Use of natural diamonds to monitor 14C AMS instrument backgrounds

NASA Astrophysics Data System (ADS)

Taylor, R. E.; Southon, John

2007-06-01

To examine one component of the instrument-based background in the University of California Keck Carbon Cycle AMS spectrometer, we have obtained measurements on a set of natural diamonds pressed into sample holders. Natural diamond samples (N = 14) from different sources within rock formations with geological ages greatly in excess of 100 Ma yielded a range of currents (∼110-250 μA 12C- where filamentous graphite typically yields ∼150 μA 12C-) and apparent 14C ages (64.9 ± 0.4 ka BP [0.00031 ± 0.00002 fm] to 80.0 ± 1.1 ka BP [0.00005 ± 0.00001 fm]). Six fragments cut from a single diamond exhibited essentially identical 14C values - 69.3 ± 0.5 ka-70.6 ± 0.5 ka BP. The oldest 14C age equivalents were measured on natural diamonds which exhibited the highest current yields.

Paleomagnetic secular variation at the Azores during the last 3 ka

NASA Astrophysics Data System (ADS)

di Chiara, Anita; Speranza, Fabio; Porreca, Massimiliano

2012-07-01

We report on 33 new paleomagnetic directions obtained from 16 lava flows emplaced in the last 3 ka on São Miguel, the largest island of the Azores. The data provide 27 well-dated directions from historical or 14C dated flows which, together with 6 directions previously gathered from the same flows by Johnson et al. (1998), yield the first paleomagnetic directional record of the last 3 ka from the Atlantic Ocean. Within-flow directions are consistent, suggesting that inclination swings from 60° to 25° and declination changes between -10° to 20° reflect variations in the geomagnetic field over the last 3 ka. To a first approximation, the declination record is consistent with predictions from CALS3k.4 and gufm1 global field models. Conversely, inclination values are lower than model predictions at two different ages: 1) four sites from the 1652 AD flow yield I = 48° instead of I = 63° predicted by gufm1; 2) data from several flows nicely mimic the inclination minimum of 800-1400 AD, but inclination values are lower by ˜10° than CALS3k.4 model predictions. By interpolating a cubic spline fit on declination / inclination versus age data, we tentatively infer the directional evolution of the geomagnetic field at the Azores from 1000 BC to 1600 AD. The obtained curve shows three tracks in virtual overlap during the 1000-800 BC, 800-500 BC, and 400-700 AD time spans.

Determination of pK(a) of felodipine using UV-Visible spectroscopy.

PubMed

Pandey, M M; Jaipal, A; Kumar, A; Malik, R; Charde, S Y

2013-11-01

In the present study, for the first time, experimental pKa value of felodipine is reported. Dissociation constant, pKa, is one of the very important physicochemical properties of drugs. It is of paramount significance from the perspective of pharmaceutical analysis and dosage form design. The method used for the pKa determination of felodipine was essentially a UV-Visible spectrophotometric method. The spectrophotometric method for the pKa determination was opted by acknowledging the established fact that spectrophotometric determination of pKa produces most precise values. The pKa of felodipine was found to be 5.07. Furthermore, the ruggedness of the determined value is also validated in this study in order to produce exact pKa of the felodipine. Copyright © 2013 Elsevier B.V. All rights reserved.

Bayesian model aggregation for ensemble-based estimates of protein pKa values

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gosink, Luke J.; Hogan, Emilie A.; Pulsipher, Trenton C.

2014-03-01

This paper investigates an ensemble-based technique called Bayesian Model Averaging (BMA) to improve the performance of protein amino acid pmore » $$K_a$$ predictions. Structure-based p$$K_a$$ calculations play an important role in the mechanistic interpretation of protein structure and are also used to determine a wide range of protein properties. A diverse set of methods currently exist for p$$K_a$$ prediction, ranging from empirical statistical models to {\\it ab initio} quantum mechanical approaches. However, each of these methods are based on a set of assumptions that have inherent bias and sensitivities that can effect a model's accuracy and generalizability for p$$K_a$$ prediction in complicated biomolecular systems. We use BMA to combine eleven diverse prediction methods that each estimate pKa values of amino acids in staphylococcal nuclease. These methods are based on work conducted for the pKa Cooperative and the pKa measurements are based on experimental work conducted by the Garc{\\'i}a-Moreno lab. Our study demonstrates that the aggregated estimate obtained from BMA outperforms all individual prediction methods in our cross-validation study with improvements from 40-70\\% over other method classes. This work illustrates a new possible mechanism for improving the accuracy of p$$K_a$$ prediction and lays the foundation for future work on aggregate models that balance computational cost with prediction accuracy.« less

Comparative analysis on inactivation kinetics of between piezotolerant and piezosensitive mutant strains of Saccharomyces cerevisiae under combinations of high hydrostatic pressure and temperature.

PubMed

Nomura, Kazuki; Kuwabara, Yuki; Kuwabara, Wataru; Takahashi, Hiroyuki; Nakajima, Kanako; Hayashi, Mayumi; Iguchi, Akinori; Shigematsu, Toru

2017-12-01

We previously obtained a pressure-tolerant (piezotolerant) and a pressure sensitive (piezosensitive) mutant strain, under ambient temperature, from Saccharomyces cerevisiae strain KA31a. The inactivation kinetics of these mutants were analyzed at 150 to 250MPa with 4 to 40°C. By a multiple regression analysis, the pressure and temperature dependency of the inactivation rate constants k values of both mutants, as well as the parent strain KA31a, were well approximated with high correlation coefficients (0.92 to 0.95). For both mutants, as well as strain KA31a, the lowest k value was shown at a low pressure levels with around ambient temperature. The k value approximately increased with increase in pressure level, and with increase and decrease in temperature. The piezosensitive mutant strain a924E1 showed piezosensitivity at all pressure and temperature levels, compared with the parent strain KA31a. In contrast, the piezotolerant mutant strain a2568D8 showed piezotolerance at 4 to 20°C, but did not show significant piezotolerance at 40°C. These results of the variable influence of temperature on pressure inactivation of these strains would be important for better understanding of piezosensitive and piezotolerant mechanisms, as well as the pressure inactivation mechanism of S. cerevisiae. Copyright © 2017 Elsevier B.V. All rights reserved.

Oxygen isotope geochemistry of Laurentide ice-sheet meltwater across Termination I

NASA Astrophysics Data System (ADS)

Vetter, Lael; Spero, Howard J.; Eggins, Stephen M.; Williams, Carlie; Flower, Benjamin P.

2017-12-01

We present a new method that quantifies the oxygen isotope geochemistry of Laurentide ice-sheet (LIS) meltwater across the last deglaciation, and reconstruct decadal-scale variations in the δ18O of LIS meltwater entering the Gulf of Mexico between ∼18 and 11 ka. We employ a technique that combines laser ablation ICP-MS (LA-ICP-MS) and oxygen isotope analyses on individual shells of the planktic foraminifer Orbulina universa to quantify the instantaneous δ18Owater value of Mississippi River outflow, which was dominated by meltwater from the LIS. For each individual O. universa shell, we measure Mg/Ca (a proxy for temperature) and Ba/Ca (a proxy for salinity) with LA-ICP-MS, and then analyze the same O. universa for δ18O using the remaining material from the shell. From these proxies, we obtain δ18Owater and salinity estimates for each individual foraminifer. Regressions through data obtained from discrete core intervals yield δ18Ow vs. salinity relationships with a y-intercept that corresponds to the δ18Owater composition of the freshwater end-member. Our data suggest that from 15.5 through 14.6 ka, estimated δ18Ow values of Mississippi River discharge from discrete core intervals range from -11‰ to -21‰ VSMOW, which is consistent with δ18O values from both regional precipitation and the low-elevation, southern margin of the LIS. During the Bølling and Allerød (14.0 through 13.3 ka), estimated δ18Ow values of Mississippi River discharge from discrete core intervals range from -22‰ to -38‰ VSMOW. These values suggest a dynamic melting history of different parts of the LIS, with potential contributions to Mississippi River outflow from both the low-elevation, southern margin of the LIS and high-elevation, high-latitude domes in the LIS interior that were transported to the ablation zone. Prior to ∼15.5 ka, the δ18Owater value of the Mississippi River was similar to that of regional precipitation or low-latitude LIS meltwater, but the Ba concentration in the Mississippi basin was affected by changes in weathering within the watershed, complicating Ba-salinity relationships in the Gulf of Mexico. After 13 ka, our data suggest Mississippi River outflow did not influence surface salinity above our Gulf of Mexico Orca Basin core site. Rather, we hypothesize that open ocean conditions prevailed as sea level rose and the paleoshoreline at the southern edge of North America retreated northward.

New 40Ar/39Ar age of the Bishop Tuff from multiple sites and sediment rate calibration for the Matuyama-Brunhes boundary

USGS Publications Warehouse

Sarna-Wojcicki, A. M.; Pringle, M.S.; Wijbrans, J.

2000-01-01

Precise dating of sanidine from proximal ash flow Bishop Tuff and air fall Bishop pumice and ash, California, can be used to derive an absolute age of the Matuyama Reversed-Brunhes Normal (M-B) paleomagnetic transition, identified stratigraphically close beneath the Bishop Tuff and ash at many sites in the western United States. An average age of 758.9 ?? 1.8 ka, standard error of the mean (SEM), was obtained for individual sanidine crystals or groups of several crystals, determined from ???70 individual analyses of sanidine separates from 11 sample groups obtained at five localities. The basal air fall pumice (757.7 ?? 1.8 ka) and overlying ash flow tuff (762.2 ?? 4.7 ka) from near the source yield essentially the same dates within errors of analysis, suggesting that the two units were emplaced close in time. A date on distal Bishop air fall ash bed at Friant, California, ???100 km to the west of the source area, is younger, 750.1 ?? 4.3 ka, but not significantly different within analytical error (??1 standard deviation). Previous dates of the Bishop Tuff, obtained by others using conventional K-Ar and the fission track method on zircons, ranged from ???650 ka to ???1.0 Ma. The most recent, generally accepted date by the K-Ar method on sanidine was 738 ?? 3 ka. We infer, as others before, that many K-Ar dates on sanidine feldspar are too young owing to incomplete degassing of radiogenic Ar during fusion in the K-Ar technique and that many older K-Ar dates are too old owing to detrital or xenocrystic contamination in the larger samples that are necessary for the technique. The new dates are similar to recent 40Ar/39Ar ages of the Bishop Tuff determined on individual samples by others but are derived from a larger proximal sample population and from multiple analysis of each sample. The results provide a definitive and precise age calibration of this widespread chronostratigraphic marker in the western United States and northeastern Pacific Ocean. We calculated the age of the M-B transition at five sites, assuming constant sedimentation rates, the age of the Bishop ash bed and one or more well-dated chronostratigraphic horizons above and below the Bishop Tuff ash bed and M-B transition, and stratigraphic separations between these datum levels. The age of the M-B transition is 774.2 ?? 2.8 ka, based on the average of eight such calculations, close to other recent determinations, and similar to that determined from the astronomically tuned polarity timescale. Our approach provides an alternative and surprisingly precise method for determining the age of the M-B and other chronostratigraphic levels. The above dates, calculated using U.S. Geological Survey values of 27.92 Ma for the Taylor Creek (TC) sanidine can be recalculated to other widely used values for these monitors. For example, using recently published values of 28.34 Ma (TC) and 523.1 Ma (McLure Mountain hornblende, MMhb-1), the resulting ages are ???774 ka for the Bishop Tuff and ash bed and ???789 ka for the M-B transition. Copyright 2000 by the American Geophysical Union.

Computational chemical analysis of unconjugated bilirubin anions and insights into pKa values clarification

NASA Astrophysics Data System (ADS)

Vega-Hissi, Esteban G.; Estrada, Mario R.; Lavecchia, Martín J.; Pis Diez, Reinaldo

2013-01-01

The pKa, the negative logarithm of the acid dissociation equilibrium constant, of the carboxylic acid groups of unconjugated bilirubin in water is a discussed issue because there are quite different experimental values reported. Using quantum mechanical calculations we have studied the conformational behavior of unconjugated bilirubin species (in gas phase and in solution modeled implicitly and explicitly) to provide evidence that may clarify pKa values because of its pathophysiological relevance. Our results show that rotation of carboxylate group, which is not restricted, settles it in a suitable place to establish stronger interactions that stabilizes the monoanion and the dianion to be properly solvated, demonstrating that the rationalization used to justify the high pKa values of unconjugated bilirubin is inappropriate. Furthermore, low unconjugated bilirubin (UCB) pKa values were estimated from a linear regression analysis.

Determination of pKa values of alendronate sodium in aqueous solution by piecewise linear regression based on acid-base potentiometric titration.

PubMed

Ke, Jing; Dou, Hanfei; Zhang, Ximin; Uhagaze, Dushimabararezi Serge; Ding, Xiali; Dong, Yuming

2016-12-01

As a mono-sodium salt form of alendronic acid, alendronate sodium presents multi-level ionization for the dissociation of its four hydroxyl groups. The dissociation constants of alendronate sodium were determined in this work by studying the piecewise linear relationship between volume of titrant and pH value based on acid-base potentiometric titration reaction. The distribution curves of alendronate sodium were drawn according to the determined pKa values. There were 4 dissociation constants (pKa 1 =2.43, pKa 2 =7.55, pKa 3 =10.80, pKa 4 =11.99, respectively) of alendronate sodium, and 12 existing forms, of which 4 could be ignored, existing in different pH environments.

Acidity of a Cu-bound histidine in the binuclear center of cytochrome C oxidase.

PubMed

Fadda, Elisa; Chakrabarti, Nilmadhab; Pomès, Régis

2005-12-01

Cytochrome c oxidase (CcO) is a crucial enzyme in the respiratory chain. Its function is to couple the reduction of molecular oxygen, which takes place in the Fea3-CuB binuclear center, to proton translocation across the mitochondrial membrane. Although several high-resolution structures of the enzyme are known, the molecular basis of proton pumping activation and its mechanism remain to be elucidated. We examine a recently proposed scheme (J. Am. Chem. Soc. 2004, 126, 1858; FEBS Lett. 2004, 566, 126) that involves the deprotonation of the CuB-bound imidazole ring of a histidine (H291 in mammalian CcO) as a key element in the proton pumping mechanism. The central feature of that proposed mechanism is that the pKa values of the imidazole vary significantly depending on the redox state of the metals in the binuclear center. We use density functional theory in combination with continuum electrostatics to calculate the pKa values, successively in bulk water and within the protein, of the Cu-bound imidazole in various Cu- and Cu-Fe complexes. From pKas in bulk water, we derived a value of -266.34 kcal.mol(-1) for the proton solvation free energy (Delta). This estimate is in close agreement with the experimental value of -264.61 kcal.mol(-1) (J. Am. Chem. Soc. 2001, 123, 7314), which reinforces the conclusion that Delta is more negative than previous values used for pKa calculations. Our approach, on the basis of the study of increasingly more detailed models of the CcO binuclear center at different stages of the catalysis, allows us to examine successively the effect of each of the two metals' redox states and of solvation on the acidity of imidazole, whose pKa is approximately 14 in bulk water. This analysis leads to the following conclusions: first, the effect of Cu ligation on the imidazole acidity is negligible regardless of the redox state of the metal. Second, results obtained for Cu-Fe complexes in bulk water indicate that Cu-bound imidazole pKa values lie within the range of 14.8-16.6 throughout binuclear redox states corresponding to the catalytic cycle, demonstrating that the effect of the Fe oxidation states is also negligible. Finally, the low-dielectric CcO proteic environment shifts the acid-base equilibrium toward a neutral imidazole, further increasing the corresponding pKa values. These results are inconsistent with the proposed role of the Cu-bound histidine as a key element in the pumping mechanism. Limitations of continuum solvation models in pKa calculations are discussed.

Effect of methylation on the side-chain pKa value of arginine.

PubMed

Evich, Marina; Stroeva, Ekaterina; Zheng, Yujun George; Germann, Markus W

2016-02-01

Arginine methylation is important in biological systems. Recent studies link the deregulation of protein arginine methyltransferases with certain cancers. To assess the impact of methylation on interaction with other biomolecules, the pKa values of methylated arginine variants were determined using NMR data. The pKa values of monomethylated, symmetrically dimethylated, and asymmetrically dimethylated arginine are similar to the unmodified arginine (14.2 ± 0.4). Although the pKa value has not been significantly affected by methylation, consequences of methylation include changes in charge distribution and steric effects, suggesting alternative mechanisms for recognition. © 2015 The Protein Society.

Molecular Paleoclimate Reconstructions over the Last 9 ka from a Peat Sequence in South China

PubMed Central

Wang, Xinxin; Huang, Xianyu; Sachse, Dirk; Ding, Weihua; Xue, Jiantao

2016-01-01

To achieve a better understanding of Holocene climate change in the monsoon regions of China, we investigated the molecular distributions and carbon and hydrogen isotope compositions (δ13C and δD values) of long-chain n-alkanes in a peat core from the Shiwangutian (SWGT) peatland, south China over the last 9 ka. By comparisons with other climate records, we found that the δ13C values of the long-chain n-alkanes can be a proxy for humidity, while the δD values of the long-chain n-alkanes primarily recorded the moisture source δD signal during 9–1.8 ka BP and responded to the dry climate during 1.8–0.3 ka BP. Together with the average chain length (ACL) and the carbon preference index (CPI) data, the climate evolution over last 9 ka in the SWGT peatland can be divided into three stages. During the first stage (9–5 ka BP), the δ13C values were depleted and CPI and Paq values were low, while ACL values were high. They reveal a period of warm and wet climate, which is regarded as the Holocene optimum. The second stage (5–1.8 ka BP) witnessed a shift to relatively cool and dry climate, as indicated by the more positive δ13C values and lower ACL values. During the third stage (1.8–0.3 ka BP), the δ13C, δD, CPI and Paq values showed marked increase and ACL values varied greatly, implying an abrupt change to cold and dry conditions. This climate pattern corresponds to the broad decline in Asian monsoon intensity through the latter part of the Holocene. Our results do not support a later Holocene optimum in south China as suggested by previous studies. PMID:27505008

Progress in the prediction of pKa values in proteins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alexov, Emil; Mehler, Ernest L.; Baker, Nathan A.

2011-12-15

The pKa-cooperative aims to provide a forum for experimental and theoretical researchers interested in protein pKa values and protein electrostatics in general. The first round of the pKa -cooperative, which challenged computational labs to carry out blind predictions against pKas experimentally determined in the laboratory of Bertrand Garcia-Moreno, was completed and results discussed at the Telluride meeting (July 6-10, 2009). This paper serves as an introduction to the reports submitted by the blind prediction participants that will be published in a special issue of PROTEINS: Structure, Function and Bioinformatics. Here we briefly outline existing approaches for pKa calculations, emphasizing methodsmore » that were used by the participants in calculating the blind pKa values in the first round of the cooperative. We then point out some of the difficulties encountered by the participating groups in making their blind predictions, and finally try to provide some insights for future developments aimed at improving the accuracy of pKa calculations.« less

Stable isotope compositions of speleothems from the last interglacial - Spatial patterns of climate fluctuations in Europe

NASA Astrophysics Data System (ADS)

Demény, Attila; Kern, Zoltán; Czuppon, György; Németh, Alexandra; Leél-Őssy, Szabolcs; Siklósy, Zoltán; Lin, Ke; Hu, Hsun-Ming; Shen, Chuan-Chou; Vennemann, Torsten W.; Haszpra, László

2017-04-01

Studies on the last interglacial (LIG) can provide information on how our environment behaved in a period of slightly higher global temperatures at about 125 ± 4 ka, even if it is not the best analogue for the Holocene. The available LIG climate proxy records are usually better preserved and can be studied at a higher resolution than those of the preceding interglacials, allowing detailed comparisons. This paper presents complex stable hydrogen, carbon and oxygen isotope records obtained for carbonate (δ13C and δ18Ocarb) and fluid inclusion hosted water (δD and δ18Ow) of a stalagmite from the Baradla Cave system in Central Europe that covers most of the LIG, as proven by U-Th dates. Comparing its C and O isotope data with records reported for other speleothem (cave-hosted carbonate) deposits from Europe revealed the complex behavior of these climate proxies, with a concerted relative increase in 18O of carbonates from 128 to 120 ka and synchronized shifts in the opposite direction after 119 ka. The hydrogen isotope analyses of inclusion-hosted water extracted from the BAR-II stalagmite also correspond to the regional climate proxy records, with meaningful deviations from global temperature trends. Beside following the general paleotemperature pattern from the climate optimum (high δD values up to -64‰ around 120 ka) to the subsequent cooling starting at about 119 ka (low δD values down to -90‰ at about 109 ka), a period between 126.5 and 123 ka with low δD values (down to -81‰) is detected in the BAR-II stalagmite. Although the isotope shifts are muted in the C-O isotope data of carbonate due to competitive fractionation processes, the δ13C data show a positive relationship with the δD pattern, indicating humidity - and possibly temperature - variations. The periods with low δD values fit well to temperature and humidity changes inferred from proxy records from western Europe to the eastern Mediterranean. Spatial distributions of these variables show, that at about 125 ± 2 ka the Mediterranean region was characterized by warm, humid conditions and enhanced seasonality with elevated winter precipitation. The combined interpretation of stable isotope data revealed that the Alpine and Mediterranean regions behaved differently during Greenland Stadial 26 (GS26, ∼119 to 116.2 ka). While the Alpine records fluctuated in close agreement with the Central Greenland ice core δ18O data, the BAR-II stalagmite show a positive δ18Ocarb anomaly. The Baradla data indicate enhanced aridity and seasonality for a part of GS26, with the relative dominance of summer precipitation and Mediterranean moisture contribution. Following the GS26 event, the effect of long-term global cooling becomes dominant in the Baradla isotope records and leads to glacial inception at about 109 ka.

The Record of Geomagnetic Excursions from a ~150 m Sediment Core: Clear Lake, Northern California

NASA Astrophysics Data System (ADS)

Levin, E.; Byrne, R.; Looy, C. V.; Wahl, D.; Noren, A. J.; Verosub, K. L.

2015-12-01

We are studying the paleomagnetic properties of a new ~150 meter drill core from Clear Lake, CA. Step-wise demagnetization of the natural remanent magnetism (NRM) yields stable directions after 20 mT, implying that the sediments are reliable recorders of geomagnetic field behavior. Several intervals of low relative paleointensity (RPI) from the core appear to be correlated with known geomagnetic excursions. At about 46 m depth, and ~33 ka according to an age model based on radiocarbon dates obtained from pollen and the Olema ash bed, a low RPI zone seems to agree with the age and duration of the Mono Lake Excursion, previously identified between 32 and 35 ka. Slightly lower in the core, at about 50 m depth and ~40 ka, noticeably low RPI values seem to be coeval with the Laschamp excursion, which has been dated at ~41 ka. A volcanic ash near the bottom of the core (141 mblf) is near the same depth as an ash identified in 1988 by Andrei Sarna-Wojcicki and others as the Loleta ash bed in a previous Clear Lake core. If the basal ash in the new core is indeed the, Loleta ash bed, then the core may date back to about 270-300 ka. Depending on the age of the lowest ash, a sequence of low RPI intervals could correlate with the Blake (120 ka), Iceland Basin (188 ka), Jamaica/Pringle Falls (211 ka), and CR0 (260 ka) excursions. Correlation of the low RPI intervals to these geomagnetic excursions will help in the development of a higher resolution chronostratigraphy for the core, resolve a long-standing controversy about a possible hiatus in the Clear Lake record, and provide information about climatically-driven changes in sedimentation.

RESEARCH PAPERS : Evidence for the Blake event in volcanic rocks from Lipari (Aeolian Archipelago)

NASA Astrophysics Data System (ADS)

Zanella, Elena; Laurenzi, Marinella A.

1998-01-01

Palaeomagnetic and geochronological measurements have been carried out on the late Pleistocene basaltic-andesitic unit of Monte Chirica-Costa Rasa, on the island of Lipari (Aeolian Archipelago). The lava flow sequence is about 10 m thick and has been sampled in detail. Magnetic properties are rather uniform; Curie temperatures of 540° to 580°C, and the saturation IRM reached at applied values of 0.1 T point to titanomagnetite as the main magnetization carrier. Thermal and AF demagnetization have shown the presence of secondary magnetization components. These were removed mostly at 450°-500°C or 20-30 mT, indicating a highly stable ChRM with directions from transitional to reverse. Where a ChRM could not be isolated by application of the demagnetization techniques, the converging remagnetization circles method gave a mean ChRM value fully comparable with that obtained from other methods. 40Ar/39Ar determinations were performed on two lava flows, in the lower and upper parts of the sequence. The former shows a transitional ChRM direction and a whole-rock age of 157+/-12 ka, the latter a reverse direction, a whole-rock age of 143+/-17 ka and a ground-mass age of 128+/-23 ka. The radiometric data and the reconstructed stratigraphy, which indicate ages of 150+/-10 ka and 104+/-3.5 ka, respectively, for the volcanic units at the bottom and top of the Monte Chirica-Costa Rasa unit, suggest that the reverse directions recorded in Lipari are related to the Blake event.

Asymmetric protonation of EmrE

PubMed Central

Morrison, Emma A.; Robinson, Anne E.; Liu, Yongjia

2015-01-01

The small multidrug resistance transporter EmrE is a homodimer that uses energy provided by the proton motive force to drive the efflux of drug substrates. The pKa values of its “active-site” residues—glutamate 14 (Glu14) from each subunit—must be poised around physiological pH values to efficiently couple proton import to drug export in vivo. To assess the protonation of EmrE, pH titrations were conducted with 1H-15N TROSY-HSQC nuclear magnetic resonance (NMR) spectra. Analysis of these spectra indicates that the Glu14 residues have asymmetric pKa values of 7.0 ± 0.1 and 8.2 ± 0.3 at 45°C and 6.8 ± 0.1 and 8.5 ± 0.2 at 25°C. These pKa values are substantially increased compared with typical pKa values for solvent-exposed glutamates but are within the range of published Glu14 pKa values inferred from the pH dependence of substrate binding and transport assays. The active-site mutant, E14D-EmrE, has pKa values below the physiological pH range, consistent with its impaired transport activity. The NMR spectra demonstrate that the protonation states of the active-site Glu14 residues determine both the global structure and the rate of conformational exchange between inward- and outward-facing EmrE. Thus, the pKa values of the asymmetric active-site Glu14 residues are key for proper coupling of proton import to multidrug efflux. However, the results raise new questions regarding the coupling mechanism because they show that EmrE exists in a mixture of protonation states near neutral pH and can interconvert between inward- and outward-facing forms in multiple different protonation states. PMID:26573622

New insights on the spectrophotometric determination of melatonin pKa values and melatonin-βCD inclusion complex formation constant

NASA Astrophysics Data System (ADS)

Zafra-Roldán, A.; Corona-Avendaño, S.; Montes-Sánchez, R.; Palomar-Pardavé, M.; Romero-Romo, M.; Ramírez-Silva, M. T.

2018-02-01

Using UV-Vis spectrophotometry a stability study of melatonin at different pH values was done in aqueous media, finding that at acidic pH melatonin is unstable when interacting with the environment, however it becomes stable protecting it from light and oxygen. From the UV-Vis spectra and SQUAD software, melatonin pKa values, in a completely protected aqueous medium, were estimated as 5.777 ± 0.011 and 10.201 ± 0.024. Using the same techniques, the melatonin and β-cyclodextrin inclusion complex formation constants were assessed at pH 3, 7 and 11.5, giving the values of log β = (3.07 ± 0.06), (2.94 ± 0.01) and (3.07 ± 0.06) M- 1, respectively. From the global acidity formation constants and the complexes' formation constants, the molar fractions were determined for each species of MT and MT - βCD, to build the molar fraction-[βCD]-pH 3D diagram and the molar fraction-pH 2D diagrams, where it was possible to observe the predominance of the MT species with and without βCD. A voltammetric study at pH 3, allowed obtaining a value of log β = (3.15 ± 0.01) M- 1, which corroborates that obtained through UV-Vis spectrophotometry, supporting strongly the rationale behind using simple, straightforward techniques.

Paleoceanographic conditions at approximately 20 and 70 ka recorded in Kikaithyris hanzawai (Brachiopoda) shells

NASA Astrophysics Data System (ADS)

Takizawa, Mamoru; Takayanagi, Hideko; Yamamoto, Koshi; Abe, Osamu; Sasaki, Keiichi; Iryu, Yasufumi

2017-10-01

The δ13C and δ18O values of fossil brachiopod shells have been widely used as paleoenvironmental proxies. In this study, we investigated intrashell and intraspecific variations in the isotopic and minor element concentrations of well-preserved shells of the brachiopod Kikaithyris hanzawai (Yabe) from the last glacial period (∼20 ka [Last Glacial Maximum; LGM] and ∼70 ka [Marine Isotope Stage 4; MIS4]), collected in the Central Ryukyus, and used these data to estimate the paleoceanographic conditions (seawater temperature, concentration of dissolved inorganic carbon [DIC], and δ13C value of DIC [δ13CDIC]). The δ13C and δ18O profiles along the maximum growth axis, obtained from the inner shell surface, show three distinct intervals, corresponding to changes in shell morphology. These results suggest that the bulk isotopic compositions of brachiopods with complex shell morphologies are unsuitable for paleoenvironmental reconstructions. Nevertheless, there exists a specific shell portion with relatively small intrashell and intraspecific variations. The past seawater temperatures derived from the δ18O values of this portion are consistent with the alkenone- and planktic foraminiferal Mg/Ca-based past seawater temperatures reported in previous studies. The past δ13CDIC values estimated from the δ13C values of the specific shell portion are within the range of the past δ13CDIC values calculated from known atmospheric and oceanographic parameters. The past DIC concentrations reconstructed from the brachiopod-based δ13CDIC values are lower than the present concentrations in the East China Sea, which can be explained by low partial pressure of CO2 during the last glacial period. These results indicate that the δ13C and δ18O values obtained from K. hanzawai shells are potential paleoenvironmental indicators. The intrashell and intraspecific variations in the K. hanzawai shells are different for each minor element. Some anomalously high Mn and Fe concentrations in the shells are probably caused by metabolic factor(s), not by meteoric diagenesis. This suggests that the minor element concentrations are useful but not perfect for distinguishing diagenetically altered and unaltered portions of the shells of K. hanzawai in the studied succession.

Arginine: Its pKa value revisited

PubMed Central

Fitch, Carolyn A; Platzer, Gerald; Okon, Mark; Garcia-Moreno E, Bertrand; McIntosh, Lawrence P

2015-01-01

Using complementary approaches of potentiometry and NMR spectroscopy, we have determined that the equilibrium acid dissociation constant (pKa value) of the arginine guanidinium group is 13.8 ± 0.1. This is substantially higher than that of ∼12 often used in structure-based electrostatics calculations and cited in biochemistry textbooks. The revised intrinsic pKa value helps explains why arginine side chains in proteins are always predominantly charged, even at pH values as great as 10. The high pKa value also reinforces the observation that arginine side chains are invariably protonated under physiological conditions of near neutral pH. This occurs even when the guanidinium moiety is buried in a hydrophobic micro-environment, such as that inside a protein or a lipid membrane, thought to be incompatible with the presence of a charged group. PMID:25808204

pKa predictions for proteins, RNAs, and DNAs with the Gaussian dielectric function using DelPhi pKa.

PubMed

Wang, Lin; Li, Lin; Alexov, Emil

2015-12-01

We developed a Poisson-Boltzmann based approach to calculate the pKa values of protein ionizable residues (Glu, Asp, His, Lys and Arg), nucleotides of RNA and single stranded DNA. Two novel features were utilized: the dielectric properties of the macromolecules and water phase were modeled via the smooth Gaussian-based dielectric function in DelPhi and the corresponding electrostatic energies were calculated without defining the molecular surface. We tested the algorithm by calculating pKa values for more than 300 residues from 32 proteins from the PPD dataset and achieved an overall RMSD of 0.77. Particularly, the RMSD of 0.55 was achieved for surface residues, while the RMSD of 1.1 for buried residues. The approach was also found capable of capturing the large pKa shifts of various single point mutations in staphylococcal nuclease (SNase) from pKa-cooperative dataset, resulting in an overall RMSD of 1.6 for this set of pKa's. Investigations showed that predictions for most of buried mutant residues of SNase could be improved by using higher dielectric constant values. Furthermore, an option to generate different hydrogen positions also improves pKa predictions for buried carboxyl residues. Finally, the pKa calculations on two RNAs demonstrated the capability of this approach for other types of biomolecules. © 2015 Wiley Periodicals, Inc.

The pKa Cooperative: A Collaborative Effort to Advance Structure-Based Calculations of pKa values and Electrostatic Effects in Proteins

PubMed Central

Nielsen, Jens E.; Gunner, M. R.; Bertrand García-Moreno, E.

2012-01-01

The pKa Cooperative http://www.pkacoop.org was organized to advance development of accurate and useful computational methods for structure-based calculation of pKa values and electrostatic energy in proteins. The Cooperative brings together laboratories with expertise and interest in theoretical, computational and experimental studies of protein electrostatics. To improve structure-based energy calculations it is necessary to better understand the physical character and molecular determinants of electrostatic effects. The Cooperative thus intends to foment experimental research into fundamental aspects of proteins that depend on electrostatic interactions. It will maintain a depository for experimental data useful for critical assessment of methods for structure-based electrostatics calculations. To help guide the development of computational methods the Cooperative will organize blind prediction exercises. As a first step, computational laboratories were invited to reproduce an unpublished set of experimental pKa values of acidic and basic residues introduced in the interior of staphylococcal nuclease by site-directed mutagenesis. The pKa values of these groups are unique and challenging to simulate owing to the large magnitude of their shifts relative to normal pKa values in water. Many computational methods were tested in this 1st Blind Prediction Challenge and critical assessment exercise. A workshop was organized in the Telluride Science Research Center to assess objectively the performance of many computational methods tested on this one extensive dataset. This volume of PROTEINS: Structure, Function, and Bioinformatics introduces the pKa Cooperative, presents reports submitted by participants in the blind prediction challenge, and highlights some of the problems in structure-based calculations identified during this exercise. PMID:22002877

Best of both worlds: combining pharma data and state of the art modeling technology to improve in Silico pKa prediction.

PubMed

Fraczkiewicz, Robert; Lobell, Mario; Göller, Andreas H; Krenz, Ursula; Schoenneis, Rolf; Clark, Robert D; Hillisch, Alexander

2015-02-23

In a unique collaboration between a software company and a pharmaceutical company, we were able to develop a new in silico pKa prediction tool with outstanding prediction quality. An existing pKa prediction method from Simulations Plus based on artificial neural network ensembles (ANNE), microstates analysis, and literature data was retrained with a large homogeneous data set of drug-like molecules from Bayer. The new model was thus built with curated sets of ∼14,000 literature pKa values (∼11,000 compounds, representing literature chemical space) and ∼19,500 pKa values experimentally determined at Bayer Pharma (∼16,000 compounds, representing industry chemical space). Model validation was performed with several test sets consisting of a total of ∼31,000 new pKa values measured at Bayer. For the largest and most difficult test set with >16,000 pKa values that were not used for training, the original model achieved a mean absolute error (MAE) of 0.72, root-mean-square error (RMSE) of 0.94, and squared correlation coefficient (R(2)) of 0.87. The new model achieves significantly improved prediction statistics, with MAE = 0.50, RMSE = 0.67, and R(2) = 0.93. It is commercially available as part of the Simulations Plus ADMET Predictor release 7.0. Good predictions are only of value when delivered effectively to those who can use them. The new pKa prediction model has been integrated into Pipeline Pilot and the PharmacophorInformatics (PIx) platform used by scientists at Bayer Pharma. Different output formats allow customized application by medicinal chemists, physical chemists, and computational chemists.

Isotopic Evidence for C4 Grass Expansion During the Last Glacial Maximum and Younger Dryas in Northern Australia

NASA Astrophysics Data System (ADS)

Johnson, B. J.; Wakeham, S.; Gelinas, Y.; Luly, J.; Miller, G.

2004-12-01

In northern and central Australia, late Quaternary records of terrestrial environmental change are rare due to generally poor preservation of pollen grains and a derth of long-term, continuous lacustrine sedimentary deposits. The Wombe mound spring in the Keep River National Park, Northern Territory, is an organic mound and isolated patch of monsoon vine thicket thought to have formed tens of thousands of years ago. In an effort to obtain a record of paleovegetation and fire history from northern Australia, a 3.4 m sediment core was recovered from the Wombe mound spring and subject to multiple types of analyses. The core represents a continuous depositional sequence with radiocarbon ages spanning the last 35 ka cal years (hereafter referred to as 35 ka). Paleovegetation was reconstructed using a combination of pollen and carbon isotopes in bulk sediment and higher plant leaf wax (HPLW) lipid biomarkers. The fire history was reconstructed from paired graphitic black carbon (GBC) and polycyclic aromatic hydrocarbon (PAH) analyses of the core sediments. Between 35 and 11 ka, the bulk organic carbon (OC) isotope data fluctuate between -22 and -15%, with the most isotopically enriched values measured at 11.4 ka. Between 12.3 and 6.8 ka, OC isotope values decrease by 13%, and remain steady from 6.8 ka to the present at -28%. There are two distinct peaks of isotopic enrichment in the higher plant leaf wax biomarkers. These two peaks coincide with the Last Glacial Maximum (LGM; 21 ka) and the Younger Dryas (YD; 11.4 ka) and represent maximum increases in C4 grasses relative to C3 plants. Relative increases in C4 grasses during the LGM in other parts of the tropics (i.e., Sacred Lake, Mt. Kenya) have been attributed to the competitive advantage of C4 plants relative to C3 plants under reduced atmospheric pCO2 and is likely the cause for C4 expansion in northern Australia. The increase in C4 grasses during the YD is reflected in the bulk sediment and HPLW isotope data and is also documented in the Sacred Lake record and may result from an increase in intensity of the easterly trade winds. GBC and PAH analyses are correlated to each other with maximum concentrations of each occurring between 28 and 30 ka and between 13 and 18 ka. The fact that these records are correlated suggests that each is an independent proxy for fire frequency at the Wombe mound spring. These periods of increased fire frequency may be associated with excessive fuel build-up and burn, or increased vulnerability of the vegetation to periods of enhanced aridity. Low GBC and PAH concentrations at approximately 20 ka and 11 ka are attributed to relatively reduced fuel loads during extreme dry events of the LGM and YD. Low GBC and PAH values during the Holocene coupled with establishment of the C3 mound spring indicate that there is very little evidence of fire over the last 8 ka preserved at the site. This likely reflects the moist microenvironment of the mound spring and not the regional fire history of the area.

Binding of mercury(II) to aquatic humic substances: Influence of pH and source of humic substances

USGS Publications Warehouse

Haitzer, M.; Aiken, G.R.; Ryan, J.N.

2003-01-01

Conditional distribution coefficients (KDOM???) for Hg(II) binding to seven dissolved organic matter (DOM) isolates were measured at environmentally relevant ratios of Hg(II) to DOM. The results show that KDOM??? values for different types of samples (humic acids, fulvic acids, hydrophobic acids) isolated from diverse aquatic environments were all within 1 order of magnitude (1022.5??1.0-1023.5??1.0 L kg-1), suggesting similar Hg(II) binding environments, presumably involving thiol groups, for the different isolates. KDOM??? values decreased at low pHs (4) compared to values at pH 7, indicating proton competition for the strong Hg(II) binding sites. Chemical modeling of Hg(II)-DOM binding at different pH values was consistent with bidentate binding of Hg(II) by one thiol group (pKa = 10.3) and one other group (pKa = 6.3) in the DOM, which is in agreement with recent results on the structure of Hg(II)-DOM bonds obtained by extended X-ray absorption fine structure spectroscopy (EXAFS).

Gradient retention prediction of acid-base analytes in reversed phase liquid chromatography: a simplified approach for acetonitrile-water mobile phases.

PubMed

Andrés, Axel; Rosés, Martí; Bosch, Elisabeth

2014-11-28

In previous work, a two-parameter model to predict chromatographic retention of ionizable analytes in gradient mode was proposed. However, the procedure required some previous experimental work to get a suitable description of the pKa change with the mobile phase composition. In the present study this previous experimental work has been simplified. The analyte pKa values have been calculated through equations whose coefficients vary depending on their functional group. Forced by this new approach, other simplifications regarding the retention of the totally neutral and totally ionized species also had to be performed. After the simplifications were applied, new prediction values were obtained and compared with the previously acquired experimental data. The simplified model gave pretty good predictions while saving a significant amount of time and resources. Copyright © 2014 Elsevier B.V. All rights reserved.

ent-Kaurenoic acid-rich extract from Mikania glomerata: In vitro activity against bacteria responsible for dental caries.

PubMed

Moreira, Monique Rodrigues; Souza, Ariana Borges; Soares, Sandra; Bianchi, Thamires Chiquini; de Souza Eugênio, Daniele; Lemes, Danieli Cristina; Martins, Carlos Henrique Gomes; da Silva Moraes, Thaís; Tavares, Denise Crispim; Ferreira, Natália Helen; Ambrósio, Sergio Ricardo; Veneziani, Rodrigo Cassio Sola

2016-07-01

Many studies have reported that medicinal plant extracts can inhibit oral pathogen growth or adhesion to surfaces and therefore reduce dental caries formation. The addition of these extracts to oral products like mouthwashes and dentifrices is considered an important strategy in caries control. In this sense, we have developed a Mikania glomerata extract with high ent-kaurenoic acid content (KAMg). So, this work describes the preparation of such extract and the development of a validated HPLC-DAD method to determine its ent-kaurenoic acid (KA) content. Herein it is also described the KAMg in vitro antibacterial evaluation against several cariogenic bacteria in comparison with KA and the investigation of further aspects of the KAMg activity. Toxicological aspects of the developed extract were evaluated by assessing its cytotoxicity and genotoxicity. KA and a KA-rich extract like KAMg showed to inhibit the growth of microorganisms responsible for dental caries at relatively low MIC (Minimum inhibitory concentration) values, albeit not as low as the MIC value obtained for chlorhexidine digluconate (CHD), the golden anticariogenic standard approved by the American Dental Association Council on Dental Therapeutics. However, KAMg was more effective to inhibit the formation of a Streptococcus mutans biofilm with four times lower MICB50 (minimum inhibitory concentration that reduces 50% of the biofilm) value as compared with CHD. Taking into account all these data and considering the absence of genotoxic and cytotoxic activity under the tested conditions, it is suggested that KAMg is a natural product to be considered as active ingredient in oral care products. Copyright © 2016 Elsevier B.V. All rights reserved.

A multiple-approach radiometric age estimate for the Rotoiti and Earthquake Flat eruptions, New Zealand, with implications for the MIS 4/3 boundary

USGS Publications Warehouse

Wilson, C.J.N.; Rhoades, D.A.; Lanphere, M.A.; Calvert, A.T.; Houghton, Bruce F.; Weaver, S.D.; Cole, J.W.

2007-01-01

Pyroclastic fall deposits of the paired Rotoiti and Earthquake Flat eruptions from the Taupo Volcanic Zone (New Zealand) combine to form a widespread isochronous horizon over much of northern New Zealand and the southwest Pacific. This horizon is important for correlating climatic and environmental changes during the Last Glacial period, but has been the subject of numerous disparate age estimates between 35.1??2.8 and 71??6 ka (all errors are 1 s.d.), obtained by a variety of techniques. A potassium-argon (K-Ar) age of 64??4 ka was previously determined on bracketing lavas at Mayor Island volcano, offshore from the Taupo Volcanic Zone. We present a new, more-precise 40Ar/39Ar age determination on a lava flow on Mayor Island, that shortly post-dates the Rotoiti/Earthquake Flat fall deposits, of 58.5??1.1 ka. This value, coupled with existing ages from underlying lavas, yield a new estimate for the age of the combined eruptions of 61.0??1.4 ka, which is consistent with U-Th disequilibrium model-age data for zircons from the Rotoiti deposits. Direct 40Ar/39Ar age determinations of plagioclase and biotite from the Rotoiti and Earthquake Flat eruption products yield variable values between 49.6??2.8 and 125.3??10.0 ka, with the scatter attributed to low radiogenic Ar yields, and/or alteration, and/or inheritance of xenocrystic material with inherited Ar. Rotoiti/Earthquake Flat fall deposits occur in New Zealand in association with palynological indicators of mild climate, attributed to Marine Isotope Stage (MIS) 3 and thus used to suggest an age that is post-59 ka. The natures of the criteria used to define the MIS 4/3 boundary in the Northern and Southern hemispheres, however, imply that the new 61 ka age for the Rotoiti/Earthquake Flat eruption deposits will provide the inverse, namely, a more accurate isochronous marker for correlating diverse changes across the MIS 4/3 boundary in the southwest Pacific. ?? 2007 Elsevier Ltd. All rights reserved.

Aqueous Speciation and Electrochemical Properties of a Water-Soluble Manganese Phthalocyanine Complex#

PubMed Central

Blakemore, James D.; Hull, Jonathan F.

2012-01-01

The speciation behavior of a water-soluble manganese(III) tetrasulfonated phthalocyanine complex was investigated with UV-visible and electron paramagnetic resonance (EPR) spectroscopies, as well as cyclic voltammetry. Parallel-mode EPR (in dimethylformamide:pyridine solvent mix) reveals a six-line hyperfine signal, centered at a g-value of 8.8, for the manganese(III) monomer, characteristic of the d4 S=2 system. The color of an aqueous solution containing the complex is dependent upon the pH of the solution; the phthalocyanine complex can exist as a water-bound monomer, a hydroxide-bound monomer, or an oxo-bridged dimer. Addition of coordinating bases such as borate or pyridine changes the speciation behavior by coordinating the manganese center. From the UV-visible spectra, complete speciation diagrams are plotted by global analysis of the pH-dependent UV-visible spectra, and a complete set of pKa values is obtained by fitting the data to a standard pKa model. Electrochemical studies reveal a pH-independent quasi-reversible oxidation event for the monomeric species, which likely involves oxidation of the organic ligand to the radical cation species. Adsorption of the phthalocyanine complex on the carbon working electrode was sometimes observed. The pKa values and electrochemistry data are discussed in the context of the development of mononuclear water-oxidation catalysts. PMID:22585306

StatisticAl Characteristics of Cloud over Beijing, China Obtained FRom Ka band Doppler Radar Observation

NASA Astrophysics Data System (ADS)

LIU, J.; Bi, Y.; Duan, S.; Lu, D.

