Resources Conservation Service (NRCS), from 1978 to 1982, collected samples from multiple soil horizons at sites within the major crop-growing regions of the conterminous U.S. This data set contains analyses of more than 3000 samples. The National Geochemical Survey, a USGS project conducted from 1997 to 2009, used a subset of the NURE-HSSR archival samples as its starting point and then collected primarily stream sediments, with occasional soils, in the parts of the U.S. not covered by the NURE-HSSR Program. This data set contains chemical analyses for more than 70,000 samples. The USGS, in collaboration with the Mexican Geological Survey and the Geological Survey of Canada, initiated soil sampling for the North American Soil Geochemical Landscapes Project in 2007. Sampling of three horizons or depths at more than 4800 sites in the U.S. was completed in 2010, and chemical analyses are currently ongoing. The NRCS initiated a project in the 1990s to analyze the various soil horizons from selected pedons throughout the U.S. This data set currently contains data from more than 1400 sites. This paper (1) discusses each data set in terms of its purpose, sample collection protocols, and analytical

  3. Watershed-Scale Geochemical Inventory of Soils by Portable X-Ray Fluorescence

    NASA Astrophysics Data System (ADS)

    Beaudette, D. E.; Stupi, L. K.; Swarowsky, A.; O'Geen, A. T.; Chang, J. F.; Gallagher, B.

    2009-12-01

    Spatial databases of geochemical data are an excellent source of point-scale information on naturally occurring toxic elements (arsenic, selenium or radon), contamination from industrial processes (lead, mercury, or cesium), mineralogical variability, and the fate of toxic compounds (i.e. sorption of pesticides to iron oxyhydroxide minerals) in soil. Sample preparation time, safety concerns associated with HF or HNO3 acid dissolution, instrument availability, and cost are all common constraints that limit the scale at which new geochemical surveys can be conducted. We used a Thermo-Fisher Niton portable X-Ray fluorescence (XRF) meter to perform comparatively rapid geochemical surveys in soils of two (35 ha) watersheds. The watersheds have contrasting parent materials, one formed from metavolcanic rock and the other from granite. The X-Ray fluorescence inventory of genetic soil horizons (n=660) was used to identify trends in soil development and landscape processes. Since soil samples are usually sieved and ground for standard laboratory characterization, the additional time required to prepare samples for XRF analysis was minimal, approximately 2 minutes for sample preparation and 6 minutes for machine scan time per sample. Preliminary analysis of the resulting geochemical data show strong spatial trends in watershed- and hillslope-scale variability in weathering indices (FeCBD:FeTotal and K:Ti), inferred mineralogy (Si:Al, Si:Al+Fe), and geologic signatures (multivariate analysis of 20 common elements). Depth trends and spatial patterns were correlated with common terrain-shape indices (slope, upslope contributing area, surface curvatures, local prominence, etc.), degree of soil development, parent material, and hydrological conditions. For example, Si:Al was higher in soils with greater upslope contributing area, and in seasonally saturated soils (Fig 1). Our findings demonstrate that portable XRF technology is a promising new tool for rapid lab-based and in situ

  4. Bioactivity of permselective PVA hydrogels with mixed ECM analogues.

    PubMed

    Nafea, Eman H; Poole-Warren, Laura A; Martens, Penny J

    2015-12-01

    The presentation of multiple biological cues, which simulate the natural in vivo cell environment within artificial implants, has recently been identified as crucial for achieving complex cellular functions. The incorporation of two or more biological cues within a largely synthetic network can provide a simplified model of multifunctional ECM presentation to encapsulated cells. Therefore, the aim of this study was to examine the effects of simultaneously and covalently incorporating two dissimilar biological molecules, heparin and gelatin, within a PVA hydrogel. PVA was functionalized with 7 and 20 methacrylate functional groups per chain (FG/c) to tailor the permselectivity of UV photopolymerized hydrogels. Both heparin and gelatin were covalently incorporated into PVA at an equal ratio resulting in a final PVA:heparin:gelatin composition of 19:0.5:0.5. The combination of both heparin and gelatin within a PVA network has proven to be stable over time without compromising the PVA base characteristics including its permselectivity to different proteins. Most importantly, this combination of ECM analogues supplemented PVA with the dual functionalities of promoting cellular adhesion and sequestering growth factors essential for cellular proliferation. Multi-functional PVA hydrogels with synthetically controlled network characteristics and permselectivity show potential in various biomedical applications including artificial cell implants.

  5. Probing riboswitch-ligand interactions using thiamine pyrophosphate analogues.

    PubMed

    Chen, Liuhong; Cressina, Elena; Dixon, Neil; Erixon, Karl; Agyei-Owusu, Kwasi; Micklefield, Jason; Smith, Alison G; Abell, Chris; Leeper, Finian J

    2012-08-14

    The Escherichia coli thiM riboswitch forms specific contacts with its natural ligand, thiamine pyrophosphate (TPP or thiamine diphosphate), allowing it to generate not only nanomolar binding affinity, but also a high degree of discrimination against similar small molecules. A range of synthetic TPP analogues have been used to probe each of the riboswitch-ligand interactions. The results show that the pyrimidine-sensing helix of thiM is exquisitely tuned to select for TPP by recognising the H-bonding donor and acceptors around its aminopyrimidine ring and also by forming π-stacking interactions that may be sensitive to the electronics of the ring. The central thiazolium ring of TPP appears to be more important for ligand recognition than previously thought. It may contribute to binding via long-range electrostatic interactions and/or by exerting an electron withdrawing effect on the pyrimidine ring, allowing its presence to be sensed indirectly and thereby allowing discrimination between thiamine (and its phosphate esters) and other aminopyrimidines found in vivo. The pyrophosphate moiety is essential for submicromolar binding affinity, but unexpectedly, it does not appear to be strictly necessary for modulation of gene expression.

  6. Herkinorin Analogues with Differential Beta-Arrestin-2 Interactions

    PubMed Central

    Tidgewell, Kevin; Groer, Chad E.; Harding, Wayne W.; Lozama, Anthony; Schmidt, Matthew; Marquam, Alfred; Hiemstra, Jessica; Partilla, John S.; Dersch, Christina