2017-12-01

It is well-known that cloud characteristics, such as top and base heights and their layering structure of micro-physical parameters, spatial coverage and temporal duration are very important factors influencing both radiation budget and its vertical partitioning as well as hydrological cycle through precipitation data. Also, cloud structure and their statistical distribution and typical values will have respective characteristics with geographical and seasonal variation. Ka band radar is a powerful tool to obtain above parameters around the world, such as ARM cloud radar at the Oklahoma US, Since 2006, Cloudsat is one of NASA's A-Train satellite constellation, continuously observe the cloud structure with global coverage, but only twice a day it monitor clouds over same local site at same local time.By using IAP Ka band Doppler radar which has been operating continuously since early 2013 over the roof of IAP building in Beijing, we obtained the statistical characteristic of clouds, including cloud layering, cloud top and base heights, as well as the thickness of each cloud layer and their distribution, and were analyzed monthly and seasonal and diurnal variation, statistical analysis of cloud reflectivity profiles is also made. The analysis covers both non-precipitating clouds and precipitating clouds. Also, some preliminary comparison of the results with Cloudsat/Calipso products for same period and same area are made.

A 20-15 ka high-resolution paleomagnetic secular variation record from Black Sea sediments - no evidence for the 'Hilina Pali excursion'?

NASA Astrophysics Data System (ADS)

Liu, Jiabo; Nowaczyk, Norbert R.; Frank, Ute; Arz, Helge W.

2018-06-01

A comprehensive magnetostratigraphic investigation on sixteen sediment cores from the southeastern Black Sea yielded a very detailed high-quality paleosecular variation (PSV) record spanning from 20 to 15 ka. The age models are based on radiocarbon dating, stratigraphic correlation, and tephrochronology. Further age constraints were obtained by correlating four meltwater events, described from the western Black Sea, ranging in age from about 17 to 15 ka, with maxima in K/Ti ratios, obtained from X-ray fluorescence (XRF) scanning, and minima in S-ratios, reflecting increased hematite content, in the studied cores. Since the sedimentation rates in the investigated time window are up to 50 cm ka-1, the obtained PSVs records enabled a stacking using 50-yr bins. A directional anomaly at 18.5 ka, associated with pronounced swings in inclination and declination, as well as a low in relative paleointensity (rPI), is probably contemporaneous with the Hilina Pali excursion, originally reported from Hawaiian lava flows. However, virtual geomagnetic poles (VGPs) calculated from Black Sea sediments are not located at latitudes lower than 60°N, which denotes normal, though pronounced secular variations. During the postulated Hilina Pali excursion, the VGPs calculated from Black Sea data migrated clockwise only along the coasts of the Arctic Ocean from NE Canada (20.0 ka), via Alaska (18.6 ka) and NE Siberia (18.0 ka) to Svalbard (17.0 ka), then looping clockwise through the Eastern Arctic Ocean.

Predicting the pKa and stability of organic acids and bases at an oil-water interface.

PubMed

Andersson, M P; Olsson, M H M; Stipp, S L S

2014-06-10

We have used density functional theory and the implicit solvent model, COSMO-RS, to investigate how the acidity constant, pKa, of organic acids and bases adsorbed at the organic compound-aqueous solution interface changes, compared to its value in the aqueous phase. The pKa determine the surface charge density of the molecules that accumulate at the fluid-fluid interface. We have estimated the pKa by comparing the stability of the protonated and unprotonated forms of a series of molecules in the bulk aqueous solution and at an interface where parts of each molecule reside in the hydrophobic phase and the rest remains in the hydrophilic phase. We found that the pKa for acids is shifted by ∼1 pH unit to higher values compared to the bulk water pKa, whereas they are shifted to lower values by a similar amount for bases. Because this pKa shift is similar in magnitude for each of the molecules studied, we propose that the pKa for molecules at a water-organic compound interface can easily be predicted by adding a small shift to the aqueous pKa. This shift is general and correlates with the functional group. We also found that the relative composition of molecules at the fluid-fluid interface is not the same as in the bulk. For example, species such as carboxylic acids are enriched at the interface, where they can dominate surface properties, even when they are a modest component in the bulk fluid. For high surface concentrations of carboxylic acid groups at an interface, such as a self-assembled monolayer, we have demonstrated that the pKa depends on the degree of deprotonation through direct hydrogen bonding between protonated and deprotonated acidic headgroups.

pKa values in proteins determined by electrostatics applied to molecular dynamics trajectories.

PubMed

Meyer, Tim; Knapp, Ernst-Walter

2015-06-09

For a benchmark set of 194 measured pKa values in 13 proteins, electrostatic energy computations are performed in which pKa values are computed by solving the Poisson-Boltzmann equation. In contrast to the previous approach of Karlsberg(+) (KB(+)) that essentially used protein crystal structures with variations in their side chain conformations, the present approach (KB2(+)MD) uses protein conformations from four molecular dynamics (MD) simulations of 10 ns each. These MD simulations are performed with different specific but fixed protonation patterns, selected to sample the conformational space for the different protonation patterns faithfully. The root-mean-square deviation between computed and measured pKa values (pKa RMSD) is shown to be reduced from 1.17 pH units using KB(+) to 0.96 pH units using KB2(+)MD. The pKa RMSD can be further reduced to 0.79 pH units, if each conformation is energy-minimized with a dielectric constant of εmin = 4 prior to calculating the electrostatic energy. The electrostatic energy expressions upon which the computations are based have been reformulated such that they do not involve terms that mix protein and solvent environment contributions and no thermodynamic cycle is needed. As a consequence, conformations of the titratable residues can be treated independently in the protein and solvent environments. In addition, the energy terms used here avoid the so-called intrinsic pKa and can therefore be interpreted without reference to arbitrary protonation states and conformations.

Propagation-related AMT design aspects and supporting experiments

NASA Technical Reports Server (NTRS)

Dessouky, Khaled; Estabrook, Polly

1991-01-01

The ACTS Mobile Terminal (AMT) is presently being developed with the goal of significantly extending commercial satellite applications and their user base. A thorough knowledge of the Ka-band channel characteristics is essential to the proper design of a commercially viable system that efficiently utilizes the valuable resources. To date, only limited tests have been performed to characterize the Ka-band channel, and they have focused on the needs of fixed terminals. As part of the value of the AMT as a Ka-band test bed is its function as a vehicle through which tests specifically applicable to the mobile satellite communications can be performed. The exact propagation environment with the proper set of elevation angles, vehicle antenna gains and patterns, roadside shadowing, rain, and Doppler is encountered. The ability to measure all of the above, as well as correlate their effects with observed communication system performance, creates an invaluable opportunity to understand in depth Ka-band's potential in supporting mobile and personal communications. This paper discusses the propagation information required for system design, the setup with ACTS that will enable obtaining this information, and finally the types of experiments to be performed and data to be gathered by the AMT to meet this objective.

Photoconductivity of CdS under high pressure

NASA Astrophysics Data System (ADS)

Savić, Pavle; Urošević, Vladeta

1987-04-01

The photoconductivity of the high-pressure (rocksalt) phase of CdS has been investigated over the 30-120 kbar pressure range. A decrease of the photo-threshold from 1.60 eV (at 30 kbar) to 1.49 eV (at 120 kbar) indicates an indirect gap semiconductor. The values obtained have been compared with the Savić-Kašanin theory.

High-Resolution Speleothem Records of the Indian Ocean Monsoon Variability of the Last 6 ka and 0,5 ka From Soqotra Island, Yemen

NASA Astrophysics Data System (ADS)

de Geest, P.; Verheyden, S.; Cheng, H.; Edwards, L. R.; Keppens, E.

2004-12-01

Soqotra is an arid tropical island in the Indian Ocean, situated between the Horn of Africa and the Arabian Peninsula. The inter-tropical convergence zone (ITCZ) passes there twice each year, resulting in a bi-annual rainy season. High-resolution \\delta18O and \\delta13C ratios of speleothems from two different caves are used to reconstruct changes in the Monsoon intensity and/or variability. Based on 10 TIMS 234U/230Th dating, two active speleothems from Hoq (S-STM1) and Kazekas Caves (S-STM5) have formed over a period of 6 ka BP and 0,5 ka BP, respectively. To obtain a detailed climate reconstruction more than 1000 \\delta13C and \\delta18O measurements were carried out, providing a time resolution between 2,5 and 10 years. In S-STM1 \\delta18O -values range between -4,5\\permil and -1,5\\permil and \\delta13C -values between -10,5\\permil and -5,5\\permil; while for S-STM5 these values range respectively between -4\\permil and -2\\permil and -7\\permil and -3\\permil (vs VPDB). Based on the comparison between \\delta18O excursions and historical meteorological data, the amount of precipitation is reflected in the \\delta18O signal. Different mechanisms for the \\delta13C are considered, such as a diminution of the C4-type vegetation during droughts, resulting in more positive \\delta13C -value or kinetic effects during the calcification process itself. Throughout the time series, co-variation occur between \\delta13C and \\delta18O -values (R2= 0,69) exhibiting long term (millennial) and short term (decadal) variations. In both stalagmites, layers of white porous calcite (WPC) (0,1-0,5mm) and dark dense calcite (DDC) (0,01-0,1mm) alternate, most probably due to seasonal variations. The WPC has more positive \\delta13C and \\delta18O -values, while the DDC shows more negative values, clearly demonstrated by high-resolution micro sampling up to a monthly to bi-weekly resolution. A positive correlation between the greyscale variations in the calcite fabric, the presumably annual growth banding and the inverse stable isotope ratios records support this hypothesis. During dry periods, less precipitation enters the cave-system, resulting in a whitish porous calcite deposition, thinner annual banding and more negative stable isotope ratios and vice versa. To better understand the climatic significance of these records, adapted Environmental Data Acquisition Systems (EDAS) are installed in and near Hoq Cave to obtain information on the actual transfer functions between climate and the proxy data in our speleothems.

Coupled molecular dynamics and continuum electrostatic method to compute the ionization pKa's of proteins as a function of pH. Test on a large set of proteins.

PubMed

Vorobjev, Yury N; Scheraga, Harold A; Vila, Jorge A

2018-02-01

A computational method, to predict the pKa values of the ionizable residues Asp, Glu, His, Tyr, and Lys of proteins, is presented here. Calculation of the electrostatic free-energy of the proteins is based on an efficient version of a continuum dielectric electrostatic model. The conformational flexibility of the protein is taken into account by carrying out molecular dynamics simulations of 10 ns in implicit water. The accuracy of the proposed method of calculation of pKa values is estimated from a test set of experimental pKa data for 297 ionizable residues from 34 proteins. The pKa-prediction test shows that, on average, 57, 86, and 95% of all predictions have an error lower than 0.5, 1.0, and 1.5 pKa units, respectively. This work contributes to our general understanding of the importance of protein flexibility for an accurate computation of pKa, providing critical insight about the significance of the multiple neutral states of acid and histidine residues for pKa-prediction, and may spur significant progress in our effort to develop a fast and accurate electrostatic-based method for pKa-predictions of proteins as a function of pH.

Climatic evolution of Marine Isotope Stage 5 and particularly the Eemian reconstructed from precisely dated speleothems from western Germany

NASA Astrophysics Data System (ADS)

Scholz, Denis; Hoffmann, Dirk L.; Spötl, Christoph; Hopcroft, Peter; Jochum, Klaus Peter; Richter, Detlev K.

2015-04-01

We present high-resolution δ18O, δ13C and trace element profiles for three stalagmites from western Germany, which grew during Marine Isotope Stage (MIS) 5. All stalagmites were precisely dated by MC-ICPMS 230Th/U-dating. Stalagmite HBSH-1 from Hüttenbläserschachthöhle grew between 130 and 80 ka and provides a climate record with decadal to centennial resolution. The other two stalagmites grew faster than HBSH 1, but their growth phases are shorter. Stalagmite HBSH 5 grew between 129 and 122 ka, whereas stalagmite BR 5 grew between 126 and 122 ka. The record of HBSH 1 shows four growth interruptions coinciding with Greenland Stadials (GS) 21, 22, 24, 25, and 26. This shows that stalagmite growth is a very sensitive proxy for cool and dry conditions in the northern hemisphere and enables us to precisely determine the timing and duration of the GS. We interpret stalagmite δ18O values as a proxy for supra-regional temperature changes in the North Atlantic realm, which is paticularly evident from their close resemblance with the δ18O values of the NGRIP and NEEM ice core records. Stalagmite δ13C values primarily reflect changes in hydrological balance and (local) vegetation and are, thus, a proxy for terrestrial climate change in central European. The δ13C record shows three pronounced negative peaks during MIS 5, and their timing is in agreement with MIS 5e, 5c and 5a. This suggests generally warm and humid climate in central Europe during these phases. The evolution of the δ18O and δ13C values during the Eemian is not parallel. The δ18O values progressively increase from 130 ka, peak at 125 ka and subsequently show a gradual decrease. The δ13C values, in contrast, start to decrease at 123 ka, show a negative peak at 120 ka and an aprupt increase at 114 ka. This suggests that the Eemian sensu strictu lasted from 124 to 114 ka, in agreement with a marine record from the Norwegian Sea and indicates and a strong influence on central European climate from high northern latitudes. We also compare our records with other MIS 5 climate records and climate modelling simulations performed with the general circulation model FAMOUS.

Glacial terminations and the Last Interglacial in the Okhotsk Sea; Their implication to global climatic changes

NASA Astrophysics Data System (ADS)

Gorbarenko, Sergey; Velivetskaya, Tatyana; Malakhov, Mikhail; Bosin, Aleksandr

2017-05-01

Paleoclimate data from the Okhotsk Sea (OS) over Terminations II and I (TII, TI), and the Last and Present Interglacial (LIG, PIG) periods were compiled in order to examine Northern Hemisphere climate and sea level changes. Based on records of four AMS 14C-dated OS cores over TI-PIG, it is argued that the OS productivity/climate, IRD (ice-rafted debris), and benthic foraminiferal oxygen isotope (δ18Obf) proxies provide representative and in-phase evidence of the Northern Hemisphere climate and continental ice sheet changes consistent with the LR 04 δ18Obf curve. Chronologies for two central OS cores over TII-LIG-cooling event 23 (C23) were constructed by correlating OS productivity proxies with well-dated δ18O records of Chinese speleothems because OS environment is modulated by East Asian Monsoon; and, as well as correlating measured magnetic paleointensity excursions with those in the dated PISO-1500 paleointensity stack. Results show several OS climatic and environment states, including TII coeval with Asian Weak Monsoon Interval (WMI) II since 136 ka, LIG with a sharp two-step transition (130.2-129 ka) and demise at С25 (116.5 ka), and last glaciation with coolings at C24 (111 ka) and C23. The OS productivity and IRD records demonstrate certain climate amelioration in the middle of WMI-II, and two insignificant cooling events inside the LIG marked by C27 (126 ka) and C26 (120.6 ka). OS δ18Obf records of both cores demonstrate a gradual trend of lighter values since around 131.5 ka BP, continuing from the onset of LIG (129 ka) to minimum values at 126 ka BP (C27), then nearly constant values until 121.5 ka, followed by a slight increase up to 120.6 ka (C26), and a subsequent strong increase up to 116.5 ka (C25). The magnitude of OS δ18Obf oscillations is 1.35‰, which is less than those in the N. Atlantic. It may therefore be suggested that this OS index probably tracks changes in continental ice sheet volume and sea level.

Direct determination of protonation states and visualization of hydrogen bonding in a glycoside hydrolase with neutron crystallography.

PubMed

Wan, Qun; Parks, Jerry M; Hanson, B Leif; Fisher, Suzanne Zoe; Ostermann, Andreas; Schrader, Tobias E; Graham, David E; Coates, Leighton; Langan, Paul; Kovalevsky, Andrey

2015-10-06

Glycoside hydrolase (GH) enzymes apply acid/base chemistry to catalyze the decomposition of complex carbohydrates. These ubiquitous enzymes accept protons from solvent and donate them to substrates at close to neutral pH by modulating the pKa values of key side chains during catalysis. However, it is not known how the catalytic acid residue acquires a proton and transfers it efficiently to the substrate. To better understand GH chemistry, we used macromolecular neutron crystallography to directly determine protonation and ionization states of the active site residues of a family 11 GH at multiple pD (pD=pH+0.4) values. The general acid glutamate (Glu) cycles between two conformations, upward and downward, but is protonated only in the downward orientation. We performed continuum electrostatics calculations to estimate the pKa values of the catalytic Glu residues in both the apo- and substrate-bound states of the enzyme. The calculated pKa of the Glu increases substantially when the side chain moves down. The energy barrier required to rotate the catalytic Glu residue back to the upward conformation, where it can protonate the glycosidic oxygen of the substrate, is 4.3 kcal/mol according to free energy simulations. These findings shed light on the initial stage of the glycoside hydrolysis reaction in which molecular motion enables the general acid catalyst to obtain a proton from the bulk solvent and deliver it to the glycosidic oxygen.

Direct determination of protonation states and visualization of hydrogen bonding in a glycoside hydrolase with neutron crystallography

PubMed Central

Wan, Qun; Parks, Jerry M.; Hanson, B. Leif; Fisher, Suzanne Zoe; Ostermann, Andreas; Schrader, Tobias E.; Graham, David E.; Coates, Leighton; Langan, Paul; Kovalevsky, Andrey

2015-01-01

Glycoside hydrolase (GH) enzymes apply acid/base chemistry to catalyze the decomposition of complex carbohydrates. These ubiquitous enzymes accept protons from solvent and donate them to substrates at close to neutral pH by modulating the pKa values of key side chains during catalysis. However, it is not known how the catalytic acid residue acquires a proton and transfers it efficiently to the substrate. To better understand GH chemistry, we used macromolecular neutron crystallography to directly determine protonation and ionization states of the active site residues of a family 11 GH at multiple pD (pD = pH + 0.4) values. The general acid glutamate (Glu) cycles between two conformations, upward and downward, but is protonated only in the downward orientation. We performed continuum electrostatics calculations to estimate the pKa values of the catalytic Glu residues in both the apo- and substrate-bound states of the enzyme. The calculated pKa of the Glu increases substantially when the side chain moves down. The energy barrier required to rotate the catalytic Glu residue back to the upward conformation, where it can protonate the glycosidic oxygen of the substrate, is 4.3 kcal/mol according to free energy simulations. These findings shed light on the initial stage of the glycoside hydrolysis reaction in which molecular motion enables the general acid catalyst to obtain a proton from the bulk solvent and deliver it to the glycosidic oxygen. PMID:26392527

Cycloalkyl-AminoMethylRhodamines: pH Dependent Photophysical Properties Tuned by Cycloalkane Ring Size

PubMed Central

Liu, Chuangjun; Best, Quinn A.; Suarez, Brian; Pertile, Jack; McCarroll, Matthew E.; Scott, Colleen N.

2015-01-01

A series of fluorescent pH probes based on the spiro-cyclic rhodamine core, aminomethylrhodamines (AMR), was synthesized and the effect of cycloalkane ring size on the acid/base properties of the AMR system was explored. The study involved a series of rhodamine 6G (cAMR6G) and rhodamine B (cAMR) pH probes with cycloalkane ring sizes from C-3 to C-6 on the spiro-cyclic amino group. It is known that the pKa value of cycloalkylamines can be tuned by the different ring sizes in accordance with the Baeyer ring strain theory. Smaller ring amines have lower pKa value, i.e. they're less basic, such that the relative order in cycloalkylamine basicity is: cyclohexyl>cyclopentyl>cyclobutyl>cyclopropyl. Herein, it was found that the pKa values of the cAMR and cAMR6G systems can also be predicted by Baeyer ring strain theory. The pKa values for the cAMR6G series were shown to be higher than the cAMR series by a value of approximately 1. PMID:25686771

Small Negative Cloud-to-Ground Lightning Reports at the KSC-ER

NASA Technical Reports Server (NTRS)

Wilson, Jennifer G.; Cummins, Kenneth L.; Krider, E. Philip

2009-01-01

'1he NASA Kennedy Space Center (KSC) and Air Force Eastern Range (ER) use data from two cloud-to-ground (CG) lightning detection networks, the CGLSS and the NLDN, and a volumetric lightning mapping array, LDAR, to monitor and characterize lightning that is potentially hazardous to ground or launch operations. Data obtained from these systems during June-August 2006 have been examined to check the classification of small, negative CGLSS reports that have an estimated peak current, [I(sup p)] less than 7 kA, and to determine the smallest values of I(sup p), that are produced by first strokes, by subsequent strokes that create a new ground contact (NGC), and by subsequent strokes that remain in a pre-existing channel (PEC). The results show that within 20 km of the KSC-ER, 21% of the low-amplitude negative CGLSS reports were produced by first strokes, with a minimum I(sup p) of-2.9 kA; 31% were by NGCs, with a minimum I(sup p) of-2.0 kA; and 14% were by PECs, with a minimum I(sup p) of -2.2 kA. The remaining 34% were produced by cloud pulses or lightning events that we were not able to classify.

Linear free-energy relationships between a single gas-phase ab initio equilibrium bond length and experimental pKa values in aqueous solution.

PubMed

Alkorta, Ibon; Popelier, Paul L A

2015-02-02

Remarkably simple yet effective linear free energy relationships were discovered between a single ab initio computed bond length in the gas phase and experimental pKa values in aqueous solution. The formation of these relationships is driven by chemical features such as functional groups, meta/para substitution and tautomerism. The high structural content of the ab initio bond length makes a given data set essentially divide itself into high correlation subsets (HCSs). Surprisingly, all molecules in a given high correlation subset share the same conformation in the gas phase. Here we show that accurate pKa values can be predicted from such HCSs. This is achieved within an accuracy of 0.2 pKa units for 5 drug molecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

pKa values of hyodeoxycholic and cholic acids in the binary mixed micelles sodium-hyodeoxycholate-Tween 40 and sodium-cholate-Tween 40: Thermodynamic stability of the micelle and the cooperative hydrogen bond formation with the steroid skeleton.

PubMed

Poša, Mihalj; Pilipović, Ana; Bećarević, Mirjana; Farkaš, Zita

2017-01-01

Due to a relatively small size of bile acid salts, their mixed micelles with nonionic surfactants are analysed. Of the special interests are real binary mixed micelles that are thermodynamically more stable than ideal mixed micelles. Thermodynamic stability is expressed with an excess Gibbs energy (G E ) or over an interaction parameter (β ij ). In this paper sodium salts of cholic (C) and hyodeoxycholic acid (HD) in their mixed micelles with Tween 40 (T40) are analysed by potentiometric titration and their pKa values are determined. Examined bile acids in mixed micelles with T40 have higher pKa values than free bile acids. The increase of ΔpKa acid constant of micellary bound C and HD is in a correlation with absolute values of an interaction parameter. According to an interaction parameter and an excess Gibbs energy, mixed micelle HD-T40 are thermodynamically more stable than mixed micelles C-T40. ΔpKa values are higher for mixed micelles with Tween 40 whose second building unit is HD, related to the building unit C. In both micellar systems, ΔpKa increases with the rise of a molar fraction of Tween 40 in binary mixtures of surfactants with sodium salts of bile acids. This suggests that, ΔpKa can be a measure of a thermodynamic stabilization of analysed binary mixed micelles as well as an interaction parameter. ΔpKa values are confirmed by determination of a distribution coefficient of HD and C in systems: water phase with Tween 40 in a micellar concentration and 1-octanol, with a change of a pH value of a water phase. Conformational analyses suggests that synergistic interactions between building units of analysed binary micelles originates from formation of hydrogen bonds between steroid OH groups and polyoxyethylene groups of the T40. Relative similarity and spatial orientation of C 3 and C 6 OH group allows cooperative formation of hydrogen bonds between T40 and HD - excess entropy in formation of mixed micelle. If a water solution of analysed binary mixtures of surfactants contains urea in concentration of 4M significant decreases of an interaction parameter value happens which confirms the importance of hydrogen bonds in synergistic interactions (urea compete in hydrogen bonds). Copyright © 2016 Elsevier Inc. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Rajesh K.; Galvin, Janine E.; Sun, Xin

We have numerically investigated the breakup of a rivulet falling over a smooth inclined plate using the volume of fluid method. The breakup the rivulet is a complex phenomenon that is dictated by many factors, such as solvent properties, contact angle, inertia, plate inclination, etc. An extensive simulation campaign was conducted wherein these factors were systematically investigated. Regimes for a stable rivulet and an unstable rivulet that leads to the breakup and formation of a droplet are examined in terms of a critical value of the Weber number (Wecr) that delineates these regimes. The effect of plate inclination on themore » breakup of the rivulet shows that the critical Weber number decreases with increased inclination angle () owing to higher liquid velocity. However, the effect is negligible beyond >60. The impact of solvent properties is characterized using the Kapitza number (Ka). Variation of Wecr with Ka shows two trends depending on the Ka value of the solvent. Solvents with lower Ka values, corresponding to high viscosities and/or low surface tensions, show smaller values of the critical Weber number and the variation is linear. While solvents with higher Ka values exhibit higher values of the Wecr and the variation in Wecr is steep. This behavior is more pronounced with increasing contact angle. Higher contact angles promote rivulet breakup so that inertia must be higher to the breakup. A phenomenological scaling for a critical Weber number with the Kapitza number and contact angle is presented that can offer insight into rivulet breakup.« less

Holocene climatic variations documented by multiple biomarker proxies from Lake Gahai on the Northeastern Tibetan Plateau

NASA Astrophysics Data System (ADS)

He, Y.; Liu, Z.; Zheng, Z.; Zhao, C.; Sun, Y.

2012-12-01

The Northeastern Tibetan Plateau is a high elevation region sensitive to large-scale climate change, thus allows us better understanding the Holocene climate interactions between the mid-latitude westerly and subtropical Asia monsoon circulations. This region is now and in the late Holocene out of the influence of Asian monsoon systems and inconsistency hydrological variations from monsoon controlled region is suggested. However, the boundary and the interactions between the westerly and the Asian monsoon circulations during the whole Holocene have not been well documented. Here we present multiple biomarker alkane and alkenone based records from Lake Gahai in the Qaidam Basin on the northeastern Tibetan Plateau to study the lake level and climate variability over the past 12,000 years. Characterized by marked alkane-based average chain length (ACL) and carbon preference index (CPI) values, our records provide unambiguous evidence of a generally dry climate from 9 to 2 ka (1 ka = 1,000 cal yr BP), and a relatively wet climate after 2 ka and before 9 ka. The occurrence of alkenones during the period of low ACL and CPI values also supports this result. Good match between our records and other earlier paleoclimatic records derived from the same basin was found, suggesting the paleoenvironment record obtained at Lake Gahai is a regional record rather than a local signal, at least in the Qaidam Basin. This generally dry climate between 9 and 2 ka was almost synchronous with the weakening of East Asian and Indian monsoon intensities. However, our data suggest an opposite moisture relation from our region and westerly controlled region. This phenomenon may lie on the interaction between westerly and monsoon systems, probably contributed to the topographic subsidence associated with stronger atmospheric convergence and rising motion on the plateau. Also this discrepancy was likely due to the enhanced evaporation than to the increased monsoon precipitation in the northeastern Tibetan Plateau, which accounts for the high temperatures.

Determination of the dissociation constants (pKa) of secondary and tertiary amines in organic media by capillary electrophoresis and their role in the electrophoretic mobility order inversion.

PubMed

Cantu, Marcelo Delmar; Hillebranda, Sandro; Carrilho, Emanuel

2005-03-11

Non-aqueous capillary electrophoresis (NACE) may provide a selectivity enhancement in separations since the analyte dissociation constants (pKa) in organic media are different from those in aqueous solutions. In this work, we have studied the inversion in mobility order observed in the separation of tertiary (imipramine (IMI) and amitryptiline (AMI)) and secondary amines (desipramine (DES) and nortryptiline (NOR)) in water, methanol, and acetonitrile. We have determined the pKa values in those solvents and the variation of dissociation constants with the temperature. From these data, and applying the Van't Hoff equation, we have calculated the thermodynamic parameters deltaH and deltaS. The pKa values found in methanol for DES, NOR, IMI, and AMI were 10.80, 10.79, 10.38, and 10.33, respectively. On the other hand, in acetonitrile an opposite relation was found since the values were 20.60, 20.67, 20.74, and 20.81 for DES, NOR, IMI, and AMI. This is the reason why a migration order inversion is observed in NACE for these solvents. The thermodynamic parameters were evaluated and presented a tendency that can be correlated with that observed for pKa values.

Isotope-coded, iodoacetamide-based reagent to determine individual cysteine pKa values by MALDI-TOF mass spectrometry

PubMed Central

Nelson, Kimberly J.; Day, Amanda E.; Zeng, Bubing B.; King, S. Bruce; Poole, Leslie B.

2008-01-01

Cysteine reactivity in enzymes is imparted to a large extent by the stabilization of the deprotonated form of the reduced cysteine (i.e. the thiolate) within the active site. While this is likely to be an important chemical attribute of many thiol-based enzymes including cysteine-dependent peroxidases (peroxiredoxins) and proteases, only relatively few pKa values have been determined experimentally. Presented here is a new technique for determining the pKa value of cysteine residues through quantitative mass spectrometry following chemical modification with an iodoacetamide-based reagent over a range of pH buffers. This isotope-coded reagent, N-phenyl iodoacetamide (iodoacetanilide), is readily prepared in deuterated (d5) and protiated (d0) versions and is more reactive toward free cysteine than is iodoacetamide. Using this approach, the pKa values for the two cysteine residues in Escherichia coli thioredoxin were determined to be 6.5 and > 10, in good agreement with previous reports using chemical modification approaches. This technique allows the pKa of specific cysteine residues to be determined in a clear, fast, and simple manner and, because cysteine residues on separate tryptic peptides are measured separately, is not complicated by the presence of multiple cysteines within the protein of interest. PMID:18162165

Ups and downs in western Crete (Hellenic subduction zone)

PubMed Central

Tiberti, Mara Monica; Basili, Roberto; Vannoli, Paola

2014-01-01

Studies of past sea-level markers are commonly used to unveil the tectonic history and seismic behavior of subduction zones. We present new evidence on vertical motions of the Hellenic subduction zone as resulting from a suite of Late Pleistocene - Holocene shorelines in western Crete (Greece). Shoreline ages obtained by AMS radiocarbon dating of seashells, together with the reappraisal of shoreline ages from previous works, testify a long-term uplift rate of 2.5–2.7 mm/y. This average value, however, includes periods in which the vertical motions vary significantly: 2.6–3.2 mm/y subsidence rate from 42 ka to 23 ka, followed by ~7.7 mm/y sustained uplift rate from 23 ka to present. The last ~5 ky shows a relatively slower uplift rate of 3.0–3.3 mm/y, yet slightly higher than the long-term average. A preliminary tectonic model attempts at explaining these up and down motions by across-strike partitioning of fault activity in the subduction zone. PMID:25022313

A record of more than 500,000 years of large-volume travertine formation in the southwestern United States and links between paleohydrology, paleoclimate, and landscape evolution

NASA Astrophysics Data System (ADS)

Priewisch, A.; Crossey, L. J.; Embid, E.; Karlstrom, K. E.; Polyak, V.; Asmerom, Y.; Ricketts, J. W.

2011-12-01

CO2 springs and associated travertine deposits offer a unique tool to better understand Cenozoic paleohydrology and paleoclimate in the context of geomorphic and neotectonic evolution of the southwestern United States. Travertine accumulations represent places of persistent and significant mantle CO2 degassing in high discharge spring systems that are found along faults and above magmatic systems. They complement speleothem records from the same regions in that they can provide better links to the surface geomorphic and neotectonic systems. New Mexico and Arizona host several exceptionally well-preserved, large-volume travertine deposits that extend from 10 - 60 km2, with thicknesses ranging from 15 to more than 60 m. Precise U-series and stable isotope analyses are underway for large travertine platforms at Mesa del Oro, NM (~27 km2), Riley North and South Mesa, NM (~60 km2), Mesa Aparejo/Belen Quarries, NM (~13 km2), and Springerville, AZ (~30 km2). New ages for the travertine deposits at Mesa del Oro are 56 ka, 253 ka, 361 ka, and more than 500 ka. The travertine deposits at Riley North and South Mesa are older than 500 ka and 207/287 ka, respectively. At Mesa Aparejo, travertine ages are 312 ka and more than 500 ka. U/Th dates from Springerville, AZ show that major travertine accumulations occurred over several time intervals: 36-100 ka, 200-280 ka and 300-350 ka. Stable isotope analyses overlap substantially, exhibiting high δ13C values, +2.0% to +8.3%, and δ18O values that range from -13.5% to -4%. High δ13C values are interpreted to be caused by rapid CO2 degassing while the range of δ18O values is interpreted to represent changing water temperatures and mixing trends of groundwater. U-series data show that travertine deposition at all of these localities overlapped temporally and that major aggradation and high volume deposition was not steady, but occurred episodically at 36-100, 200-280, and 300-380 ka. Times of high accumulation rates are interpreted as times of high groundwater flow and hence as a proxy for regional paleohydrology/paleoclimate controls while the locations of the travertine occurrences (along faults of the Jemez lineament and Rio Grande rift) reflect more local CO2-discharge (tectonic) controls. These travertine occurrences are important indicators of the extent of past natural CO2 leakage that can inform carbon sequestration models both in areas of modern CO2 gas fields (Springerville) and at sites of potential paleo-gas fields. The travertine platforms now occupy positions high in the landscape (inverted topography) and also provide data on the scales and timing of regional landscape denudation.

Breakup of a liquid rivulet falling over an inclined plate: Identification of a critical Weber number

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Rajesh K.; Galvin, Janine E.; Whyatt, Greg A.

2017-05-01

We have numerically investigated the breakup of a rivulet falling over a smooth inclined plate using the volume of fluid method. The breakup the rivulet is a complex phenomenon that is dictated by many factors, such as solvent properties, contact angle, inertia, plate inclination, etc. An extensive simulation campaign was conducted wherein these factors were systematically investigated. Regimes for a stable rivulet and an unstable rivulet that leads to the breakup and formation of a droplet are examined in terms of a critical value of the Weber number (Wecr) that delineates these regimes. The effect of plate inclination on themore » breakup of the rivulet shows that the critical Weber number decreases with increased inclination angle () owing to higher liquid velocity. However, the effect is negligible beyond >60. The impact of solvent properties is characterized using the Kapitza number (Ka). Variation of Wecr with Ka shows two trends depending on the Ka value of the solvent. Solvents with lower Ka values, corresponding to high viscosities and/or low surface tensions, show smaller values of the critical Weber number and the variation is linear. While solvents with higher Ka values exhibit higher values of the Wecr and the variation in Wecr is steep. This behavior is more pronounced with increasing contact angle. Higher contact angles promote rivulet breakup so that inertia must be higher to the breakup. A phenomenological scaling for a critical Weber number with the Kapitza number and contact angle is presented that can offer insight into rivulet breakup.« less

Paleohydrology and paleochemistry of Lake Manitoba, Canada: the isotope and ostracode records

USGS Publications Warehouse

Last, W.M.; Teller, J.T.; Forester, R.M.

1994-01-01

Lake Manitoba, the largest lake in the Prairie region of North America, contains a fine-grained sequence of late Pleistocene and Holocene sediment that documents a complex postglacial history. This record indicates that differential isostatic rebound and changing climate have interacted with varying drainage basin size and hydrologic budget to create significant variations in lake level and limnological conditions. During the initial depositional period in the basin, the Lake Agassiz phase (???12-9 ka), ??18O of ostracodes ranged from -16??? to -5??? (PDB), implying the lake was variously dominated by cold, dilute glacial meltwater and warm to cold, slightly saline water. Candona subtriangulata, which prefers cold, dilute water, dominates the most negative ??18O intervals, when the basin was part of proglacial Lake Agassiz. At times during this early phase, the ??18O of the lake abruptly shifted to higher values; euryhaline taxa such as C. rawsoni or Limnocythere ceriotuberosa, and halobiont taxa such as L. staplini or L. sappaensis are dominant in these intervals. This positive covariance of isotope and ostracode records implies that the lake level episodically fell, isolating the Lake Manitoba basin from the main glacial lake. ??18O values from inorganic endogenic Mg-calcite in the post-Agassiz phase of Lake Manitoba trend from -4??? at 8 ka to -11??? at 4.5 ka. We interpret that this trend indicates a gradually increasing influence of isotopically low (-20??? SMOW) Paleozoic groundwater inflow, although periods of increased evaporation during this time may account for zones of less negative isotopic values. The ??18O of this inorganic calcite abruptly shifts to higher values (-6???) after ???4.5 ka due to the combined effects of increased evaporative enrichment in a closed basin lake and the increased contribution of isotopically high surface water inflow on the hydrologic budget. After ???2 ka, the ??18O of the Mg-calcite fluctuates between -13??? and -7???, implying short-term variability in the lake's hydrologic budget, with values indicating the lake varied from outflow-dominated to evaporation-dominated. The ??13C values of Mg-calcite remain nearly constant from 8 to 4.5 ka and then trend to higher values upward in the section. This pattern suggests primary productivity in the lake was initially constant but gradually increased after 4.5 ka. ?? 1994 Kluwer Academic Publishers.

A comparative study of amplitude calibrations for the East Asia VLBI Network: A priori and template spectrum methods

NASA Astrophysics Data System (ADS)

Cho, Ilje; Jung, Taehyun; Zhao, Guang-Yao; Akiyama, Kazunori; Sawada-Satoh, Satoko; Kino, Motoki; Byun, Do-Young; Sohn, Bong Won; Shibata, Katsunori M.; Hirota, Tomoya; Niinuma, Kotaro; Yonekura, Yoshinori; Fujisawa, Kenta; Oyama, Tomoaki

2017-12-01

We present the results of a comparative study of amplitude calibrations for the East Asia VLBI Network (EAVN) at 22 and 43 GHz using two different methods of an "a priori" and a "template spectrum", particularly on lower declination sources. Using observational data sets of early EAVN observations, we investigated the elevation-dependence of the gain values at seven stations of the KaVA (KVN and VERA Array) and three additional telescopes in Japan (Takahagi 32 m, Yamaguchi 32 m, and Nobeyama 45 m). By comparing the independently obtained gain values based on these two methods, we found that the gain values from each method were consistent within 10% at elevations higher than 10°. We also found that the total flux densities of two images produced from the different amplitude calibrations were in agreement within 10% at both 22 and 43 GHz. By using the template spectrum method, furthermore, the additional radio telescopes can participate in KaVA (i.e., EAVN), giving a notable sensitivity increase. Therefore, our results will constrain the detailed conditions in order to measure the VLBI amplitude reliably using EAVN, and discuss the potential of possible expansion to telescopes comprising EAVN.

The timing and duration of the Last Interglacial Asian Monsoon

NASA Astrophysics Data System (ADS)

Yuan, D.; Cheng, H.; Edwards, R.; Kelly, M.; Qing, J.; Lin, Y.; Zhang, M.

2002-12-01

An accurate estimate for the timing and duration of regional and global climate change associated with the Last Interglacial is important for elucidating climate change mechanisms. We present a 230Th-dated δ18O record of 2 stalagmites (D3 and D4) from Dongge Cave, southern China (25°N, 109°E, an area affected by East Asian and Indian Monsoons), which record Asian Monsoon history over 3 periods, 160-110 ka, 65-43 ka and 15.5 ka - present. The stalagmites have different precipitation environments and water flow paths as indicated by different growth histories, growth rates and δ234U values. D3 grew faster between 123-118 ka (12 vs. 0.4 cm/ka), but D4 grew faster between 138-126 ka (3.4 vs. 0.7 cm/ka). The mean initial δ234U value of D3 is -272 (range of -261 to -287). D4 values are higher (mean = -78, range of -27 to -160). Despite these differences, both have similar large δ18O variations for the interval over which both were active (148 to 113 ka), suggesting that water-rock interactions and kinetic fractionation did not affect δ18O values significantly. Dongge Cave stalagmites exhibit features similar to the Younger Dryas (YD) and the Bolling/Allerod as recorded in Greenland ice cores (GISP, 1997) and stalagmites from Hulu Cave, eastern China (Wang et al., 2001). The Dongge YD lies between 12640 +/-140 and 11550 +/-80 years BP, synchronous with Greenland and Hulu Cave YD analogues. Similar to Hulu Cave, light Dongge Cave δ18O excursions correspond to heavy isotopic excursions in Greenland, consistent with a positive correlation between the intensity of the Asian summer monsoon and Greenland temperature. The most prominent feature in the Dongge record is a peak that approximates a square wave and is contemporaneous with at least portions of the Last Interglacial sea level high. Dongge Termination II is a large, abrupt negative shift in δ18O (>3 per mil). The mid-point is at 129.3 +/-0.9 ka, based on direct dating of D4. D3 gives an age indistinguishable from this value. If D4 growth rate is linear over the transition, as implied by long term stable growth rates (from 144 to 124 ka), the transition takes less than 500 y, with most of it taking less than 200 y. The Dongge Last Interglacial also ends with an abrupt δ18O shift (about 4 per mil). The midpoint is at 119.6 +/-0.6 ka based on direct dating of D3. D4 gives an age indistinguishable from this value. Assuming linear growth, the main portion of the transition took less than 700 y. Combining the onset and end ages of the Dongge Last Interglacial, the duration is 9.7 +/-1.1 ka, from 129.3 +/-0.9 ka to 119.6 +/-0.6 ka, remarkably similar to some estimates of full Last Interglacial sea levels. The timing is broadly consistent with orbital forcing of the Monsoon, although the abrupt shifts require the involvement of other mechanisms (e.g. changes in circulation). Dongge Termination II lags Devils Hole Termination II, some fraction of sea level Termination II, and likely Vostok temperature, Vostok CO2, and eastern Pacific sea surface temperature. However, there is some evidence that it coincides within error with the final rise in sea level to full Last Interglacial elevations. It may well be that Monsoon Termination II is an orbitally-forced event at the end of a sequence of events not directly caused by orbital forcing. As such it may mark the inception of full interglacial conditions world-wide. Orbital forcing may be necessary for full interglacial conditions, but not for many of the shifts toward interglacial conditions observed to prior to Dongge Termination II.

Holocene water mass history off NE Greenland - A first high-resolution sediment record from the western Fram Strait

NASA Astrophysics Data System (ADS)

Zehnich, Marc; Palme, Tina; Spielhagen, Robert F.; Hass, H. Christian; Bauch, Henning A.

2017-04-01

While the Holocene history of the eastern Fram Strait seems well investigated, no high-resolution paleoenvironmental records were available from the western Fram Strait so far. A new sedimentary record, obtained during expedition PS93.1 (2015) of RV Polarstern on the outermost NE Greenland shelf, allows for the first time to reconstruct Holocene changes in near-surface salinities, temperature, stratification and water masses (polar waters vs. Atlantic Water), potentially related to variations of the freshwater and sea ice export from the Arctic Ocean. The 260 cm long sedimentary record from site PS93/025 (80.5°N, 8.5°W) was investigated for sediment composition, foraminifer contents, grain size variations (sortable silt) and the isotopic composition of planktic foraminifers. Radiocarbon datings reveal an age of 10.2 cal-ka for the core base and continuous sedimentation throughout most of the Holocene. The sediments are generally very fine-grained (<2% sand). The grain size record reveals a fining-upwards trend and sediments from <6.5 cal-ka consist of <0.5% coarse fraction. A comparison of foraminifer and coarse fraction abundances shows strong similarities. Apparently the contribution of coarse terrestrial material from iceberg transport was extremely low throughout the last 10.2 cal-ka. Foraminifer abundances (both planktic and benthic) are high in Early Holocene sediments until ca. 7 cal-ka and decrease rapidly thereafter. This is interpreted to reflect a relatively strong advection of Atlantic Water to the NW Fram Strait, which correlates well with similar findings on the eastern side of the Arctic Gateway. Sortable silt grain sizes are high (27-32 µm) in the older part of the record and gradually decrease between 7 cal-ka and 4 cal-ka. After ca. 4 cal-ka, sortable silt shows values of 20-22 µm and little variation. Considering also the grain-size distribution curves, we propose a decline of bottom current velocities on the outer NE Greenland shelf after 7 cal-ka, related to a decrease of Atlantic Water advection. These preliminary results reveal a strong coupling of Holocene environments on both sides of the Fram Strait.

A new sampling strategy for cosmogenic surface exposure dating of moraines: Amalgamated Boulder Chips (ABCs)

NASA Astrophysics Data System (ADS)

Akif Sarıkaya, M.; Çiner, Attila; Yıldırım, Cengiz

2017-04-01

Cosmogenic surface exposure dating has been applied to date numerous moraines worldwide. The geochronological data obtained from these studies have improved our knowledge on the timing of glaciation and allow us to reconstruct the paleoclimate. Due to the geomorphic complications after deposition, such as degradation, exhumation, bedrock erosion, snow cover and toppling of boulders, several (n>5) large boulder (>1-2 m) samples should be dated to obtain a reliable age distribution. Generally, the ages on a well-preserved moraine surface show unimodal normal distribution. Frequently, erosion, exhumation and boulder toppling are blamed for the younger outliers. On the other hand, although infrequent, older outliers will indicate inherited nuclide concentration from pre-exposure to cosmic radiation. To obtain the true age of a moraine deposit, one needs to collect several samples that not only greatly increases the budget of the project but also is time consuming. To overcome this problem, we developed a new sampling strategy for dating moraine surfaces by cosmogenic nuclides. We collected rock chips (each 20-50 grams) from large boulder (>1 m) tops located on the crest of moraines. Fourteen to 32 boulders were chosen for sampling every 20 m. All rock chips were amalgamated to make one sample. To test the suitability of the method, we also sampled 3 large boulders (>1 m), as it is done classically, from the same surface. The age results from the two Late Pleistocene moraines and one rock glacier surface show no difference in terms of boulder exposure ages. Three 36Cl ages from one single lateral moraine in Çimi Valley of Geyikdaǧ, central Taurus, Turkey, are 11.9±0.9 ka, 14.0±1.1 ka and 11.9±0.9 ka (all ages have no erosion corrections) and yield a mean age of 12.6±0.9 ka, while the amalgamated boulder chips' (ABCs) age is 12.0±0.9 ka. Another well developed terminal moraine (so called Zor Moraine) in the Güneycik Valley of Geyikdaǧ, yielded ages as 4.9±0.4 ka, 7.7±0.6 ka and 3.7±0.3 ka, while the ABCs' age is 6.4±0.6 ka. The rock glacier boulder samples yielded ages of 12.2±0.9 ka, 14.0±1.0 ka and 9.2±0.8 ka, while the rock glacier ABCs' age is 10.7±0.9 ka. These results clearly indicate that the age obtained from ABCs is reliable and can safely replace classical methodology that requires collection of several samples from a moraine surface. The use of ABCs sampling strategy will considerably decrease the time and budget allocated to date a landform. This work was supported by TUBITAK 112Y139 project.

Uncovering the determinants of a highly perturbed tyrosine pKa in the active site of ketosteroid isomerase.

PubMed

Schwans, Jason P; Sunden, Fanny; Gonzalez, Ana; Tsai, Yingssu; Herschlag, Daniel

2013-11-05

Within the idiosyncratic enzyme active-site environment, side chain and ligand pKa values can be profoundly perturbed relative to their values in aqueous solution. Whereas structural inspection of systems has often attributed perturbed pKa values to dominant contributions from placement near charged groups or within hydrophobic pockets, Tyr57 of a Pseudomonas putida ketosteroid isomerase (KSI) mutant, suggested to have a pKa perturbed by nearly 4 units to 6.3, is situated within a solvent-exposed active site devoid of cationic side chains, metal ions, or cofactors. Extensive comparisons among 45 variants with mutations in and around the KSI active site, along with protein semisynthesis, (13)C NMR spectroscopy, absorbance spectroscopy, and X-ray crystallography, was used to unravel the basis for this perturbed Tyr pKa. The results suggest that the origin of large energetic perturbations are more complex than suggested by visual inspection. For example, the introduction of positively charged residues near Tyr57 raises its pKa rather than lowers it; this effect, and part of the increase in the Tyr pKa from the introduction of nearby anionic groups, arises from accompanying active-site structural rearrangements. Other mutations with large effects also cause structural perturbations or appear to displace a structured water molecule that is part of a stabilizing hydrogen-bond network. Our results lead to a model in which three hydrogen bonds are donated to the stabilized ionized Tyr, with these hydrogen-bond donors, two Tyr side chains, and a water molecule positioned by other side chains and by a water-mediated hydrogen-bond network. These results support the notion that large energetic effects are often the consequence of multiple stabilizing interactions rather than a single dominant interaction. Most generally, this work provides a case study for how extensive and comprehensive comparisons via site-directed mutagenesis in a tight feedback loop with structural analysis can greatly facilitate our understanding of enzyme active-site energetics. The extensive data set provided may also be a valuable resource for those wishing to extensively test computational approaches for determining enzymatic pKa values and energetic effects.

Uncovering the Determinants of a Highly Perturbed Tyrosine pKa in the Active Site of Ketosteroid Isomerase†

PubMed Central

Schwans, Jason P.; Sunden, Fanny; Gonzalez, Ana; Tsai, Yingssu; Herschlag, Daniel

2013-01-01

Within the idiosyncratic enzyme active site environment, side chain and ligand pKa values can be profoundly perturbed relative to their values in aqueous solution. Whereas structural inspection of systems has often attributed perturbed pKa values to dominant contributions from placement near to charged groups or within hydrophobic pockets, Tyr57 of a P. putida ketosteroid isomerase (KSI) mutant, suggested to have a pKa perturbed by nearly 4 units to 6.3, is situated within a solvent-exposed active site devoid of cationic side chains, metal ions, or cofactors. Extensive comparisons among 45 variants with mutations in and around the KSI active site, along with protein semi-synthesis, 13C NMR spectroscopy, absorbance spectroscopy, and x-ray crystallography, was used to unravel the basis for this perturbed Tyr pKa. The results suggest that the origin of large energetic perturbations are more complex than suggested by visual inspection. For example, the introduction of positively charged residues near Tyr57 raises its pKa rather than lowers it; this effect, and part of the increase in the Tyr pKa from introduction of nearby anionic groups arise from accompanying active site structural rearrangements. Other mutations with large effects also cause structural perturbations or appear to displace a structured water molecule that is part of a stabilizing hydrogen bond network. Our results lead to a model in which three hydrogen bonds are donated to the stabilized ionized Tyr, with these hydrogen bond donors, two Tyr side chains and a water molecule, positioned by other side chains and by a water-mediated hydrogen bond network. These results support the notion that large energetic effects are often the consequence of multiple stabilizing interactions, rather than a single dominant interaction. Most generally, this work provides a case study for how extensive and comprehensive comparisons via site-directed mutagenesis in a tight feedback loop with structural analysis can greatly facilitate our understanding of enzyme active site energetics. The extensive dataset provided may also be a valuable resource for those wishing to extensively test computational approaches for determining enzymatic pKa values and energetic effects. PMID:24151972

Small negative cloud-to-ground lightning reports at the NASA Kennedy Space Center and Air Force Eastern Range

NASA Astrophysics Data System (ADS)

Wilson, Jennifer G.; Cummins, Kenneth L.; Krider, E. Philip

2009-12-01

The NASA Kennedy Space Center (KSC) and Air Force Eastern Range (ER) use data from two cloud-to-ground (CG) lightning detection networks, the Cloud-to-Ground Lightning Surveillance System (CGLSS) and the U.S. National Lightning Detection Network™ (NLDN), and a volumetric lightning mapping array, the Lightning Detection and Ranging (LDAR) system, to monitor and characterize lightning that is potentially hazardous to launch or ground operations. Data obtained from these systems during June-August 2006 have been examined to check the classification of small, negative CGLSS reports that have an estimated peak current, ∣Ip∣ less than 7 kA, and to determine the smallest values of Ip that are produced by first strokes, by subsequent strokes that create a new ground contact (NGC), and by subsequent strokes that remain in a preexisting channel (PEC). The results show that within 20 km of the KSC-ER, 21% of the low-amplitude negative CGLSS reports were produced by first strokes, with a minimum Ip of -2.9 kA; 31% were by NGCs, with a minimum Ip of -2.0 kA; and 14% were by PECs, with a minimum Ip of -2.2 kA. The remaining 34% were produced by cloud pulses or lightning events that we were not able to classify.

Cloud-to-ground lightning activity in Colombia: A 14-year study using lightning location system data

NASA Astrophysics Data System (ADS)

Herrera, J.; Younes, C.; Porras, L.

2018-05-01

This paper presents the analysis of 14 years of cloud-to-ground lightning activity observation in Colombia using lightning location systems (LLS) data. The first Colombian LLS operated from 1997 to 2001. After a few years, this system was upgraded and a new LLS has been operating since 2007. Data obtained from these two systems was analyzed in order to obtain lightning parameters used in designing lightning protection systems. The flash detection efficiency was estimated using average peak current maps and some theoretical results previously published. Lightning flash multiplicity was evaluated using a stroke grouping algorithm resulting in average values of about 1.0 and 1.6 for positive and negative flashes respectively and for both LLS. The time variation of this parameter changes slightly for the years considered in this study. The first stroke peak current for negative and positive flashes shows median values close to 29 kA and 17 kA respectively for both networks showing a great dependence on the flash detection efficiency. The average percentage of negative and positive flashes shows a 74.04% and 25.95% of occurrence respectively. The daily variation shows a peak between 23 and 02 h. The monthly variation of this parameter exhibits a bimodal behavior typical of the regions located near The Equator. The lightning flash density was obtained dividing the study area in 3 × 3 km cells and resulting in maximum average values of 25 and 35 flashes km- 2 year- 1 for each network respectively. A comparison of these results with global lightning activity hotspots was performed showing good correlation. Besides, the lightning flash density variation with altitude shows an inverse relation between these two variables.

Seawater-derived neodymium isotope records in the Chukchi Sea, western Arctic Ocean during Holocene: implications for oceanographic circulation

NASA Astrophysics Data System (ADS)

Lee, Borom; Nam, Seung-Il; Huh, Youngsook; Lee, Mi Jung

2015-04-01

Changes in oceanographic circulation in the Artic have a large influence on the global oceanic and climate system of the Earth through the geological times. In particular, freshwater input from the North Pacific to the western Arctic Ocean affects the Atlantic meridional overturning circulation (AMOC) after the opening of the Bering Strait. Seawater-derived neodymium isotope in marine sediments has been used as a proxy to trace the origin of water masses and oceanic circulation system. The global average residence time of Nd is shorter than the global ocean mixing time and dissolved Nd in seawater behaves quasi-conservatively. In the modern Arctic Ocean, the Nd isotope distribution is dominated by Atlantic source water, although the circum-Arctic riverine discharge and Pacific-derived waters also have noticeable impacts. In this study, we investigated seawater-derived neodymium isotope records from a sediment core recovered from the Chukchi Sea to understand the changes in hydrograhic circulation of the western Arctic during the Holocene. A gravity core, ARA02B 01A, was collected on the northern shelf of the Chukchi Sea (73°37.8939'N, 166°30.9838'W, ca. 111 m in water depth) during the RV Araon expedition in 2011. To obtain seawater-derived Nd records, we extracted Fe-Mn oxide coatings as an authigenic fraction from bulk sediments by leaching with acid-reducing solution after removing carbonate by leaching with acetic acid. Our preliminary results might show a general pattern of increasing radiogenic ɛNd values through Holocene intervals. Therefore, it implies that ɛNd results may be related with variations in the intensity of Bering Strait inflow during the last ~9.31 ka BP. The radiogenic trend was strongly pronounced from the late Holocene (ɛNd -7.23; ca. 8.84 ka BP) to the middle Holocene (ɛNd -4.78; ca. 6.18 ka BP) and vaguely during the middle Holocene. After 4.13 ka BP, ɛNd values were increased again from -4.86 to -4.03 at 0.57 ka BP. But 87Sr/86Sr values vary from 0.70929 to 0.70991 throughout the whole sediment core and they might be higher than the Sr isotopic value of modern seawater (0.70918). This implies that the leachates may not be preserved past seawater signal. Thus, our preliminary results indicate that further studies for assessment of leaching methods and for other reliable seawater-derived records (including authigenic carbonates, i.e., foraminiferal and bivalve shells which are found in sediment cores) are necessary.

The Mars Global Surveyor Ka-Band Link Experiment (MGS/KaBLE-II)

NASA Astrophysics Data System (ADS)

Morabito, D.; Butman, S.; Shambayati, S.

1999-01-01

The Mars Global Surveyor (MGS) spacecraft, launched on November 7, 1996, carries an experimental space-to-ground telecommunications link at Ka-band (32 GHz) along with the primary X-band (8.4-GHz) downlink. The signals are simultaneously transmitted from a 1.5-m-diameter parabolic antenna on MGS and received by a beam-waveguide (BWG) research and development (R&D) 34-meter a ntenna located in NASA's Goldstone Deep Space Network (DSN) complex near Barstow, California. This Ka-band link experiment (KaBLE-II) allows the performances of the Ka-band and X-band signals to be compared under nearly identical conditions. The two signals have been regularly tracked during the past 2 years. This article presents carrier-signal-level data (P_c/N_o) for both X-band and Ka-band acquired over a wide range of station elevation angles, weather conditions, and solar elongation angles. The cruise phase of the mission covered the period from launch (November 7, 1996) to Mars orbit capture (September 12, 1997). Since September 12, 1997, MGS has been in orbit around Mars. The measurements confirm that Ka-band could increase data capacity by at least a factor of three (5 dB) as compared with X-band. During May 1998, the solar corona experiment, in which the effects of solar plasma on the X-band and Ka-band links were studied, was conducted. In addition, frequency and difference frequency (f_x - f_(Ka)/3.8), ranging, and telemetry data results are presented. MGS/KaBLE-II measured signal strengths (for 54 percent of the experiments conducted) that were in reasonable agreement with predicted values based on preflight knowledge, and frequency residuals that agreed between bands and whose statistics were consistent with expected noise sources. For passes in which measured signal strengths disagreed with predicted values, the problems were traced to known deficiencies, for example, equipment operating under certain conditions, such as a cold Ka-band solid-state power amplifier (SSPA) temperature, and a degraded response at higher frequencies in certain modes. These efforts had continued with Deep Space 1 (DS1), launched in October 1998, which also emits Ka-band and X-band signals.

Holocene Paleosecular Variation From Dated Lava Flows on East Maui (Hawaii)

NASA Astrophysics Data System (ADS)

Herrero-Bervera, E.; Valet, J.

2006-12-01

A quasi-static inclination anomaly and low secular variation seem to dominate the historical and the long-term time averaged field in central Pacific. The period covering the past 10 kyr is crucial to study the field variability and to fill the gap between historical field measurements and long-term paleomagnetic records. We have conducted a paleomagnetic study of 13 sites of basaltic lava flows from the Maui island with 14C ages between 10.3 and 0.015 Ka. Two other sites dated at 45 Ka and 730 Ka were also sampled. Eight to ten samples from each site were demagnetized using thermal treatment and companion specimens from the same samples were demagnetized by alternating fields (af). Thermomagnetic and hysteresis measurements indicated that magnetite (575 degrees C) in fine grains was the dominant magnetic carrier, although in many cases we observed also a low-temperature phase which is likely carried by titanomagnetite with low titanium content. The existence of relatively high coercivities associated with these two mineralogical phases generated overlapping components which could not be properly isolated using af demagnetization. Successful results were obtained after thermal demagnetization for 13 sites with a mean inclination of 34.2 degrees +/-9 degrees. The mean inclination (Inc = 36.3 degrees) of the eleven sites younger than 10.5 Ka is very close to the value (37 degrees) of the geocentric axial dipole (GAD) at the site latitude, but the angular dispersion of 6.7 degrees for the VGPs about the spin axis is significantly lower than the predictions of the models of paleosecular variation at this latitude. The inclination variations for the past 10 Kyr are in excellent agreement with the very detailed dataset which has previously been obtained from the Big Island of Hawaii. The mean inclination is slightly lower than expected but this is likely caused by the lack of records between 5 and 7 ka B.P. Thus, there is no striking evidence for a magnetic anomaly under Hawaii during this period and the recently published records obtained for the past millions of years neither show any conclusive evidence in favor of a long-term persistent anomaly. However all studies report a very low dispersion of the VGPs which reflects low secular variation and likely low non-dipole field during the Holocene.

Density Functional Theory Calculation of pKa's of Thiols in Aqueous Solution Using Explicit Water Molecules and the Polarizable Continuum Model.

PubMed

Thapa, Bishnu; Schlegel, H Bernhard

2016-07-21

The pKa's of substituted thiols are important for understanding their properties and reactivities in applications in chemistry, biochemistry, and material chemistry. For a collection of 175 different density functionals and the SMD implicit solvation model, the average errors in the calculated pKa's of methanethiol and ethanethiol are almost 10 pKa units higher than for imidazole. A test set of 45 substituted thiols with pKa's ranging from 4 to 12 has been used to assess the performance of 8 functionals with 3 different basis sets. As expected, the basis set needs to include polarization functions on the hydrogens and diffuse functions on the heavy atoms. Solvent cavity scaling was ineffective in correcting the errors in the calculated pKa's. Inclusion of an explicit water molecule that is hydrogen bonded with the H of the thiol group (in neutral) or S(-) (in thiolates) lowers error by an average of 3.5 pKa units. With one explicit water and the SMD solvation model, pKa's calculated with the M06-2X, PBEPBE, BP86, and LC-BLYP functionals are found to deviate from the experimental values by about 1.5-2.0 pKa units whereas pKa's with the B3LYP, ωB97XD and PBEVWN5 functionals are still in error by more than 3 pKa units. The inclusion of three explicit water molecules lowers the calculated pKa further by about 4.5 pKa units. With the B3LYP and ωB97XD functionals, the calculated pKa's are within one unit of the experimental values whereas most other functionals used in this study underestimate the pKa's. This study shows that the ωB97XD functional with the 6-31+G(d,p) and 6-311++G(d,p) basis sets, and the SMD solvation model with three explicit water molecules hydrogen bonded to the sulfur produces the best result for the test set (average error -0.11 ± 0.50 and +0.15 ± 0.58, respectively). The B3LYP functional also performs well (average error -1.11 ± 0.82 and -0.78 ± 0.79, respectively).

Breakup of a liquid rivulet falling over an inclined plate: Identification of a critical Weber number

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Rajesh K.; Galvin, Janine E.; Whyatt, Greg A.

Here, we have numerically investigated the breakup of a rivulet falling over a smooth inclined plate using the volume of fluid method. The breakup the rivulet is a complex phenomenon that is dictated by many factors, such as solvent properties, contact angle, inertia, plate inclination, etc. An extensive simulation campaign was conducted wherein these factors were systematically investigated. Regimes for a stable rivulet and an unstable rivulet that leads to the breakup and formation of a droplet are examined in terms of a critical value of the Weber number (We cr) that delineates these regimes. The effect of plate inclinationmore » on the breakup of the rivulet shows that the critical Weber number decreases with increased inclination angle (θ) owing to higher liquid velocity. However, the effect is negligible beyond θ > 60°. The impact of solvent properties is characterized using the Kapitza number (Ka). Variation of We cr with Ka shows two trends depending on the Ka value of the solvent. Solvents with lower Ka values, corresponding to high viscosities and/or low surface tensions, show smaller values of the critical Weber number and the variation is linear. While solvents with higher Ka values exhibit higher values of the We cr and the variation in We cr is steep. This behavior is more pronounced with increasing contact angle. Higher contact angles promote rivulet breakup so that inertia must be higher to the breakup. As a result, a phenomenological scaling for a critical Weber number with the Kapitza number and contact angle is presented that can offer insight into rivulet breakup.« less

Breakup of a liquid rivulet falling over an inclined plate: Identification of a critical Weber number

DOE PAGES

Singh, Rajesh K.; Galvin, Janine E.; Whyatt, Greg A.; ...

2017-05-04

Here, we have numerically investigated the breakup of a rivulet falling over a smooth inclined plate using the volume of fluid method. The breakup the rivulet is a complex phenomenon that is dictated by many factors, such as solvent properties, contact angle, inertia, plate inclination, etc. An extensive simulation campaign was conducted wherein these factors were systematically investigated. Regimes for a stable rivulet and an unstable rivulet that leads to the breakup and formation of a droplet are examined in terms of a critical value of the Weber number (We cr) that delineates these regimes. The effect of plate inclinationmore » on the breakup of the rivulet shows that the critical Weber number decreases with increased inclination angle (θ) owing to higher liquid velocity. However, the effect is negligible beyond θ > 60°. The impact of solvent properties is characterized using the Kapitza number (Ka). Variation of We cr with Ka shows two trends depending on the Ka value of the solvent. Solvents with lower Ka values, corresponding to high viscosities and/or low surface tensions, show smaller values of the critical Weber number and the variation is linear. While solvents with higher Ka values exhibit higher values of the We cr and the variation in We cr is steep. This behavior is more pronounced with increasing contact angle. Higher contact angles promote rivulet breakup so that inertia must be higher to the breakup. As a result, a phenomenological scaling for a critical Weber number with the Kapitza number and contact angle is presented that can offer insight into rivulet breakup.« less

The stereospecificity and catalytic efficiency of the tryptophan synthase-catalysed exchange of the α-protons of amino acids

PubMed Central

2004-01-01

13C-NMR has been used to follow the tryptophan synthase (EC 4.2.1.20) catalysed hydrogen–deuterium exchange of the pro-2R and pro-2S protons of [2-13C]glycine at pH 7.8. 1H-NMR has also been used to follow the tryptophan-synthase-catalysed hydrogen–deuterium exchange of the α-protons of a range of L- and D-amino acids at pH 7.8. The pKa values of the α-protons of these amino acids have been estimated and we have determined whether or not their exchange rates can be predicted from their pKa values. With the exception of tryptophan and norleucine, the stereospecificities of the first-order α-proton exchange rates are independent of the size and electronegativity of the amino acid R-group. Similar results are obtained with the second-order α-proton exchange rates, except that both L-tryptophan and L-serine have much higher stereospecificities than all the other amino acids studied. PMID:15107013

Ionization state and structure of l-1,2-dipalmitoylphosphatidylglycerol monolayers at the liquid/air interface.

PubMed

Maltseva, Elena; Shapovalov, Vladimir L; Möhwald, Helmuth; Brezesinski, Gerald

2006-01-19

Phosphatidylglycerols are components of biological membranes. The phase behavior of these phospholipids was extensively investigated. However, there is still no definite picture about the dependence of the ionization state and monolayer structure on subphase composition. The major problem of previous investigations is that none of the methods used allow obtaining the ionization degree directly. In the present work we apply techniques developed in the past decades for Langmuir monolayers: infrared reflection absorption spectroscopy (IRRAS) as well as X-ray diffraction and reflectivity techniques, which provide straightforward information about structure and ionization state of a L-1,2-dipalmitoylphosphatidylglycerol (DPPG) monolayer. The Gouy-Chapman model is applied to evaluate the intrinsic pKa. Therewith, the ionization degree can be determined even at low pH values. The experimental titration curves are in good agreement with theoretical curves based on the Gouy-Chapman model. The obtained instrinic pKa amounts to 1. The ionization degree of a DPPG monolayer is independent of the monovalent cation size. In contrast, the structure of a DPPG monolayer is strongly affected by the type of divalent cations.

A transportable 50 kA dual mode lightning simulator

NASA Technical Reports Server (NTRS)

Salisbury, K.; Lloyd, S.; Chen, Y. G.

1991-01-01

A transportable lightning simulator was designed, built and tested, which is capable of delivering more than 50 kA to an 8 micro-H test object. The simulator was designed to be a versatile device in the lightning laboratory while meeting the requirements of MIL-STD-1757A for component E current waveforms. The system is capable of operating in either a ringing mode with a Q greater than 5 and a nominal frequency of 160 kHz, or a unipolar mode with no hardware configuration changes. The ringing mode is obtained by the LCR series circuit formed by the pulse generator and test object. The unipolar mode is obtained by closing an electrically triggered crowbar switch at peak current. The simulator exceeds the peak current requirement and rate of rise requirements for MIL-STD-1757A in both the ringing and unipolar modes. The pulse half width in the unipolar mode is in excess of 50 microsec and the action is in excess of 10(exp 5) A(exp 2)s. The design, component values, and test results are presented.

Effects of alkyl chain length and solvents on thermodynamic dissociation constants of the ionic liquids with one carboxyl group in the alkyl chain of imidazolium cations.

PubMed

Chen, Yuehua; Wang, Huiyong; Wang, Jianji

2014-05-01

Thermodynamic dissociation constants of the Brønsted acidic ionic liquids (ILs) are important for their catalytic and separation applications. In this work, a series of imidazolium bromides with one carboxylic acid substitute group in their alkyl chain ([{(CH2)nCOOH}mim]Br, n = 1,3,5,7) have been synthesized, and their dissociation constants (pKa) at different ionic strengths have been determined in aqueous and aqueous organic solvents at 0.1 mole fraction (x) of ethanol, glycol, iso-propanol, and dimethyl sulfoxide by potentiometric titrations at 298.2 K. The standard thermodynamic dissociation constants (pKa(T)) of the ILs in these solvents were calculated from the extended Debye-Hückel equation. It was found that the pKa values increased with the increase of ionic strength of the media and of the addition of organic solvent in water. The pKa(T) values also increased with the increase of the alkyl chain length of cations of the ILs. In addition, the effect of solvent nature on pKa(T) values is interpreted from solvation of the dissociation components and their Gibbs energy of transfer from water to aqueous organic solutions.

Hydroclimate variability of High Arctic Svalbard during the Holocene inferred from hydrogen isotopes of leaf waxes

NASA Astrophysics Data System (ADS)

Balascio, Nicholas L.; D'Andrea, William J.; Gjerde, Marthe; Bakke, Jostein

2018-03-01

The response of the Arctic hydrologic cycle to global warming includes changes in precipitation patterns and moisture availability associated with variable sea ice extent and modes of atmospheric circulation. Reconstructions of past hydroclimate changes help constrain the natural range of these systems, identify the manners in which they respond to different forcing mechanisms, and reveal their connections to other components of the climate system, all of which lead to a better understanding of present and future changes. Here we examine hydroclimate changes during the Holocene in the High Arctic archipelago of Svalbard by reconstructing the isotopic composition of precipitation. We measured the hydrogen isotopic composition (δD values) of leaf wax compounds (n-alkanes; C25-C31) in a sediment core from Lake Hakluytvatnet on the island of Amsterdamøya, northwest Spitsbergen. We interpret δD values of mid-chain (C25) and long-chain (C29, C31) length n-alkanes to represent changes in the isotopic composition of lake water and precipitation over the last 12.9 ka. After deglaciation of the catchment, water supply became restricted and the lake experienced significant evaporative isotopic enrichment indicating warmer conditions from 12.8 to 7.5 ka. The isotope values suggest an increase in the delivery of moisture from warmer sub-polar air masses between 12.8 and 9.5 ka, followed by generally warm, but unstable conditions between 9.5 and 7.5 ka, possibly indicating a response to meltwater forcing. Sedimentary evidence indicates a hiatus in deposition c. 7.5-5.0 ka, likely as a result of desiccation of the lake. At c. 5.0 ka lacustrine sedimentation resumed and over the last 5 ka there was a progressive increase in the influence of polar air masses and colder conditions, which culminated in an abrupt shift to colder conditions at c. 1.8 ka. This late Holocene cooling ended c. 0.18 ka, when isotopic data indicate warmer conditions and greater influence of moisture derived from lower latitudes.

Standard Observing Bands: Is Now the Time to Replace S/X with X/Ka?

NASA Technical Reports Server (NTRS)

Jacobs, C. S.; Lanyi, G. E.; Naudet, C. J.

2004-01-01

In this paper we will argue that the VLBI community should be developing a road map to transition from S/X to simultaneous X and Ka-band (32 GHz) observations. There are both negative and positive reasons for planning such a transition. On the negative side, we will outline concerns that S-band observations may be headed toward obsolescence. On the positive side, we will refer to evidence that X/Ka has potential for providing a more stable reference frame than S/X. We will propose timetables for a transition to X/Ka observing starting from the current status of X/Ka and plans that are now taking shape. First X/Ka fringes were obtained in 2001 with the Deep Space Network. Future plans will be discussed including a proposed X/Ka-band upgrade to the VLBA. Lastly, we will consider the need for a period of overlap between S/X and X/Ka so that the long and rich history of astrometric and geodetic VLBI is not compromised.

Physical-chemical properties and the reactivity of pyridoxine and pyrrolidone carboxylate and their protolytic forms.

PubMed

Golovenko, N Ya; Larionov, V B; Karpova, O V

2016-01-01

Preparation Methadoxine is equimolar salt, which cationic component (pyridoxine) is 3-oxypyridine derivative, possessing B6-vitamine like activity, while anionic component is the cyclic lactame of glutamic acid. Since biopharmaceutical and pharmacological properties of this drug depend on biochemical transformation its components, of the aim of this work was to determine the structure of possible ionized pyridoxine and pyrrolidone carboxylate forms and their reaction ability in biochemical processes. Physical-chemical properties of compounds (pKa, logP, logD, proton donor/acceptor quantity, solubility (g/l)) were calculated with ACD/pKaDB program or obtained from Pub-Med physical/chemical properties database. UV spectra of compounds were obtained after dissolution in different pH solutions (1.0, 4.5 and 6.8). It was found that at different pH values one can observe changes of the absorption spectra due to the presence of prevailing amount of the protonated form. An analysis of both pKa, logP and logD indicators and reactive functional groups of Methadoxine components has revealed that they can be protonated in different regions of gastro-intestinal tract, that influences their solubility in hydrophilic and lypophilic media. Pharmacological properties of pyridoxine and pyrrolidone carboxylate themselves are performed after their preliminary biotransformation to active metabolites. Only ionic interaction between Methadoxine components in the substance composition can appear, that provides its pharmaceutical stability and ensures its activity only in the organism conditions.

Time-dependent oral absorption models

NASA Technical Reports Server (NTRS)

Higaki, K.; Yamashita, S.; Amidon, G. L.

2001-01-01

The plasma concentration-time profiles following oral administration of drugs are often irregular and cannot be interpreted easily with conventional models based on first- or zero-order absorption kinetics and lag time. Six new models were developed using a time-dependent absorption rate coefficient, ka(t), wherein the time dependency was varied to account for the dynamic processes such as changes in fluid absorption or secretion, in absorption surface area, and in motility with time, in the gastrointestinal tract. In the present study, the plasma concentration profiles of propranolol obtained in human subjects following oral dosing were analyzed using the newly derived models based on mass balance and compared with the conventional models. Nonlinear regression analysis indicated that the conventional compartment model including lag time (CLAG model) could not predict the rapid initial increase in plasma concentration after dosing and the predicted Cmax values were much lower than that observed. On the other hand, all models with the time-dependent absorption rate coefficient, ka(t), were superior to the CLAG model in predicting plasma concentration profiles. Based on Akaike's Information Criterion (AIC), the fluid absorption model without lag time (FA model) exhibited the best overall fit to the data. The two-phase model including lag time, TPLAG model was also found to be a good model judging from the values of sum of squares. This model also described the irregular profiles of plasma concentration with time and frequently predicted Cmax values satisfactorily. A comparison of the absorption rate profiles also suggested that the TPLAG model is better at prediction of irregular absorption kinetics than the FA model. In conclusion, the incorporation of a time-dependent absorption rate coefficient ka(t) allows the prediction of nonlinear absorption characteristics in a more reliable manner.

Description of an aircraft lightning and simulated nuclear electromagnetic pulse (NEMP) threat based on experimental data

NASA Technical Reports Server (NTRS)

Rustan, Pedro L., Jr.

1987-01-01

Lightning data obtained by measuring the surface electromagnetic fields on a CV-580 research aircraft during 48 lightning strikes between 1500 and 18,000 feet in central Florida during the summers of 1984 and 1985, and nuclear electromagnetic pulse (NEMP) data obtained by surface electromagnetic field measurements using a 1:74 CV-580 scale model, are presented. From one lightning event, maximum values of 3750 T/s for the time rate of change of the surface magnetic flux density, and 4.7 kA for the peak current, were obtained. From the simulated NEMP test, maximum values of 40,000 T/s for the time rate of change of the surface magnetic flux density, and 90 A/sq m for the total normal current density, were found. The data have application to the development of a military aircraft lightning/NEMP standard.

Stalagmite geochemistry and the timing of the last interglacial-glacial transition in Central Europe (NE Hungary)

NASA Astrophysics Data System (ADS)

Siklosy, Z.; Demeny, A.; Pilet, S.; Leel-Ossy, Sz.; Lin, K.; Shen, C.-C.

2009-04-01

Speleothems can provide accurate chronologies for reconstructions of climate change by combination of U/Th dating and climate-related geochemical compositions. Geochemical studies of speleothems from Central Europe are mostly based on stable C and O isotope analyses, thus, complex geochemical studies combining isotope and trace element measurements are needed for more reliable climate models for this transitional area between oceanic and continental regions. We present stable H-C-O isotope and trace element records obtained on speleothems covering the Last Interglacial (MIS 5e) and the transition to MIS 5d. A stalagmite from Baradla Cave grew from 127.5 to 110 ka. Accelerated growth rates have been detected by U/Th age data in the 127 to 126 ka and 119 to 117 ka parts. Trace element compositions and 230Th/232Th ratios suggest changes in the hydrological regime, whereby early calcite precipitates formed in fissures during the dry and cold glacial period were dissolved by the starting flux of infiltrating meteoric water (producing elevated dissolved ion concentration but low detrital Th component), then the increasing amount of dripwater during the interglacial period resulted in trace element dilution. Temperature and precipitation amount variations are also reflected by the stable isotope compositions. Oxygen isotope composition shows a continuous increase from 127.5 ka until about 118 ka most probably related to temperature rise, whereas C isotope values are shifted in negative direction suggesting increasing humidity in accordance with trace element contents. The presumably warmest period at ca. 118 ka is associated with rather arid climate as indicated by peak d18O values coinciding with the highest dD values of fluid inclusion water. This is followed by a pronounced negative shift in both O and H isotope values, similarly to recent Alpine studies (Meyer et al., 2008), most probably related to cooling. Hydrogen isotope compositions of fluid inclusion water evaluated together with calculated oxygen isotope compositions of water indicate warming and increasing significance of summer precipitation at the latest period of the last interglacial, then increasing importance of winter precipitation and/or changes in oceanic source composition during the cooling phase. The good agreement with other (Alpine and marine) records indicate a synchronous climate change. However, after a negative shift in the wet/warm phase (increasing soil activity), C isotope values start to increase already at about 119 ky BP, warning to the use of the two isotope systems as event correlation tools. In conclusion, our combined isotope and trace element study indicate a complex pattern of temperature and humidity variations during and right after the Last Interglacial. Acknowledgements — This study was financially supported by the Hungarian Scientific Research Fund (OTKA T 049713). Measurements of U-Th isotopic compositions and and 230Th dates were supported by the National Science Council grants (94-2116-M002-012, 97-2752-M002-004-PAE & -005-PAE to C.C.S.). [Meyer, M.; Spötl, C.; Mangini, A. (2008): The demise of the Last Interglacial recorded in isotopically dated speleothems from the Alps. Quaternary Science Reviews, 27, 476-496.

A MIS 9/MIS 8 speleothem record of hydrological variability from Macedonia (F.Y.R.O.M.)

NASA Astrophysics Data System (ADS)

Regattieri, Eleonora; Zanchetta, Giovanni; Isola, Ilaria; Bajo, Petra; Perchiazzi, Natale; Drysdale, Russell N.; Boschi, Chiara; Hellstrom, John C.; Francke, Alexander; Wagner, Bernd

2018-03-01

The period corresponding to Marine Isotope Stages 9 (MIS 9) offers the opportunity to study orbital and sub-orbital scale climate variability under boundary conditions different from those of better studied intervals such as the Holocene and the Last Interglacial. Yet, it is poorly represented in independently-dated continental archives around the Mediterranean Region. Here, we present a speleothem stable isotope record (δ18O and δ13C) from the Former Yugoslavian Republic of Macedonia (F.Y.R.O.M., southern Balkans), which consists of two periods of growth broadly covering the ca. 332 to 292 ka and the ca. 264 to 248 ka intervals (MIS 9e-b and late MIS 8). We interpret the speleothem δ18O as mostly related to regional hydrology, with variations that can be interpreted as due to changes in rainfall amount, with higher/lower values associated to drier/wetter condition. This interpretation is corroborated by a change in mineralogical composition between aragonite and calcite at ca. 328 ka, which marks increasing precipitation at the onset of MIS 9 and occurs within a trend of decreasing δ18O values. Also the comparison with the multiproxy climate record available from the nearby Lake Ohrid seems to support the proposed interpretation. The MIS 9e interglacial appears to be characterized by wettest conditions between ca. 326 and 321 ka, i.e. lasting ca. 5 kyr. Decreasing precipitation and enhanced millennial scale variability matches the glacial inception (MIS9 d to b), with drier events at ca. 319 ka (ca. 2 kyr long) and 310 ka (ca. 1 kyr long), and a major rainfall reduction between 306 and 298 ka. The latter is followed by a prominent wetter period between 298 and 295 ka, for which carbon data values suggest high infiltration rate. Rainfall decreases again after 295 ka, and remain low until the growth interruption at ca. 292 ka. Resumption of the growth and progressive soil development, expressed by the carbon isotope record, occurred during the late part of MIS 8. Despite the rather high temporal uncertainty (average 6 ka), the speleothem hydrological record complements the environmental information provided by the Lake Ohrid record and also fits well to the framework of regional and extra-regional variability, showing similarities with pollen records from southern and western Europe, both at orbital and at sub-orbital time scale.

Does the commonly used pH-stat method with back titration really quantify the enzymatic digestibility of lipid drug delivery systems? A case study on solid lipid nanoparticles (SLN).

PubMed

Heider, Martha; Hause, Gerd; Mäder, Karsten

2016-12-01

Enzymatic digestion of lipid drug carriers is very important. Commonly, pancreatin induced formation of fatty acids is monitored by the pH-stat method, which provides a fast, but unspecific readout. However, according to the literature, the pKa values of long chain fatty acids are strongly dependent on the local environment and might vary between 4.2 and 10.15. The high pKa values would lead to an incomplete detection of the lipid digestion and false results. In order to investigate these issues in more detail, we produced cetyl palmitate solid lipid nanoparticles (CP-SLN) stabilized with poloxamer 188 or polysorbate 80. The digestion of CP-SLN was investigated by two different and independent readouts. A HPTLC assay was used in addition to the pH-stat method (with or without back titration). An incomplete digestion of CP-SLN was observed with all methods. Partial digestion of polysorbate 80 contributed to the formation of fatty acids. Depending on the investigated system and the experimental conditions (FaSSIF or FeSSIF) the results of both readout methods were comparable or not. For example, in FeSSIF conditions, the values detected by HPTLC were roughly twice as high as the pH-stat results. Our findings on solid lipids agree with data from Helbig et al. on lipid emulsions, where a gas chromatography method detected much higher values than the pH-stat assay (Food Hydrocoll. 28 (2012) 10-19). The results of our pH-stat experiments with back titration at different pH values showed increased values for fatty acids from pH 7.5 to pH 10. The values obtained by back titration at high pH values (pH 9 or higher) did exceed the digestion values measured by HPTLC. Therefore, we conclude that the pH-stat method might give the same results as more specific reference methods, but it might also both under- (without back titration) or overestimate (with back titration) the enzymatic digestion of lipid drug delivery systems. A further outcome of our study was the proof that lipase is the main enzyme involved in the digestion of the solid wax cetyl palmitate, because CP-SLN loaded with the inhibitor orlistat were not digestible and gave similar values as the corresponding control samples. In summary, our experimental results confirm the theoretical considerations (based on published pKa values) that the pH-stat method will not detect all fatty acids quantitatively. The very strong impact of the local environment on the pKa value of long chain fatty acids is a serious limitation and might lead to misleading interpretations. Copyright © 2016 Elsevier B.V. All rights reserved.

Geomagnetic Field Intensity during the Neolith in the Central East European Plain

NASA Astrophysics Data System (ADS)

Nachasova, I. E.; Pilipenko, O. V.; Markov, G. P.; Gribov, S. K.; Tsetlin, Yu. B.

2018-05-01

The conducted archeomagnetic studies resulted in data on variations in the geomagnetic field intensity in the central East European Plain (Sakhtysh I site area, ϕ = 56°48' N, λ = 40°33' E) during the time interval of 5-3 ka BC. The geomagnetic field intensity varied mainly within the range of 30-60 μT. In the first half of the 5th millennium BC, the mean level of geomagnetic field intensity was about 35 μT. In the second half of the 5th-early 4th millennium BC, it rose to about 50 μT and then decreased again to reach a mean value of about 40 μT in the period of 4-3 ka BC. Comparison of the geomagnetic field intensity variation based on the obtained data and the data on the Caucasus region for the same time interval demonstrates a certain similarity.

Paleomagnetic record for the past 80 ka from the Mahanadi basin, Bay of Bengal

NASA Astrophysics Data System (ADS)

Usapkar, A.; Dewangan, P.; Mazumdar, A.; Krishna, K. S.; Ramprasad, T.; Badesab, F. K.; Patil, M.; Gaikwad, V. V.

2018-01-01

High resolution paleomagnetic investigations were performed on a 50.08 m long sediment core (MD161/20) from Mahanadi basin, Bay of Bengal. Core yielded reliable paleomagnetic results for top 20 m below seafloor (mbsf) which spans about 80 ka. Based on the analysis of rock magnetic data, the core is subdivided into five distinct Zones: Zone 1 and Zone 2 cover top 20 mbsf and do not show any abrupt change in magnetic mineralogy, concentration and grain size. Zones 3 and 5 show significant reduction in χLF, χARM and SIRM due to dissolution of magnetic minerals. Zone 4 shows moderate values of χLF and SIRM. The low value of χARM suggests that magnetic signal is mostly carried by magnetic grains in PSD/MD state. The paleomagnetic data for the top 20 mbsf show four prominent geomagnetic excursions at ∼9 mbsf, ∼13.5 to 15 mbsf, ∼16.3 mbsf and ∼18 to 18.2 mbsf. The age-depth relationship is established using stratigraphic correlation between well-dated sedimentary core NGHP-01-19B and the core MD161/20. The ages of the observed excursions correspond to ∼18 to 20 ka, ∼42 to 49 ka, ∼54 to 57 ka and ∼69 to 70 ka. The excursions at ∼42 to 49 ka, ∼54 to 57 ka, and ∼67 to 70 ka is similar to the known excursions the Laschamp and the split Norwegian-Greenland Sea events (NGS-I and NGS-II). The excursion at 18-20 ka is not observed globally and may be related to lithological/sedimentological changes occurring during last glacial maxima (LGM). The virtual geomagnetic path (VGP) of Laschamp excursion traces clockwise loop. All excursions identified in present study fall in the periods of relatively low paleointensity.

Comparative transcriptome analysis and identification of candidate effectors in two related rust species (Gymnosporangium yamadae and Gymnosporangium asiaticum).

PubMed

Tao, Si-Qi; Cao, Bin; Tian, Cheng-Ming; Liang, Ying-Mei

2017-08-23

Rust fungi constitute the largest group of plant fungal pathogens. However, a paucity of data, including genomic sequences, transcriptome sequences, and associated molecular markers, hinders the development of inhibitory compounds and prevents their analysis from an evolutionary perspective. Gymnosporangium yamadae and G. asiaticum are two closely related rust fungal species, which are ecologically and economically important pathogens that cause apple rust and pear rust, respectively, proved to be devastating to orchards. In this study, we investigated the transcriptomes of these two Gymnosporangium species during the telial stage of their lifecycles. The aim of this study was to understand the evolutionary patterns of these two related fungi and to identify genes that developed by selection. The transcriptomes of G. yamadae and G. asiaticum were generated from a mixture of RNA from three biological replicates of each species. We obtained 49,318 and 54,742 transcripts, with N50 values of 1957 and 1664, for G. yamadae and G. asiaticum, respectively. We also identified a repertoire of candidate effectors and other gene families associated with pathogenicity. A total of 4947 pairs of putative orthologues between the two species were identified. Estimation of the non-synonymous/synonymous substitution rate ratios for these orthologues identified 116 pairs with Ka/Ks values greater than1 that are under positive selection and 170 pairs with Ka/Ks values of 1 that are under neutral selection, whereas the remaining 4661 genes are subjected to purifying selection. We estimate that the divergence time between the two species is approximately 5.2 Mya. This study constitutes a de novo assembly and comparative analysis between the transcriptomes of the two rust species G. yamadae and G. asiaticum. The results identified several orthologous genes, and many expressed genes were identified by annotation. Our analysis of Ka/Ks ratios identified orthologous genes subjected to positive or purifying selection. An evolutionary analysis of these two species provided a relatively precise divergence time. Overall, the information obtained in this study increases the genetic resources available for research on the genetic diversity of the Gymnosporangium genus.

Mechanistic Studies of the Yeast Polyamine Oxidase Fms1: Kinetic Mechanism, Substrate Specificity, and pH Dependence†

PubMed Central

Adachi, Mariya S.; Torres, Jason M.; Fitzpatrick, Paul F.

2010-01-01

The flavoprotein oxidase Fms1 from Saccharomyces cerevisiae catalyzes the oxidation of spermine and N1-acetylspermine to yield spermidine and 3-aminopropanal or N-acetyl-3-aminopropanal. The kinetic mechanism of the enzyme has been determined with both substrates. The initial velocity patterns are ping-pong, consistent with reduction being kinetically irreversible. Reduction of Fms1 by either substrate is biphasic. The rate constant for the rapid phase varies with the substrate concentration, with limiting rates for reduction of the enzyme of 126 and 1410 s−1 and apparent Kd values of 24.3 and 484 μM for spermine and N1-acetylspermine, respectively. The rapid phase is followed by a concentration-independent phase that is slower than turnover. The reaction of the reduced enzyme with oxygen is monophasic, with a rate constant of 402 mM−1 s−1 with spermine at 25 °C, and 204 mM−1 s−1 with N1-acetylspermine at 4 °C, pH 9.0. This step is followed by rate-limiting product dissociation. The kcat/Kamine-pH profiles are bell-shaped, with an average pKa value of 9.3 with spermine and pKa values of 8.3 and 9.6 with N1-acetylspermine. Both profiles are consistent with the active forms of substrates having two charged nitrogens. The pH profiles for the rate constant for flavin reduction show pKa values of 8.3 and 7.2 for spermine and N1-acetylspermine, respectively, for groups that must be unprotonated; these pKa values are assigned to the substrate N4. The kcat/KO2-pH profiles show pKa values of 7.5 for spermine and 6.8 for N1-acetylspermine. With both substrates, the kcat value decreases when a single residue is protonated. PMID:21067138

Computational Investigation of the pH Dependence of Loop Flexibility and Catalytic Function in Glycoside Hydrolases*

PubMed Central

Bu, Lintao; Crowley, Michael F.; Himmel, Michael E.; Beckham, Gregg T.

2013-01-01

Cellulase enzymes cleave glycosidic bonds in cellulose to produce cellobiose via either retaining or inverting hydrolysis mechanisms, which are significantly pH-dependent. Many fungal cellulases function optimally at pH ∼5, and their activities decrease dramatically at higher or lower pH. To understand the molecular-level implications of pH in cellulase structure, we use a hybrid, solvent-based, constant pH molecular dynamics method combined with pH-based replica exchange to determine the pKa values of titratable residues of a glycoside hydrolase (GH) family 6 cellobiohydrolase (Cel6A) and a GH family 7 cellobiohydrolase (Cel7A) from the fungus Hypocrea jecorina. For both enzymes, we demonstrate that a bound substrate significantly affects the pKa values of the acid residues at the catalytic center. The calculated pKa values of catalytic residues confirm their proposed roles from structural studies and are consistent with the experimentally measured apparent pKa values. Additionally, GHs are known to impart a strained pucker conformation in carbohydrate substrates in active sites for catalysis, and results from free energy calculations combined with constant pH molecular dynamics suggest that the correct ring pucker is stable near the optimal pH for both Cel6A and Cel7A. Much longer molecular dynamics simulations of Cel6A and Cel7A with fixed protonation states based on the calculated pKa values suggest that pH affects the flexibility of tunnel loops, which likely affects processivity and substrate complexation. Taken together, this work demonstrates several molecular-level effects of pH on GH enzymes important for cellulose turnover in the biosphere and relevant to biomass conversion processes. PMID:23504310

Predicting p Ka values from EEM atomic charges

PubMed Central

2013-01-01

The acid dissociation constant p Ka is a very important molecular property, and there is a strong interest in the development of reliable and fast methods for p Ka prediction. We have evaluated the p Ka prediction capabilities of QSPR models based on empirical atomic charges calculated by the Electronegativity Equalization Method (EEM). Specifically, we collected 18 EEM parameter sets created for 8 different quantum mechanical (QM) charge calculation schemes. Afterwards, we prepared a training set of 74 substituted phenols. Additionally, for each molecule we generated its dissociated form by removing the phenolic hydrogen. For all the molecules in the training set, we then calculated EEM charges using the 18 parameter sets, and the QM charges using the 8 above mentioned charge calculation schemes. For each type of QM and EEM charges, we created one QSPR model employing charges from the non-dissociated molecules (three descriptor QSPR models), and one QSPR model based on charges from both dissociated and non-dissociated molecules (QSPR models with five descriptors). Afterwards, we calculated the quality criteria and evaluated all the QSPR models obtained. We found that QSPR models employing the EEM charges proved as a good approach for the prediction of p Ka (63% of these models had R2 > 0.9, while the best had R2 = 0.924). As expected, QM QSPR models provided more accurate p Ka predictions than the EEM QSPR models but the differences were not significant. Furthermore, a big advantage of the EEM QSPR models is that their descriptors (i.e., EEM atomic charges) can be calculated markedly faster than the QM charge descriptors. Moreover, we found that the EEM QSPR models are not so strongly influenced by the selection of the charge calculation approach as the QM QSPR models. The robustness of the EEM QSPR models was subsequently confirmed by cross-validation. The applicability of EEM QSPR models for other chemical classes was illustrated by a case study focused on carboxylic acids. In summary, EEM QSPR models constitute a fast and accurate p Ka prediction approach that can be used in virtual screening. PMID:23574978

Weak acid-concentration Atot and dissociation constant Ka of plasma proteins in racehorses.

PubMed

Stampfli, H R; Misiaszek, S; Lumsden, J H; Carlson, G P; Heigenhauser, G J

1999-07-01

The plasma proteins are a significant contributor to the total weak acid concentration as a net anionic charge. Due to potential species difference, species-specific values must be confirmed for the weak acid anionic concentrations of proteins (Atot) and the effective dissociation constant for plasma weak acids (Ka). We studied the net anion load Atot of equine plasma protein in 10 clinically healthy mature Standardbred horses. A multi-step titration procedure, using a tonometer covering a titration range of PCO2 from 25 to 145 mmHg at 37 degrees C, was applied on the plasma of these 10 horses. Blood gases (pH, PCO2) and electrolytes required to calculate the strong ion difference ([SID] = [(Na(+) + K(+) + Ca(2+) + Mg(2+))-(Cl(-) + Lac(-) + PO4(2-))]) were simultaneously measured over a physiological pH range from 6.90-7.55. A nonlinear regression iteration to determine Atot and Ka was performed using polygonal regression curve fitting applied to the electrical neutrality equation of the physico-chemical system. The average anion-load Atot for plasma protein of 10 Standardbred horses was 14.89 +/- 0.8 mEq/l plasma and Ka was 2.11 +/- 0.50 x 10(-7) Eq/l (pKa = 6.67). The derived conversion factor (iterated Atot concentration/average plasma protein concentration) for calculation of Atot in plasma is 0.21 mEq/g protein (protein-unit: g/l). This value compares closely with the 0.24 mEq/g protein determined by titration of Van Slyke et al. (1928) and 0.22 mEq/g protein recently published by Constable (1997) for horse plasma. The Ka value compares closely with the value experimentally determined by Constable in 1997 (2.22 x 10(7) Eq/l). Linear regression of a set of experimental data from 5 Thoroughbred horses on a treadmill exercise test, showed excellent correlation with the regression lines not different from identity for the calculated and measured variables pH, HCO3 and SID. Knowledge of Atot and Ka for the horse is useful especially in exercise studies and in clinical conditions to quantify the mechanisms of the acid-base disturbances occurring.

Determination of pKa and the corresponding structures of quinclorac using combined experimental and theoretical approaches

NASA Astrophysics Data System (ADS)

Song, Dean; Sun, Huiqing; Jiang, Xiaohua; Kong, Fanyu; Qiang, Zhimin; Zhang, Aiqian; Liu, Huijuan; Qu, Jiuhui

2018-01-01

As an emerging environmental contaminant, the herbicide quinclorac has attracted much attention in recent years. However, a very fundamental issue, the acid dissociation of quinclorac has not yet to be studied in detail. Herein, the pKa value and the corresponding structures of quinclorac were systematically investigated using combined experimental and theoretical approaches. The experimental pKa of quinclorac was determined by the spectrophotometric method to be 2.65 at 25 °C with ionic strength of 0.05 M, and was corrected to be 2.56 at ionic strength of zero. The molecular structures of quinclorac were then located by employing the DFT calculation. The anionic quinclorac was directly located with the carboxylic group perpendicular to the aromatic ring, while neutral quinclorac was found to be the equivalent twin structures. The result was further confirmed by analyzing the UV/Vis and MS-MS2 spectra from both experimental and theoretical viewpoints. By employing the QSPR approach, the theoretical pKa of QCR was determined to be 2.50, which is excellent agreement with the experimental result obtained herein. The protonation of QCR at the carboxylic group instead of the quinoline structure was attributed to the weak electronegative property of nitrogen atom induced by the electron-withdrawing groups. It is anticipated that this work could not only help in gaining a deep insight into the acid dissociation of quinclorac but also offering the key information on its reaction and interaction with others.

Sensing of hydrophobic cavity of serum albumin by an adenosine analogue: fluorescence correlation and ensemble spectroscopic studies.

PubMed

Nag, Moupriya; Bera, Kallol; Chakraborty, Sandipan; Basak, Soumen

2013-10-05

Adenosine is a naturally occurring purine nucleoside that plays important role in various biochemical processes. We have studied the binding of TNP-Ado (trinitrophenylated-adenosine), a fluorescent analogue of adenosine (which itself is a weak fluorophore), with a model transport protein, bovine serum albumin (BSA). The binding affinity was determined using Fluorescence correlation spectroscopy (FCS) and compared with its value obtained from macroscopic fluorescence spectroscopic studies. Fluorescence and circular dichroism (CD) spectroscopies were employed together with molecular docking study to locate the probable binding site of TNP-Ado on BSA and its effect on the conformation and stability of BSA. Fluorescence studies showed that TNP-Ado binds to BSA in 1:1 stoichiometry via an entropically favoured process. Induced CD spectra revealed that a chiro-optical switching of TNP-Ado occurs upon binding to BSA. Results on urea-induced denaturation of BSA and docking study suggested that the binding site for the ligand is in the hydrophobic subdomain IIA of BSA, consistent with the results of other measurements. This study establishes TNP-Ado as a sensor of hydrophobic regions in proteins like serum albumin, having the capability of detecting a minimum concentration of 140ng/ml protein. FCS measurement of binding interaction of rhodamine-labeled TNP-Ado (RTNP-Ado) with BSA yielded an association constant of KFCS=(1.03±0.06) × 10(4)M(-1). The association constants (Ka) obtained for binding of BSA with rhodamine-free (i.e. TNP-Ado) and rhodamine-labeled (RTNP-Ado) ligands, obtained using the ensemble spectroscopic technique, were (2.3±0.06) × 10(5)M(-1) and (3.4±0.03) × 10(4)M(-1), respectively. The difference between the values of Ka for the free and labeled ligands suggests that fluorescent labeling of small molecules perceptibly interferes with the binding process. On the other hand, the difference in Ka obtained by FCS and ensemble techniques is due to the fact that while the former measures the change in the diffusion constant (i.e. size) of RTNP-Ado upon binding to BSA, the latter focuses on the change of tryptophan emission properties of BSA due to the presence of bound RTNP-Ado. Copyright © 2013 Elsevier B.V. All rights reserved.

Paleoclimate reconstruction in the Levant region from the petrography and the geochemistry of a MIS 5 stalagmite from the Kanaan Cave, Lebanon

NASA Astrophysics Data System (ADS)

Nehme, C.; Verheyden, S.; Noble, S. R.; Farrant, A. R.; Delannoy, J. J.; Claeys, P.

2015-07-01

Lying at the transition between the temperate Mediterranean domain and subtropical deserts, the Levant is a key area to study the palaeoclimatic response over glacial-interglacial cycles. This paper presents a precisely dated last interglacial (MIS 5) stalagmite (129-84 ka) from the Kanaan Cave, Lebanon. Variations in growth rate and isotopic records indicate a warm humid phase at the onst of the last interglacial at ~129 ka that lasted until ~125 ka. A gradual shift in speleothem isotopic composition (125-122 ka) is driven mainly by the δ18O source effect of the Eastern Mediterranean surface waters during Sapropel S5. The onset of glacial inception began after ~122 ka, interrupted by a short wet pulse during Sapropel S4. Low growth rates and enriched oxygen and carbon values until ~84 ka indicate a transition to drier conditions during Northern Hemisphere glaciation.

Reconstruction of MIS 5 climate in the central Levant using a stalagmite from Kanaan Cave, Lebanon

NASA Astrophysics Data System (ADS)

Nehme, C.; Verheyden, S.; Noble, S. R.; Farrant, A. R.; Sahy, D.; Hellstrom, J.; Delannoy, J. J.; Claeys, P.

2015-12-01

Lying at the transition between the temperate Mediterranean domain and subtropical deserts, the Levant is a key area to study the palaeoclimatic response over glacial-interglacial cycles. This paper presents a precisely dated last interglacial (MIS 5) stalagmite (129-84 ka) from the Kanaan Cave, Lebanon. Variations in growth rate and isotopic records indicate a warm humid phase at the onset of the last interglacial at ~ 129 ka that lasted until ~ 125 ka. A gradual shift in speleothem isotopic composition (125-122 ka) is driven mainly by the δ18O source effect of the eastern Mediterranean surface waters during sapropel 5 (S5). The onset of glacial inception began after ~ 122 ka, interrupted by a short wet pulse during the sapropel 4 (S4) event. Low growth rates and enriched oxygen and carbon values until ~ 84 ka indicate a transition to drier conditions during Northern Hemisphere glaciation.

Explanation to the difference in the ketyl radical formation yields of benzophenone and benzil

NASA Astrophysics Data System (ADS)

Okutsu, Tetsuo; Muramatsu, Hidenori; Horiuchi, Hiroaki; Hiratsuka, Hiroshi

2005-03-01

p Ka values of benzophenone ketyl and benzil ketyl radicals were determined as 9.4 and 12.4, respectively. We can successfully explain the difference in quantum yield of the proton transfer between benzophenone ketyl and benzil ketyl radicals by these values. Reaction enthalpies of the proton transfer are the same (-80 kJ mol -1) for these radicals, and the difference in p Ka value can be explained by that reaction entropies. Reaction entropies between two radicals are discussed by the possible structure of the radicals.

Source of the Organic Matter and Land-Marine Interaction Phases in Great Rann of Kachch Basin, India

NASA Astrophysics Data System (ADS)

Khonde, N. N.; Bhushan, R.; Agnihotri, R.; Maurya, D. M.; Chamyal, L. S.

2017-12-01

Using δ13C and C/N ratio of sedimentary organic matter (OM) in 14C AMS dated sediment core from central Great Rann of Kachchh (GRK) basin, we track sediment dispositional history since 18 ka BP. Temporal changes in the δ13C and C/N ratios were inferred in terms of OM source, which could be function of river discharge, relative sea level changes, and also due to land-cover changes in the catchment area. The down core variations in TOC vs TC doesn't show significant correlation suggesting diverse origin of the OM in GRK sediments. Between 18-13 ka BP, pulses of high C/N ratio (18-34) and depleted δ13C (average -23‰; with respect to typical marine -21‰) values hint terrestrially derived OM in rather overall marine environment. High terrestrial OM input from riverine inputs in post glacial period could be relatable to intense monsoonal conditions. Later to this phase, between 14-10 ka BP, C/N ratios show large fluctuations indicating rapidly fluctuating environment, albeit δ13C remains relatively stable at -21‰ typical of marine OM. A significant positive incursion in C/N ratio (45-60) is seen during early-mid Holocene time ( 10-6 ka BP) with and highly depleted δ13C ( -25‰) values indicating enhanced terrestrial OM input. This could be owing to increased riverine fluxes to the basin under intensified monsoonal climate. Between 6-2.5 ka BP during mid-Holocene, C/N ratios shows declining trend with enriched δ13C values, suggesting presence of marine OM source at the core-site. This overlaps with the weaker monsoonal conditions prevailing in the northwest India. Lake records from Rajasthan also support this contention. After 2.5 ka BP, C/N ratios indicate marine OM values, whereas δ13C fluctuates from marine to terrestrial values indicating `mixed-source' of the OM during this period, most likely due to unstable land-marine conditions and large-scale reworking of sediments.

A 74 or 75 ka Age for the Toba Super-eruption? Resolving the Debate.

NASA Astrophysics Data System (ADS)

Storey, M.; Roberts, R. G.; Haslam, M.

2015-12-01

The Toba super-eruption in Sumatra, ~74,000 years ago, was the largest terrestrial volcanic event of the Quaternary. Some have proposed that the eruption produced widespread perturbations of climate and ecosystems. Evaluation of the environmental impact of the eruption and linkage to rapid climate oscillations recorded in ice core, sediment and speleothem records requires an accurate and precise age for the event, with uncertainties at the centurial level. Two recent studies, however, have proposed quite different 40Ar/39Ar ages for this volcanic event of 73.88 ± 0.32 ka (Storey et al., 2012) and 75.0 ± 0.9 ka (Mark et al, 2014), with both uncertainties expressed at 1σ, leading to radically different interpretations of its global impact. 40Ar/39Ar is a relative dating method, in which the unknown is run against a mineral standard of known age. Storey et al (2012) obtained their age estimate using a new-generation, multi-collector noble gas mass spectrometer (NU Instruments Noblesse) equipped with ion-counters, while Mark et al. (2014) used an earlier generation of lower resolution, single-collector mass spectrometer (MAP 215-50). Both studies used the same mineral standard (Alder Creek sanidine, ACs), except that Mark et al. (2014) used an older value, which accounts for the discrepancy in ages between the two studies. The value used by Mark et al. for ACs is geologically implausible, because it results in older 40Ar/39Ar dates than the youngest co-existing zircon U/Pb CATIMS ages (e.g., Rivera et al., 2013, 2014). Use of the same value for ACs as used by Storey et al. (2012) results in an identical, but less precise, astronomically calibrated age of 73.9 ± 0.9 ka for the Mark et al. data. Here, we review combined U/Pb and 40Ar/39Ar age data (both published and unpublished) for a number of Quaternary and older volcanic ash deposits, and U/Th ages for late Quaternary speleothems. These data strongly support the age assigned to ACs by Storey et al. (2012) and Rivera et al. (2013) and, hence, an astronomically calibrated age of 73.9 ka age for the Toba super-eruption. This confirms the original high-precision 40Ar/39Ar age determination of Storey et al. (2012) Storey et al., 2012, PNAS, 109, 18684-18688; Rivera et al., 2013, Chem. Geol., 345, 87-98; Rivera et al., 2014, Geol. 42 643-646; Mark et al, 2014, Quat. Geochron. 21, 90-103

The Significance of Acid/Base Properties in Drug Discovery

PubMed Central

Manallack, David T.; Prankerd, Richard J.; Yuriev, Elizabeth; Oprea, Tudor I.; Chalmers, David K.

2013-01-01

While drug discovery scientists take heed of various guidelines concerning drug-like character, the influence of acid/base properties often remains under-scrutinised. Ionisation constants (pKa values) are fundamental to the variability of the biopharmaceutical characteristics of drugs and to underlying parameters such as logD and solubility. pKa values affect physicochemical properties such as aqueous solubility, which in turn influences drug formulation approaches. More importantly, absorption, distribution, metabolism, excretion and toxicity (ADMET) are profoundly affected by the charge state of compounds under varying pH conditions. Consideration of pKa values in conjunction with other molecular properties is of great significance and has the potential to be used to further improve the efficiency of drug discovery. Given the recent low annual output of new drugs from pharmaceutical companies, this review will provide a timely reminder of an important molecular property that influences clinical success. PMID:23099561

Nonquaternary Cholinesterase Reactivators.

DTIC Science & Technology

1982-08-30

c, a plot (not shown) of pKa versus Hammet substituent constant (a )42 is also linear and conforms p to equation (5) pKa - (7.63 ±0.02) - (.63 ±0.05...dissociates to the active oximate form, we have defined an effective bimolecular reactivation rate constant as in equation (6) keff ’ kb [1 + antilog(pKa...type 1 compounds generally exhibit low activity as reactivators. In terms of keff values [see equation (6)] for reactivation of ethyl methylphosphonyl

Petrology and geochronology of lavas from Ka'ula Volcano: Implications for rejuvenated volcanism of the Hawaiian mantle plume

NASA Astrophysics Data System (ADS)

Garcia, Michael O.; Weis, Dominique; Jicha, Brian R.; Ito, Garrett; Hanano, Diane

2016-07-01

Marine surveying and submersible sampling of Ka'ula Volcano, located 100 km off the axis of the Hawaiian chain, revealed widespread areas of young volcanism. New 40Ar/39Ar and geochemical analyses of the olivine-phyric submarine and subaerial volcanic rocks show that Ka'ula is shrouded with 1.9-0.5 Ma alkalic basalts. The ages and chemistry of these rocks overlap with rejuvenated lavas on nearby, northern Hawaiian Island shields (Ni'ihau, Kaua'i and South Kaua'i Swell). Collectively, these rejuvenated lavas cover a vast area (∼7000 km2), much more extensive than any other area of rejuvenated volcanism worldwide. Ka'ula rejuvenated lavas range widely in alkalinity and incompatible element abundances (e.g., up to 10× P2O5 at a given MgO value) and ratios indicating variable degrees of melting of a heterogeneous source. Heavy REE elements in Ka'ula lavas are pinned at a mantle normalized Yb value of 10 ± 1, reflecting the presence of garnet in the source. Trace element ratios indicate the source also contained phlogopite and an Fe-Ti oxide. The new Ka'ula ages show that rejuvenated volcanism was nearly coeval from ∼0.3 to 0.6 Ma along a 450 km segment of the Hawaiian Islands (from West Maui to north of Ka'ula). The ages and volumes for rejuvenated volcanism are inconsistent with all but one geodynamic melting model proposed to date. This model advocates a significant contribution of pyroxenite to rejuvenated magmas. Analyses of olivine phenocryst compositions suggest a major (33-69%) pyroxenite component in Ka'ula rejuvenated lavas, which correlates positively with radiogenic Pb isotope ratios for Ka'ula. This correlation is also observed in lavas from nearby South Kaua'i lavas, as was reported for Atlantic oceanic islands. The presence of pyroxenite in the source may have extended the duration and volume of Hawaiian rejuvenated volcanism.

Determination of acidity constants of curcumin in aqueous solution and apparent rate constant of its decomposition

NASA Astrophysics Data System (ADS)

Bernabé-Pineda, Margarita; Ramírez-Silva, María. Teresa; Romero-Romo, Mario; González-Vergara, Enrique; Rojas-Hernández, Alberto

2004-04-01

The stability of curcumin (H 3Cur) in aqueous media is improved when the systems in which it is present are at high pH values (higher than 11.7), fitting a model describable by a pseudo-zero order with a rate constant k' for the disappearance of the Cur 3- species of 1.39 (10 -9) M min -1. There were three acidity constants measured for the curcumin as follows: p KA3=10.51±0.01 corresponding to the equilibrium HCur 2-=Cur 3-+H +, a p KA2=9.88±0.02 corresponding to the equilibrium H 2Cur -=HCur -2+H +. These p KA values were attributed to the hydrogen of the phenol part of the curcumin, while the p KA1=8.38±0.04 corresponds to the equilibrium H 3Cur=H 2Cur -+H + and is attributed the acetylacetone type group. Formation of quinoid structures play an important role in the tautomeric forms of the curcumin in aqueous media, which makes the experimental values differ from the theoretically calculated ones, depending on the conditions adopted in the study.

The Alleret Maar lacustrine sequence (French Massif Central): a 150 ka long early-middle Pleistocene continental paleoenvironmental record.

NASA Astrophysics Data System (ADS)

Nomade, S.; Pastre, J.; Guillou, H.; Gauthier, A.; Scaillet, S.

2008-12-01

Lacustrine maar sequences of the French Massif Central are of great interest for paleoclimatic and paleoenvironmental reconstructions of mid-latitudes Quaternary continental environments. In particular, the western Velay region yields exceptional sequences spanning the last 450 ka (Reille et al., J. Quat. Sci. 2000). However, older sequences remain largely unknown despite the presence of interbedded alkaline tephras allowing precise absolute radiochronological control of many lacustrine squences. The Alleret maar is a 1500 m wide phreatomagmatic crater that provides a long lacustrine sequence (41 m). The upper part of this sequence (AL2 core, 14.6 m) was studied between 2005 and 2006 (Pastre et al., C. R. Acad Sci, 2007). A 39Ar/40Ar date (557 ± 5ka) obtained from an interbedded tephra layer located at 7m as well as the associated pollen data attribute the beginning of this sequence to the MIS 15. Thanks to the AL3 core recovered in 2005 (40.6 m, CNRS Meudon) several new tephra layers were discovered in the bottom part of this lacustrine sequence. Three new 39Ar/40Ar ages (single crystal analyses) from trachytic tephra layers were obtained at the LSCE Argon Laboratory (France). These layers are located at -30.2, -36.2 and -39.2m. Ages obtained relative to the ACR-2 flux standard (1,201Ma, Kuiper et al., Science, 2008) range from 692 ± 6 ka (MSWD: 2.3, n=18) for the youngest (-30.2m) to 726 ± 9Ka Ka (MSWD: 2.2, n=12) for the lowest tephra located at -39.2m. These new dates indicate a relatively homogeneous deposition rate of 3.5cm/ka and that the last 10 meters cover the MIS 17-MIS18 period. According to these current radiochronological data the complete lacustrine sequence last more than 150ka. Ongoing sedimentary and pollen studies will allow to extend the paleoenvironmental and paleoclimatic records of the French Massif Central towards the beginning of the early middle Pleistocene.

Ka-band propagation studies using the ACTS propagation terminal and the CSU-CHILL multiparameter, Doppler radar

NASA Technical Reports Server (NTRS)

Beaver, J.; Turk, J.; Bringi, V. N.

1995-01-01

An increase in the demand for satellite communications has led to an overcrowding of the current spectrums being used - mainly at C and Ku bands. To alleviate this overcrowding, new technology is being developed to open up the Ka-band for communications use. One of the first experimental communications satellites using this technology is NASA's Advanced Communications Technology Satellite (ACTS). In Sept. 1993, ACTS was deployed into a geostationary orbit near 100 deg W longitude. The ACTS system employs two Ka-band beacons for propagation experiments, one at 20.185 GHz and another at 27.505 GHz. Attenuation due to rain and tropospheric scintillations will adversely affect new technologies proposed for this spectrum. Therefore, before being used commercially, propagation effects at Ka-band must be studied. Colorado State University is one of eight sites across the United States and Canada conducting propagations studies; each site is equipped with the ACTS propagation terminal (APT). With each site located in a different climatic zone, the main objective of the propagation experiment is to obtain monthly and yearly attenuation statistics. Each site also has secondary objectives that are site dependent. At CSU, the CSU-CHILL radar facility is being used to obtain polarimetric radar data along the ACTS propagation path. During the expected two to four year period of the project, it is hoped to study several significant weather events. The S-band radar will be used to obtain Ka-band attenuation estimates and to initialize propagation models that have been developed, to help classify propagation events measured by the APT. Preliminary attenuation estimates for two attenuation events will be shown here - a bright band case that occurred on 13 May 1994 and a convective case that occurred on 20 Jun. 1994. The computations used to obtain Ka-band attenuation estimates from S-band radar data are detailed. Results from the two events are shown.

A computational study of ultrafast acid dissociation and acid-base neutralization reactions. I. The model.

PubMed

Maurer, Patrick; Thomas, Vibin; Rivard, Ugo; Iftimie, Radu

2010-07-28

Ultrafast, time-resolved investigations of acid-base neutralization reactions have recently been performed using systems containing the photoacid 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) and various Bronsted bases. Two conflicting neutralization mechanisms have been formulated by Mohammed et al. [Science 310, 83 (2005)] and Siwick et al. [J. Am. Chem. Soc. 129, 13412 (2007)] for the same acid-base system. Herein an ab initio molecular dynamics based computational model is formulated, which is able to investigate the validity of the proposed mechanisms in the general context of ground-state acid-base neutralization reactions. Our approach consists of using 2,4,6-tricyanophenol (exp. pKa congruent with 1) as a model for excited-state HPTS( *) (pKa congruent with 1.4) and carboxylate ions for the accepting base. We employ our recently proposed dipole-field/quantum mechanics (QM) treatment [P. Maurer and R. Iftimie, J. Chem. Phys. 132, 074112 (2010)] of the proton donor and acceptor molecules. This approach allows one to tune the free energy of neutralization to any desired value as well as model initial nonequilibrium hydration effects caused by a sudden increase in acidity, making it possible to achieve a more realistic comparison with experimental data than could be obtained via a full-QM treatment of the entire system. It is demonstrated that the dipole-field/QM model reproduces correctly key properties of the 2,4,6-tricyanophenol acid molecule including gas-phase proton dissociation energies and dipole moments, and condensed-phase hydration structure and pKa values.

Synchrotron Radiation and the Far-Infrared and Mid-Infrared Spectra of Ncncs

NASA Astrophysics Data System (ADS)

Winnewisser, Manfred; Winnewisser, Brenda P.; De Lucia, Frank C.; Tokaryk, Dennis; Ross, Stephen Cary; Billinghurst, Brant E.

2014-06-01

The large-amplitude in-plane bending vibration of NCNCS at 85 wn has a potential energy function which includes a barrier to linearity with a height of about 285 wn. The topology of the surface of the space defined by this two-dimensional potential function exhibits non-trivial monodromy. Therefore an energy/momentum map for a quantum system with its motion determined by such a potential takes the form of a lattice which contains a defect associated with the top of the barrier. In NCNCS, the wavenumber values of the fundamental vibrational excitation and the barrier height mean that easily accessible energy levels allow us to observe 3 bending vibrational levels below and 3 above the barrier, yet still below all of the other vibrational levels, allowing the study of all the levels in the neighborhood of the defect. In three measuring campaigns at the Canadian Light Source in May of the years 2011, 2012, and 2013 we have now obtained 8 of the 9 fundamental vibrational band systems of NCNCS in high resolution, in particular that of the large-amplitude bend in the FIR. So far only a-type spectra have been assigned. Thus we have now determined the Δvb = 1, and ΔKa = 0 vibrational intervals (using bent molecule notation) but do not yet have experimental values for either rotational ΔKa = +/- 1 intervals nor ro-vibrational Δvb = 1, ΔKa = +/- 1 intervals. In May of 2014 we will have our last measuring campaign and hope to observe the more elusive b-type transitions.

Prediction Of pKa From Chemical Structure Using Free And Open-Source Tools

EPA Science Inventory

The ionization state of a chemical, reflected in pKa values, affects lipophilicity, solubility, protein binding and the ability of a chemical to cross the plasma membrane. These properties govern the pharmacokinetic parameters such as absorption, distribution, metabolism, excreti...

Reconstruction of precipitation variability in the Strait of Yucatan associated with latitudinal shifts in the position of the Intertropical Convergence Zone since the Last Glacial Maximum

NASA Astrophysics Data System (ADS)

Staines-Urías, Francisca; Seidenkrantz, Marit-Solveig; Fischel, Andrea; Kuijpers, Antoon

2017-04-01

The elemental composition of sediments from gravity core HOLOVAR11-03 provides a ca. 40 ka record of past climate variability in the Strait of Yucatan, between the Caribbean Sea and the Gulf of Mexico, a region where precipitation variability is determined by the seasonal position of the Intertropical Convergence Zone (ITCZ). Within this region, sea level pressure decreases and rainfall increases as the ITCZ moves north of the equator in response to increased solar insolation in the Northern Hemisphere during boreal summer. In contrast, as the ITCZ retracts southward towards the equator during boreal winter, rainfall diminishes and the regional sea level pressure gradient strengthens. On interannual, multidecadal and millennial timescales, fluctuations in the average latitudinal position of the ITCZ in response to insolation forcing modulate the intensity and duration of the seasonal regimens, determining average regional precipitation and, ultimately, the elemental composition of the marine sedimentary record. Regionally, higher titanium and iron content in marine sediments reflect greater terrigenous input from inland runoff, indicating greater precipitation, hence a more northerly position of the ITCZ. Correspondingly, Ti and Fe concentration data were used to reconstruct regional rainfall variability since the Last Glacial Maxima (LGM ˜24 cal ka BP). HOLOVAR11-03 age model (based on 4 AMS 14C dates obtained from multi-specific samples of planktic foraminifera) shows stable sedimentation rates in the area throughout the cored period. Nonetheless, higher terrestrial mineral input is observed since the LGM and all through the last glacial termination (24 to 12 cal ka BP), indicating a period of increased precipitation. In contrast, lower Ti and Fe values are typical for the period between 12 and 8 cal ka BP, indicating reduced precipitation. A positive trend characterizes the following interval, showing a return to wetter conditions lasting until 5 cal ka BP. Notably, records of sea-surface temperature from the Caribbean indicate similar variability, with among others, colder than present conditions in the early Holocene indicating a more northerly mean ITCZ position, followed by warmer surface waters and a weaker tradewind associated with a southward displacement of the ITCZ, further illustrating the strong link between precipitation variability and oceanographic conditions in the region. After 5 cal ka BP, Ti and Fe values remain fairly stable at an intermediate level until shortly after 2 cal ka BP, when a sudden increase in Fe content is observed. At this time, a significant increase in precipitation has also been inferred from the δ18O signal of ostracods and gastropods in lake sediments from the Yucatan Peninsula and a stalagmite δ18O monsoon reconstruction from mainland Mexico. The drastic increment in Fe content also marks the beginning of a shift towards rapidly decreasing Ti and Fe values, suggesting an increasingly drier climate. Decrease inland runoff/precipitation during the late Holocene has also been observed in stalagmite and lacustrine δ18O signals from nearby locations, altogether indicating a southward displacement of the ITCZ.

A robust, multisite Holocene history of drift ice off northern Iceland: Implications for North Atlantic climate

USGS Publications Warehouse

Andrews, John T.; Darby, D.; Eberle, D.; Jennings, A.E.; Moros, M.; Ogilvie, A.

2009-01-01

An important indicator of Holocene climate change is provided by evidence for variations in the extent of drift ice. A proxy for drift ice in Iceland waters is provided by the presence of quartz. Quantitative x-ray diffraction analysis of the < 2 mm sediment fraction was undertaken on 16 cores from around Iceland. The quartz weight (wt.)% estimates from each core were integrated into 250-yr intervals between ????'0.05 and 11.7 cal. ka BP. Median quartz wt.% varied between 0.2 and 3.4 and maximum values ranged between 2.8 and 11.8 wt.%. High values were attained in the early Holocene and minimum values were reached 6 - 7 cal. ka BP. Quartz wt.% then rose steadily during the late Holocene. Our data exhibit no correlation with counts on haematite-stained quartz (HSQ) grains from VM129-191 west of Ireland casting doubt on the ice-transport origin. A pilot study on the provenance of Fe oxide grains in two cores that cover the last 1.3 and 6.1 cal. ka BP indicated a large fraction of the grains between 1 and 6 cal. ka BP were from either Icelandic or presently unsampled sources. However, there was a dramatic increase in Canadian and Russian sources from the Arctic Ocean ???1 cal. ka BP. These data may indicate the beginning of an Arctic Oscillation-like climate mode. ?? 2009 SAGE Publications.

RLE Progress Report Number 122.

DTIC Science & Technology

1980-01-01

generator capable of delivering 20 kA of current at 1.5 MV. Both the pipe and the diode region are immersed in the uniform axial magnetic field of a...it decays into a slow space-charge wave and a TM wave of the guide. The dispersion PR No. 122 100 I ____ W/Wp (wi,ki) BEAM FRAME (a) .. ( 3, k3) ka ...to regular operation with well-confined plasmas and plasma currents of approximately as high as 300 kA . We recall that the reference design value of

20180318 - Prediction Of pKa From Chemical Structure Using Free And Open-Source Tools (ACS Spring)

EPA Science Inventory

The ionization state of a chemical, reflected in pKa values, affects lipophilicity, solubility, protein binding and the ability of a chemical to cross the plasma membrane. These properties govern the pharmacokinetic parameters such as absorption, distribution, metabolism, excreti...

Benthic ostracode δ13C as sensor for early Holocene establishment of modern circulation patterns in Central Europe

NASA Astrophysics Data System (ADS)

Schwalb, Antje; Dean, Walter; Güde, Hans; Hanisch, Sabine; Sobek, Sebastian; Wessels, Martin

2013-04-01

Shells from adult specimen of the benthic ostracodes Limnocytherina sanctipatricii and Leucocythere mirabilis selected from a 8.7 m long piston core provide continuous stable oxygen and carbon records for the past approximately 16 ka. Oxygen isotopes from both species show identical values and track the general North Atlantic and European temperature history since deglaciation in great detail. Values of ostracode δ18O values suggest that about 16 cal ka the average annual air temperatures were about 11 °C colder than today. Carbon isotopic values from both species of ostracodes are similar during the Lateglacial and early Holocene, and show an overall decrease from -4‰ to -7‰ that is probably related to an increase in photosynthetic productivity in the water column, as suggested by an increase in organic carbon, delivering 13C-depleted organic matter to the bottom waters (carbon pump). About 9 cal ka only L. mirabilis δ13C values decreased about -2.5‰ within 300 years. Higher δ13C variability and ecological evidence suggests that L. mirabilis represents a summer signal, whereas L. sanctipatricii displays a more subdued annual average. After about 7 cal ka another -1.5% decrease for both species, accompanied by an increase in magnetic susceptibility, a decrease in carbonate content, and more positive bulk carbonate isotope values followed, suggesting higher detrital-clastic input into the lake. In order to provide a possible mechanism explaining the negative L. mirabilis δ13C-values, sediment pore water profiles of O2 and CH4 in short cores collected from sites distal to proximal to the Alpine Rhine River delta, were inspected. Sediments in cores from more proximal sites to the Rhine delta become anoxic at shallower sediment depth due to the decay of high allochthonous organic carbon input to the sediment, which greatly increases concentrations of methane in pore waters closer to the Rhine inflow. When methane is oxidized close to the sediment-water-interface, 13C-depleted carbon is added to pore water DIC that is then available for incorporation into ostracode shells. This mechanism suggests that about 9 cal ka the oxygen supply to the bottom waters, especially in summer, decreased. This stimulated methanogenesis close to the sediment-water-interface, and provided δ13C-depleted carbon to benthic dwellers. Independent evidence for methanogenesis is provided by the increase in concentration of tetrahymanol after about 9 cal ka coincident with the decrease in δ13C of L. mirabilis. We suggest that about 9 cal ka the northward retreat of the Northern Hemisphere Ice Sheets, and consequently the polar front, left the alpine region affected by a more oceanic climate, characterized by warmer winters as they occur today especially during the positive North Atlantic Oscillation Index phase. More frequently incomplete mixing of the water column may have shifted the decay of organic matter faster to anaerobic conditions in surficial sediments especially during summer. By about 7 cal ka the North Atlantic region had probably warmed sufficiently to increase precipitation in Central Europe and consequently detrital-clastic runoff to Lake Constance.

Influence of affinity on antibody determination in microtiter ELISA systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peterman, J.H.; Voss, E.W. Jr.; Butler, J.E.

1986-03-01

Theoretically, all immunoassays are affinity (Ka) dependent when the product of the antibody (Ab) Ka and the free epitope concentration is less than 10. Thus, the degree of dependence on Ka depends on the concentration of available antigen in the system. The authors examined the binding of /sup 125/I-anti-fluorescein (a-FLU) monoclonal antibodies of different affinities to FLU-gelatin adsorbed on Immunlon 2 microtiter plates. Data obtained were in general agreement with our theoretical predictions; the percent of /sup 125/I-a-FLU which bound correlated with Ka, as did the shape of the titration curves. Measurement of 5 a-FLU monoclonals by the ELISA showedmore » that the determination of Ab concentrations depends on the FLU-gelatin concentration, epitope density, and on the relationship between the Kas of test samples and the reference standard Ab preparation. Thus the ELISA is Ka dependent and should not be used routinely to estimate the absolute amount to Ab in unknown samples. However, the Ka dependency of the ELISA might provide a convenient assay for the estimation of the relative functional Ka (rfKa) of antibody preparations.« less

Linear diffusion model dating of cinder cones in Central Anatolia, Turkey

NASA Astrophysics Data System (ADS)

O'Sadnick, L. G.; Reid, M. R.; Cline, M. L.; Cosca, M. A.; Kuscu, G.

2013-12-01

The progressive decrease in slope angle, cone height and cone height/width ratio over time provides the basis for geomorphic dating of cinder cones using linear diffusion models. Previous research using diffusion models to date cinder cones has focused on the cone height/width ratio as the basis for dating cones of unknown age [1,2]. Here we apply linear diffusion models to dating cinder cones. A suite of 16 cinder cones from the Hasandağ volcano area of the Neogene-Quaternary Central Anatolian Volcanic Zone, for which samples are available, were selected for morphologic dating analysis. New 40Ar/39Ar dates for five of these cones range from 62 × 4 to 517 × 9 ka. Linear diffusion models were used to model the erosional degradation of each cone. Diffusion coefficients (κ) for the 5 cinder cones with known ages were constrained by comparing various modeled slope profiles to the current slope profile. The resulting κ is 7.5×0.5 m2kyr-1. Using this κ value, eruption ages were modeled for the remaining 11 cinder cones and range from 53×3 to 455×30 ka. These ages are within the range of ages previously reported for cinder cones in the Hasandağ region. The linear diffusion model-derived ages are being compared to additional new 40Ar/39Ar dates in order to further assess the applicability of morphological dating to constrain the ages of cinder cones. The relatively well-constrained κ value we obtained by applying the linear diffusion model to cinder cones that range in age by nearly 500 ka suggests that this model can be used to date cinder cones. This κ value is higher than the well-established value of κ =3.9 for a cinder cone in a similar climate [3]. Therefore our work confirms the importance of determining appropriate κ values from nearby cones with known ages. References 1. C.A. Wood, J. Volcanol. Geotherm. Res. 8, 137 (1980) 2. D.M. Wood, M.F. Sheridan, J. Volcanol. Geotherm. Res. 83, 241 (1998) 3. J.D. Pelletier, M.L. Cline, Geology 35, 1067 (2007)

Determination of radiocarbon reservoir age of Lake Van by mineral magnetic and geochemical analysis

NASA Astrophysics Data System (ADS)

Makaroglu, Ozlem; Namik Cagatay, M.; Pesonen, Lauri J.; Orbay, Naci

2017-04-01

Lake Van is the largest soda lake in the world, located on the east Anatolian Plateau in Turkey. Its varved sediments provide an excellent archive of high-resolution paleoclimate record for the Near East. Varve counting and radiocarbon methods are therefore important dating techniques for investigating the Lake Van sedimentary paleoclimate record. In here we present detailed magnetic and geochemical record of Lake Van. We have studied 4.56 m (core VP0801) and 4.70 m (core VP0807) long cores recovered from 80 m and 65 m water depths located in SE and SW of Lake Van, respectively. Here, we have benefited from magnetic properties with associated remanent magnetization of the sediments from Lake Van to correlate the cores which contain of tephra layers. The cores cover the last 8.4 ka and lithologically include three laminated sedimentary units. From top to the bottom, the units were dated 4.2 ka BP-present, 5.4-4.2 ka BP and older than 5.4 ka BP. We identified tephra layers previously dated by varve counting, and used the varve ages to obtain age models for the cores. We also obtained a total of eight Accelerator Mass Spectrometry (AMS) 14C dates from total organic carbon (TOC) in the two cores, close to the tephra layers. Comparison of the varve ages of the AMS 14C dated samples with their corresponding AMS 14C dates indicates large differences, suggesting significant reservoir ages that range from 2.8 to 2.5 ka for 3.0-2.4 varve ka BP and from 2.8 to 3.3 ka for 8.0-5.9 varve ka BP. The results suggest that the reservoir age of the organic matter increases with the varve age of the sediments. This increase is mainly related to the rate of supply of "dead" carbon from the old carbonate rocks in the watershed of Lake Van, which was relatively higher during 8.4-5.9 ka than during 3.0-2.4 ka BP because of the higher atmospheric precipitation and higher rate of biochemical weathering during the former period.

Full-vector geomagnetic field records from the East Eifel, Germany

NASA Astrophysics Data System (ADS)

Monster, Marilyn W. L.; Langemeijer, Jaap; Wiarda, Laura R.; Dekkers, Mark J.; Biggin, Andy J.; Hurst, Elliot A.; Groot, Lennart V. de

2018-01-01

To create meaningful models of the geomagnetic field, high-quality directional and intensity input data are needed. However, while it is fairly straightforward to obtain directional data, intensity data are much scarcer, especially for periods before the Holocene. Here, we present data from twelve flows (age range ∼ 200 to ∼ 470 ka) in the East Eifel volcanic field (Germany). These sites had been previously studied and are resampled to further test the recently proposed multi-method palaeointensity approach. Samples are first subjected to classic palaeomagnetic and rock magnetic analyses to optimise the subsequent palaeointensity experiments. Four different palaeointensity methods - IZZI-Thellier, the multispecimen method, calibrated pseudo-Thellier, and microwave-Thellier - are being used in the present study. The latter should be considered as supportive because only one or two specimens per site could be processed. Palaeointensities obtained for ten sites pass our selection criteria: two sites are successful with a single approach, four sites with two approaches, three more sites work with three approaches, and one site with all four approaches. Site-averaged intensity values typically range between 30 and 35 μT. No typically low palaeointensity values are found, in line with paleodirectional results which are compatible with regular palaeosecular variation of the Earth's magnetic field. Results from different methods are remarkably consistent and generally agree well with the values previously reported. They appear to be below the average for the Brunhes chron; there are no indications for relatively higher palaeointensities for units younger than 300 ka. However, our young sites could be close in age, and therefore may not represent the average intensity of the paleofield. Three of our sites are even considered coeval; encouragingly, these do yield the same palaeointensity within uncertainty bounds.

Thiolated alkyl-modified carbomers: Novel excipients for mucoadhesive emulsions.

PubMed

Bonengel, Sonja; Hauptstein, Sabine; Leonaviciute, Gintare; Griessinger, Julia; Bernkop-Schnürch, Andreas

2015-07-30

The aim of this study was the design and evaluation of mucoadhesive emulsifying polymeric excipients. Three thiol bearing ligands with increasing pKa values of their sulfhydryl group, namely 4-aminothiophenol (pKa=6.86), l-cysteine (pKa=8.4) and d/l-homocysteine (pKa=10.0) were coupled to the polymeric backbone of alkyl-modified carbomer (PA1030). Resulting conjugates displayed 818.5μmol 4-aminothiophenol, 698.5μmol cysteine and 651.5μmol homocysteine per gram polymer and were evaluated regarding the reactivity of thiol groups, emulsifying and mucoadhesive properties. In general, the synthesized conjugates showed a pH dependent reactivity, whereby the fastest oxidation occurred in PA1030-cysteine, as almost no free thiol groups could be detected after 120min. Emulsification of medium chain triglycerides was feasible with all synthesized conjugates leading to oil-in-water-emulsions. Emulsions with PA1030-cysteine displayed the highest stability and the smallest droplet size among the tested formulations. Oxidation and consequently cross-linking of the thiomers prior to the emulsification process led to an overall decreased emulsion stability. Evaluating mucosal residence time of thiomer emulsions on porcine buccal mucosa, a 9.2-fold higher amount of formulation based on PA1030-cysteine remained on the mucosal tissue within 3h compared to the unmodified polymer. According to these results, the highest reactive ligand l-cysteine seems to be most promising in order to obtain thiolated polymers for the preparation of mucoadhesive o/w-emulsions. Copyright © 2015 Elsevier B.V. All rights reserved.

Accurate pKa calculation of the conjugate acids of alkanolamines, alkaloids and nucleotide bases by quantum chemical methods.

PubMed

Gangarapu, Satesh; Marcelis, Antonius T M; Zuilhof, Han

2013-04-02

The pKa of the conjugate acids of alkanolamines, neurotransmitters, alkaloid drugs and nucleotide bases are calculated with density functional methods (B3LYP, M08-HX and M11-L) and ab initio methods (SCS-MP2, G3). Implicit solvent effects are included with a conductor-like polarizable continuum model (CPCM) and universal solvation models (SMD, SM8). G3, SCS-MP2 and M11-L methods coupled with SMD and SM8 solvation models perform well for alkanolamines with mean unsigned errors below 0.20 pKa units, in all cases. Extending this method to the pKa calculation of 35 nitrogen-containing compounds spanning 12 pKa units showed an excellent correlation between experimental and computational pKa values of these 35 amines with the computationally low-cost SM8/M11-L density functional approach. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiple scattering effects on the Linear Depolarization Ratio (LDR) measured during CaPE by a Ka-band air-borne radar

NASA Technical Reports Server (NTRS)

Iguchi, Toshio; Meneghini, Robert

1993-01-01

Air-borne radar measurements of thunderstorms were made as part of the CaPE (Convection and Precipitation/Electrification) experiment in Florida in July 1991. The radar has two channels, X-band (10 GHz) and Ka-band (34.5 GHz), and is capable of measuring cross-polarized returns as well as co-polarized returns. In stratiform rain, the cross-polarized components can be observed only at the bright band region and from the surface reflection. The linear depolarization ratios (LDR's) measured at X-band and Ka-band at the bright band are nearly equal. In convective rain, however, the LDR in Ka-band often exceeds the X-band LDR by several dB, and sometimes by more than 10 dB, reaching LDR values of up to -5 dB over heavy convective rain. For randomly oriented hydrometeors, such high LDR values cannot be explained by single scattering from non-spherical scattering particles alone. Because the LDR by single backscatter depends weakly on the wavelength, the difference between the Ka-band and X-band LDR's suggests that multiple scattering effects prevail in the Ka-band LDR. In order to test this inference, the magnitude of the cross-polarized component created by double scattering was calculated using the parameters of the airborne radar, which for both frequencies has beamwidths of 5.1 degrees and pulse widths of 0.5 microsecond. Uniform rain beyond the range of 3 km is assumed.

Climatic implications of correlated upper Pleistocene glacial and fluvial deposits on the Cinca and Gallego rivers, NE Spain

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lewis, Claudia J; Mcdonald, Eric; Sancho, Carlos

We correlate Upper Pleistocene glacial and fluvial deposits of the Cinca and Gallego River valleys (south central Pyrenees and Ebro basin, Spain) using geomorphic position, luminescence dates, and time-related trends in soil development. The ages obtained from glacial deposits indicate glacial periods at 85 {+-} 5 ka, 64 {+-} 11 ka, and 36 {+-} 3 ka (from glacial till) and 20 {+-} 3 ka (from loess). The fluvial drainage system, fed by glaciers in the headwaters, developed extensive terrace systems in the Cinca River valley at 178 {+-} 21 ka, 97 {+-} 16 ka, 61 {+-} 4 ka, 47 {+-}more » 4 ka, and 11 {+-} 1 ka, and in the Gallego River valley at 151 {+-} 11 ka, 68 {+-} 7 ka, and 45 {+-} 3 ka. The times of maximum geomorphic activity related to cold phases coincide with Late Pleistocene marine isotope stages and heinrich events. The maximum extent of glaciers during the last glacial occurred at 64 {+-} 11 ka, and the terraces correlated with this glacial phase are the most extensive in both the Cinca (61 {+-} 4 ka) and Gallego (68 {+-} 7 ka) valleys, indicating a strong increase in fluvial discharge and availability of sediments related to the transition to deglaciation. The global Last Glacial Maximum is scarcely represented in the south central Pyrenees owing to dominantly dry conditions at that time. Precipitation must be controlled by the position of the Iberian Peninsula with respect to the North Atlantic atmospheric circulation system. The glacial systems and the associated fluvial dynamic seem sensitive to (1) global climate changes controlled by insolation, (2) North Atlantic thermohaline circulation influenced by freshwater pulses into the North Atlantic, and (3) anomalies in atmospheric circulation in the North Atlantic controlling precipitation on the Iberian peninsula. The model of glacial and fluvial evolution during the Late Pleistocene in northern Spain could be extrapolated to other glaciated mountainous areas in southern Europe.« less

Development of a phantom and a methodology for evaluation of depth kerma and kerma index for dental cone beam computed tomography.

PubMed

Batista, W O; Navarro, M V T; Maia, A F

2013-12-01

Basically, all modalities of diagnostic radiology require phantoms suitable for dosimetric evaluations. New technologies frequently arise unaccompanied of tools for dosimetric evaluations and quality control. In this study, a low-cost phantom and a consequent proposed methodology for dosimetric evaluations in cone beam computed tomography (CBCT) were presented. The developed phantom has typical dimensions of the human face, was built in polymethyl methacrylate and filled with water. Three devices with different technological concepts were evaluated and a proposed index, kerma index-height product (PKIH), was defined as an option to the use of air kerma-area product. The results of this study show relatively uniform kerma profiles for scanners with field of views (FOVs) of large diameters and non-uniform for FOVs of small diameters. With regard to the values obtained for the kerma indexes, much higher values were found for the equipment FOVs with small diameter compared with the values of the two other equipment that have larger diameters. The results indicate that (1) there is a need for special phantoms for use in CBCT, (2) the use of P(KA) in the evaluation of protocols on different equipment can lead to false interpretations and (3) the new index is a suitable alternative for the use of P(KA) in CBCT.

Determination of the pKa of the N-terminal amino group of ubiquitin by NMR

PubMed Central

Oregioni, Alain; Stieglitz, Benjamin; Kelly, Geoffrey; Rittinger, Katrin; Frenkiel, Tom

2017-01-01

Ubiquitination regulates nearly every aspect of cellular life. It is catalysed by a cascade of three enzymes and results in the attachment of the C-terminal carboxylate of ubiquitin to a lysine side chain in the protein substrate. Chain extension occurs via addition of subsequent ubiquitin molecules to either one of the seven lysine residues of ubiquitin, or via its N-terminal α-amino group to build linear ubiquitin chains. The pKa of lysine side chains is around 10.5 and hence E3 ligases require a mechanism to deprotonate the amino group at physiological pH to produce an effective nucleophile. In contrast, the pKa of N-terminal α-amino groups of proteins can vary significantly, with reported values between 6.8 and 9.1, raising the possibility that linear chain synthesis may not require a general base. In this study we use NMR spectroscopy to determine the pKa for the N-terminal α-amino group of methionine1 of ubiquitin for the first time. We show that it is 9.14, one of the highest pKa values ever reported for this amino group, providing a rational for the observed need for a general base in the E3 ligase HOIP, which synthesizes linear ubiquitin chains. PMID:28252051

Ka-Band, RF MEMS Switches on CMOS Grade Silicon with a Polyimide Interface Layer

NASA Technical Reports Server (NTRS)

Ponchak, George E.; Varaljay, Nicholas C.; Papapolymerou, John

2003-01-01

For the first time, RF MEMS switcbes on CMOS grade Si witb a polyimide interface layer are fabricated and characterized. At Ka-Band (36.6 GHz), an insertion loss of 0.52 dB and an isolation of 20 dB is obtained.

Neuroprotective effect of Arthrospira (Spirulina) platensis against kainic acid-neuronal death.

PubMed

Pérez-Juárez, Angélica; Chamorro, Germán; Alva-Sánchez, Claudia; Paniagua-Castro, Norma; Pacheco-Rosado, Jorge

2016-08-01

Context Arthrospira (Spirulina) platensis (SP) is a cyanobacterium which has attracted attention because of its nutritional value and pharmacological properties. It was previously reported that SP reduces oxidative stress in the hippocampus and protects against damaging neurobehavioural effects of systemic kainic acid (KA). It is widely known that the systemic administration of KA induces neuronal damage, specifically in the CA3 hippocampal region. Objective The present study determines if the SP sub-chronic treatment has neuroprotective properties against KA. Materials and methods Male SW mice were treated with SP during 24 d, at doses of 0, 200, and 800 mg/kg, once daily, and with KA (35 mg/kg, ip) as a single dose on day 14. After the treatment, a histological analysis was performed and the number of atrophic neuronal cells in CA3 hippocampal region was quantified. Results Pretreatment with SP does not protect against seizures induced by KA. However, mortality in the SP 200 and the SP 800 groups was of 20%, while for the KA group, it was of 60%. A single KA ip administration produced a considerable neuronal damage, whereas both doses of SP sub-chronic treatment reduced the number of atrophic neurons in CA3 hippocampal region with respect to the KA group. Discussion The SP neurobehaviour improvement after KA systemic administration correlates with the capacity of SP to reduce KA-neuronal death in CA3 hippocampal cells. This neuroprotection may be related to the antioxidant properties of SP. Conclusion SP reduces KA-neuronal death in CA3 hippocampal cells.

Monsoon source shifts during the drying mid-Holocene: Biomarker isotope based evidence from the core 'monsoon zone' (CMZ) of India

NASA Astrophysics Data System (ADS)

Sarkar, Saswati; Prasad, Sushma; Wilkes, Heinz; Riedel, Nils; Stebich, Martina; Basavaiah, Nathani; Sachse, Dirk

2015-09-01

A better understanding of past variations of the Indian Summer Monsoon (ISM), that plays a vital role for the still largely agro-based economy in India, can lead to a better assessment of its potential impact under global climate change scenarios. However, our knowledge of spatiotemporal patterns of ISM strength is limited due to the lack of high-resolution, continental paleohydrological records. Here, we reconstruct centennial-scale hydrological variability during the Holocene associated to changes in the intensity of the ISM based on a record of lipid biomarker abundances and compound-specific stable isotopic composition of a 10 m long sediment core from saline-alkaline Lonar Lake, situated in the core 'monsoon zone' of central India. We identified three main periods of distinct hydrology during the Holocene in central India. The period between 10.1 and 6 cal ka BP was likely the wettest during the Holocene. Lower average chain length (ACL) index values (29.4-28.6) and negative δ13Cwax values (-34.8‰ to -27.8‰) of leaf wax n-alkanes indicate the dominance of woody C3 vegetation in the catchment, and negative δDwax values (concentration weighted average) (-171‰ to -147‰) suggest a wet period due to an intensified monsoon. After 6 cal ka BP, a gradual shift to less negative δ13Cwax values (particularly for the grass derived n-C31) and appearance of the triterpene lipid tetrahymanol, generally considered as a marker for salinity and water column stratification, mark the onset of drier conditions. At 5.1 cal ka BP an increasing flux of leaf wax n-alkanes along with the highest flux of tetrahymanol indicate a major lowering of the lake level. Between 4.8 and 4 cal ka BP, we find evidence for a transition to arid conditions, indicated by high and strongly variable tetrahymanol flux. In addition, a pronounced shift to less negative δ13Cwax values, in particular for n-C31 (-25.2‰ to -22.8‰), during this period indicates a change of dominant vegetation to C4 grasses. In agreement with other proxy data, such as deposition of evaporite minerals, we interpret this period to reflect the driest conditions in the region during the last 10.1 ka. This transition led to protracted late Holocene arid conditions after 4 ka with the presence of a permanent saline lake, supported by the sustained presence of tetrahymanol and more positive average δDwax values (-122‰ to -141‰). A late Holocene peak of cyanobacterial biomarker input at 1.3 cal ka BP might represent an event of lake eutrophication, possibly due to human impact and the onset of cattle/livestock farming in the catchment. A unique feature of our record is the presence of a distinct transitional period between 4.8 and 4 cal ka BP, which was characterized by some of the most negative δDwax values during the Holocene (up to -180‰), when all other proxy data indicate the driest conditions during the Holocene. These negative δDwax values can as such most reasonably be explained by a shift in moisture source area and/or pathways or rainfall seasonality during this transitional period. We hypothesize that orbital induced weakening of the summer solar insolation and associated reorganization of the general atmospheric circulation, as a possible southward displacement of the tropical rainbelt, led to an unstable hydroclimate in central India between 4.8 and 4 ka. Our findings shed light onto the sequence of changes during mean state changes of the monsoonal system, once an insolation driven threshold has been passed, and show that small changes in solar insolation can be associated with major hydroclimate changes on the continents, a scenario that may be relevant with respect to future changes in the ISM system.

Surface-exposure ages of Front Range moraines that may have formed during the Younger Dryas, 8.2 cal ka, and Little Ice Age events

USGS Publications Warehouse

Benson, L.; Madole, R.; Kubik, P.; McDonald, R.

2007-01-01

Surface-exposure (10Be) ages have been obtained on boulders from three post-Pinedale end-moraine complexes in the Front Range, Colorado. Boulder rounding appears related to the cirque-to-moraine transport distance at each site with subrounded boulders being typical of the 2-km-long Chicago Lakes Glacier, subangular boulders being typical of the 1-km-long Butler Gulch Glacier, and angular boulders being typical of the few-hundred-m-long Isabelle Glacier. Surface-exposure ages of angular boulders from the Isabelle Glacier moraine, which formed during the Little Ice Age (LIA) according to previous lichenometric dating, indicate cosmogenic inheritance values ranging from 0 to ???3.0 10Be ka.11Surface-exposure ages in this paper are labeled 10Be; radiocarbon ages are labeled 14C ka, calendar and calibrated radiocarbon ages are labeled cal ka, and layer-based ice-core ages are labeled ka. 14C ages, calibrated 14C ages, and ice core ages are given relative to AD 1950, whereas 10Be ages are given relative to the sampling date. Radiocarbon ages were calibrated using CALIB 5.01 and the INTCAL04 data base Stuiver et al. (2005). Ages estimated using CALIB 5.01 are shown in terms of their 1-sigma range. Subangular boulders from the Butler Gulch end moraine yielded surface-exposure ages ranging from 5 to 10.2 10Be ka. We suggest that this moraine was deposited during the 8.2 cal ka event, which has been associated with outburst floods from Lake Agassiz and Lake Ojibway, and that the large age range associated with the Butler Gulch end moraine is caused by cosmogenic shielding of and(or) spalling from boulders that have ages in the younger part of the range and by cosmogenic inheritance in boulders that have ages in the older part of the range. The surface-exposure ages of eight of nine subrounded boulders from the Chicago Lakes area fall within the 13.0-11.7 10Be ka age range, and appear to have been deposited during the Younger Dryas interval. The general lack of inheritance in the eight samples probably stems from the fact that only a few thousand years intervened between the retreat of the Pinedale glacier and the advance of the Chicago Lakes glacier; in addition, bedrock in the Chicago Lakes cirque area may have remained covered with snow and ice during that interval, thus partially shielding the bedrock from cosmogenic radiation.

Biogenic silica from the BDP93 drill site and adjacent areas of the Selenga Delta, Lake Baikal, Siberia

USGS Publications Warehouse

Colman, Steven M.; Peck, John A.; Hatton, Josephine; Karabanov, Eugene B.; King, John W.

1999-01-01

Biogenic silica contents of sediments on the lower Selenga Delta and Buguldeika saddle in Lake Baikal show distinct fluctuations that reflect changes in diatom productivity, and ultimately, climate. The pattern of the upper 50 m of the section, dating from about 334 ka, is similar to that of the marine oxygen-isotope record, increasingly so as the younger sediments become progressively finer grained and less locally derived with time. The last two interglaciations are marked by biogenic silica abundances similar to those of the Holocene. The equivalent of marine oxygen-isotope stage 3 is distinctly intermediate in character between full glacial and full interglacial biogenic silica values. Following near-zero values during the last glacial maximum, biogenic silica began to increase at about 13 ka. The rise in biogenic silica to Holocene values was interrupted by an abrupt decrease during Younger Dryas time, about 11 to 10 14C ka.

Danngarrd-Oscar events recorded in a terrestrial sequence in central British Columbia, Canada

NASA Astrophysics Data System (ADS)

Ward, B. C.; Geertsema, M.; Telka, A.; Mathewes, R.

2012-12-01

The Indianpoint section, 90 km southeast of Prince George, presents a >25 ka record of paleoenvironmental changes from non-glacial MIS 3 time to just before Late Wisconsinan (MIS2) ice from the Cordilleran Ice Sheet overran the site. Detailed plant and insect macrofossil and pollen analyses were carried out on a 5-6 m thick fine-grained unit. It represents a small lake, based on aquatic plants and insects, and taxa indicative of riparian or shoreline environments. A total of 11 radiocarbon ages, most obtained on willow (Salix) twigs provide chronological control for 8 levels. Radiocarbon ages of >44 ka (CAMS-96170) and 46.5 ka (CAMS 93938) were obtained near the base and are associated with spruce macrofossils (abundant needles, seeds and seed wings) and high spruce pollen. Between 37.0 ka (CAMS115785) and 25.9 ka (CAMS117312) alternations between open spruce forest and tundra with minor willow and birch occur. In the upper 2.5 m of the section, between 24.5 ka (CAMS 93940) and 20.4 ka (CAMS 93939), the vegetation changes to dry shrub tundra, dominated again by willow with minor birch. Most pollen from this interval comes from herbs such as sedges, grasses and Artemisia. Also present are characteristic insects such as the weevil Vitavitus thulius and the ground beetles Trichocellus mannerheimi, Pteriostichus (Cryobius) nivalis, and Amara alpina that are presently only found in dry tundra habitats. The decrease in the occurrence of willow and birch in the upper 40-50 cm reflects increasingly harsh conditions as glaciers approached the site. An age of 19.9 ka (AA44045) has been obtained on a willow twig 20-30 cm below where the unit is truncated by a Late Wisconsinan till. The lacustrine unit of the Indianpoint section spans >25 ka and records climatic variation during MIS 3 and deterioration associated with the growth of the Cordilleran Ice Sheet during the Late Wisconsinan (MIS 2). The alternations in the middle portion of the record are thought to represent Danngarrd-Oscar events recorded in the GISP2 Greenland Ice Core. The increasingly dry and cold conditions indicated by the macrofossil assemblage likely reflect the growth of ice in the Coast Mountains that would reduce the availability of moisture to the Interior Plateau from Pacific air masses. This is confirmed by reconstruction of the growth of the Cordilleran Ice Sheet during the Late Wisconsinan based on published radiocarbon dates.

A population pharmacokinetic analysis of sildenafil citrate in patients with erectile dysfunction

PubMed Central

Milligan, Peter A; Marshall, Scott F; Karlsson, Mats O

2002-01-01

Aims To analyse the pharmacokinetics of sildenafil citrate in patients with erectile dysfunction in order to characterize covariate relationships and assist in the development of rational dosage strategies. Methods A population pharmacokinetic sampling strategy was incorporated into five phase III clinical study protocols. Overall, 2077 patients, 1335 of whom received sildenafil, were asked to take an additional dose of study drug before their scheduled clinic visits on four or five occasions throughout the study duration. A single plasma sample was obtained at random times postdose (range 1–7 h), and a total of 4582 samples were assayed (average 3.4 samples per individual). Results For the population average patient (age 58 years; aspartate transaminase [AST], 24 IU l−1; weight, 87 kg; not receiving CYP3A4 potential inhibitors), typical values for sildenafil (mean±SE) were 58.5±1.4 l h−1 for apparent clearance (CL/F), 310±6.92 l for volume of distribution (V/F), and 2.6±0.176 h−1 for first-order absorption constant (ka). The value for ka is associated with meal consumption within 2 h predose, at all other times ka was equivalent to an instantaneous bolus administration. The interindividual variabilities were 29% for CL/F, 20% for V/F, and 210% for ka. Over a dose range of 25–100 mg sildenafil, the pharmacokinetics exhibited dose proportionality. There was evidence of nonproportionality (40% increase on average) in relative bioavailability with respect to the 200-mg dose (P < 0.001) relative to the other doses. Age, AST concentration, and co-administration with CYP3A4 potential inhibitors significantly influenced CL/F of sildenafil (P < 0.001, for each relationship). For age and AST, the extent of the linear relationships (extrapolated from population average values) included a 4% decrease in CL/F for every decade increase and a 6% decrease in CL/F for every 10-unit increase, respectively. Following co-administration of CYP3A4 potential inhibitors, a 14% decrease in CL/F was estimated. Only body weight was found to significantly (P < 0.001) influence V/F (a 6% increase in V/F for every 10-kg increase). Conclusions The pharmacokinetics of, and covariate influences on, sildenafil in patients with erectile dysfunction were shown to be consistent with those demonstrated in phase I volunteer studies. PMID:11879259

Water Sampling While Under Way , Proceedings of a Symposium and Workshops, February 11-12, 1980.

DTIC Science & Technology

1980-01-01

W, and consequently W/R, will be small. To illustrate these points, values of kl, kA , and W are comparedin Table 1 for a typical, round, galvanized...7 TABLE I COMPARISON OF SAMPLER CABLE AND TYPICAL ELECTROMECHANICAL CABLE Characteristic k1 kA k W Electromechanical 0.40 1 0.40 1.5 t 2 Sampler...configurations obviously do not suffer in static (i.e., constant speed) performance since the factors k1 and kA are the same with or without the voids, assuming

Computing pKa Values with a Mixing Hamiltonian Quantum Mechanical/Molecular Mechanical Approach.

PubMed

Liu, Yang; Fan, Xiaoli; Jin, Yingdi; Hu, Xiangqian; Hu, Hao

2013-09-10

Accurate computation of the pKa value of a compound in solution is important but challenging. Here, a new mixing quantum mechanical/molecular mechanical (QM/MM) Hamiltonian method is developed to simulate the free-energy change associated with the protonation/deprotonation processes in solution. The mixing Hamiltonian method is designed for efficient quantum mechanical free-energy simulations by alchemically varying the nuclear potential, i.e., the nuclear charge of the transforming nucleus. In pKa calculation, the charge on the proton is varied in fraction between 0 and 1, corresponding to the fully deprotonated and protonated states, respectively. Inspired by the mixing potential QM/MM free energy simulation method developed previously [H. Hu and W. T. Yang, J. Chem. Phys. 2005, 123, 041102], this method succeeds many advantages of a large class of λ-coupled free-energy simulation methods and the linear combination of atomic potential approach. Theory and technique details of this method, along with the calculation results of the pKa of methanol and methanethiol molecules in aqueous solution, are reported. The results show satisfactory agreement with the experimental data.

Constraining Seasonal and Vertical Distributions of Planktonic Foraminifera for Paleoclimate Reconstruction Since MIS3 at the Axial Seamount, Juan de Fuca Ridge

NASA Astrophysics Data System (ADS)

Chen, S. L.; Ravelo, A. C.; Clague, D. A.

2015-12-01

The California Current is an upwelling region with dynamic interactions between circulation, biological productivity and ecology. A 77 cm piston push core was taken from the Juan de Fuca Ridge Axial Seamount using a Remotely Operated Vehicle (ROV) (2213m, 45.55º N, 130.08º W), an active submarine volcano ~480 km off Oregon's coast. Five radiocarbon dates indicate that the sediment ranges from 42.6 ka at 77 cm to 17.6 ka at 15 cm, with an average sediment accumulation rate of 2.47 cm/ka from 77-15 cm, and an average rate of 0.85 cm/ka during the postglacial period (<17.6 ka). Multiple species of planktic foraminifera from the core representing subtropical, subartic, and arctic fauna have been used to constrain changes in vertical and seasonal temperature since Marine Isotope Stage 3 (MIS3). Measurements of δ18O of the upwelling species Globigerina bulloides, the thermocline dwelling species Neogloboquadrina dutertrei, and the warm mixed-layer species Orbulina universa are offset from each other, reflecting vertical and seasonal variation among the planktonic foraminifera. Of the three species, G. bulloides shows the least variation in δ18O, possibly indicating that marked changes in temperature are masking changes in the δ18O of seawater due to global ice volume changes. G. bulloides and O. universa δ18O values are similar in MIS 3 and diverge with time, indicating the development of strong seasonal succession of species, since the last glacial maximum. Bulk nitrogen isotopes and nitrogen flux provide additional constraints on upwelling strength and insight into local biological productivity and nutrient dynamics. Obtaining Mg/Ca data will clarify the δ 18O interpretation except deep in the core where metal-bearing authigenic precipitates affect Mg concentrations. These climatic proxies together provide insight into how global climate change and local seamount volcanism impacts regional productivity in the California Current.

10Be concentrations of Red soils in Southwest Japan and its possibility of dating

NASA Astrophysics Data System (ADS)

Maejima, Y.; Matsuzaki, H.; Nakano, C.

2004-08-01

10Be concentrations of six Red soils distributed in Southwest Japan ranged from 0.8 × 108 to 2.7 × 109 atoms g-1, and minimum absolute ages were estimated by inventory of meteoric 10Be. The results are follows: Red soils on Toyota derived from granite (⩽25 ka), Kashii derived from Tertiary shale (⩽24 ka), Akiyoshidai derived from limestone (⩽110 ka), Okinawa Island derived from Kunigami gravel bed (⩽9 ka) and Ogasawara Island derived from agglomerate and Boninite (⩽22 and ⩽7 ka) were obtained, respectively. Soil age except with Akiyoshidai indicated younger age. It suggested that the loss of 10Be from the soil was caused by leaching of 10Be or by soil erosion, and 10Be is susceptible to leaching out from these Red soils under the humid climate condition such as Southwest Japan.

Pilot program on patient dosimetry in pediatric interventional cardiology in Chile

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ubeda, Carlos; Vano, Eliseo; Miranda, Patricia

2012-05-15

Purpose: The aim of this study was to present the results of a pilot program on patient dosimetry carried out in Chile during the last 5 yr, using a biplane x-ray angiography system settled for pediatrics. This research was conducted in Latin America under the auspices of the International Atomic Energy Agency (IAEA) supporting programs on radiological protection (RP) of patients. Methods: Patient age, gender, weight, height, number of cine series, total number of cine frames, fluoroscopy time, and two dosimetric quantities [air kerma-area product (P{sub ka}) and cumulative dose (CD) at the patient entrance reference point] were recorded formore » each procedure. Results: The study includes 544 patients grouped into four age groups. The distributions by age group were 150 for <1 yr; 203 for 1 to <5 yr; 97 for 5 to <10 yr; and 94 for 10 to <16 yr. Median values of P{sub ka} and CD for the four age groups were 0.94, 1.46, 2.13, and 5.03 Gy cm{sup 2} and 23.9, 26.8, 33.5, and 51.6 mGy, respectively. No significant statistical differences were found between diagnostic and therapeutic procedures. A moderate correlation (r = 0.64) was seen between P{sub ka} and patient weight. Conclusions: The dose values reported in this paper were lower than those published in the previous work for the same age groups as a result of the optimization actions carried out by cardiologists and medical physicists with the support of the IAEA. Methodology and results will be used as a starting point for a wider survey in Chile and Latin America with the goal to obtain regional diagnostic reference levels as recently recommended by the International Commission on Radiological Protection for interventional procedures.« less

Sr/Ca proxy sea-surface temperature reconstructions from modern and holocene Montastraea faveolata specimens from the Dry Tortugas National Park

USGS Publications Warehouse

Flannery, Jennifer A.; Poore, Richard Z.

2013-01-01

Sr/Ca ratios from skeletal samples from two Montastraea faveolata corals (one modern, one Holocene, ~6 Ka) from the Dry Tortugas National Park were measured as a proxy for sea-surface temperature (SST). We sampled coral specimens with a computer-driven triaxial micromilling machine, which yielded an average of 15 homogenous samples per annual growth increment. We regressed Sr/Ca values from resulting powdered samples against a local SST record to obtain a calibration equation of Sr/Ca = -0.0392 SST + 10.205, R = -0.97. The resulting calibration was used to generate a 47-year modern (1961-2008) and a 7-year Holocene (~6 Ka) Sr/Ca subannually resolved proxy record of SST. The modern M. faveolata yields well-defined annual Sr/Ca cycles ranging in amplitude from ~0.3 and 0.5 mmol/mol. The amplitude of ~0.3 to 0.5 mmol/mol equates to a 10-15°C seasonal SST amplitude, which is consistent with available local instrumental records. Summer maxima proxy SSTs calculated from the modern coral Sr/ Ca tend to be fairly stable: most SST maxima from 1961–2008 are 29°C ± 1°C. In contrast, winter minimum SST calculated in the 47-year modern time-series are highly variable, with a cool interval in the early to mid-1970s. The Holocene (~6 Ka) Montastraea faveolata coral also yields distinct annual Sr/Ca cycles with amplitudes ranging from ~0.3 to 0.6 mmol/mol. Absolute Sr/Ca values and thus resulting SST estimates over the ~7-year long record are similar to those from the modern coral. We conclude that Sr/Ca from Montastraea faveolata has high potential for developing subannually resolved Holocene SST records.

Follitropin receptors in rat testis. Characterization with enzymatically 125I-labeled human follitropin.

PubMed

Ketelslegers, J M; Catt, K J

1978-07-03

The interaction between enzymatically radioiodinated human follitropin and the follitropin receptors in testis homogenate was investigated in immature and adult rats. The 125I-labeled human follitropin exhibited high binding activity with specific binding of up to 17% in the presence of an excess of testis homogenate. Approx. 50% of the bound hormone could be eluted at pH 5, and the receptor purified tracer exhibited a 3.6-fold increase in binding activity when compared with the original tracer preparation. Quantitative analysis of equilibrium binding data was performed with corrections for the measured specific activity and maximum binding activity of the tracer hormone. The equilibrium association constants (Ka) determined 24 degrees C were not significantly different in immature and adult rat testis, and the mean value for Ka was 3.9 . 10(9) M-1. At 37 degrees C, the Ka value obtained using immature rat testis was 1.3 . 10(10) M-1. The association of 125I-labeled human follitropin with immature rat testis homogenate was time and temperature dependent. In the presence of an excess of unlabeled hormone, 30--60% of the preformed hormone . receptor complex was dissociated after 24 h incubation. A specific and sensitive radioligand-receptor assay for follitropin was developed using immature rat testis homogenate. The minimum detectable dose of purified human follitropin was 0.6 ng, and human urinary and pituitary follitropin, ovine follitropin and pregnant mare serum gonadotropin reacted in the assay with equivalent slopes. The potencies of highly purified pregnent mare serum gonadotropin and highly purified human follitropin were similar in the radioligand-receptor assay, consistent with the follitropin bioactivity of the equine gonadotropin.

Characterization of the proton binding sites of extracellular polymeric substances in an anaerobic membrane bioreactor.

PubMed

Liu, Yi; Chang, Sheng; Defersha, Fantahun M

2015-07-01

This paper focuses on the characterization of the chemical compositions and acidic constants of the extracellular polymeric substances (EPSs) in an anaerobic membrane bioreactor treating synthetic brewery wastewater by using chemical analysis, linear programming analysis (LPA) of titration data, and FT-IR analysis. The linear programming analysis of titration data revealed that the EPSs have proton binding sites with pKa values from pKa ≤ 6, between 6 and 7, and approximately 9.8. The strong acidic sites (pKa ≤ 6) and some weak acidic sites (7.5 < pKa < 9.0) were found to be readily removed by 0.45-μm membrane filtration. In addition, the FT-IR analysis confirmed the presence of proteins, carbohydrates, nucleic acids, and lipids in the EPS samples. Based on the FT-IR analysis and the main chemical functional groups at the bacterial cell surfaces, the identified proton binding sites were related to carboxyl, phosphate, and hydroxyl/amine groups with pKa values of 4.6 ± 0.7, 6.6 ± 0.01, and 9.7 ± 0.1, respectively, with the corresponding respective intensities of 0.31 ± 0.05, 0.96 ± 0.3, and 1.53 ± 0.3 mmole/g-EPS. The pKa values and intensities of the proton binding sites are the fundamental molecular properties of EPSs that affect the EPS charge, molecular interactions, and metal complexation characteristics. Determination of such properties can advance Derjaguin-Landau-Verwey-Overbeek (DLVO)-based concentration polarization modeling, facilitate the estimation of the osmotic pressure of the EPS concentration polarization layers, and lead to a deeper understanding of the role of metal complexation in membrane fouling. Copyright © 2015 Elsevier Ltd. All rights reserved.

40Ar/39Ar Dating of the Brunhes-Matuyama Geomagnetic Field Reversal.

PubMed

Baksi, A K; Hsu, V; McWilliams, M O; Farrar, E

1992-04-17

Magnetostratigraphic studies are widely used in conjunction with the geomagnetic polarity time scale (GPTS) to date events in the range 0 to 5 million years ago. A critical tie point on the GPTS is the potassium-argon age of the most recent (Brunhes-Matuyama) geomagnetic field reversal. Astronomical values for the forcing frequencies observed in the oxygen isotope record in Ocean Drilling Project site 677 suggest that the age of this last reversal is 780 ka (thousand years ago), whereas the potassium-argon-based estimate is 730 ka. Results from 4039; Ar incremental heating studies on a series of lavas from Maui that straddle the Brunhes-Matuyama reversal give an age of 783 + 11 ka, in agreement with the astronomically derived value. The astronomically based technique appears to be a viable tool for dating young sedimentary sequences.

The IUPAC aqueous and non-aqueous experimental pKa data repositories of organic acids and bases.

PubMed

Slater, Anthony Michael

2014-10-01

Accurate and well-curated experimental pKa data of organic acids and bases in both aqueous and non-aqueous media are invaluable in many areas of chemical research, including pharmaceutical, agrochemical, specialty chemical and property prediction research. In pharmaceutical research, pKa data are relevant in ligand design, protein binding, absorption, distribution, metabolism, elimination as well as solubility and dissolution rate. The pKa data compilations of the International Union of Pure and Applied Chemistry, originally in book form, have been carefully converted into computer-readable form, with value being added in the process, in the form of ionisation assignments and tautomer enumeration. These compilations offer a broad range of chemistry in both aqueous and non-aqueous media and the experimental conditions and original reference for all pKa determinations are supplied. The statistics for these compilations are presented and the utility of the computer-readable form of these compilations is examined in comparison to other pKa compilations. Finally, information is provided about how to access these databases.

The IUPAC aqueous and non-aqueous experimental pKa data repositories of organic acids and bases

NASA Astrophysics Data System (ADS)

Slater, Anthony Michael

2014-10-01

Accurate and well-curated experimental pKa data of organic acids and bases in both aqueous and non-aqueous media are invaluable in many areas of chemical research, including pharmaceutical, agrochemical, specialty chemical and property prediction research. In pharmaceutical research, pKa data are relevant in ligand design, protein binding, absorption, distribution, metabolism, elimination as well as solubility and dissolution rate. The pKa data compilations of the International Union of Pure and Applied Chemistry, originally in book form, have been carefully converted into computer-readable form, with value being added in the process, in the form of ionisation assignments and tautomer enumeration. These compilations offer a broad range of chemistry in both aqueous and non-aqueous media and the experimental conditions and original reference for all pKa determinations are supplied. The statistics for these compilations are presented and the utility of the computer-readable form of these compilations is examined in comparison to other pKa compilations. Finally, information is provided about how to access these databases.

Sea-level records at ~80 ka from tectonically stable platforms: Florida and Bermuda

USGS Publications Warehouse

Ludwig, K. R.; Muhs, D.R.; Simmons, K.R.; Halley, R.B.; Shinn, E.A.

1996-01-01

Studies from technically active coasts on New Guinea and Barbados have suggested that sea level at ???80 ka was significantly lower than present, whereas data from the Atlantic and Pacific coasts of North America indicate an ???80 ka sea level close to that of the present. We determined ages of corals from a shallow submerged reef off the Florida Keys and an emergent marine deposit on Bermuda. Both localities are on tectonically stable platforms distant from plate boundaries. Uranium-series ages show that corals at both localities grew during the ???80 ka sea-level highstand, and geologic data show that sea level at that time was no lower than 7-9 m below present (Florida) and may have been 1-2 m above present (Bermuda). The ice-volume discrepancy of the 80 ka sea-level estimates is greater than the volume of the Greenland or West Antarctic ice sheets. Comparison of our ages with high-latitude insolation values indicates that the sea-level stand near the present at ???80 ka could have been orbitally forced.

Holocene paleosecular variation from dated lava flows on Maui (Hawaii)

NASA Astrophysics Data System (ADS)

Herrero-Bervera, Emilio; Valet, Jean-Pierre

2007-05-01

Low inclination and low secular variation seem to be present for at least the past 5 Myear in central Pacific. The period covering the past 10 kyear is crucial to the study of the field variability and to fill the gap between historical field measurements and long-term paleomagnetic records. We have conducted a paleomagnetic study of 13 sites of basaltic lava flows from Maui island with 14C ages between 10.3 and 0.2 ka. Two other sites dated at 45 and 730 ka were also sampled. Eight to 10 samples from each site were demagnetized using thermal treatment and companion specimens from the same samples were demagnetized by alternating fields (af). Thermomagnetic and hysteresis measurements indicated that magnetite (575 °C) in fine grains was the dominant magnetic carrier, although in many cases we also observed a low-temperature phase which is likely carried by titanomagnetite with low titanium content. The existence of relatively high coercivities associated with these two mineralogical phases generated overlapping components which could not be properly isolated using af demagnetization. Successful results were obtained after thermal demagnetization for 13 sites with a mean inclination of 36.9 ± 4°. The mean inclination (inc. = 36.3°) of the eleven sites younger than 10.5 ka is also very close to the value (37°) of the geocentric axial dipole (GAD) at the site latitude, but the angular dispersion of the virtual geomagnetic poles (VGPs) about the spin axis (9° with N = 13 and 6.7° with N = 11) is significantly lower than the predictions of the models of paleosecular variation at this latitude. The inclination variations for the past 10 kyear are in excellent agreement with the very detailed dataset which has previously been obtained from the big island of Hawaii. The mean inclination of all volcanic records ( N = 132) is 1.8° lower than expected, but this is likely caused by the lack of records between 5 and 7 ka B.P. We note also that the inclinations from Lake Waiau sediments (big island) are shallower than those of the volcanic records (Mauna Kea, Hawaii) and were thus probably affected by compaction. We infer that there is no striking evidence for an inclination anomaly under Hawaii during this period, being aware of the need for additional records covering at least the 5-7 ka B.P. time interval. The absence of a systematic deviation going beyond the dispersion of the inclinations obtained for the past millions of years neither pleads for a significant long-term persistent anomaly. However, all studies report a low dispersion of the VGPs which must reflect low secular variation.

Setting Age Limits for TT-OSL Dating - the Local Effect

NASA Astrophysics Data System (ADS)

Faershtein, G.; Porat, N.; Guralnik, B.; Matmon, A.

2017-12-01

Luminescence dating techniques, especially Optically Stimulated Luminescence (OSL) on quartz, are widely used for dating middle Pleistocene to late Holocene sediments from different geological settings. The dating limit of a particular luminescence method depends on signal saturation and its thermal stability. The OSL signal saturates at doses of 200 Gy, equivalent to ages of 150-300 ka. Thermally Transferred OSL (TT-OSL) is a developmental technique, which potentially extends the luminescence dating range up to 1000 ka. For the Chinese Loess Plateau, experiments have shown that the natural TT-OSL signal saturates at 2200 Gy (Chapot et al., 2016). Regarding thermal stability, different studies report a wide range of estimates (0.24-861 Ma), suggesting that the thermal lifetime of TT-OSL is (i) currently poorly constrained, and (ii) may vary both by sample and region. Here, we investigated the dating limit of TT-OSL, using quartz of Nilotic origin (Israel), obtained from two sediment sections of similar depth but different dose rates. Natural dose response curves (DRC) of the TT-OSL signal were constructed for each section separately. In both sections, luminescence intensity grows sub-linearly up to 450 Gy, beyond which it remains constant with depth. The absence of equivalent doses (De) over 600 Gy, at both sections (as well as elsewhere regionally), suggest that TT-OSL signal saturation may be an intrinsic property, related to quartz provenance, and independent of the specific ionizing dose rate at each section. The thermal stability of TT-OSL was investigated on a modern sample from one section, using a combination of analytical techniques (varying heating rates, and isothermal storage). The obtained TT-OSL lifetimes range between 105-107 ka, and reinforce a significant inter sample variability. A synthesis of our results suggests that TT-OSL ages of Nilotic quartz derived from De values over 450 Gy, are likely underestimates, and should be treated as minimum ages. The limiting value of 600 Gy for local quartz TT-OSL is likely representative of a steady-state between TT-OSL trap filling due to ionizing radiation, and the concurrent thermal empting of these traps.

40Ar/39Ar chronology and paleomagnetism of Quaternary basaltic lavas from the Perşani Mountains (East Carpathians)

NASA Astrophysics Data System (ADS)

Panaiotu, C. G.; Jicha, B. R.; Singer, B. S.; Ţugui, A.; Seghedi, I.; Panaiotu, A. G.; Necula, C.

2013-08-01

Quaternary volcanism in the Perşani Mountains forms an Na-alkali basaltic province inside the bend area of the Carpathians in the southeastern part of Europe. Previous K-Ar ages and paleomagnetic data reveal several transitional virtual geomagnetic poles, which were tentatively associated with the Cobb Mountain subchron and a Brunhes chron excursion. We report a new paleomagnetic and rock-magnetic study coupled with 40Ar/39Ar geochronology to better constrain the age of geomagnetic reversals or excursions that might be recorded and the timing of volcanism. Of the paleomagnetic directions obtained from sampled lava flows 4 are reversed polarity, 19 are normal polarity and 16 have transitional polarity. 40Ar/39Ar plateau ages determined from incremental heating experiments on groundmass indicate that two of the reversely magnetized lavas erupted at 1142 ± 41 and 800 ± 25 ka, four of the normally magnetized lavas erupted at 1060 ± 10, 1062 ± 24, 684 ± 21, and 683 ± 28 ka, and two transitionally magnetized lavas formed at 1221 ± 11 and 799 ± 21 ka. Both the new 40Ar/39Ar ages and the paleomagnetic data suggest at least five episodes of volcanic activity with the most active periods during the Jaramillo and Brunhes chrons. This results shows that the last phases of alkalic and calc-alkaline magmatism in the South-East Carpathians were contemporaneous. The age of the older transitionally magnetized lava flow is within error of recent unspiked K-Ar and astrochronologic ages for the reversal that defines the onset of the Cobb Mountain normal polarity subchron. The age of the younger transitional lava is similar to that of an excursion that preceded the Matuyama-Brunhes polarity reversal and which has come to be known as the Matuyama-Brunhes precursor. Omitting the excursion data, the dispersion of the virtual geomagnetic poles (around 19°) is larger than the expected value around 45°N from the global compilation, but closer to the value obtained only from the Time Averaged geomagnetic Field Initiative studies.

Calculation of the Transition Matrix for the Scattering of Acoustic Waves from a Thin Elastic Spherical Shell Using the ATILA Finite Element Code

DTIC Science & Technology

1994-03-01

products of radial Hankel functions and spherical harmonics. The chosen driving frequency was 474 Hz, corresponding to a value of ka 1, where k is the...spherical harmonics. The chosen driving frequency was 474 Hz, corresponding to a value of ka = 1, where k is the wavenumber of sound in water and a is...wife Adriana for her support, understanding, and for her help in typing this thesis. vi I. INTRODUCTION The utilization of sonar systems in

Microsatellite instability in keratoacanthoma, a benign skin tumor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Honchel, R.; Halling, K.C.; Pittelkow, M.R.

1994-09-01

Keratocanthoma (KA) is a benign, spontaneously regressing epithelial tumor of the skin. KA is generally sporadic but also occurs in patients with the Muir-Torre syndrome (MTS), an inherited disorder characterized by the development in an individual of at least one sebaceous tumor and one visceral malignancy (usually colorectal cancer). As a result of the recent identification of microsatellite instability (MIN) in a KA from a patient with MTS and because of the benign nature of these tumors, we surveyed a group of randomly selected KA for MN. Paraffin-embedded tissue from 53 patients were analyzed for MIN. Of the 53 KA`smore » examined, 6 demonstrated MIN at two or more loci. Two of the patients with MIN+ KA also had colonic adenocarcinomas, and paraffin-embedded tissue obtained from one of these patients also demonstrated MIN at multiple loci. Interestingly, two patients with KA that did not demonstrate MIN had colon tumors that did exhibit MIN. Of the 8 patients demonstrating MIN in at least one tumor, one has a history consistent with hereditary nonpolyposis colorectal cancer (HNPCC), two have MTS, and three additional patients have features suggestive, but not diagnostic, of HNPCC. Two KA that were MIN+ appear to be sporadic since the patients had no associated visceral or sebaceous tumors, and no apparent family history of colon cancer. A 2 bp somatic deletion in exon 3 of the hMSH2 gene was identified in one of the sporadic MIN+ KA, suggesting that the genes responsible for HNPCC are also responsible for MIN in KA.« less

Volcanic CO2 Emissions and Glacial Cycles: Coupled Oscillations

NASA Astrophysics Data System (ADS)

Burley, J. M.; Huybers, P. J.; Katz, R. F.

2016-12-01

Following the mid-Pleistocene transition, the dominant period of glacial cycles changed from 40 ka to 100 ka. It is broadly accepted that the 40 ka glacial cycles were driven by cyclical changes in obliquity. However, this forcing does not explain the 100 ka glacial cycles. Mechanisms proposed for 100 ka cycles include isostatic bed depression and proglacial lakes destabilising the Laurentide ice sheet, non-linear responses to orbital eccentricity, and Antarctic ice sheets influencing deep-ocean stratification. None of these are universally accepted. Here we investigate the hypothesis that variations in volcanic CO2 emissions can cause 100 ka glacial cycles. Any proposed mechanism for 100 ka glacial cycles must give the Earth's climate system a memory of 10^4 - 10^5years. This timescale is difficult to achieve for surface processes, however it is possible for the solid Earth. Recent work suggests volcanic CO2 emissions change in response to glacial cycles [1] and that there could be a 50 ka delay in that response [2]. Such a lagged response could drive glacial cycles from 40 ka cycles to an integer multiple of the forcing period. Under what conditions could the climate system admit such a response? To address this, we use a simplified climate model modified from Huybers and Tziperman [3]. Our version comprises three component models for energy balance, ice sheet growth and atmospheric CO2 concentration. The model is driven by insolation alone with other components varying according to a system of coupled, differential equations. The model is run for 500 ka to produce several glacial cycles and the resulting changes in global ice volume and atmospheric CO2 concentration.We obtain a switch from 40 ka to 100 ka cycles as the volcanic CO2 response to glacial cycles is increased. These 100 ka cycles are phase-locked to obliquity, lasting 80 or 120 ka. Whilst the MOR response required (in this model) is larger than plausible estimates based on [2], it illustrates the potential of MOR CO2 feedbacks to generate 100 ka glacial cycles [1] Huybers & Langmuir, 2009[2] Burley & Katz, 2015 [3] Huybers & Tziperman, 2008

The accretion rate of extraterrestrial 3He based on oceanic 230Th flux and the relation to Os isotope variation over the past 200,000 years in an Indian Ocean core

NASA Astrophysics Data System (ADS)

Marcantonio, Franco; Turekian, Karl K.; Higgins, Sean; Anderson, Robert F.; Stute, Martin; Schlosser, Peter

1999-07-01

In the eastern equatorial Indian Ocean, the flux of extraterrestrial 3He, a proxy of interplanetary dust particles (IDPs), has been relatively constant over the past 200 ka. The flux is equal to (1.1±0.4)×10 -12 cm 3 STP cm -2 ka -1, a value obtained using the xs 230Th profiling method. Variations in mass accumulation rates (MARs) derived assuming a constant extraterrestrial 3He flux have a 40-ka periodicity similar to that observed in the δ 18O-derived MARs. This frequency is similar to that of the Earth's obliquity. Measured 187Os/ 188Os ratios are less radiogenic than present-day seawater (0.49-0.98), reflecting the mixing of Os derived from extraterrestrial, terrigenous and hydrogenous sources. When coupled with He data measured on the same samples, Os isotope data yield important information about the terrigenous component supplied to the eastern equatorial Indian Ocean. The amount of Os in the sample derived from the extraterrestrial component can be deduced with the help of the helium systematics. Once corrected for the extraterrestrial component of Os, Os isotope signatures, in conjunction with the 4He concentrations, suggest a supply of terrigenous material from Indonesian ultramafic and Himalayan crustal sources that clearly varies through time.

Radiometric 81Kr dating identifies 120,000-year-old ice at Taylor Glacier, Antarctica

PubMed Central

Buizert, Christo; Baggenstos, Daniel; Jiang, Wei; Purtschert, Roland; Petrenko, Vasilii V.; Lu, Zheng-Tian; Müller, Peter; Kuhl, Tanner; Lee, James; Severinghaus, Jeffrey P.; Brook, Edward J.

2014-01-01

We present successful 81Kr-Kr radiometric dating of ancient polar ice. Krypton was extracted from the air bubbles in four ∼350-kg polar ice samples from Taylor Glacier in the McMurdo Dry Valleys, Antarctica, and dated using Atom Trap Trace Analysis (ATTA). The 81Kr radiometric ages agree with independent age estimates obtained from stratigraphic dating techniques with a mean absolute age offset of 6 ± 2.5 ka. Our experimental methods and sampling strategy are validated by (i) 85Kr and 39Ar analyses that show the samples to be free of modern air contamination and (ii) air content measurements that show the ice did not experience gas loss. We estimate the error in the 81Kr ages due to past geomagnetic variability to be below 3 ka. We show that ice from the previous interglacial period (Marine Isotope Stage 5e, 130–115 ka before present) can be found in abundance near the surface of Taylor Glacier. Our study paves the way for reliable radiometric dating of ancient ice in blue ice areas and margin sites where large samples are available, greatly enhancing their scientific value as archives of old ice and meteorites. At present, ATTA 81Kr analysis requires a 40–80-kg ice sample; as sample requirements continue to decrease, 81Kr dating of ice cores is a future possibility. PMID:24753606

Radiometric 81Kr dating identifies 120,000-year-old ice at Taylor Glacier, Antarctica.

PubMed

Buizert, Christo; Baggenstos, Daniel; Jiang, Wei; Purtschert, Roland; Petrenko, Vasilii V; Lu, Zheng-Tian; Müller, Peter; Kuhl, Tanner; Lee, James; Severinghaus, Jeffrey P; Brook, Edward J

2014-05-13

We present successful (81)Kr-Kr radiometric dating of ancient polar ice. Krypton was extracted from the air bubbles in four ∼350-kg polar ice samples from Taylor Glacier in the McMurdo Dry Valleys, Antarctica, and dated using Atom Trap Trace Analysis (ATTA). The (81)Kr radiometric ages agree with independent age estimates obtained from stratigraphic dating techniques with a mean absolute age offset of 6 ± 2.5 ka. Our experimental methods and sampling strategy are validated by (i) (85)Kr and (39)Ar analyses that show the samples to be free of modern air contamination and (ii) air content measurements that show the ice did not experience gas loss. We estimate the error in the (81)Kr ages due to past geomagnetic variability to be below 3 ka. We show that ice from the previous interglacial period (Marine Isotope Stage 5e, 130-115 ka before present) can be found in abundance near the surface of Taylor Glacier. Our study paves the way for reliable radiometric dating of ancient ice in blue ice areas and margin sites where large samples are available, greatly enhancing their scientific value as archives of old ice and meteorites. At present, ATTA (81)Kr analysis requires a 40-80-kg ice sample; as sample requirements continue to decrease, (81)Kr dating of ice cores is a future possibility.

The Crystal Structure of a hCA VII Variant Provides Insights into the Molecular Determinants Responsible for Its Catalytic Behavior.

PubMed

Buonanno, Martina; Di Fiore, Anna; Langella, Emma; D'Ambrosio, Katia; Supuran, Claudiu T; Monti, Simona Maria; De Simone, Giuseppina

2018-05-24

Although important progress has been achieved in understanding the catalytic mechanism of Carbonic Anhydrases, a detailed picture of all factors influencing the catalytic efficiency of the various human isoforms is still missing. In this paper we report a detailed structural study and theoretical pKa calculations on a hCA VII variant. The obtained data were compared with those already known for another thoroughly investigated cytosolic isoform, hCA II. Our structural studies show that in hCA VII the network of ordered water molecules, which connects the zinc bound solvent molecule to the proton shuttle His64, is altered compared to hCA II, causing a reduction of the catalytic efficiency. Theoretical calculations suggest that changes in solvent network are related to the difference in pKa of the proton shuttle in the two enzymes. The residue that plays a major role in determining the diverse pKa values of the proton shuttle is the one in position four, namely His for hCA II and Gly for hCA VII. This residue is located on the protein surface, outside of the active site cavity. These findings are in agreement with our previous studies that highlighted the importance of histidines on the protein surface of hCA II (among which His4) as crucial residues for the high catalytic efficiency of this isoform.

Paleomagnetism of the Pleistocene Tequila Volcanic Field (Western Mexico)

NASA Astrophysics Data System (ADS)

Rodríguez Ceja, M.; Goguitchaichvili, A.; Calvo-Rathert, M.; Morales-Contreras, J.; Alva-Valdivia, L.; Rosas Elguera, J.; Urrutia Fucugauchi, J.; Delgado Granados, H.

2006-10-01

This paper presents new paleomagnetic results from 24 independent cooling units in Tequila area (western Trans-Mexican Volcanic Belt). These units were recently dated by means of state-of-the-art 40Ar-39Ar method (Lewis-Kenedy et al., 2005) and span from 1130 to 150 ka. The characteristic paleodirections are successfully isolated for 20 cooling units. The mean paleodirection, discarding intermediate polarity sites, is I = 29.6°, D = 359.2°, k = 26, α95 = 7.1°, n = 17, which corresponds to the mean paleomagnetic pole position Plat = 85.8°, Plong = 84.3°, K = 27.5, A95 = 6.9°. These directions are practically undistinguishable from the expected Plestocene paleodirections, as derived from reference poles for the North American polar wander curve and in agreement with previously reported directions from western Trans-Mexican Volcanic Belt. This suggests that no major tectonic deformation occurred in studied area since early-middle Plestocene to present. The paleosecular variation is estimated trough the study of the scatter of virtual geomagnetic poles giving SF = 15.4 with SU = 19.9 and SL = 12.5 (upper and lower limits respectively). These values are consistent with those predicted by the latitude-dependent variation model of McFadden et al. (1991) for the last 5 Myr. The interesting feature of the paleomagnetic record obtained here is the occurrence of an intermediate polarity at 671± 13 ka which may correspond the worldwide observed Delta excursion at about 680-690 ka. This gives the volcanic evidence of this event. Two independent lava flows dated as 362± 13 and 354± 5 ka respectively, yield transitional paleodirections as well, probably corresponding to the Levantine excursion.

Development of Monopole Interaction Models for Ionic Compounds. Part I: Estimation of Aqueous Henry's Law Constants for Ions and Gas Phase pKa Values for Acidic Compounds.

PubMed

Hilal, S H; Saravanaraj, A N; Carreira, L A

2014-02-01

The SPARC (SPARC Performs Automated Reasoning in Chemistry) physicochemical mechanistic models for neutral compounds have been extended to estimate Henry's Law Constant (HLC) for charged species by incorporating ionic electrostatic interaction models. Combinations of absolute aqueous pKa values, relative pKa values in the gas phase, and aqueous HLC for neutral compounds have been used to develop monopole interaction models that quantify the energy differences upon moving an ionic solute molecule from the gas phase to the liquid phase. Inter-molecular interaction energies were factored into mechanistic contributions of monopoles with polarizability, dipole, H-bonding, and resonance. The monopole ionic models were validated by a wide range of measured gas phase pKa data for 450 acidic compounds. The RMS deviation error and R(2) for the OH, SH, CO2 H, CH3 and NR2 acidic reaction centers (C) were 16.9 kcal/mol and 0.87, respectively. The calculated HLCs of ions were compared to the HLCs of 142 ions calculated by quantum mechanics. Effects of inter-molecular interaction of the monopoles with polarizability, dipole, H-bonding, and resonance on acidity of the solutes in the gas phase are discussed. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative accuracy of the simplified strong ion equation to predict serum pH in dogs.

PubMed

Cave, N J; Koo, S T

2015-01-01

Electrochemical approach to the assessment of acid-base states should provide a better mechanistic explanation of the metabolic component than methods that consider only pH and carbon dioxide. Simplified strong ion equation (SSIE), using published dog-specific values, would predict the measured serum pH of diseased dogs. Ten dogs, hospitalized for various reasons. Prospective study of a convenience sample of a consecutive series of dogs admitted to the Massey University Veterinary Teaching Hospital (MUVTH), from which serum biochemistry and blood gas analyses were performed at the same time. Serum pH was calculated (Hcal+) using the SSIE, and published values for the concentration and dissociation constant for the nonvolatile weak acids (Atot and Ka ), and subsequently Hcal+ was compared with the dog's actual pH (Hmeasured+). To determine the source of discordance between Hcal+ and Hmeasured+, the calculations were repeated using a series of substituted values for Atot and Ka . The Hcal+ did not approximate the Hmeasured+ for any dog (P = 0.499, r(2) = 0.068), and was consistently more basic. Substituted values Atot and Ka did not significantly improve the accuracy (r(2) = 0.169 to <0.001). Substituting the effective SID (Atot-[HCO3-]) produced a strong association between Hcal+ and Hmeasured+ (r(2) = 0.977). Using the simplified strong ion equation and the published values for Atot and Ka does not appear to provide a quantitative explanation for the acid-base status of dogs. Efficacy of substituting the effective SID in the simplified strong ion equation suggests the error lies in calculating the SID. Copyright © 2015 The Authors. Journal of Veterinary Internal Medicine published by Wiley Periodicals, Inc. on behalf of the American College of Veterinary Internal Medicine.

High Power High Efficiency Ka-Band Power Combiners for Solid-State Devices

NASA Technical Reports Server (NTRS)

Freeman, Jon C.; Wintucky, Edwin G.; Chevalier, Christine T.

2006-01-01

Wide-band power combining units for Ka-band are simulated for use as MMIC amplifier applications. Short-slot couplers as well as magic-tees are the basic elements for the combiners. Wide bandwidth (5 GHz) and low insertion (approx.0.2 dB) and high combining efficiencies (approx.90 percent) are obtained.

pKa of fentanyl varies with temperature: implications for acid-base management during extremes of body temperature.

PubMed

Thurlkill, Richard L; Cross, David A; Scholtz, J Martin; Pace, C Nick

2005-12-01

The pKa of fentanyl has not been measured previously at varying extremes of body temperature. The goal of this laboratory investigation was to test the hypothesis that the pKa of fentanyl changes with temperature. The investigation involved measuring the pKa values of aqueous fentanyl at varying temperatures. The investigation was conducted in a controlled laboratory environment. No human or animal subjects were involved. Because no live subjects were involved in the investigation, no interventions were necessary. This paper reports the effect of temperature on the pKa of fentanyl. The pKa of aqueous fentanyl was measured at 15 degrees C, 25 degrees C, 37 degrees C, 42 degrees C, and 47.5 degrees C by potentiometric titration in 0.01 mmol/L of potassium chloride after extensive degassing. Data were analyzed using the least squares method with an appropriately fitting equation. The pKa of fentanyl was found to change in a similar manner to the neutral point of water at varying temperatures. This finding has implications for the bioavailability of fentanyl at extremes of body temperature in association with the clinical acid-base management of the patient. Clinical implications for differing methods of intraoperative acid-base management at varying temperatures are discussed.

Modification of wave-cut and faulting-controlled landforms.

USGS Publications Warehouse

Hanks, T.C.; Bucknam, R.C.; Lajoie, K.R.; Wallace, R.E.

1984-01-01

From a casual observation that the form of degraded fault scarps resembles the error function, this investigation proceeds through an elementary diffusion equation representation of landform evolution to the application of the resulting equations to the modern topography of scarplike landforms. The value of K = 1 GKG (K = 'mass diffusivity'; 1 GKG = 1m2/ka) may be generally applicable as a good first approximation, to the modification of alluvial terranes within the semiarid regions of the western United States. The Lake Bonneville shoreline K is the basis for dating four sets of fault scarps in west-central Utah. The Drum Mountains fault scarps date at 3.6 to 5.7 ka BP. Fault scarps along the eastern base of the Fish Springs Range are very young, 3 ka BP. We estimate the age of fault scarps along the western flank of the Oquirrh Mountains to be 32 ka B.P. Fault scarps along the NE margin of the Sheeprock Mountains are even older, 53 ka BP. -from Authors

pKa cycling of the general acid/base in glycoside hydrolase families 33 and 34.

PubMed

Yu, Haibo; Griffiths, Thomas M

2014-03-28

Glycoside hydrolase families 33 and 34 catalyse the hydrolysis of terminal sialic acid residues from sialyl oligosaccharides and glycoconjugates with a net retention of the stereochemistry at the anomeric centre. It is generally believed that the conserved aspartic acid in the active site functions as a general acid to protonate the hydroxyl group of the departing aglycone during glycosylation, and then as a general base to facilitate the nucleophilic attack of the water molecule on the intermediate state during the deglycosylation reaction. The dual role of the general acid/base places specific demands upon its protonation state, and thus pKa values. However, it is not fully understood how this catalytic residue can achieve such pKa cycling during catalysis. We present both MM and combined QM/MM simulations to characterise the pKa values of the proposed catalytic general acid/base in the glycoside hydrolase families 33 and 34. Collectively, our study suggests that the binding of anionic substrates and the local solvation properties along with the neutralisation of the nearby glutamic acid upon glycosylation modulate the electrostatic environment around the general acid/base to achieve its proper protonation states.

Developing hybrid approaches to predict pKa values of ionizable groups

PubMed Central

Witham, Shawn; Talley, Kemper; Wang, Lin; Zhang, Zhe; Sarkar, Subhra; Gao, Daquan; Yang, Wei

2011-01-01

Accurate predictions of pKa values of titratable groups require taking into account all relevant processes associated with the ionization/deionization. Frequently, however, the ionization does not involve significant structural changes and the dominating effects are purely electrostatic in origin allowing accurate predictions to be made based on the electrostatic energy difference between ionized and neutral forms alone using a static structure. On another hand, if the change of the charge state is accompanied by a structural reorganization of the target protein, then the relevant conformational changes have to be taken into account in the pKa calculations. Here we report a hybrid approach that first predicts the titratable groups, which ionization is expected to cause conformational changes, termed “problematic” residues, then applies a special protocol on them, while the rest of the pKa’s are predicted with rigid backbone approach as implemented in multi-conformation continuum electrostatics (MCCE) method. The backbone representative conformations for “problematic” groups are generated with either molecular dynamics simulations with charged and uncharged amino acid or with ab-initio local segment modeling. The corresponding ensembles are then used to calculate the pKa of the “problematic” residues and then the results are averaged. PMID:21744395

Photoelectric return-stroke velocity and peak current estimates in natural and triggered lightning

NASA Technical Reports Server (NTRS)

Mach, Douglas M.; Rust, W. David

1989-01-01

Two-dimensional photoelectric return stroke velocities from 130 strokes are presented, including 86 negative natural, 41 negative triggered, one positive triggered, and two positive natural return strokes. For strokes starting near the ground and exceeding 500 m in length, the average velocity is 1.3 + or - 0.3 X 10 to the 8th m/s for natural return strokes and 1.2 + or - 0.3 X 10 to the 8th m/s for triggered return strokes. For strokes with lengths less than 500 m, the average velocities are slightly higher. Using the transmission line model (TLM), the shortest segment one-dimensional return stroke velocity, and either the maximum or plateau electric field, it is shown that natural strokes have a peak current distribution that is lognormal with a median value of 16 kA (maximum E) or 12 kA (plateau E). Triggered lightning has a medium peak current value of 21 kA (maximum E) or 15 kA (plateau E). Correlations are found between TLM peak currents and velocities for triggered and natural subsequent return strokes, but not between TLM peak currents and natural first return stroke velocities.

On the Basicity of 8-Phenylsulfanyl Quipazine Derivatives: New Potential Serotonergic Agents.

PubMed

Pieńko, T; Taciak, P P; Mazurek, A P

2015-07-09

A protonation state of serotonergic ligands plays a crucial role in their pharmacological activity. In this research, the basicity of 8-phenylsulfanyl quipazine derivatives as new potential serotonergic agents was studied. The most favorable protonation sites were determined in the gas and aqueous phases. In water, a solvation effect promoting the protonation of the N3 atom overcomes a positive charge delocalization phenomenon favoring a N1 atom protonation. The most stable conformations of neutral and protonated molecules in gas and water were found. It was demonstrated that a diprotonation reaction may occur. The most favorable among the diprotonated structures is the molecule with the N1 and N3 atoms protonated. A calculation of the pKa and pKa2 in water of a set of monosubstituted 8-phenylsulfanyl quipazine derivatives was performed using B3LYP/6-31G(d) and the SMD continuum solvation model. Enthalpic and entropic contributions to the pKa and pKa2 in gas and water were separated for a rationalization of a substituent effect on values of the pKa and pKa2. The relationship of the proton affinity and the solvation enthalpy in water with some reactivity descriptors, such as the Fukui function, the molecular electrostatic potential (MEP), and the global softness, was investigated. The order of the pKa values is the most controlled by the entropy. The diprotonation reaction, despite having an unfavorable enthalpy in water, is driven entropically. Final state effects in the diprotonated species were analyzed with the triadic formula. Results of a calculation of the theoretical basicity of the 8-phenylsulfanyl quipazines indicate that they should be monoprotonated on the N3 atom in the CNS environment. Diprotonation of the studied compounds may occur in very acidic body fluids such as the gastric juice.

IRD evidence for Heinrich Events H1 and H2 on the NJ Margin

NASA Astrophysics Data System (ADS)

Christensen, B. A.; Calabrese, J.; O'Neill, C.; Goff, J. A.

2011-12-01

Recent seismic reflection studies suggest icebergs grounded on the late Pleistocene New Jersey margin (Goff and Austin, 2009) during Heinrich events H1 (~17 cal Ka), H2 (~23 cal Ka), H3 (~30 cal Ka) and H4 (~37 cal Ka). We tested this hypothesis by analyzing sediments on the upper NJ continental slope, near the area where icebergs were found. Ocean Drilling Program Site 1073A is located at 39°13.5214'N, 72°16.5461'W in 639 m water depth. The greater water depth increases the likelihood of preservation and improves the stratigraphic control. We obtained elemental measurements for Site 1073A Cores 1-6 using the X-ray Fluorescence (XRF) Core Scanner at the MARUM IODP core repository, University of Bremen. Cores were scanned at 10kV and 30kV to obtain a full suite of elements for analysis, with XRF data collected between 1 and 10 cm intervals. The values are reported in areas for the elements and were then converted to elemental ratios (Ca/Sr, Si/Sr, K/Al, and Si/Ti) for analysis. The origin of a Heinrich layer within an IRD belt can be identified by geochemical measures along with magnetic susceptibility and the presence of detrital materials that reflect its provenance (Hemming, 2004). Following analyses for Atlantic Ocean IRD by Hodell et al. (2008), higher Si/Sr values indicate abundant detrital silicates and low biogenic carbonate. Abundant detrital carbonate is identified by higher Ca/Sr values. K/Al may be used as a proxy for weathered matter being deposited and is a good indicator of terrigenous material (Yarincik, 2000). Si/Ti ratios may be used as a proxy for organic and siliceous productivity (Agnihotri, 2008). The elemental analysis was ground-truthed with grain size analysis at 10 cm intervals. Grain size analysis reveals large particles in a finer matrix at 123 cm and 284 cm. We interpret these as IRD. A linear sedimentation age model places the IRD around the time of Heinrich events H1 and H2. Age control is provided for the late Pleistocene principally by radiocarbon methods (McHugh and Olsson, 2002); however, the age model is not unequivocal so we present results for a few interpretations (linear sedimentation rates, and modeled). Nonetheless, the IRD is consistent with the timing of H1 and H2. While the IRD are obvious from the grain size analysis, we were not able to identify IRD from XRF elemental analyses. This may because the sediments are derived locally rather than transported from the higher latitudes, rendering IRD identification a function of grain size (anomalously large particles in a marine setting) rather than geochemistry. Alternatively, the particles were not close enough to the surface to impact the XRF response. This study provides further evidence for the presence of icebergs on the late Pleistocene NJ margin.

Perforating elastic fibers ('elastic fiber trapping') in the differentiation of keratoacanthoma, conventional squamous cell carcinoma and pseudocarcinomatous epithelial hyperplasia.

PubMed

Shah, Kabeer; Kazlouskaya, Viktoryia; Lal, Karan; Molina, David; Elston, Dirk M

2014-02-01

Keratoacanthoma (KA), an epithelial neoplasm occurring in sun-exposed skin of the elderly, is considered a well-differentiated form of conventional squamous cell carcinoma (SCC) that often follows a course of spontaneous regression. Distinguishing KA from conventional SCC or pseudocarcinomatous epithelial hyperplasia ensures proper diagnosis, treatment and management. For some time, perforating elastic fibers have been utilized in differentiating KA from SCC. This phenomenon may also occur in association with scars and hypertrophic lupus erythematosus (LE). To assess the diagnostic utility of perforating elastic fibers, we compared their incidence in KA, SCC, scars with overlying pseudocarcinomatous hyperplasia, hypertrophic LE, hypertrophic lichen planus (LP) and lichen simplex chronicus (LSC). A retrospective case search identified 359 lesions and the presence of perforating elastic fibers was evaluated using routinely stained sections. This phenomenon was documented in all studied groups except hypertrophic LP. The incidence was found to be 71% in KA, 37% in SCC, and was lowest in inflammatory conditions with associated pseudocarcinomatous hyperplasia (hypertrophic LP 0%, hypertrophic LE 5.9% and LSC 28.2%). The observed frequency in pseudocarcinomatous hyperplasia overlying scars (57.8%) vs. KA (71%) was not statistically different. Although elastic fiber trapping has potential value as a diagnostic criterion for KA, dermatopathologists should consider its limitations. Its diagnostic utility was greatest in distinguishing KA from hypertrophic LE and hypertrophic LP. Conversely, elastic trapping is not helpful differentiating pseudocarcinomatous hyperplasia from recurrent/persistent KA following surgery. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Phase and frequency structure of superradiance pulses generated by relativistic Ka-band backward-wave oscillator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rostov, V. V.; Romanchenko, I. V.; Elchaninov, A. A.

2016-08-15

Phase and frequency stability of electromagnetic oscillations in sub-gigawatt superradiance (SR) pulses generated by an extensive slow-wave structure of a relativistic Ka-band backward-wave oscillator were experimentally investigated. Data on the frequency tuning and radiation phase stability of SR pulses with a variation of the energy and current of electron beam were obtained.

Reverberation Mapping of the Kepler target KA1858+48

NASA Astrophysics Data System (ADS)

Pei, Liuyi; Barth, A. J.; Malkan, M. A.; Cenko, S. B.; Clubb, K. I.; Filippenko, A. V.; Gates, E. L.; Horst, J.; Joner, M. D.; Leonard, D. C.; Sand, D. J.

2013-01-01

KA1858+48 is a Seyfert 1 galaxy at redshift 0.078 and is among the brightest active galaxies being monitored by the Kepler mission. We have carried out a reverberation mapping program designed to measure the broad-line region size and estimate the mass of the black hole in KA1858+48. We obtained spectroscopic data using the Kast Spectrograph at the Lick 3 m telescope during dark runs from late winter through fall of 2012, by requesting an observation on each night that the Kast Spectrograph was mounted on the telescope. We also obtained V-band images from the Nickel 1 m telescope at Lick Observatory, the 0.9 m telescope at Brigham Young University West Mountain Observatory, the Faulkes Telescope North at the Las Cumbres Observatory Global Telescope, the KAIT telescope at Lick Observatory, and the 1 m telescope at Mt. Laguna Observatory. The H-beta light curve shows a lag time of approximately 12 days with respect to the V-band continuum flux variations. We will present the continuum and emission-line light curves, cross-correlation lag measurements, and a preliminary estimate of the black hole mass in KA1858+48.

A Precise Method for Processing Data to Determine the Dissociation Constants of Polyhydroxy Carboxylic Acids via Potentiometric Titration.

PubMed

Huang, Kaixuan; Xu, Yong; Lu, Wen; Yu, Shiyuan

2017-12-01

The thermodynamic dissociation constants of xylonic acid and gluconic acid were studied via potentiometric methods, and the results were verified using lactic acid, which has a known pKa value, as a model compound. Solutions of xylonic acid and gluconic acid were titrated with a standard solution of sodium hydroxide. The determined pKa data were processed via the method of derivative plots using computer software, and the accuracy was validated using the Gran method. The dissociation constants associated with the carboxylic acid group of xylonic and gluconic acids were determined to be pKa 1  = 3.56 ± 0.07 and pKa 1  = 3.74 ± 0.06, respectively. Further, the experimental data showed that the second deprotonation constants associated with a hydroxyl group of each of the two acids were pKa 2  = 8.58 ± 0.12 and pKa 2  = 7.06 ± 0.08, respectively. The deprotonation behavior of polyhydroxy carboxylic acids was altered using various ratios with Cu(II) to form complexes in solution, and this led to proposing a hypothesis for further study.

Paleoclimate in continental northwestern Europe during the Eemian and early Weichselian (125-97 ka): insights from a Belgian speleothem

NASA Astrophysics Data System (ADS)

Vansteenberge, Stef; Verheyden, Sophie; Cheng, Hai; Edwards, R. Lawrence; Keppens, Eddy; Claeys, Philippe

2016-07-01

The last interglacial serves as an excellent time interval for studying climate dynamics during past warm periods. Speleothems have been successfully used for reconstructing the paleoclimate of last interglacial continental Europe. However, all previously investigated speleothems are restricted to southern Europe or the Alps, leaving large parts of northwestern Europe undocumented. To better understand regional climate changes over the past, a larger spatial coverage of European last interglacial continental records is essential, and speleothems, because of their ability to obtain excellent chronologies, can provide a major contribution. Here, we present new, high-resolution data from a stalagmite (Han-9) obtained from the Han-sur-Lesse Cave in Belgium. Han-9 formed between 125.3 and ˜ 97 ka, with interruptions of growth occurring at 117.3-112.9 and 106.6-103.6 ka. The speleothem was investigated for its growth, morphology and stable isotope (δ13C and δ18O) composition. The speleothem started growing relatively late within the last interglacial, at 125.3 ka, as other European continental archives suggest that Eemian optimum conditions were already present during that time. It appears that the initiation of Han-9 growth is caused by an increase in moisture availability, linked to wetter conditions around 125.3 ka. The δ13C and δ18O proxies indicate a period of relatively stable conditions after 125.3 ka; however, at 120 ka the speleothem δ18O registered the first signs of regionally changing climate conditions, being a modification of ocean source δ18O linked to an increase in ice volume towards the Marine Isotope Stage (MIS) 5e-5d transition. At 117.5 ka, drastic vegetation changes are recorded by Han-9 δ13C immediately followed by a cessation of speleothem growth at 117.3 ka, suggesting a transition to significantly dryer conditions. The Han-9 record covering the early Weichselian displays larger amplitudes in both isotope proxies and changes in stalagmite morphology, evidencing increased variability compared to the Eemian. Stadials that appear to be analogous to those in Greenland are recognized in Han-9, and the chronology is consistent with other European (speleothem) records. Greenland Stadial 25 is reflected as a cold/dry period within Han-9 stable isotope proxies, and the second interruption in speleothem growth occurs simultaneously with Greenland Stadial 24.

The Relative Rates of Secondary Hydration in Basalt and Rhyolite, and the use of δD as a Paleoclimate Indicator: Implications for Paleoenvironmental and Volcanic Degassing Studies

NASA Astrophysics Data System (ADS)

Seligman, A. N.; Bindeman, I. N.

2014-12-01

The δD-H2O correlation is important for volcanic degassing and secondary hydration trends. We utilize the caibration of the TC/EA - MAT 253 continuous flow system, which permits us to analyze wt.% H2O and its δD extracted from 1-8 mg of glass with as little as 0.1 wt% H2O. Tephra that has been secondarily hydrated with meteoric water is widely used as a paleoenvironmental tool, but the rate of secondary hydration, the relative amounts of primary magmatic (degassed) and secondary meteoric water, and the retention of primary and secondary δD values are not well understood. To quantify these processes, we use a natural experiment involving dated Holocene tepha in Kamchatka and Oregon. Our research illustrates the drastic difference in hydration rates between silicic (hydrated after ~1.5 ka) and mafic tephra, which is not hydrated in the Holocene (similar to results for submarine volcanic glasses), and andesitic tephra with intermediate degrees of hydration. The 0.05-7.3 ka basaltic scoria from Klyuchevskoy volcano retains ≤0.45 wt.% primary magmatic H2O, with δD values from -99 to -121 ‰. Four other 0.05-7.6 ka basaltic tephra units from Kamchatka with <57 wt.% SiO2 all have wt.% H2O 0.21-0.84 and δD values ranging from -90 - -145 ‰. The 1.0-7.6 ka andesitic tephra have slightly higher water contents (0.9-3.0 %) and slightly lower δD values (-113 - -146 ‰). Seven 0.3-7.9 ka silicic samples with SiO2 >65 wt.% have higher (1.5 -3.4) wt.% H2O and δD values between -115 - -160 ‰. We interpret the lower δD values and higher water contents (opposite of the magmatic degassing trend) to be a characteristic of secondary hydration in regions of higher latitude such as Kamchatka and Oregon. We are also investigating 7.7 ka Mt. Mazama tephra in Oregon that are known to be fully hydrated and cover nearly 5000 km2 northeast of Crater Lake and range in elevation from ~1.3-1.9 km to understand the δD and δ18O details of the hydrated water's correspondence with local Holocene meteoric waters. In the future, we plan to use a combination of δD in mid-high latitude precipitation to delineate δD-H2O hydration trends to better understand the distinction between primary magmatic and secondary meteoric water in volcanic glass, and the exchange of hydrogen isotopes between OH- and H2Omol sites in volcanic glass.

Climate variability during the Holocene inferred from northeastern Iberian speleothems

NASA Astrophysics Data System (ADS)

Moreno, A.; Bartolomé, M.; Sancho, C.; Belmonte, Á.; Stoll, H.; Cacho, I.; Edwards, R. L.; Hellstrom, J.

2012-04-01

Although the general climate trends during the Holocene in the Iberian Peninsula have been well described after the study of marine and lacustrine records, many questions regarding the timing of some of the events together with the characterization of the higher-frequency climate variability are still poorly understood. New speleothem records from several caves in northeastern Iberia provide data to explore Holocene climate changes. The selected caves are located in a latitudinal transect from the Pyrenees to the Iberian Range and placed at different altitude. Two of them, 5 de Agosto and Pot au Feu, belong to the same karstic complex in Cotiella massif (Central Pyrenees, 1600 m asl). Seso Cave, also in the Central Pyrenees but at 781 m of altitude, and Molinos cave, a cavity very rich in speleothems located at 1040 m in the Iberian Range, complete the transect. Although in all the caves precipitation coming from Atlantic fronts dominates over the year, a significant Mediterranean influence, specially in summer months, is identified after rainfall monitoring. Speleothem formation during the Holocene occurred at a very low pace in 5 de Agosto cave (80yrs/mm) and increased dramatically at low-altitude caves and during particular periods proved to be wetter (eg. Early Holocene in Molinos cave, less than 10yr/mm). In Seso and Pot au Feu caves, up to seven studied speleothems only grew during short climatic events such as the Iron Cold Period (3000-2500 cal yr BP) or the Little Ice Age (1300-1850 yr AD) that, although cold, were particularly humid periods in northeastern Spain. First stable isotope results highlight the importance of comparing speleothems with similar growing rates and from the same cave to extract climate information and discard other influences. From the integration of four stalagmites from Molinos cave covering since the Holocene onset to 2000 cal yrs BP, the Early Holocene (11.7-8.5 ka BP) with d13C values between -11 and - 9‰ appears as the wetter interval. The highest isotopic values are reached during Middle Holocene (8.5-5.5 ka BP) while there is a tendency towards more negative values during Late Holocene (last 5000 yrs). The range of d18O values is low (about 2‰) but still lighter values during Early Holocene and heavier afterwards are well marked. Shorter events characterized by more negative d13C values are observed at 4 ka, 6 ka, 7.5 ka, 8.2, 8.7, 9.2, 10.3 ka and interpreted as cold but probably wetter periods with denser vegetation cover and soil development over the cave. However, changes in the source of precipitation (Atlantic vs Mediterranean) or the influence of fresh-water outbursts in North Atlantic can not be neglected.

40Ar/39Ar ages for deep (˜3.3 km) samples from the Hawaii Scientific Drilling Project, Mauna Kea volcano, Hawaii

NASA Astrophysics Data System (ADS)

Jourdan, Fred; Sharp, Warren D.; Renne, Paul R.

2012-05-01

The Hawaii Scientific Drilling Project recovered core from a 3.5 km deep hole from the flank of Mauna Kea volcano, providing a long, essentially continuous record of the volcano's physical and petrologic development that has been used to infer the chemical and physical characteristics of the Hawaiian mantle plume. Determining a precise accumulation rate via 40Ar/39Ar dating of the shield-stage tholeiites, which constitute 95-98% of the volcano's volume is challenging. We applied40Ar/39Ar dating using laser- and furnace-heating in two laboratories (Berkeley and Curtin) to samples of two lava flows from deep in the core (˜3.3 km). All determinations yield concordant isochron ages, ranging from 612 ± 159 to 871 ± 302 ka (2σ; with P ≥ 0.90). The combined data yield an age of 681 ± 120 ka (P = 0.77) for pillow lavas near the bottom of the core. This new age, when regressed with 40Ar/39Ar isochron ages previously obtained for tholeiites higher in the core, defines a constant accumulation rate of 8.4 ± 2.6 m/ka that can be used to interpolate the ages of the tholeiites in the HSDP core with a mean uncertainty of about ±83 ka. For example at ˜3300 mbsl, the age of 664 ± 83 ka estimated from the regression diverges at the 95% confidence level from the age of 550 ka obtained from the numerical model of DePaolo and Stolper (1996). The new data have implications for the timescale of the growth of Hawaiian volcanoes, the paleomagnetic record in the core, and the dynamics of the Hawaiian mantle plume.

Holocene soil pH changes and East Asian summer monsoon evolution derived from loess brGDGTs in the northeastern Tibetan Plateau

NASA Astrophysics Data System (ADS)

Duan, Y.; Sun, Q.; Zhao, H.

2017-12-01

GDGTs-based proxies have been used successfully to reconstruct paleo-temperature from loess-paleosol sequences during the past few years. However, the pH variations of loess sediments derived from GDGTs covering the geological history remain poorly constrained. Here we present two pH records spanning the last 12 ka (1ka=1000years) based on the modified cyclization ratio index (CBT') of the branched GDGTs using regional CBT'-pH empirical relationship from two well-dated loess-paleosol sections (YWY14 and SHD09) in the northeastern Tibetan Plateau. The results indicate that a slightly alkaline condition occurred during 12 8.5 ka with pH values ranging from 6.98 to 7.24, then CBT'-derived pH decreased from 8.5 to 6.5 ka with values from 7.19 to 6.49 and gradually increased thereafter. The reconstructed pH values from topmost samples can be well compared with instrumental pH values of the surrounding surface soil. The lowest intervals of CBT'-derived pH values during the mid-Holocene in our records are consistent with the results of highest tree pollen percentage from the adjacent lake sediments and regional weakest aeolian activities, which reveals that the moisture maximum during that period, but conflicted with previous results of the wettest early-Holocene inferred from speleothem or ostracod shell oxygen isotope (δ18O) values. Taking together, we conclude that Holocene humidity evolution (wettest middle Holocene) in response to the East Asian summer monsoon (EASM) changes exerts important control on pH variations of loess deposits in northeastern Tibetan Plateau. CBT'-derived pH variations can be potentially used as an indicator of EASM evolution reconstructions. In addition, we argue that speleothem or ostracod shell δ18O records are essentially a signal of the isotopic composition of precipitations rather than EASM intensity.

Climatic variability during the penultimate interglacial (MIS 7) and glacial (MIS 6) periods recorded in a speleothem from Kanaan cave, Lebanon (Central Levant)

NASA Astrophysics Data System (ADS)

Nehme, Carole; Verheyden, Sophie; Breitenbach, Sebastian F. M.; Gillikin, David P.; Verheyden, Anouk; Cheng, Hai; Edwards, Laurence; Hellstrom, John; Noble, Stephen R.; Farrant, Andrew R.; Sahy, Diana; Goovaerts, Thomas; Salem, Ghada; Claeys, Philippe

2017-04-01

Little is known about terrestrial climate dynamics of the Levant during the penultimate interglacial-glacial period. A well-dated stalagmite ( 194 to 154 ka) from Kanaan cave, located near the Mediterranean in Lebanon, is examined for its petrography, growth history, and stable isotope geochemistry to answer the climate instability pattern of the glacial MIS 6 and possible wet phases. A highly resolved continental climate record from the northern Levant has been recovered from this precisely U-Th-dated speleothem, spanning the late penultimate interglacial (equivalent of the MIS 7) to the mid-penultimate glacial period ( MIS 6). The stalagmite grew slowly and discontinuously with an unstable isotopic pattern from 194 and at least up to 178 ka. Subsequently, the stalagmite ceased growing from 169.5 to 163.1 ka (interpolated ages) with a hiatus of ca. 6.24 ka according to the model age. However, low δ 18O and δ 13C values indicate generally cold, but overall more humid climate compared to the last glacial (MIS 3). Higher growth rates during the mid-penultimate glacial period ( 163-154 ka) are most probably linked to increased water recharge in the vadose zone. A short More distinct layering in the upper section compared to the basal part of the stalagmite suggests stronger seasonality from 163 ka to 154 ka. Negative oxygen and carbon isotope excursions were found at ˜155.5 ka, ˜156 ka, between ˜159.6 and ˜160.1 ka and at ˜162.6 ka. The inferred Kanaan cave humid intervals during the mid-penultimate period follow variations of pollen records in the Eastern and Western Mediterranean basins and correlate well with the synthetic Greenland records and East Asian Summer Monsoon Interstadials, indicating short warm/wet periods similar to the D-O events during MIS 4-3 in the Eastern Mediterranean region.

Absolute single-ion solvation free energy scale in methanol determined by the lithium cluster-continuum approach.

PubMed

Pliego, Josefredo R; Miguel, Elizabeth L M

2013-05-02

Absolute solvation free energy of the lithium cation in methanol was calculated by the cluster-continuum quasichemical theory of solvation. Clusters with up to five methanol molecules were investigated using X3LYP, MP2, and MP4 methods with DZVP, 6-311+G(2df,2p), TZVPP+diff, and QZVPP+diff basis sets and including the cluster solvation through the PCM and SMD continuum models. Our calculations have determined a value of -118.1 kcal mol(-1) for the solvation free energy of the lithium, in close agreement with a value of -116.6 kcal mol(-1) consistent with the TATB assumption. Using data of solvation and transfer free energy of a pair of ions, electrode potentials and pKa, we have obtained the solvation free energy of 25 ions in methanol. Our analysis leads to a value of -253.6 kcal mol(-1) for the solvation free energy of the proton, which can be compared with the value of -263.5 kcal mol(-1) obtained by Kelly et al. using the cluster pair approximation. Considering that this difference is due to the methanol surface potential, we have estimated that it corresponds to -0.429 V.

Collected Reprints-1975. Volume I.

DTIC Science & Technology

1977-02-01

ces ca u sed b y iiic reased sea state in (lie stretch variable (~ ) from cu rrent . ‘ 1(b~ + Ka ) - D, V1”In order to grap h i ca ll y disp lay...mw) and similarly those values of (800- I IOU mini ) is all constrained w DN < (DN — Ka ) are clipped. Equation 0~ DiV~ (0-O. 29 mW cm 2 sr~ ). The low...York . 1 1)4 pgs . vice , NAS ..\\ (‘R-l 333115: 1-73 -I (1”4~~ . Spring- Ka h l e , K. ( 19 3 8) , ‘I tin Ils’ drol. Mari n e M i t , 66. field , Va

Resistive Wall Modes Identification and Control in RFX-mod low qedge tokamak discharges

NASA Astrophysics Data System (ADS)

Baruzzo, Matteo; Bolzonella, Tommaso; Cavazzana, Roberto; Marchiori, Giuseppe; Marrelli, Lionello; Martin, Piero; Paccagnella, Roberto; Piovesan, Paolo; Piron, Lidia; Soppelsa, Anton; Zanca, Paolo; in, Yongkyoon; Liu, Yueqiang; Okabayashi, Michio; Takechi, Manabu; Villone, Fabio

2011-10-01

In this work the MHD stability of RFX mode tokamak discharges with qedge < 3 will be studied. The target plasma scenario is characterized by a plasma current 100kA

Solid State pH Sensor Based on Light Emitting Diodes (LED) As Detector Platform

PubMed Central

Lau, King Tong; Shepherd, R.; Diamond, Danny; Diamond, Dermot

2006-01-01

A low-power, high sensitivity, very low-cost light emitting diode (LED)-based device developed for low-cost sensor networks was modified with bromocresol green membrane to work as a solid-state pH sensor. In this approach, a reverse-biased LED functioning as a photodiode is coupled with a second LED configured in conventional emission mode. A simple timer circuit measures how long (in microsecond) it takes for the photocurrent generated on the detector LED to discharge its capacitance from logic 1 (+5 V) to logic 0 (+1.7 V). The entire instrument provides an inherently digital output of light intensity measurements for a few cents. A light dependent resistor (LDR) modified with similar sensor membrane was also used as a comparison method. Both the LED sensor and the LDR sensor responded to various pH buffer solutions in a similar way to obtain sigmoidal curves expected of the dye. The pKa value obtained for the sensors was found to agree with the literature value.

Ebw Assisted Plasma Current Startup in Mast

NASA Astrophysics Data System (ADS)

Shevchenko, Vladimir; Saveliev, Alexander

2009-04-01

EBW current drive assisted plasma current start-up has been demonstrated for the first time in a tokamak. It was shown that plasma currents up to 17 kA can be generated non-inductively by 100 kW of RF power injected. With optimized vertical field ramps, plasma currents up to 33 kA have been achieved without the use of solenoid flux. With limited solenoid assist (0.2 V × 20 ms, less than 0.5% of total solenoid flux), plasma currents up to 55 kA have been generated and sustained further non-inductively. Experimentally obtained plasma currents are consistent with Fokker-Planck modelling.

Hydrometeor discrimination in melting layer using multiparameter airborne radar measurement

NASA Technical Reports Server (NTRS)

Kumagai, H.; Meneghini, R.; Kozu, T.

1992-01-01

Results from a multiparameter airborne radar/radiometer experiment (the Typhoon experiment) are presented. The experiment was conducted in the western Pacific with the NASA DC-8 aircraft, in which a dual-wavelength at X-band and Ka-band and dual-polarization at X-band radar was installed. The signatures of dBZ(X), dBZ(Ka), LDR (linear depolarization ratio) at X-band and DZ=dBZ(X)-dBZ(Ka) are discussed for the data obtained in the penetration of the typhoon Flo. With emphasis on discrimination of hydrometeor particles, some statistical features of the brightband in stratiform rain are discussed.

Calculating pKa values for substituted phenols and hydration energies for other compounds with the first-order Fuzzy-Border continuum solvation model

PubMed Central

Sharma, Ity; Kaminski, George A.

2012-01-01

We have computed pKa values for eleven substituted phenol compounds using the continuum Fuzzy-Border (FB) solvation model. Hydration energies for 40 other compounds, including alkanes, alkenes, alkynes, ketones, amines, alcohols, ethers, aromatics, amides, heterocycles, thiols, sulfides and acids have been calculated. The overall average unsigned error in the calculated acidity constant values was equal to 0.41 pH units and the average error in the solvation energies was 0.076 kcal/mol. We have also reproduced pKa values of propanoic and butanoic acids within ca. 0.1 pH units from the experimental values by fitting the solvation parameters for carboxylate ion carbon and oxygen atoms. The FB model combines two distinguishing features. First, it limits the amount of noise which is common in numerical treatment of continuum solvation models by using fixed-position grid points. Second, it employs either second- or first-order approximation for the solvent polarization, depending on a particular implementation. These approximations are similar to those used for solute and explicit solvent fast polarization treatment which we developed previously. This article describes results of employing the first-order technique. This approximation places the presented methodology between the Generalized Born and Poisson-Boltzmann continuum solvation models with respect to their accuracy of reproducing the many-body effects in modeling a continuum solvent. PMID:22815192

Environmental status of the Jilantai Basin, North China, on the northwestern margin of the modern Asian summer monsoon domain during Marine Isotope Stage 3

NASA Astrophysics Data System (ADS)

Fan, Yuxin; Wang, Yongda; Mou, Xuesong; Zhao, Hui; Zhang, Fu; Zhang, Fan; Liu, Wenhao; Hui, Zhengchuang; Huang, Xiaozhong; Ma, Jun

2017-10-01

Two drill cores were obtained from the Jilantai sub-depression (JLT(d)) and the neighboring Dengkou sub-uplift (DK(u)), within a huge, former lake basin in northern China. From an analysis of the lithology and pollen assemblages, combined with radiocarbon dating of extracted pollen and OSL dating of extracted quartz, we concluded the following: JLT(d) was continuously occupied by lakes since 85 ka; however, DK(u), the neighboring sub-uplift, was covered by lakes during 80-74 ka, 50-44 ka, 32.5-27.5 ka and <13 ka, and covered by sand during 44-32.5 ka and 27.5-13 ka. The evidence from lithology and dating results supports the occurrence of lakes on DK(u) during Marine Isotope Stage (MIS) 3. Evidence from shorelines, previously published cores, and the sedimentary and chronological evidence presented in this paper indicate the occurrence of a sub-humid environment, characterized by the occurrence of lakes separated by dunes, in the Jilantai Basin during MIS 3. However, further work is needed to understand the environmental significance of the co-existence of lakes and dunes during MIS 3, although a sub-humid climate background during MIS 3 is supported by well-dated geological archives along the western front of the present-day Asian Summer Monsoon domain and its eastern extensional area.

Improving Cry8Ka toxin activity towards the cotton boll weevil (Anthonomus grandis).

PubMed

Oliveira, Gustavo R; Silva, Maria C M; Lucena, Wagner A; Nakasu, Erich Y T; Firmino, Alexandre A P; Beneventi, Magda A; Souza, Djair S L; Gomes, José E; de Souza, José D A; Rigden, Daniel J; Ramos, Hudson B; Soccol, Carlos R; Grossi-de-Sa, Maria F

2011-09-09

The cotton boll weevil (Anthonomus grandis) is a serious insect-pest in the Americas, particularly in Brazil. The use of chemical or biological insect control is not effective against the cotton boll weevil because of its endophytic life style. Therefore, the use of biotechnological tools to produce insect-resistant transgenic plants represents an important strategy to reduce the damage to cotton plants caused by the boll weevil. The present study focuses on the identification of novel molecules that show improved toxicity against the cotton boll weevil. In vitro directed molecular evolution through DNA shuffling and phage display screening was applied to enhance the insecticidal activity of variants of the Cry8Ka1 protein of Bacillus thuringiensis. Bioassays carried out with A. grandis larvae revealed that the LC50 of the screened mutant Cry8Ka5 toxin was 3.15-fold higher than the wild-type Cry8Ka1 toxin. Homology modelling of Cry8Ka1 and the Cry8Ka5 mutant suggested that both proteins retained the typical three-domain Cry family structure. The mutated residues were located mostly in loops and appeared unlikely to interfere with molecular stability. The improved toxicity of the Cry8Ka5 mutant obtained in this study will allow the generation of a transgenic cotton event with improved potential to control A. grandis.

Improving Cry8Ka toxin activity towards the cotton boll weevil (Anthonomus grandis)

PubMed Central

2011-01-01

Background The cotton boll weevil (Anthonomus grandis) is a serious insect-pest in the Americas, particularly in Brazil. The use of chemical or biological insect control is not effective against the cotton boll weevil because of its endophytic life style. Therefore, the use of biotechnological tools to produce insect-resistant transgenic plants represents an important strategy to reduce the damage to cotton plants caused by the boll weevil. The present study focuses on the identification of novel molecules that show improved toxicity against the cotton boll weevil. In vitro directed molecular evolution through DNA shuffling and phage display screening was applied to enhance the insecticidal activity of variants of the Cry8Ka1 protein of Bacillus thuringiensis. Results Bioassays carried out with A. grandis larvae revealed that the LC50 of the screened mutant Cry8Ka5 toxin was 3.15-fold higher than the wild-type Cry8Ka1 toxin. Homology modelling of Cry8Ka1 and the Cry8Ka5 mutant suggested that both proteins retained the typical three-domain Cry family structure. The mutated residues were located mostly in loops and appeared unlikely to interfere with molecular stability. Conclusions The improved toxicity of the Cry8Ka5 mutant obtained in this study will allow the generation of a transgenic cotton event with improved potential to control A. grandis. PMID:21906288

Sea ice cover variability and river run-off in the western Laptev Sea (Arctic Ocean) since the last 18 ka

NASA Astrophysics Data System (ADS)

Hörner, T.; Stein, R.; Fahl, K.; Birgel, D.

2015-12-01

Multi-proxy biomarker measurements were performed on two sediment cores (PS51/154, PS51/159) with the objective reconstructing sea ice cover (IP25, brassicasterol, dinosterol) and river-runoff (campesterol, β-sitosterol) in the western Laptev Sea over the last 18 ka with unprecedented temporal resolution. The sea ice cover varies distinctly during the whole time period. The absence of IP25 during 18 and 16 ka indicate that the western Laptev Sea was mostly covered with permanent sea ice (pack ice). However, a period of temporary break-up of the permanent ice coverage occurred at c. 17.2 ka (presence of IP25). Very little river-runoff occurred during this interval. Decreasing terrigenous (riverine) input and synchronous increase of marine produced organic matter around 16 ka until 7.5 ka indicate the gradual establishment of a marine environment in the western Laptev Sea related to the onset of the post-glacial transgression of the shelf. Strong river run-off and reduced sea ice cover characterized the time interval between 15.2 and 12.9 ka, including the Bølling/Allerød warm period (14.7 - 12.9 ka). Moreover, the DIP25 Index (ratio of HBI-dienes and IP25) might document the presence of Atlantic derived water at the western Laptev Sea shelf area. A sudden return to severe sea ice conditions occurred during the Younger Dryas (12.9 - 11.6 ka). This abrupt climate change was observed in the whole circum-Arctic realm (Chukchi Sea, Bering Sea, Fram Strait and Laptev Sea). At the onset of the Younger Dryas, a distinct alteration of the ecosystem (deep drop in terrigenous and phytoplankton biomarkers) may document the entry of a giant freshwater plume, possibly relating to the Lake Agassiz outburst at 13 ka. IP25 concentrations increase and higher values of the PIP25 Index during the last 7 ka reflect a cooling of the Laptev Sea spring season. Moreover, a short-term variability of c. 1.5 thousand years occurred during the last 12 ka, most probably following Bond Cycles.

Vibrational tug-of-war: The pKA dependence of the broad vibrational features of strongly hydrogen-bonded carboxylic acids

NASA Astrophysics Data System (ADS)

Van Hoozen, Brian L.; Petersen, Poul B.

2018-04-01

Medium and strong hydrogen bonds give rise to broad vibrational features frequently spanning several hundred wavenumbers and oftentimes exhibiting unusual substructures. These broad vibrational features can be modeled from first principles, in a reduced dimensional calculation, that adiabatically separates low-frequency modes, which modulate the hydrogen bond length, from high-frequency OH stretch and bend modes that contribute to the vibrational structure. Previously this method was used to investigate the origin of an unusual vibrational feature frequently found in the spectra of dimers between carboxylic acids and nitrogen-containing aromatic bases that spans over 900 cm-1 and contains two broad peaks. It was found that the width of this feature largely originates from low-frequency modes modulating the hydrogen bond length and that the structure results from Fermi resonance interactions. In this report, we examine how these features change with the relative acid and base strength of the components as reflected by their aqueous pKA values. Dimers with large pKA differences are found to have features that can extend to frequencies below 1000 cm-1. The relationships between mean OH/NH frequency, aqueous pKA, and O-N distance are examined in order to obtain a more rigorous understanding of the origin and shape of the vibrational features. The mean OH/NH frequencies are found to correlate well with O-N distances. The lowest OH stretch frequencies are found in dimer geometries with O-N distances between 2.5 and 2.6 Å. At larger O-N distances, the hydrogen bonding interaction is not as strong, resulting in higher OH stretch frequencies. When the O-N distance is smaller than 2.5 Å, the limited space between the O and N determines the OH stretch frequency, which gives rise to frequencies that decrease with O-N distances. These two effects place a lower limit on the OH stretch frequency which is calculated to be near 700 cm-1. Understanding how the vibrational features of strongly hydrogen-bonded structures depend on the relative pKA and other structural parameters will guide studies of biological structures and analysis of proton transfer studies using photoacids.

40Ar/39Ar geochronology of submarine Mauna Loa volcano, Hawaii

NASA Astrophysics Data System (ADS)

Jicha, Brian R.; Rhodes, J. Michael; Singer, Brad S.; Garcia, Michael O.

2012-09-01

New geochronologic constraints refine the growth history of Mauna Loa volcano and enhance interpretations of the petrologic, geochemical, and isotopic evolution of Hawaiian magmatism. We report results of 40Ar/39Ar incremental heating experiments on low-K, tholeiitic lavas from the 1.6 km high Kahuku landslide scarp cutting Mauna Loa's submarine southwest rift zone, and from lavas in a deeper section of the rift. Obtaining precise40Ar/39Ar ages from young, tholeiitic lavas containing only 0.2-0.3 wt.% K2O is challenging due to their extremely low radiogenic 40Ar contents. Analyses of groundmass from 45 lavas yield 14 new age determinations (31% success rate) with plateau and isochron ages that agree with stratigraphic constraints. Lavas collected from a 1250 m thick section in the landslide scarp headwall were all erupted around 470 ± 10 ka, implying an extraordinary period of accumulation of ˜25 mm/yr, possibly correlating with the peak of the shield-building stage. This rate is three times higher than the estimated vertical lava accumulation rate for shield-building at Mauna Kea (8.6 ± 3.1 mm/yr) based on results from the Hawaii Scientific Drilling Project. Between ˜470 and 273 ka, the lava accumulation rate along the southwest rift zone decreased dramatically to ˜1 mm/yr. We propose that the marked reduction in lava accumulation rate does not mark the onset of post-shield volcanism as previously suggested, but rather indicates the upward migration of the magma system as Mauna Loa evolved from a submarine stage of growth to one that is predominantly subaerial, thereby cutting off supply to the distal rift zone. Prior to ˜250 ka, lavas with Loihi-like isotopic signatures were erupted along with lavas having typical Mauna Loa values, implying greater heterogeneity in the plume source earlier in Mauna Loa's growth. In addition to refining accumulation rates and the isotopic evolution of the lavas erupted along the southwest rift zone, our new40Ar/39Ar results constrain the eruption of the Ninole Basalts from 227 to 108 ka and provide maximum estimates on the timing of the Ka Lae and South Kona landslides.

High-resolution K-Ar dating of a complex magmatic system: The example of Basse-Terre Island (French West Indies)

NASA Astrophysics Data System (ADS)

Ricci, J.; Quidelleur, X.; Pallares, C.; Lahitte, P.

2017-10-01

For the first time in the Lesser Antilles volcanic arc, we combine for one island, 123 K-Ar ages, with 133 major and trace elements geochemical analyses, in order to better constrain the volcanic history of Basse-Terre Island. In this study, nine new ages have been obtained from the southern part of the island, and complemented with eighty-three new major and trace element analyses of samples collected across the island. The southern part of Basse-Terre Island has been the loci of volcanic activity since the last 200 kyr. It is characterized by the construction of the Grande-Découverte Volcanic Complex (GDVC) composed by the Grande-Découverte - Soufrière (GDS) and the Trois-Rivières Madeleine Field (TRMF). After the onset of construction at least at 205 ± 28 ka, the GDVC displays strikingly continuous activity between 140 ± 13 and 56 ± 3 ka, followed by a 30 kyr volcanic hiatus, which is coeval with the hiatus also observed for the TRMF activity. Two new ages of 125 ± 14 and 140 ± 13 ka obtained on a lava flow from the Grande-Découverte caldera wall suggest the presence of a depression, resulting of a major flank collapse and/or explosive event, before 140 ka. Finally, a new age of 9 ± 6 ka, obtained from outcrops exposed on the edge of the Class River, in the north of the GDVC, allows us to calculate channel incision rates between 11 and 56 mm/yr. These values are consistent with incision rates determined on other volcanic islands with similar climates. In a broad sense, the petrology and geochemistry of Basse-Terre Island rocks appear fairly homogeneous, with mainly andesite and basaltic-andesite rocks and typical features of volcanic-arc lavas. Nevertheless, in detail, various magmatic processes can be discerned. Most variations are principally controlled by crystal-melt fractionation-accumulation, but major and trace elements also highlight episodic magmatic recharge, involving magma mixing. There are also indications for assimilation of crustal rocks with continental affinity, as well as mantle input of slab-derived fluids. Trace element ratios suggest the presence of at least two different magmatic sources characterized by different partial melting rates and different continental contributions for Basse-Terre Island. Different massifs show a bimodal behavior, with the Basal Complex, the Axial Chain (Piton de Bouillante and Southern Axial Chain), the Monts-Caraïbes volcanoes and the Sans-Toucher volcano in the first group, and the Septentrional Chain, and the Grande-Découverte Volcanic Complex (GDS and TRMF) in the second. Given the unique amount of time-constrained geochemical data, this study provides a complete and detailed investigation of volcanic evolution in the central part of the Lesser Antilles active arc.

A growth path for deep space communications

NASA Technical Reports Server (NTRS)

Layland, J. W.; Smith, J. G.

1987-01-01

Increased Deep Space Network (DPN) receiving capability far beyond that now available for Voyager is achievable through a mix of increased antenna aperture and increased frequency of operation. In this note a sequence of options are considered: adding midsized antennas for arraying with the existing network at X-band; converting to Ka-band and adding array elements; augmenting the DSN with an orbiting Ka-band station; and augmenting the DSN with an optical receiving capability, either on the ground or in space. Costs of these options are compared as means of achieving significantly increased receiving capability. The envelope of lowest costs projects a possible path for moving from X-band to Ka-band and thence to optical frequencies, and potentially for moving from ground-based to space-based apertures. The move to Ka-band is clearly of value now, with development of optical communications technology a good investment for the future.

Development of Methods for the Determination of pKa Values

PubMed Central

Reijenga, Jetse; van Hoof, Arno; van Loon, Antonie; Teunissen, Bram

2013-01-01

The acid dissociation constant (pKa) is among the most frequently used physicochemical parameters, and its determination is of interest to a wide range of research fields. We present a brief introduction on the conceptual development of pKa as a physical parameter and its relationship to the concept of the pH of a solution. This is followed by a general summary of the historical development and current state of the techniques of pKa determination and an attempt to develop insight into future developments. Fourteen methods of determining the acid dissociation constant are placed in context and are critically evaluated to make a fair comparison and to determine their applications in modern chemistry. Additionally, we have studied these techniques in light of present trends in science and technology and attempt to determine how these trends might affect future developments in the field. PMID:23997574

Extreme Basicity of Biguanide Drugs in Aqueous Solutions: Ion Transfer Voltammetry and DFT Calculations.

PubMed

Langmaier, Jan; Pižl, Martin; Samec, Zdeněk; Záliš, Stanislav

2016-09-22

Ion transfer voltammetry is used to estimate the acid dissociation constants Ka1 and Ka2 of the mono- and diprotonated forms of the biguanide drugs metformin (MF), phenformin (PF), and 1-phenylbiguanide (PB) in an aqueous solution. Measurements gave the pKa1 values for MFH(+), PFH(+), and PBH(+) characterizing the basicity of MF, PF, and PB, which are significantly higher than those reported in the literature. As a result, the monoprotonated forms of these biguanides should prevail in a considerably broader range of pH 1-15 (MFH(+), PFH(+)) and 2-13 (PBH(+)). DFT calculations with solvent correction were performed for possible tautomeric forms of neutral, monoprotonated, and diprotonated species. Extreme basicity of all drugs is confirmed by DFT calculations of pKa1 for the most stable tautomers of the neutral and protonated forms with explicit water molecules in the first solvation sphere included.

Non-Linear Response to Holocene Insolation Forcing Recorded by High-Resolution Lake Sediment Records Across Iceland

NASA Astrophysics Data System (ADS)

Geirsdottir, A.; Miller, G. H.; Axford, Y.

2009-12-01

Many Icelandic lakes have sedimentation rates in excess of 1 m ka-1 throughout the Holocene. Such high rates offer the potential for decadally resolved (or better) records of environmental change at this sensitive North Atlantic site. Abundant well-defined tephra provide a secure geochronology. The fidelity of the common climate proxies biogenic silica (BSi) and total organic carbon (TOC), was tested by comparing these proxies in three lakes with very different catchment characteristics. Hestvatn (HST, 60 m deep) in southern Iceland receives overflow from a large river originating in the glaciated highlands of central Iceland, whereas the nearby lake Vestra Gislholtsvatn (VGHV, 15 m deep) has a small, low elevation catchment without glaciers. Haukadalsvatn (HAK, 42 m deep), in northwestern Iceland, has a large, high relief catchment. The BSi record from HAK has been shown to reflect April-May temperatures, with BSi highest when spring temperatures are at their maximum. The first- and second-order trends in BSi are similar in all three lakes for most of the Holocene. This supports the contention that BSi reflects primary productivity, and is less influenced by changes in sedimentation rate. In all three lakes, BSi reaches a maximum value shortly after 8 ka, and then declines gradually toward present, reflecting a relatively late Holocene thermal maximum, potentially due to the influence of meltwater from the lingering Laurentide Ice Sheet. A steady reduction in summer insolation determines this first-order trend towards lower BSi through the middle and late Holocene. Large, abrupt departures from the overall decrease in BSi characterize all three records after 8 ka. Following each rapid BSi decrease, BSi usually exhibits a step-function change, re-equilibrating at a lower BSi value. Some of the strongest departures (ca. 6 ka, 4 to 4.5 ka and ca. 3 ka) may be related to Icelandic volcanism, but the lack of a full recovery to pre-existing values after the eruptions suggests a change in state occurred in the catchments of the lakes. TOC reflects the balance between changes in primary productivity within the lakes, which appears to dominate the early and middle Holocene, and the flux of soil carbon to the lake during periods of catchment instability that dominates the record after ~2.5 ka. In HAK TOC the flux of soil carbon to the lake is high when cold summers are accompanied by dry, windy winters. The two southern lakes exhibit a substantial overprinting after settlement, although the northern and southern records start to depart ca. 1.5 ka, well before settlement, possibly reflecting an earlier onset of late Holocene cooling off northwest Iceland than in the south where the Irminger current maintains warmer coastal temperatures.

Test of 60 kA coated conductor cable prototypes for fusion magnets

NASA Astrophysics Data System (ADS)

Uglietti, D.; Bykovsky, N.; Sedlak, K.; Stepanov, B.; Wesche, R.; Bruzzone, P.

2015-12-01

Coated conductors could be promising materials for the fabrication of the large magnet systems of future fusion devices. Two prototype conductors (flat cables in steel conduits), each about 2 m long, were manufactured using coated conductor tapes (4 mm wide) from Super Power and SuperOx, with a total tape length of 1.6 km. Each flat cable is assembled from 20 strands, each strand consisting of a stack of 16 tapes surrounded by two half circular copper profiles, twisted and soldered. The tapes were measured at 12 T and 4.2 K and the results of the measurements were used for the assessment of the conductor electromagnetic properties at low temperature and high field. The two conductors were assembled together in a sample that was tested in the European Dipole (EDIPO) facility. The current sharing temperatures of the two conductors were measured at background fields from 8 T up to 12 T and for currents from 30 kA up to 70 kA: the measured values are within a few percent of the values expected from the measurements on tapes (short samples). After electromagnetic cycling, T cs at 12 T and 50 kA decreased from about 12 K to 11 K (about 10%), corresponding to less than 3% of I c.

Structural origins of pH and ionic strength effects on protein stability. Acid denaturation of sperm whale apomyoglobin.

PubMed

Yang, A S; Honig, B

1994-04-15

A recently developed approach to calculate the pH dependence of protein stability from three-dimensional structure information is applied to the analysis of acid denaturation of sperm whale apomyoglobin. The finite difference Poisson-Boltzmann method is used to calculate pKa values and these are used to obtain titration curves for the folded protein as well as for compact intermediates. The total electrostatic free energy change involved in apomyoglobin unfolding is then evaluated. Calculations are carried out of the unfolding free energy of the native (N) and the compact intermediate (I) of apomyoglobin relative to the unfolded state (U) over a range of pH at various ionic strengths. The contributions from key ionizable groups to the unfolding process are discussed. For the acid-induced partial unfolding of apomyoglobin near pH 5, the transition from N to I is found to be driven by three histidines that are exposed when the B, C, D and E helices unfold. Similarly, the unfolding of the compact intermediate I consisting of the A, G and H helices is driven primarily by a few carboxylic acids with low pKa values in the compact state. This picture is in contrast to the view which attributes acid denaturation to electrostatic repulsion resulting from the build up of positive charge. In fact, charge-charge interactions in myoglobin are found to be attractive at all pH values where the protein unfolds. pH-dependent changes in these interactions contribute to acid denaturation but other electrostatic effects, such as hydrogen bonding and solvation, are important as well. The effect of increasing ionic strength on unfolding is attributed to the decrease of attractive charge-charge interactions which destabilize the N state relative to I, but stabilize the I state relative to U by reducing the pKa shifts of a few critical carboxylic acids. The I state is found to be more stable than U at neutral pH thus accounting for its presence as an intermediate on the protein folding pathway. Our results have implications for the origins of compact intermediates or "molten globule" states.

Potential effects of alpha-recoil on uranium-series dating of calcrete

USGS Publications Warehouse

Neymark, L.A.

2011-01-01

Evaluation of paleosol ages in the vicinity of Yucca Mountain, Nevada, at the time the site of a proposed high-level nuclear waste repository, is important for fault-displacement hazard assessment. Uranium-series isotope data were obtained for surface and subsurface calcrete samples from trenches and boreholes in Midway Valley, Nevada, adjacent to Yucca Mountain. 230Th/U ages of 33 surface samples range from 1.3 to 423 thousand years (ka) and the back-calculated 234U/238U initial activity ratios (AR) are relatively constant with a mean value of 1.54 ± 0.15 (1σ), which is consistent with the closed-system behavior. Subsurface calcrete samples are too old to be dated by the 230Th/U method. U-Pb data for post-pedogenic botryoidal opal from a subsurface calcrete sample show that these subsurface calcrete samples are older than ~ 1.65 million years (Ma), old enough to have attained secular equilibrium had their U-Th systems remained closed. However, subsurface calcrete samples show U-series disequilibrium indicating open-system behavior of 238U daughter isotopes, in contrast with the surface calcrete, where open-system behavior is not evident. Data for 21 subsurface calcrete samples yielded calculable 234U/238U model ages ranging from 130 to 1875 ka (assuming an initial AR of 1.54 ± 0.15, the mean value calculated for the surface calcrete samples). A simple model describing continuous α-recoil loss predicts that the 234U/238U and 230Th/238U ARs reach steady-state values ~ 2 Ma after calcrete formation. Potential effects of open-system behavior on 230Th/U ages and initial 234U/238U ARs for younger surface calcrete were estimated using data for old subsurface calcrete samples with the 234U loss and assuming that the total time of water-rock interaction is the only difference between these soils. The difference between the conventional closed-system and open-system ages may exceed errors of the calculated conventional ages for samples older than ~ 250 ka, but is negligible for younger soils.

Thermodynamics of Host–Guest Interactions between Fullerenes and a Buckycatcher

PubMed Central

2015-01-01

1H NMR and isothermal titration calorimetry (ITC) experiments were employed to obtain reliable thermodynamic data for the formation of the 1:1 inclusion complexes of fullerenes C60 and C70 with the buckycatcher (C60H28). NMR measurements were done in toluene-d8 and chlorobenzene-d5 at 288, 298, and 308 K, while the ITC titrations were performed in toluene, chlorobenzene, o-dichlorobenzene, anisole, and 1,1,2,2-tetrachloroethane at temperatures from 278 to 323 K. The association constants, Ka, obtained with both techniques are in very good agreement. The thermodynamic data obtained by ITC indicate that generally the host–guest association is enthalpy-driven. Interestingly, the entropy contributions are, with rare exceptions, slightly stabilizing or close to zero. Neither ΔH nor ΔS is constant over the temperature range studied, and these thermodynamic functions exhibit classical enthalpy/entropy compensation. The ΔCp values calculated from the temperature dependence of the calorimetric ΔH values are negative for the association of both fullerenes with the buckycatcher in toluene. The negative ΔCp values are consistent with some desolvation of the host-cavity and the guest in the inclusion complexes, C60@C60H28 and C70@C60H28. PMID:25248285

Validation of SARAL/AltiKa data in the Amazon basin

NASA Astrophysics Data System (ADS)

Santos da Silva, Joecila; Calmant, Stephane; Medeiros Moreira, Daniel; Oliveira, Robson; Conchy, Taina; Gennero, Marie-Claude; Seyler, Frederique

2015-04-01

SARAL/AltiKa is a link between past missions (since it flies on the ERS-ENVISAT orbit with Ku band nadir altimeters in LRM) and future missions such as SWOT's Ka band interferometry swaths. In the present study, we compare the capability of its altimeter AltiKa to that of previous missions working in the Ku band such as ENVISAT and Jason-2 in retrieving water levels over the Amazon basin. Same as for the aforementioned preceding missions, the best results were obtained with the ICE-1 retracking algorithm. We qualitatively analyze the impact of rainfalls in the loss of measurements. Since making long -multi mission- time series is of major importance either for hydro-climatic studies or for basin management, we also present an estimate of the altimeter bias in order that the SARAL series of water level can be appended to those of these previous missions.

Deletion of uncharacterized domain from α-1,3-glucanase of Bacillus circulans KA-304 enhances heterologous enzyme production in Escherichia coli.

PubMed

Yano, Shigekazu; Suyotha, Wasana; Zanma, Sumika; Konno, Hiroyuki; Cherdvorapong, Vipavee; Wakayama, Mamoru

2018-05-08

α-1,3-Glucanase (Agl-KA) of Bacillus circulans KA-304 consists of an N-terminal discoidin domain (DS1), a carbohydrate binding module family 6 (CBM6), threonine and proline repeats (TP), a second discoidin domain (DS2), an uncharacterized conserved domain (UCD), and a C-terminal catalytic domain. Previously, we reported that DS1, CBM6, and DS2 have α-1,3-glucan-binding activity and contribute to α-1,3-glucan hydrolysis. In this study, UCD deletion mutant (AglΔUCD) was constructed, and its properties were compared with those of Agl-KA. α-1,3-Glucan hydrolyzing, α-1,3-glucan binding, and protoplast-forming activities of AglΔUCD were almost the same as those of Agl-KA. k cat /K m values of AgΔUCD and Agl-KA were 11.4 and 11.1 s -1 mg -1 mL, respectively. AglΔUCD and Agl-KA exhibited similar characteristics, such as optimal pH, pH stability, optimal temperature, and thermostability. These results suggest that UCD is not α-1,3-glucan-binding and flexible linker domain, and that deletion of UCD does not affect the affinity of N-terminal binding domains and the catalytic action of the C-terminal domain. Subsequently, heterologous UCenzyme productivity of AglΔD in Escherichia coli was compared with that of Agl-KA. The productivity of AglΔUCD was about 4-fold larger than that of Agl-KA after an 8-h induction at 30°C. In the case of induction at 20°C, the productivity of AglΔUCD was also larger than that of Agl-KA. These findings indicate that deletion of only UCD enhances the enzyme productivity in E. coli.

Global Electric Circuit Diurnal Variation Derived from Storm Overflight and Satellite Optical Lightning Datasets

NASA Technical Reports Server (NTRS)

Mach, Douglas M.; Blakeslee, R. J.; Bateman, M. J.; Bailey, J. C.

2011-01-01

We have combined analyses of over 1000 high altitude aircraft observations of electrified clouds with diurnal lightning statistics from the Lightning Imaging Sensor (LIS) and Optical Transient Detector (OTD) to produce an estimate of the diurnal variation in the global electric circuit. Using basic assumptions about the mean storm currents as a function of flash rate and location, and the global electric circuit, our estimate of the current in the global electric circuit matches the Carnegie curve diurnal variation to within 4% for all but two short periods of time. The agreement with the Carnegie curve was obtained without any tuning or adjustment of the satellite or aircraft data. Mean contributions to the global electric circuit from land and ocean thunderstorms are 1.1 kA (land) and 0.7 kA (ocean). Contributions to the global electric circuit from ESCs are 0.22 kA for ocean storms and 0.04 kA for land storms. Using our analysis, the mean total conduction current for the global electric circuit is 2.0 kA.

Apparent Interfacial Fracture Toughness of Resin/Ceramic Systems

PubMed Central

Della Bona, A.; Anusavice, K.J.; Mecholsky, J.J.

2008-01-01

We suggest that the apparent interfacial fracture toughness (KA) may be estimated by fracture mechanics and fractography. This study tested the hypothesis that the KA of the adhesion zone of resin/ceramic systems is affected by the ceramic microstructure. Lithia disilicate-based (Empress2-E2) and leucite-based (Empress-E1) ceramics were surface-treated with hydrofluoric acid (HF) and/or silane (S), followed by an adhesive resin. Microtensile test specimens (n = 30; area of 1 ± 0.01 mm2) were indented (9.8 N) at the interface and loaded to failure in tension. We used tensile strength (σ) and the critical crack size (c) to calculate KA (KA = Yσc1/2) (Y = 1.65). ANOVA and Weibull analyses were used for statistical analyses. Mean KA (MPa•m1/2) values were: (E1HF) 0.26 ± 0.06; (E1S) 0.23 ± 0.06; (E1HFS) 0.30 ± 0.06; (E2HF) 0.31 ± 0.06; (E2S) 0.13 ± 0.05; and (E2HFS) 0.41 ± 0.07. All fractures originated from indentation sites. Estimation of interfacial toughness was feasible by fracture mechanics and fractography. The KA for the systems tested was affected by the ceramic microstructure and surface treatment. PMID:17062746

Global climate simulations at 3000-year intervals for the last 21 000 years with the GENMOM coupled atmosphere–ocean model

USGS Publications Warehouse

Alder, Jay R.; Hostetler, Steven W.

2015-01-01

We apply GENMOM, a coupled atmosphere–ocean climate model, to simulate eight equilibrium time slices at 3000-year intervals for the past 21 000 years forced by changes in Earth–Sun geometry, atmospheric greenhouse gases (GHGs), continental ice sheets, and sea level. Simulated global cooling during the Last Glacial Maximum (LGM) is 3.8 ◦C and the rate of post-glacial warming is in overall agreement with recently published temperature reconstructions. The greatest rate of warming occurs between 15 and 12 ka (2.4 ◦C over land, 0.7 ◦C over oceans, and 1.4 ◦C globally) in response to changes in radiative forcing from the diminished extent of the Northern Hemisphere (NH) ice sheets and increases in GHGs and NH summer insolation. The modeled LGM and 6 ka temperature and precipitation climatologies are generally consistent with proxy reconstructions, the PMIP2 and PMIP3 simulations, and other paleoclimate data–model analyses. The model does not capture the mid-Holocene “thermal maximum” and gradual cooling to preindustrial (PI) global temperature found in the data. Simulated monsoonal precipitation in North Africa peaks between 12 and 9 ka at values ∼ 50 % greater than those of the PI, and Indian monsoonal precipitation peaks at 12 and 9 ka at values ∼ 45 % greater than the PI. GENMOM captures the reconstructed LGM extent of NH and Southern Hemisphere (SH) sea ice. The simulated present-day Antarctica Circumpolar Current (ACC) is ∼ 48 % weaker than the observed (62 versus 119 Sv). The simulated present-day Atlantic Meridional Overturning Circulation (AMOC) of 19.3 ± 1.4 Sv on the Bermuda Rise (33◦ N) is comparable with observed value of 18.7 ± 4.8 Sv. AMOC at 33◦ N is reduced by ∼ 15 % during the LGM, and the largest post-glacial increase (∼ 11 %) occurs during the 15 ka time slice.

Lysosomotropic properties of weakly basic anticancer agents promote cancer cell selectivity in vitro.

PubMed

Ndolo, Rosemary A; Luan, Yepeng; Duan, Shaofeng; Forrest, M Laird; Krise, Jeffrey P

2012-01-01

Drug distribution in cells is a fundamentally important, yet often overlooked, variable in drug efficacy. Many weakly basic anticancer agents accumulate extensively in the acidic lysosomes of normal cells through ion trapping. Lysosomal trapping reduces the activity of anticancer drugs, since anticancer drug targets are often localized in the cell cytosol or nucleus. Some cancer cells have defective acidification of lysosomes, which causes a redistribution of trapped drugs from the lysosomes to the cytosol. We have previously established that such differences in drug localization between normal and cancer cells can contribute to the apparent selectivity of weakly basic drugs to cancer cells in vitro. In this work, we tested whether this intracellular distribution-based drug selectivity could be optimized based on the acid dissociation constant (pKa) of the drug, which is one of the determinants of lysosomal sequestration capacity. We synthesized seven weakly basic structural analogs of the Hsp90 inhibitor geldanamycin (GDA) with pKa values ranging from 5 to 12. The selectivity of each analog was expressed by taking ratios of anti-proliferative IC(50) values of the inhibitors in normal fibroblasts to the IC(50) values in human leukemic HL-60 cells. Similar selectivity assessments were performed in a pair of cancer cell lines that differed in lysosomal pH as a result of siRNA-mediated alteration of vacuolar proton ATPase subunit expression. Optimal selectivity was observed for analogs with pKa values near 8. Similar trends were observed with commercial anticancer agents with varying weakly basic pKa values. These evaluations advance our understanding of how weakly basic properties can be optimized to achieve maximum anticancer drug selectivity towards cancer cells with defective lysosomal acidification in vitro. Additional in vivo studies are needed to examine the utility of this approach for enhancing selectivity.

Lysosomotropic Properties of Weakly Basic Anticancer Agents Promote Cancer Cell Selectivity In Vitro

PubMed Central

Ndolo, Rosemary A.; Luan, Yepeng; Duan, Shaofeng; Forrest, M. Laird; Krise, Jeffrey P.

2012-01-01

Drug distribution in cells is a fundamentally important, yet often overlooked, variable in drug efficacy. Many weakly basic anticancer agents accumulate extensively in the acidic lysosomes of normal cells through ion trapping. Lysosomal trapping reduces the activity of anticancer drugs, since anticancer drug targets are often localized in the cell cytosol or nucleus. Some cancer cells have defective acidification of lysosomes, which causes a redistribution of trapped drugs from the lysosomes to the cytosol. We have previously established that such differences in drug localization between normal and cancer cells can contribute to the apparent selectivity of weakly basic drugs to cancer cells in vitro. In this work, we tested whether this intracellular distribution-based drug selectivity could be optimized based on the acid dissociation constant (pKa) of the drug, which is one of the determinants of lysosomal sequestration capacity. We synthesized seven weakly basic structural analogs of the Hsp90 inhibitor geldanamycin (GDA) with pKa values ranging from 5 to 12. The selectivity of each analog was expressed by taking ratios of anti-proliferative IC50 values of the inhibitors in normal fibroblasts to the IC50 values in human leukemic HL-60 cells. Similar selectivity assessments were performed in a pair of cancer cell lines that differed in lysosomal pH as a result of siRNA-mediated alteration of vacuolar proton ATPase subunit expression. Optimal selectivity was observed for analogs with pKa values near 8. Similar trends were observed with commercial anticancer agents with varying weakly basic pKa values. These evaluations advance our understanding of how weakly basic properties can be optimized to achieve maximum anticancer drug selectivity towards cancer cells with defective lysosomal acidification in vitro. Additional in vivo studies are needed to examine the utility of this approach for enhancing selectivity. PMID:23145164

Streptococcal adhesin SspA/B analogue peptide inhibits adherence and impacts biofilm formation of Streptococcus mutans

PubMed Central

Ito, Tatsuro; Ichinosawa, Takahiro; Shimizu, Takehiko

2017-01-01

Streptococcus mutans, the major causative agent of dental caries, adheres to tooth surfaces via the host salivary glycoprotein-340 (gp340). This adherence can be competitively inhibited by peptides derived from the SspA/B adhesins of Streptococcus gordonii, a human commensal microbe that competes for the same binding sites. Ssp(A4K-A11K), a double-lysine substituted SspA/B peptide analogue, has been shown to exhibit superior in vitro binding affinity for a gp340-derived peptide (SRCRP2), suggesting that Ssp(A4K-A11K) may be of clinical interest. In the present work, we tested the inhibitory effects of Ssp(A4K-A11K) on adherence and biofilm formation of S. mutans by reconstructing an artificial oral environment using saliva-coated polystyrene plates and hydroxyapatite disks. Bacterial adherence (adherence period: 1 h) was assessed by an enzyme-linked immunosorbent assay using biotinylated bacterial cells. Biofilm formation (periods: 8, 11, or 14 h) was assessed by staining and imaging of the sessile cells, or by recovering biofilm cells and plating for cell counts. The pH values of the culture media were measured as a biofilm acidogenicity indicator. Bactericidality was measured by loss of optical density during culturing in the presence of the peptide. We observed that 650 μM Ssp(A4K-A11K) significantly inhibited adherence of S. mutans to saliva-coated polystyrene; a similar effect was seen on bacterial affinity for SRCRP2. Ssp(A4K-A11K) had lesser effects on the adherence of commensal streptococci. Pretreatment of polystyrene and hydroxyapatite with 650 μM Ssp(A4K-A11K) significantly attenuated biofilm formation, whether tested with glucose- or sucrose-containing media. The SspA/B peptide’s activity did not reflect bactericidality. Strikingly, pH in Ssp-treated 8-h (6.8 ± 0.06) and 11-h (5.5 ± 0.06) biofilms showed higher values than the critical pH. Thus, Ssp(A4K-A11K) acts by inhibiting bacterial adherence and cariogrnic biofilm formation. We further consider these results in the context of the safety, specificity, and stability properties of the Ssp(A4K-A11K) peptide. PMID:28394940

Defense Waste Processing Facility Canister Closure Weld Current Validation Testing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Korinko, P. S.; Maxwell, D. N.

Two closure welds on filled Defense Waste Processing Facility (DWPF) canisters failed to be within the acceptance criteria in the DWPF operating procedure SW4-15.80-2.3 (1). In one case, the weld heat setting was inadvertently provided to the canister at the value used for test welds (i.e., 72%) and this oversight produced a weld at a current of nominally 210 kA compared to the operating procedure range (i.e., 82%) of 240 kA to 263 kA. The second weld appeared to experience an instrumentation and data acquisition upset. The current for this weld was reported as 191 kA. Review of the datamore » from the Data Acquisition System (DAS) indicated that three of the four current legs were reading the expected values, approximately 62 kA each, and the fourth leg read zero current. Since there is no feasible way by further examination of the process data to ascertain if this weld was actually welded at either the target current or the lower current, a test plan was executed to provide assurance that these Nonconforming Welds (NCWs) meet the requirements for strength and leak tightness. Acceptance of the welds is based on evaluation of Test Nozzle Welds (TNW) made specifically for comparison. The TNW were nondestructively and destructively evaluated for plug height, heat tint, ultrasonic testing (UT) for bond length and ultrasonic volumetric examination for weld defects, burst pressure, fractography, and metallography. The testing was conducted in agreement with a Task Technical and Quality Assurance Plan (TTQAP) (2) and applicable procedures.« less

Orbital forced frequencies in the 975000 year pollen record from Tenagi Philippon (Greece)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mommersteeg, H.J.P.M.; Young, R.; Wijmstra, T.A.

Frequency analysis was applied to different time series obtained from the 975 ka pollen record of Tenagi Philippon (Macedonia, Greece). These time series are characteristic of different vegetation types related to specific climatic conditions. Time control of the 196 m deep core was based on 11 finite {sup 14}C dates in the upper 17 m, magnetostratigraphy and correlation with the marine oxygen isotope stratigraphy. Maximum entropy spectrum analyses and thomson multi-taper spectrum analysis were applied using the complete time series. Periods of 95-99, 40-45. 24.0-25.5 and 19-21 ka which can be related to orbital forcing, as well as periods ofmore » about 68, 30 ka and of about 15.5, 13.5, 12 and 10.5 ka were detected. The detected periods of about 68, 30 ka and 16, 14, 12, 10.5 ka are likely to be harmonics and combination tones of the periods related to orbital forcing. The period of around 30 ka is possibly a secondary peak of obliquity. To study the stability of the detected periods through time, analysis with a moving window was employed. Signals in the eccentricity band were detected clearly during the last 650 ka. In the precession band, detected periods of about 24 ka show an increase in amplitude during the last 650 ka. The evolution of orbital frequencies during the last 1.0 Ma is in general agreement with the results of other marine and continental time series. Time series related to different climatic settings showed a different response to orbital forcing. Time series of vegetational elements sensitive to changes in net precipitation were forced in the precession and obliquity bands. Changes in precession caused changes in the monsoon system, which indirectly had a strong influence on the climatic history of Greece. Time series of vegetational elements which are more indicative of changes in annual temperature are forced in the eccentricity band. 54 refs., 12 figs., 3 tabs.« less

Intrinsic acid-base properties of a hexa-2'-deoxynucleoside pentaphosphate, d(ApGpGpCpCpT): neighboring effects and isomeric equilibria.

PubMed

Domínguez-Martín, Alicia; Johannsen, Silke; Sigel, Astrid; Operschall, Bert P; Song, Bin; Sigel, Helmut; Okruszek, Andrzej; González-Pérez, Josefa María; Niclós-Gutiérrez, Juan; Sigel, Roland K O

2013-06-17

The intrinsic acid-base properties of the hexa-2'-deoxynucleoside pentaphosphate, d(ApGpGpCpCpT) [=(A1∙G2∙G3∙C4∙C5∙T6)=(HNPP)⁵⁻] have been determined by ¹H NMR shift experiments. The pKa values of the individual sites of the adenosine (A), guanosine (G), cytidine (C), and thymidine (T) residues were measured in water under single-strand conditions (i.e., 10% D₂O, 47 °C, I=0.1 M, NaClO₄). These results quantify the release of H⁺ from the two (N7)H⁺ (G∙G), the two (N3)H⁺ (C∙C), and the (N1)H⁺ (A) units, as well as from the two (N1)H (G∙G) and the (N3)H (T) sites. Based on measurements with 2'-deoxynucleosides at 25 °C and 47 °C, they were transferred to pKa values valid in water at 25 °C and I=0.1 M. Intramolecular stacks between the nucleobases A1 and G2 as well as most likely also between G2 and G3 are formed. For HNPP three pKa clusters occur, that is those encompassing the pKa values of 2.44, 2.97, and 3.71 of G2(N7)H⁺, G3(N7)H⁺, and A1(N1)H⁺, respectively, with overlapping buffer regions. The tautomer populations were estimated, giving for the release of a single proton from five-fold protonated H₅(HNPP)(±) , the tautomers (G2)N7, (G3)N7, and (A1)N1 with formation degrees of about 74, 22, and 4%, respectively. Tautomer distributions reveal pathways for proton-donating as well as for proton-accepting reactions both being expected to be fast and to occur practically at no "cost". The eight pKa values for H₅(HNPP)(±) are compared with data for nucleosides and nucleotides, revealing that the nucleoside residues are in part affected very differently by their neighbors. In addition, the intrinsic acidity constants for the RNA derivative r(A1∙G2∙G3∙C4∙C5∙U6), where U=uridine, were calculated. Finally, the effect of metal ions on the pKa values of nucleobase sites is briefly discussed because in this way deprotonation reactions can easily be shifted to the physiological pH range. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ku/Ka band observations over polar ice sheets

NASA Astrophysics Data System (ADS)

Thibaut, Pierre; Lasne, Yannick; Guillot, Amandine; Picot, Nicolas; Rémy, Frédérique

2015-04-01

For the first time, comparisons between Ku and Ka altimeter measurements are possible thanks to the new AltiKa instrument embarked onboard the Saral mission launched on February 25, 2013. This comparison is of particular interest when dealing with ice sheet observations because both frequencies have different penetration characteristics. We propose in this paper to revisit the estimation of the ice sheet topography (and other related parameters) with altimeter systems and to present illustrations of the differences observed in Ku and Ka bands using AltiKa, Envisat/RA-2 but also Cryosat-2 measurements. Working on AltiKa waveforms in the frame of the PEACHI project has allowed us to better understand the impact of the penetration depth on the echo shape, to improve the estimation algorithm and to compare its output with historical results obtained on Envisat and ERS missions. In particular, analyses at cross-overs of the Cryosat-2 and Saral data will be presented. Sentinel-3 mission should be launch during 2015. Operating in Ku band and in delay/doppler mode, it will be crucial to account for penetration effects in order to accurately derive the ice sheet heights and trends. The results of the work presented here, will benefit to the Sentinel-3 mission.

Quaternary record of aridity and mean annual precipitation based on δ15N in ratite and dromornithid eggshells from Lake Eyre, Australia.

PubMed

Newsome, Seth D; Miller, Gifford H; Magee, John W; Fogel, Marilyn L

2011-12-01

The cause(s) of the late Pleistocene megafauna extinction on the Australian continent remains largely unresolved. Unraveling climatic forcing mechanisms from direct or indirect human agents of ecosystem alteration has proven to be extremely difficult in Australia due to the lack of (1) well-dated vertebrate fossils and (2) paleo-environmental and -ecological records spanning the past approximately 100 ka when regional climatic conditions are known to have significantly varied. We have examined the nitrogen isotope composition (δ(15)N) of modern emu (Dromaius novaehollandiae) eggshells collected along a precipitation gradient in Australia, along with modern climatological data and dietary δ(15)N values. We then used modern patterns to interpret an approximately 130-ka record of δ(15)N values in extant Dromaius and extinct Genyornis newtoni eggshells from Lake Eyre to obtain a novel mean annual precipitation (MAP) record for central Australia spanning the extinction interval. Our data also provide the first detailed information on the trophic ecology and environmental preferences of two closely related taxa, one extant and one extinct. Dromaius eggshell δ(15)N values show a significant shift to higher values during the Last Glacial Maximum and Holocene, which we interpret to indicate more frequent arid conditions (<200 mm MAP), relative to δ(15)N from samples just prior to the megafauna extinction. Genyornis eggshells had δ(15)N values reflecting wetter nesting conditions overall relative to those of coeval Dromaius, perhaps indicating that Genyornis was more reliant on mesic conditions. Lastly, the Dromaius eggshell record shows a significant decrease in δ(13)C values prior to the extinction, whereas the Genyornis record does not. Neither species showed a concomitant change in δ(15)N prior to the extinction, which suggests that a significant change in vegetation surrounding Lake Eyre occurred prior to an increase in local aridity.

Deciphering the paleoseismic history of the central Dead Sea fault (Yammouneh fault, Lebanon) based on multiple luminescence dating techniques

NASA Astrophysics Data System (ADS)

Le Beon, M.; Tseng, Y. C.; Klinger, Y.; Elias, A.; Kunz, A.; Sursock, A.; Daeron, M.; Tapponnier, P.; Jomaa, R.

2017-12-01

The Yammouneh fault is the main strike-slip branch of the Dead Sea fault system in Lebanon. The morphology of the northern Yammouneh fault is characterized by a series of basins that represent archives for Late Pleistocene paleo-environments and paleo-earthquakes. We excavated a 4-m-deep trench across the fault in the Jbab el-Homr basin that revealed a succession of remarkable, very thin palustrine and lacustrine layers, ruptured by at least 17 earthquakes. Absolute ages of 4 samples from 0.5 to 3.7 m depth are obtained by optically stimulated luminescence dating on fine-grain quartz and on fine-grain K-feldspar using both infrared luminescence at 50˚C (IRSL50) and at a high temperature of 225˚C (pIRIR225). A fair agreement is obtained between the quartz ages (from 26.5 ± 3.1 ka at 0.5 m depth to 30.3 ± 3.4 ka at 3.7 m depth) and the pIRIR225 ages (from 26.2 ± 2.3 ka at 0.5 m depth to 25.8 ± 2.1 ka at 3.7 m depth), while the fading-corrected IRSL50 ages are systematically younger (from 18.3 ± 1.6 ka at 0.5 m depth to 21.4 ± 1.8 ka at 3.7 m depth). As proposed in earlier studies, we hypothesize that the IRSL50 fading rate is underestimated. The sedimentary sequence may reflect deposition in a marsh or shallow lake in a pro-glacial environment at a time when a glacier may have occupied the summits of Mount Lebanon. Erosion may have been dominant after the Last Glacial Maximum. Regarding paleo-earthquakes, 14 surface-rupturing events occurred during 3.8 ka with a mean return time of 270 years and probable clustering, while only 2-11 events occurred since 26.5 ka. Firstly, we explain the lack of events since 26.5 ka by the existence of another fault branch, which suggests that the active fault zone migrated with time. Secondly, the shorter mean recurrence time in Jbab compared to the Yammouneh site, located 30 km south may be explained by temporal variations in the earthquake cycle, different locations relative to fault segmentation, or by high-resolution of the stratigraphy in Jbab that allowed recording smaller-magnitude events that may have been missed in the thicker strata of Yammouneh.

The importance of pre-annealing treatment for ESR dating of mollusc shells: A key study for İsmil in Konya closed Basin/Turkey

NASA Astrophysics Data System (ADS)

Ekici, Gamze; Sayin, Ulku; Aydin, Hulya; Isik, Mesut; Kapan, Sevinc; Demir, Ahmet; Engin, Birol; Delikan, Arif; Orhan, Hukmu; Biyik, Recep; Ozmen, Ayhan

2018-02-01

In this study, Electron Spin Resonance (ESR) spectroscopy is used to determine the geological ages of fossil mollusc shells systematically collected from two different geological splitting at İsmil Location (37.72769° N, 33.17781° E) in eastern part of Konya. According to the assessment of obtained ESR ages, the importance of pre-annealing treatment emphasize in the case of g=2.0007 dating signal is overlapped with the other signals arisen from short lived radicals that cause the wrong age calculation. To overcome this problem, the samples are pre-annealed at 180°C for 16 minutes and, in this case ESR ages are re-calculated for g=1.9973 dating signal. Dose response curves are obtained using 1.9973 signals after pre-annealing treatments for each samples. ESR ages of samples are obtained in the range of 138 ± 38 ka and 132 ± 30 ka (Upper Pleistocene) according to the Early Uranium Uptake model and the results are in good agreement with the estimated ages from stratigraphic and paleontological correlation by geologists. Thus, it is suggested that especially in the case of 2.0007 dating signal cannot been used due to superimposition case, the signal with 1.9973 g value can be used for dating after pre-annealing treatment. The results reports the first ESR ages on shells collected from İsmil Location and highlight the importance of pre-annealing treatment. This study is supported by TUBITAK 114Y237 research project.

Temporal survey of electron number density and electron temperature in the exhaust of a megawatt MPD-arc thruster.

NASA Technical Reports Server (NTRS)

Michels, C. J.; Rose, J. R.; Sigman, D. R.

1972-01-01

Temporal and radial profiles are obtained 30 cm downstream from the anode for two peak arc currents (11.2 kA and 20 kA) and for various auxiliary magnetic fields (0, 1.0 T, and 2.0 T) using the Thomson scattering technique. Average density and temperature are relatively constant for over 100 microseconds with significant fluctuations. Radial profiles obtained are relatively flat for 4 cm from the axis. Compared to earlier 20 cm data, the exhaust density has decreased significantly, the average temperature has not changed, and the density ?hole' with an auxiliary magnetic field has enlarged.

Structure, hydrolysis, and diffusion of aqueous vanadium ions from Car-Parrinello molecular dynamics

NASA Astrophysics Data System (ADS)

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2016-09-01

A molecular level understanding of the properties of electroactive vanadium species in aqueous solution is crucial for enhancing the performance of vanadium redox flow batteries. Here, we employ Car-Parrinello molecular dynamics simulations based on density functional theory to investigate the hydration structures, first hydrolysis reaction, and diffusion of aqueous V2+, V3+, VO2+, and VO 2+ ions at 300 K. The results indicate that the first hydration shell of both V2+ and V3+ contains six water molecules, while VO2+ is coordinated to five and VO 2+ to three water ligands. The first acidity constants (pKa) estimated using metadynamics simulations are 2.47, 3.06, and 5.38 for aqueous V3+, VO 2+ , and VO2+, respectively, while V2+ is predicted to be a fairly weak acid in aqueous solution with a pKa value of 6.22. We also show that the presence of chloride ions in the first coordination sphere of the aqueous VO 2+ ion has a significant impact on water hydrolysis leading to a much higher pKa value of 4.8. This should result in a lower propensity of aqueous VO 2+ for oxide precipitation reaction in agreement with experimental observations for chloride-based electrolyte solutions. The computed diffusion coefficients of vanadium species in water at room temperature are found to increase as V 3 + < VO 2 + < V O 2 + < V 2 + and thus correlate with the simulated hydrolysis constants, namely, the higher the pKa value, the greater the diffusion coefficient.

The overuse of the implant motor: effect on the output torque in overloading condition.

PubMed

Lee, Du-Hyeong; Cho, Sung-Am; Lee, Cheong-Hee; Lee, Kyu-Bok

2015-06-01

The overloading of the motor affects its performance. The output torque of the implant motor under overloading condition has not been reported. The purpose of this study was to determine the reliability and the tendency of the output torque when an implant motor is consecutively used. Three implant motors were evaluated: SurgicXT/X-SG20L (NSK), INTRAsurg300/CL3-09 (KaVo), and XIP10/CRB26LX (Saeshin). The output torque was measured using an electronic torque gauge fixed with jigs. For the 40 and 50 Ncm torque settings, 300 measurements were taken at 30 rpm. Repeated measures of analysis of variance (ANOVA) and one-way ANOVA were used to compare the torque values within each group and between the groups. As repeating measures, the output torque values decreased gradually compared with the baseline. In within-group analysis, the different torque value from the first measurement appeared earliest in NSK motor, followed in order by Saeshin and KaVo motors. NSK motor showed a different torque decrease between 40 and 50 Ncm settings (p < .05). Intergroup analysis revealed Saeshin motor to have the least deviation from the baseline, followed by KaVo motor. NSK motor had the most inconsistent torque at the 6, 8, 9, and 10 repeat counts (p < .05). The actual torque decreases when the surgical motor is continuously used. The NSK motor showed more significant decreases in torque than KaVo and Saeshin motors in overloading condition. © 2014 Wiley Periodicals, Inc.

VizieR Online Data Catalog: Photometry/spectroscopic measurements for KA1858+4850 (Pei+, 2014)

NASA Astrophysics Data System (ADS)

Pei, L.; Barth, A. J.; Aldering, G. S.; Briley, M. M.; Carroll, C. J.; Carson, D. J.; Cenko, S. B.; Clubb, K. I.; Cohen, D. P.; Cucchiara, A.; Desjardins, T. D.; Edelson, R.; Fang, J. J.; Fedrow, J. M.; Filippenko, A. V.; Fox, O. D.; Furniss, A.; Gates, E. L.; Gregg, M.; Gustafson, S.; Horst, J. C.; Joner, M. D.; Kelly, P. L.; Lacy, M.; Laney, C. D.; Leonard, D. C.; Li, W.; Malkan, M. A.; Margon, B.; Neeleman, M.; Nguyen, M. L.; Prochaska, J. X.; Ross, N. R.; Sand, D. J.; Searcy, K. J.; Shivvers, I. S.; Silverman, J. M.; Smith, G. H.; Suzuki, N.; Smith, K. L.; Tytler, D.; Werk, J. K.; Worseck, G.

2017-05-01

We employed the Lick Observatory 3 m Shane telescope with the Kast Spectrograph and five other ground-based telescopes to spectroscopically and photometrically monitor KA1858+4850 from 2012 February to November. Reverberation mapping requires a continuum light curve with high sampling cadence and S/N. To achieve this, we obtained V-band images from ground-based telescopes and used aperture photometry to construct a light curve for KA1858+4850 that has nearly nightly sampling for a span of 290 days. For several reasons, we chose to use the V-band light curve rather than the Kepler light curve for reverberation measurements. (2 data files).

Flowstone compositions as indicators of centennial fluctuations of hydrological balance in Central Europe during the late Holocene

NASA Astrophysics Data System (ADS)

Demény, Attila; Kern, Zoltán; Molnár, Mihály; Czuppon, György; Leél-Őssy, Szabolcs; Surányi, Gergely; Gilli, Adrian

2017-04-01

Flowstones formed from springs in the Baradla and Béke Caves, North-east Hungary were drilled at several locations, and their sites were monitored for temperature, CO2 level in cave air, water and carbonate compositions for three years. The monitoring results suggest that the carbonate precipitated close to equilibrium with the local water. The non-systematic distribution of stable isotope and chemical compositions along sections on the surfaces of flowstone occurrences indicate irregular formation and the possibility of hiatuses within the flowstones' edifices. Approximately 40 cm long drill cores were extracted from the „Nagy-tufa" flowstone of the Béke Cave (BNT-2 core) and the Havasok flowstone of the Baradla Cave. U-Th dating efforts resulted in very large age uncertainties for the BNT-2 core, owing to detrital Th contamination. Therefore, in addition to the U-Th dating, AMS radiocarbon analyses were conducted to establish reliable age-depth models. The raw 14C ages were corrected for the dead carbon fraction (dfc) using radiocarbon results obtained for samples that yielded also accurate U-Th ages. Calibration and age-depth modeling have been performed using the OxCal v4.2.4. software. The data prove that the flowstones in the studied caves were formed contemporarily, covering the last 4 ka with two major hiatuses around 3.5 and 1 ka BP. Inclusion-hosted water contents, stable carbon and oxygen isotope compositions of carbonate, and hydrogen isotope composition of inclusion-hosted water as well as Si contents were determined for the two cores and compared with regional paleoclimate records for the period of 3.5 to 1 ka BP. The water contents, δ13Ccarb values and Si contents show correspondence with paleoprecipitation proxies from Central Europe to western Anatolia, while the paleotemperature estimates obtained using the δDwater values were in agreement with temperature reconstructions derived from paleobiological proxies from nearby lake sediments. The inferred paleohumidity variations agree also with water level changes of Lake Balaton (Western Hungary) assumed on the base of settlement migrations revealed by archeological excavations. These correlations indicate that the flowstone data provide valuable information about the regional water balance fluctuations for the late Holocene. The study was financed by the Hungarian Research Fund (OTKA NK 101664).

Lake level and climate records of the last 90 ka from the Northern Basin of Lake Van, eastern Turkey

NASA Astrophysics Data System (ADS)

Çağatay, M. N.; Öğretmen, N.; Damcı, E.; Stockhecke, M.; Sancar, Ü.; Eriş, K. K.; Özeren, S.

2014-11-01

Sedimentary, geochemical and mineralogical analyses of the ICDP cores recovered from the Northern Basin (NB) of Lake Van provide evidence of lake level and climatic changes related to orbital and North Atlantic climate system over the last 90 ka. High lake levels are generally observed during the interglacial and interstadial periods, which are marked by deposition of varved sediments with high total organic carbon (TOC), total inorganic carbon (TIC), low detrital influx (high Ca/F) and high δ18O and δ13C values of authigenic carbonate. During the glacial and stadial periods of 71-58 ka BP (Marine Isotope Stage 4, MIS4) and end of last glaciation-deglaciation (30-14.5 ka BP; MIS3) relatively low lake levels prevailed, and grey homogeneous to faintly laminated clayey silts were deposited at high sedimentation and low organic productivity rates. Millennial-scale variability of the proxies during 60-30 ka BP (MIS3 is correlated with the Dansgaard-Oeschger (D-O)) and Holocene abrupt climate events in the Atlantic. These events are characterized by laminated sediments, with high TOC, TIC, Ca/Fe, δ18O and δ13C values. The Lake Van NB records correlate well in the region with the climate records from the lakes Zeribar and Urmia in Iran and the Sofular Cave in NW Anatolia, but are in general in anti-phase to those from the Dead Sea Basin (Lake Lisan) in the Levant. The relatively higher δ18O values (0 to -0.4‰) for the interglacial and interstadial periods in the Lake Van NB section are due to the higher temperature and seasonality of precipitation and higher evaporation, whereas the lower values (-0.8 to -2‰) during the glacial and stadial periods are caused mainly by relative decrease in both temperature and seasonality of precipitation. The high δ18O values (up to 4.2‰) during the Younger Dryas, together with the presence of dolomite and low TOC contents, supports evaporative conditions and low lake level. A gradual decrease in the δ18O values from an average of -0.4‰ during the humid early Holocene to an average of -3.5‰ during the more arid late Holocene suggests an increasing contribution of winter precipitation. The changes in the seasonality of precipitation in eastern Anatolia are probably caused by changes in the temperatures of North Atlantic and Mediterranean and in the strength of Siberian High.

Climate variability in the past ∼19,000 yr in NE Tibetan Plateau inferred from biomarker and stable isotope records of Lake Donggi Cona

NASA Astrophysics Data System (ADS)

Saini, Jeetendra; Günther, Franziska; Aichner, Bernhard; Mischke, Steffen; Herzschuh, Ulrike; Zhang, Chengjun; Mäusbacher, Roland; Gleixner, Gerd

2017-02-01

We investigated 4.84-m-long sediment record spanning over the Late Glacial and Holocene from Lake Donggi Cona to be able to reconstruct circulation pattern on the Tibetan Plateau (TP). Presently, Lake Donggi Cona is located at the boundaries of Westerlies and Asian monsoon circulations in the northeastern TP. However, the exact timing and stimulating mechanisms for climatic changes and monsoon shifts in this region are still debated. We used a 19-ka-long stable isotope record of sedimentary n-alkanes to address this discrepancy by providing insights into paleohydrological conditions. The δD of nC23 is influenced by lake water evaporation; the δD values of sedimentary nC29 are mainly controlled by moisture source and temperature changes. Long-chain n-alkanes dominate over the core whereas three mean clusters (i.e. microbial, aquatic and terrestrial) can be inferred. Multi-proxies suggest five major episodes in the history of Lake Donggi Cona. The Lake Donggi Cona record indicates that the Late Glacial (18.4-14.8 cal ka BP) was dominated by low productivity of mainly microbial and aquatic organisms. Relatively low δD values suggest low temperatures and moist conditions eventually caused by stronger Westerlies, winter monsoon and melt-water influence. Likely, the shift (∼17.9 cal ka BP) from microbial to enhanced aquatic input suggests either a change from deep to shallow water lake or a break in local stratification. Between 14.8 and 13.0 cal ka BP, variable climatic conditions prevailed. Although the Westerlies weekend, the increase in temperature enhanced the permafrost and snow melting (displayed by a high sedimentary accumulation rate). Higher δD values indicate increasingly arid conditions with higher temperatures which eventually lead to high evaporative conditions and lowest lake levels. Low vegetation cover and high erosion rates led to high sediment accumulation resulting in stratification followed by anoxia in the terminal lake. From 13.0 to 9.2 cal ka BP, lowered values of δD along with high contents of terrestrial organic matter marked the early-Holocene warming indicating a further strengthening of summer precipitation and higher lake levels. A cooling trend was observed in the mid-Holocene between 9.2 and 3.0 cal ka BP accompanied by higher moisture availability (displayed by lowered δD values) caused by reduced evaporative conditions due to a drop in temperature and recovering Westerlies. After 3.0 cal ka BP, a decrease in lake productivity and cold and semi-arid conditions prevailed suggesting lower lake levels and reduced moisture from recycled air masses and Westerlies. We propose that the summer monsoon was the predominant moisture source during the Bølling-Allerød warm complex and early-Holocene followed by Westerlies in mid-to-late Holocene period. Stable carbon isotope values ∼ - 32‰ indicate the absence of C4-type vegetation in the region contradicting with their presence in the Lake Qinghai record. The δD record from lake Donggi Cona highlights the importance of the interplay between Westerlies and summer monsoon circulation at this location, which is highly dynamic in northeastern plateau compared to the North Atlantic circulation and insolation changes. Consequently lake Donggi Cona might be an important anchor point for environmental reconstructions on the Tibetan Plateau.

Dating of the youngest volcanoes of Ardeche (Massif Central, France) using 40Ar/39Ar and unspiked K/Ar

NASA Astrophysics Data System (ADS)

Nomade, Sebastien; Sasco, Romain; Guillou, Herve; Scao, Vincent; Kissel, Catherine; Genty, Dominique

2014-05-01

Since the first description in 1778 of the relationship between prismatic basaltic flow and volcano in the high valleys of the Ardèche (Faujas Saint-Font, 1778), "L'Ardèche", a small region at the south-west of Massif Central, became worldwide famous among volcanologists. This volcanism is found dispersed over an area of more than 20 km2 and is made of strombolian cones and prismatic flows filling NS to NW-SE valleys. This volcanism has then been considered as one of the most recent one in the entire Massif Central (40 ka to 170 ka, TL ages, Guérin et al., 2007). Unfortunately and despite several attempts over the last 25 years this volcanism has never been dated using radio-isotopic methods. The two main reasons usually advocated to explain this lack of success were the young age of the volcanism itself and the large amounts of mantle and lower crust xenoliths in the lavas (Guérin et al., 2007). In this contribution, we will present combined 40Ar/39Ar ages and unspiked K/Ar results obtained on five lava flows. The obtained ages range from 26 ± 5.5 ka to 55 ± 6.0 ka (1s, full propagated uncertainty relative to ACS-2 at 1.194Ma, Nomade et al., 2005). The ages from three of the investigated lava flows coming from distinct cones, are clustered between 26 ± 5.5 ka and 34 ± 4 ka. These cones are found stretched along a NW-SE tectonic accident. These first radio-isotopic constraints prove that the volcanic activity occurred during the last glacial period and is as young as "la chaîne de Puys" located in the northern part of the Massif Central. Incidentally, the volcanic activity is contemporaneous with the first Aurignacian occupation and related art found in the Chauvet cave (37-29 ka, Valladas et al., 2005) localized only 35 km SE. Based on both the spatial and chronological coincidences reported above we suggest that the Aurignacian population(s) that lived in this area have witnessed one or several of these eruptions.

The rise and fall of Lake Bonneville between 45 and 10.5 ka

USGS Publications Warehouse

Benson, L.V.; Lund, S.P.; Smoot, J.P.; Rhode, D.E.; Spencer, R.J.; Verosub, K.L.; Louderback, L.A.; Johnson, C.A.; Rye, R.O.; Negrini, R.M.

2011-01-01

A sediment core taken from the western edge of the Bonneville Basin has provided high-resolution proxy records of relative lake-size change for the period 45.1-10.5 calendar ka (hereafter ka). Age control was provided by a paleomagnetic secular variation (PSV)-based age model for Blue Lake core BL04-4. Continuous records of ??18O and total inorganic carbon (TIC) generally match an earlier lake-level envelope based on outcrops and geomorphic features, but with differences in the timing of some hydrologic events/states. The Stansbury Oscillation was found to consist of two oscillations centered on 25 and 24 ka. Lake Bonneville appears to have reached its geomorphic highstand and began spilling at 18.5 ka. The fall from the highstand to the Provo level occurred at 17.0 ka and the lake intermittently overflowed at the Provo level until 15.2 ka, at which time the lake fell again, bottoming out at ~14.7 ka. The lake also fell briefly below the Provo level at ~15.9 ka. Carbonate and ??18O data indicate that between 14.7 and 13.1 ka the lake slowly rose to the Gilbert shoreline and remained at about that elevation until 11.6 ka, when it fell again. Chemical and sedimentological data indicate that a marsh formed in the Blue Lake area at 10.5 ka.Relatively dry periods in the BL04-4 records are associated with Heinrich events H1-H4, suggesting that either the warming that closely followed a Heinrich event increased the evaporation rate in the Bonneville Basin and (or) that the core of the polar jet stream (PJS) shifted north of the Bonneville Basin in response to massive losses of ice from the Laurentide Ice Sheet (LIS) during the Heinrich event. The second Stansbury Oscillation occurred during Heinrich event H2, and the Gilbert wet event occurred during the Younger Dryas cold interval. Several relatively wet events in BL04-4 occur during Dansgaard-Oeschger (DO) warm events.The growth of the Bear River glacier between 32 and 17 ka paralleled changes in the values of proxy indicators of Bonneville Basin wetness and terminal moraines on the western side of the Wasatch Mountains have ages ranging from 16.9 to 15.2 ka. This suggests a near synchroneity of change in the hydrologic and cryologic balances occurring in the Bonneville drainage system and that glacial extent was linked to lake size. ?? 2010.

Genetic variation in RPS6KA1, RPS6KA2, RPS6KB1, RPS6KB2, and PDK1 and risk of colon or rectal cancer

PubMed Central

Slattery, Martha L.; Lundgreen, Abbie; Herrick, Jennifer S.; Wolff, Roger K.

2010-01-01

RPS6KA1, RPS6KA2, RPS6KB1, RPS6KB2, and PDK1 are involved in several pathways central to the carcinogenic process, including regulation of cell growth, insulin, and inflammation. We evaluated genetic variation in their candidate genes to obtain a better understanding of their association with colon and rectal cancer. We used data from two population-based case-control studies of colon (n=1574 cases, 1940 controls) and rectal (n=791 cases, 999 controls) cancer. We observed genetic variation in RPS6KA1, RPS6KA2, and PRS6KB2 were associated with risk of developing colon cancer while only genetic variation in RPS6KA2 was associated with altering risk of rectal cancer. These genes also interacted significantly with other genes operating in similar mechanisms, including Akt1, FRAP1, NFκB1, and PIK3CA. Assessment of tumor markers indicated that these genes and this pathway may importantly contributed to CIMP+ tumors and tumors with KRAS2 mutations. Our findings implicate these candidate genes in the etiology of colon and rectal cancer and provide information on how these genes operate with other genes in the pathway. Our data further suggest that this pathway may lead to CIMP+ and KRAS2-mutated tumors. PMID:21035469

Residues in the H+ Translocation Site Define the pKa for Sugar Binding to LacY†

PubMed Central

Smirnova, Irina; Kasho, Vladimir; Sugihara, Junichi; Choe, Jun-Yong; Kaback, H. Ronald

2009-01-01

A remarkably high pKa of approximately 10.5 has been determined for sugar-binding affinity to the lactose permease of Escherichia coli (LacY), indicating that, under physiological conditions, substrate binds to fully protonated LacY. We have now systematically tested site-directed replacements for the residues involved in sugar binding, as well as H+ translocation and coupling, in order to determine which residues may be responsible for this alkaline pKa. Mutations in the sugar-binding site (Glu126, Trp151, Glu269) markedly decrease affinity for sugar but do not alter the pKa for binding. In contrast, replacements for residues involved in H+ translocation (Arg302, Tyr236, His322, Asp240, Glu325, Lys319) exhibit pKa values for sugar binding that are either shifted toward neutral pH or independent of pH. Values for the apparent dissociation constant for sugar binding (Kdapp) increase greatly for all mutants except neutral replacements for Glu325 or Lys319, which are characterized by remarkably high affinity sugar binding (i.e., low Kdapp) from pH 5.5 to pH 11. The pH dependence of the on- and off-rate constants for sugar binding measured directly by stopped-flow fluorometry implicates koff as a major factor for the affinity change at alkaline pH and confirms the effects of pH on Kdapp inferred from steady-state fluorometry. These results indicate that the high pKa for sugar binding by wild-type LacY cannot be ascribed to any single amino acid residue but appears to reside within a complex of residues involved in H+ translocation. There is structural evidence for water bound in this complex, and the water could be the site of protonation responsible for the pH dependence of sugar binding. PMID:19689129

A ~25 ka Indian Ocean monsoon variability record from the Andaman Sea

USGS Publications Warehouse

Rashid, H.; Flower, B.P.; Poore, R.Z.; Quinn, T.M.

2007-01-01

Recent paleoclimatic work on terrestrial and marine deposits from Asia and the Indian Ocean has indicated abrupt changes in the strength of the Asian monsoon during the last deglaciation. Comparison of marine paleoclimate records that track salinity changes from Asian rivers can help evaluate the coherence of the Indian Ocean monsoon (IOM) with the larger Asian monsoon. Here we present paired Mg/Ca and δ18O data on the planktic foraminifer Globigerinoides ruber (white) from Andaman Sea core RC12-344 that provide records of sea-surface temperature (SST) and δ18O of seawater (δ18Osw) over the past 25,000 years (ka) before present (BP). Age control is based on nine accelerator mass spectrometry (AMS) dates on mixed planktic foraminifera. Mg/Ca-SST data indicate that SST was ∼3 °C cooler during the last glacial maximum (LGM) than the late Holocene. Andaman Sea δ18Osw exhibited higher than present values during the Lateglacial interval ca 19–15 ka BP and briefly during the Younger Dryas ca 12 ka BP. Lower than present δ18Osw values during the BØlling/AllerØd ca 14.5–12.6 ka BP and during the early Holocene ca 10.8–5.5 ka BP are interpreted to indicate lower salinity, reflect some combination of decreased evaporation–precipitation (E–P) over the Andaman Sea and increased Irrawaddy River outflow. Our results are consistent with the suggestion that IOM intensity was stronger than present during the BØlling/AllerØd and early Holocene, and weaker during the late glaciation, Younger Dryas, and the late Holocene. These findings support the hypothesis that rapid climate change during the last deglaciation and Holocene included substantial hydrologic changes in the IOM system that were coherent with the larger Asian monsoon.

Multiple constraints on the age of a Pleistocene lava dam across the Little Colorado River at Grand Falls, Arizona

USGS Publications Warehouse

Duffield, W.; Riggs, N.; Kaufman, D.; Champion, D.; Fenton, C.; Forman, S.; McIntosh, W.; Hereford, R.; Plescia, J.; Ort, M.

2006-01-01

The Grand Falls basalt lava flow in northern Arizona was emplaced in late Pleistocene time. It flowed 10 km from its vent area to the Little Colorado River, where it cascaded into and filled a 65-m-deep canyon to form the Grand Falls lava dam. Lava continued ???25 km downstream and ???1 km onto the far rim beyond where the canyon was filled. Subsequent fluvial sedimentation filled the reservoir behind the dam, and eventually the river established a channel along the margin of the lava flow to the site where water falls back into the pre-eruption canyon. The ca. 150 ka age of the Grand Falls flow provided by whole-rock K-Ar analysis in the 1970s is inconsistent with the preservation of centimeter-scale flow-top features on the surface of the flow and the near absence of physical and chemical weathering on the flow downstream of the falls. The buried Little Colorado River channel and the present-day channel are at nearly the same elevation, indicating that very little, if any, regional downcutting has occurred since emplacement of the flow. Newly applied dating techniques better define the age of the lava dam. Infrared-stimulated luminescence dating of silty mudstone baked by the lava yielded an age of 19.6 ?? 1.2 ka. Samples from three noneroded or slightly eroded outcrops at the top of the lava flow yielded 3He cosmogenic ages of 16 ?? 1 ka, 17 ?? 1 ka, and 20 ?? 1 ka. A mean age of 8 ?? 19 ka was obtained from averaging four samples using the 40Ar/39Ar step-heating method. Finally, paleomagnetic directions in lava samples from two sites at Grand Falls and one at the vent area are nearly identical and match the curve of magnetic secular variation at ca. 15 ka, 19 ka, 23 ka, and 28 ka. We conclude that the Grand Falls flow was emplaced at ca. 20 ka. ?? 2006 Geological Society of America.

Implications of Bishop Tuff zircon U-Pb ages for rates of zircon growth and magma accumulation

NASA Astrophysics Data System (ADS)

Reid, M. R.; Schmitt, A. K.

2012-12-01

Rates of geologic processes obtained from natural studies rely on accurate geochronologic information. An important benchmark in geochronology as well as a valuable source of insights into the evolution of voluminous explosive eruptions is the >600 km3 Bishop Tuff (BT). A recently determined weighted mean 206Pb/238U date of 767.1±0.9 ka for a BT zircon population [1] is indistinguishable from the recalibrated 40Ar/39Ar sanidine date of 767.4±2.2 ka [2], potentially providing a key intercalibration point between astronomical and radio-isotopic dating approaches. Consequences of these results are linear zircon growth rates of >1×10-14 cm/sec and magma accumulation rates of >200 km3/ka. In contrast, spatially selective SIMS U-Pb dating of BT zircons yielded mean pre-eruption ages of 850 ka [3], a difference that raises questions about the validity of intercalibration between U-Pb and K-Ar dating methods and the history of magma accumulation. We obtained new SIMS analyses of the BT zircons using more spatially and analytically sensitive methods and verifying our accuracy against the TIMS dated Quaternary zircon 61.308A (2.488±0.002 Ma). Analyses were performed on zircon rims and on oriented cross-sections exposed during optical interferometry-calibrated serial sectioning removing the outermost ~31 μm. Sputtering by a 100 nA ion beam versus the normally employed 10-12 nA beam resulted in enhanced radiogenic Pb yields and analytical uncertainties for Quaternary zircon approaching the U-Pb age reproducibility of the primary zircon standard (~1-2 % for AS3). Ages obtained at ~31 μm depth (representing <5% of crystal growth in most cases) average 892±26ka (MSWD=0.29), corroborating previous evidence for residence times of several tens of ka. Rim ages average 781±22 ka (MSWD=0.61), overlapping Ar/Ar determinations of eruption age and corroborating the importance of near-eruption aged zircon growth. Our results confirm the presence of BT zircon domains that predate eruption by tens of ka, domains that could be difficult to detect by single crystal analyses. SIMS analyses can selectively sample more interior portions of grains whereas whole grain TIMS analyses will be volumetrically biased towards the outermost ~20% of the BT zircons. Spots centered on BT zircon cores sample a domain representing only a few volume percent of the crystal; if mantled completely by eruption-aged growth, single crystal zircon ages are predicted to be <5 ka older than eruption, extrapolating from the SIMS dates. When, compared to grain interiors, the greater average near-rim U concentrations are factored into this mass balance, the influence of these older domains is further diminished. A scenario that can at least partially reconcile the disparate zircon dates in the context of evolution of the BT and the dynamics of zircon crystallization is as follows: (1) zircon nucleation and relatively rapid growth an average of ~100 ka before eruption; (2) significant decay in zircon growth rates as temperatures and Zr melt gradients relax; and, finally, (3) mantling of earlier zircon cores by rejuvenation and renewed BT zircon growth during the lead-up to eruption. Comparisons between spot and single grain dating show that most zircon growth likely occurred close to eruption. [1] Crowley et al., 2007.Geology 35, 1123. [2] Rivera et al., 2011. Earth Planet. Sci. Lett. 311, 420. [3] Simon and Reid, 2005. Earth Planet. Sci. Lett. 235, 123.

New insights on lithofacies architecture, sedimentological characteristics and volcanological evolution of pre-caldera (> 22 ka), multi-phase, scoria- and spatter-cones at Somma-Vesuvius

NASA Astrophysics Data System (ADS)

Sparice, Domenico; Scarpati, Claudio; Perrotta, Annamaria; Mazzeo, Fabio Carmine; Calvert, Andrew T.; Lanphere, Marvin A.

2017-11-01

Pre-caldera (> 22 ka) lateral activity at Somma-Vesuvius is related to scoria- and spatter-cone forming events of monogenetic or polygenetic nature. A new stratigraphic, sedimentological, textural and lithofacies investigation was performed on five parasitic cones (Pollena cones, Traianello cone, S. Maria a Castello cone and the recently found Terzigno cone) occurring below the Pomici di Base (22 ka) Plinian products emplaced during the first caldera collapse at Somma-Vesuvius. A new Ar/Ar age of 23.6 ± 0.3 ka obtained for the Traianello cone as well as the absence of a paleosol or reworked material between the S. Maria a Castello cone and the Pomici di Base deposits suggest that such cone-forming eruptions occurred near the upper limit of the pre-caldera period (22-39 ky). The stratigraphy of three of these eccentric cones (Pollena cones and Traianello cone) exhibits erosion surfaces, exotic tephras, volcaniclastic layers, paleosols, unconformity and paraconformity between superimposed eruptive units revealing their multi-phase, polygenetic evolution related to activation of separate vents and periods of quiescence. Such eccentric cones have been described as composed of scoria deposits and pure effusive lavas by previous authors. Lavas are here re-interpreted as welded horizons (lava-like) composed of coalesced spatter fragments whose pyroclastic nature is locally revealed by relicts of original fragments and remnants of clast outlines. These welded horizons show, locally, rheomorphic structures allowing to define them as emplaced as clastogenic lava flows. The lava-like facies is transitional, upward and downward, to less welded facies composed of agglutinated to unwelded spatter horizons in which clasts outlines are increasingly discernible. Such textural characteristics and facies variation are consistent with a continuous fall deposition of Hawaiian fire-fountains episodes alternated with Strombolian phases emplacing loose scoria deposits. High enrichment factor values, measured in the scoria deposits, imply the ejection of large proportion of ash even during Strombolian events.

Airborne Radar Observations of Severe Hailstorms: Implications for Future Spaceborne Radar

NASA Technical Reports Server (NTRS)

Heymsfield, Gerald M.; Tian, Lin; Li, Lihua; McLinden, Matthew; Cervantes, Jaime I.

2013-01-01

A new dual-frequency (Ku and Ka band) nadir-pointing Doppler radar on the high-altitude NASA ER-2 aircraft, called the High-Altitude Imaging Wind and Rain Airborne Profiler (HIWRAP), has collected data over severe thunderstorms in Oklahoma and Kansas during the Midlatitude Continental Convective Clouds Experiment (MC3E). The overarching motivation for this study is to understand the behavior of the dualwavelength airborne radar measurements in a global variety of thunderstorms and how these may relate to future spaceborne-radar measurements. HIWRAP is operated at frequencies that are similar to those of the precipitation radar on the Tropical Rainfall Measuring Mission (Ku band) and the upcoming Global Precipitation Measurement mission satellite's dual-frequency (Ku and Ka bands) precipitation radar. The aircraft measurements of strong hailstorms have been combined with ground-based polarimetric measurements to obtain a better understanding of the response of the Ku- and Ka-band radar to the vertical distribution of the hydrometeors, including hail. Data from two flight lines on 24 May 2011 are presented. Doppler velocities were approx. 39m/s2at 10.7-km altitude from the first flight line early on 24 May, and the lower value of approx. 25m/s on a second flight line later in the day. Vertical motions estimated using a fall speed estimate for large graupel and hail suggested that the first storm had an updraft that possibly exceeded 60m/s for the more intense part of the storm. This large updraft speed along with reports of 5-cm hail at the surface, reflectivities reaching 70 dBZ at S band in the storm cores, and hail signals from polarimetric data provide a highly challenging situation for spaceborne-radar measurements in intense convective systems. The Ku- and Ka-band reflectivities rarely exceed approx. 47 and approx. 37 dBZ, respectively, in these storms.

Predicting the Burden of Revision Knee Arthroplasty: Simulation of a 20-Year Horizon.

PubMed

Guerrero-Ludueña, Richard E; Comas, Mercè; Espallargues, Mireia; Coll, Moisès; Pons, Miquel; Sabatés, Santiago; Allepuz, Alejandro; Castells, Xavier

2016-01-01

To estimate future utilization scenarios for knee arthroplasty (KA) revision in the Spanish National Health System in the short- and long-term and their impact on primary KA utilization. A discrete-event simulation model was built to represent KA utilization for 20 years (2012-2031) in the Spanish National Health System. Data on KA utilization from 1997 to 2011 were obtained from the minimum data set. Three scenarios of future utilization of primary KA (1, fixed number since 2011; 2, fixed age- and sex-adjusted rates since 2011; and 3, projection using a linear regression model) were combined with two prosthesis survival functions (W [worse survival], from a study including primary KA from 1995 to 2000; and B [better survival], from the Catalan Registry of Arthroplasty, including primary KA from 2005 to 2013). The simulation results were analyzed in the short-term (2015) and the long-term (2030). Variations in the number of revisions depended on both the primary utilization rate and the survival function applied, ranging from increases of 8.3% to 31.6% in the short- term and from 38.3% to 176.9% in the long-term, corresponding to scenarios 1-B and 3-W, respectively. The prediction of increases in overall surgeries ranged from 0.1% to 22.3% in the short-term and from 3.7% to 98.2% in the long-term. Projections of the burden of KA provide a quantitative basis for future policy decisions on the concentration of high-complexity procedures, the number of orthopedic surgeons required to perform these procedures, and the resources needed. Copyright © 2016 International Society for Pharmacoeconomics and Outcomes Research (ISPOR). Published by Elsevier Inc. All rights reserved.

Millennial-scale variability to 735 ka: High-resolution climate records from Santa Barbara Basin, CA

NASA Astrophysics Data System (ADS)

White, Sarah M.; Hill, Tessa M.; Kennett, James P.; Behl, Richard J.; Nicholson, Craig

2013-06-01

Determining the ultimate cause and effect of millennial-scale climate variability remains an outstanding problem in paleoceanography, partly due to the lack of high-resolution records predating the last glaciation. Recent cores from Santa Barbara Basin provide 2500-5700 year "windows" of climate with 10-50 year resolution. Ages for three cores, determined by seismic stratigraphic correlation, oxygen isotope stratigraphy, and biostratigraphy, date to 293 ka (MIS 8), 450 ka (MIS 12), and 735 ka (MIS 18). These records sample the Late Pleistocene, during which the 100 kyr cycle strengthened and the magnitude of glacial-interglacial cyclicity increased. Thus, these records provide a test of the dependence of millennial-scale behavior on variations in glacial-interglacial cyclicity. The stable isotopic (δ18O) composition of planktonic foraminifera shows millennial-scale variability in all three intervals, with similar characteristics (duration, cyclicity) to those previously documented during MIS 3 at this site. Stadial G. bulloides δ18O values are 2.75-1.75‰ (average 2.25‰) and interstadial values are 1.75-0.5‰ (average 1‰), with rapid (decadal-scale) interstadial and stadial initiations of 1-2‰, as in MIS 3. Interstadials lasted 250-1600 years and occurred every 650-1900 years. Stadial paleotemperatures were 3.5-9.5°C and interstadial paleotemperatures were 7.5-13°C. Upwelling, evidenced by planktonic foraminiferal assemblages and δ13C, increased during interstadials, similar to MIS 3; high productivity during some stadials was reminiscent of the Last Glacial Maximum. This study builds upon previous records in showing that millennial-scale shifts were an inherent feature of Northern Hemisphere glacial climates since 735 ka, and they remained remarkably constant in the details of their amplitude, cyclicity, and temperature variability.

Temperature dependence of interfacial structures and acidity of clay edge surfaces

NASA Astrophysics Data System (ADS)

Liu, Xiandong; Lu, Xiancai; Cheng, Jun; Sprik, Michiel; Wang, Rucheng

2015-07-01

In the pursuit of a microscopic understanding of the effects of temperature on the surface reactivity of clay minerals, we conducted first principles molecular dynamics (FPMD) simulations to study the interfacial structures and acidity of clay edge surfaces at elevated temperatures. The common edge surfaces ((0 1 0) and (1 1 0) types) of phyllosilicates were investigated at 348 K and 423 K, and the results were compared with those previously derived at ambient conditions. We found that the stable surface sites are the same as at ambient conditions, including tbnd Al(OH2)2 (6-fold Al), tbnd Al(OH2) (5-fold Al) and tbnd Si(OH) on the (0 1 0) facet, and tbnd Al(OH2), tbnd Al(OH)Sitbnd and tbnd Si(OH) on the (1 1 0) surface. The FPMD-based vertical energy gap technique was applied to compute the acidity constants of edge sites and the resulting pKa values show a decreasing trend with temperature. The results demonstrate that although changes in the point of zero charge of the entire material are insignificant up to 348 K, the decrease in surface pKa can be 3 pKa units, while it can be as large as 6 pKa units up to 423 K. The derived interface structures and pKa values can be used in future experimental and modeling research, e.g., in interpreting experiments and predicting the surface complexation of metal cations and organics. This study therefore provides a physical basis for investigating the interfacial processes of clay minerals in environments that experience elevated P-T conditions, such as sedimentary basins and geological nuclear waste repositories.

The effect of varied pH on the luminescence characteristics of antibody-mercaptoacetic acid conjugated ZnS nanowires

NASA Astrophysics Data System (ADS)

Chaudhry, Madeeha; Rehman, Malik Abdul; Gul, Asghari; Qamar, Raheel; Bhatti, Arshad Saleem

2017-11-01

We demonstrate here that the effect of varied pH of the media on the photoluminescence (PL) properties of mercaptoacetic acid (MAA) and digoxin antibody (Ab) conjugated zinc sulphide (ZnS) nanowires. The charge-transfer kinetics from MAA to ZnS and vice versa showed a profound effect on the luminescence of ZnS defect states. The PL intensity of the ZnS defect states showed strong dependence on the value of pH with respect to the pKa of MAA. The carboxyl and thiol group of MAA in the protonated (pH < pKa) and deprotonated (pH > pKa) states resulted in the quenched PL intensity. While for pH ∼ pKa, the PL intensity was regained as there was equal probability of both protonated and deprotonated carboxyl and thiol groups. These findings indicated that pH of the environment is a key parameter for the use of MAA-Ab conjugated ZnS nanowires as an optical biomarker.

Preliminary paleomagnetic results from the Coyote Creek Outdoor Classroom drill hole, Santa Clara Valley, California

USGS Publications Warehouse

Mankinen, Edward A.; Wentworth, Carl M.

2003-01-01

Paleomagnetic samples were obtained from cores taken during the drilling of a research well along Coyote Creek in San Jose, California, in order to use the geomagnetic field behavior recorded in those samples to provide age constraints for the sediment encountered. The well reached a depth of 308 meters and material apparently was deposited largely (entirely?) during the Brunhes Normal Polarity Chron, which lasted from 780 ka to the present time. Three episodes of anomalous magnetic inclinations were recorded in parts of the sedimentary sequence; the uppermost two we correlate to the Mono Lake (~30 ka) geomagnetic excursion and 6 cm lower, tentatively to the Laschamp (~45 ka) excursion. The lowermost anomalous interval occurs at 305 m and consists of less than 10 cm of fully reversed inclinations underlain by 1.5 m of normal polarity sediment. This lower anomalous interval may represent either the Big Lost excursion (~565 ka) or the polarity transition at the end of the Matuyama Reversed Polarity Chron (780 ka). The average rates of deposition for the Pleistocene section in this well, based on these two alternatives, are approximately 52 or 37 cm/kyr, respectively.

Improvement of Thermal Interruption Capability in Self-blast Interrupting Chamber for New 245kV-50kA GCB

NASA Astrophysics Data System (ADS)

Shinkai, Takeshi; Koshiduka, Tadashi; Mori, Tadashi; Uchii, Toshiyuki; Tanaka, Tsutomu; Ikeda, Hisatoshi

Current zero measurements are performed for 245kV-50kA-60Hz short line fault (L90) interruption tests with a self-blast interrupting chamber (double volume system) which has the interrupting capability up to 245kV-50kA-50Hz L90. Lower L90 interruption capability is observed for longer arcing time although very high pressure rise is obtained. It may be caused by higher blowing temperature and lower blowing density for longer arcing time. Interruption criteria and a optimization method of the chamber design are discussed to improve L90 interruption capability with it. The new chambers are designed at 245kV-50kA-60Hz to improve gas density in thermal volume for long arcing time. 245kV-50kA-60Hz L90 interruptions are performed with the new chamber. The suggested optimization method is an efficient tool for the self-blast interrupting chamber design although study of computing methods is required to calculate arc conductance around current zero as a direct criterion for L90 interruption capability with higher accuracy.

Relict slope rings and talus flatirons in the Colorado Piedmont: Origin, chronology and paleoenvironmental implications

NASA Astrophysics Data System (ADS)

Gutiérrez, Francisco; Morgan, Matthew L.; Matthews, Vincent; Gutiérrez, Mateo; Jiménez-Moreno, Gonzalo

2015-02-01

In the Colorado Piedmont, talus flatiron chronosequences are associated with buttes that consist of erodible arkosic sandstone and resistant caprock. Following the removal of the caprock, some buttes evolve into crater-like relict slope rings resulting from the differential erosion of the soft bedrock in the core of the hills. These unique landforms are only documented in the Colorado Piedmont. Their development is attributed to the unusually high erodibility contrast between the low-cohesion sandy bedrock and the bouldery colluvial armor. The talus flatiron sequences and relict slope rings mapped in the three studied areas record alternating periods of accumulation and incision in the slopes that are likely controlled by changes in moisture availability and vegetation cover density. The obtained OSL dates place slope accumulation phases at > 124 ka, and ca. 73 ka, 50-40 ka, 15 ka, and 10-6 ka. A comparison of these geochronological data with paleoclimatic records from the region suggests that colluvium deposition occurred during periods of denser vegetation cover, which are controlled by climate changes. Further investigations, including additional and more accurate geochrological data from the relict slopes, will help to better understand the paleoclimatic significance of these largely unknown morphostratigraphic features.

Salinization of porewater in a multiple aquitard-aquifer system in Jiangsu coastal plain, China

NASA Astrophysics Data System (ADS)

Li, Jing; Liang, Xing; Zhang, Yanian; Liu, Yan; Chen, Naijia; Abubakari, Alhassan; Jin, Menggui

2017-12-01

Chemical and isotopic compositions were analyzed in porewater squeezed from a clayey aquitard in Jiangsu coastal plain, eastern China, to interpret the salinity origin, chemical evolution and water-mass mixing process. A strong geochemical fingerprint was obtained with an aligned Cl/Br ratio of 154 in the salinized aquitard porewater over a wide Cl- concentration range (396-9,720 mg/L), indicating that porewater salinity is likely derived from a mixing with old brine with a proportion of less than 20%. Very small contributions of brine exerted limited effects on water stable isotopes. The relationships between porewater δ18O and δD indicate that shallow and intermediate porewaters could be original seawater and were subsequently diluted with modern meteoric water, whereas deep porewaters with depleted stable isotopic values were probably recharged during a cooler period and modified by evaporation and seawater infiltration. The cation-Cl relationship and mineralogy of associated strata indicate that porewater has been chemically modified by silicate weathering and ion-exchange reactions. 87Sr/86Sr ratios of 0.7094-0.7112 further confirm the input source of silicate minerals. Numerical simulations were used to evaluate the long-term salinity evolution of the deep porewater. The alternations of boundary conditions (i.e., the third aquifer mixed with brine at approximately 70 ka BP, followed by recharge of glacial meltwater at 20-25 ka BP, and then mixing with Holocene seawater at 7-10 ka BP) are responsible for the shift in porewater salinity. These timeframes correspond with the results of previous studies on ancient marine transgression-regression in Jiangsu coastal plain.

Prediction of pKa Values for Neutral and Basic Drugs based on Hybrid Artificial Intelligence Methods.

PubMed

Li, Mengshan; Zhang, Huaijing; Chen, Bingsheng; Wu, Yan; Guan, Lixin

2018-03-05

The pKa value of drugs is an important parameter in drug design and pharmacology. In this paper, an improved particle swarm optimization (PSO) algorithm was proposed based on the population entropy diversity. In the improved algorithm, when the population entropy was higher than the set maximum threshold, the convergence strategy was adopted; when the population entropy was lower than the set minimum threshold the divergence strategy was adopted; when the population entropy was between the maximum and minimum threshold, the self-adaptive adjustment strategy was maintained. The improved PSO algorithm was applied in the training of radial basis function artificial neural network (RBF ANN) model and the selection of molecular descriptors. A quantitative structure-activity relationship model based on RBF ANN trained by the improved PSO algorithm was proposed to predict the pKa values of 74 kinds of neutral and basic drugs and then validated by another database containing 20 molecules. The validation results showed that the model had a good prediction performance. The absolute average relative error, root mean square error, and squared correlation coefficient were 0.3105, 0.0411, and 0.9685, respectively. The model can be used as a reference for exploring other quantitative structure-activity relationships.

Temporal survey of electron number density and electron temperature in the exhaust of a megawatt MPD-Arc thruster

NASA Technical Reports Server (NTRS)

Michels, C. J.; Rose, J. R.; Sigman, D. R.

1971-01-01

Temporal and radial profiles are obtained 30 cm downstream from the anode for two peak arc currents (11.2 kA and 20 kA) and for various auxiliary magnetic fields (0, 1.0 T, and 2.0T) using the Thomson scattering technique. Average density and temperature are relatively constant for over 100 microseconds with significant fluctuations. Radial profiles obtained are relatively flat for 4 cm from the axis. Compared to earlier 20 cm data, the exhaust density has decreased significantly, the average temperature (4.6 eV) has not changed, and the density hole with an auxiliary magnetic field has enlarged.

Biomarker evidence for increasing aridity in south-central India over the Holocene

NASA Astrophysics Data System (ADS)

Sarkar, S.; Wilkes, H.; Prasad, S.; Brauer, A.; Basavaiah, N.; Strecker, M. R.; Sachse, D.

2012-12-01

Summer monsoonal rainfall has played an important role in the development and sustenance of the largely agro-based economy in the Indian subcontinent in the recent past. A better understanding of past variations in monsoonal rainfall can therefore lead to an assessment of its potential impact on early human societies. However, our knowledge of spatiotemporal patterns of past monsoon strength, as inferred from proxy records, is limited due to the lack of high-resolution paleo-hydrological records from continental archives. Here, we reconstruct centennial-scale hydrological variability associated with changes in the intensity of the Indian Summer Monsoon based on a record of lipid biomarker abundances and compound-specific stable isotopic composition of a 10-m-long sediment core from saline-alkaline Lonar Lake, situated in the core 'monsoon zone' of south-central India. We identified three periods of distinct hydrology over the Holocene in south-central India. The period between 10.4 and 6.5 ka BP was characterized by a relatively high abundance of land-plant biomarkers, such as long-chain n-alkanes. The composition of these leaf-wax n-alkanes (weighted average of concentration of different chain-length n-alkanes, expressed as the ACL index) and their negative δ13C (-30‰ to -33 ‰) indicate the dominance of woody C3 vegetation in the catchment, and negative δD (-170‰ to -175‰) values argue for a wet period due to an intensified monsoon. Rapid fluctuations in abundance of both terrestrial and aquatic biomarkers between 6.5 and 4 ka BP indicate an unstable lake ecosystem, culminating in a transition to arid conditions. Higher ACL values and a pronounced shift to more positive δ13C values (up to -22‰) of leaf-wax n-alkanes over this period indicate a change of dominant vegetation to C4 grasses. Along with a 40‰ increase in leaf wax n-alkane δD values, which likely resulted from less rainfall and/or higher plant evapotranspiration, we interpret this period to reflect the driest conditions in the region during the last 10 ka. This transition led to protracted late Holocene arid conditions and a permanent saline lake. This is supported by the great abundance of the triterpene lipid tetrahymanol, generally considered as a marker for water-column stratification and salinity. A late Holocene peak of algal/cyanobacterial biomarker input at 1.3 ka BP may represent an event of lake eutrophication, possibly due to human impact and cattle/livestock farming in the catchment. Our record suggests substantial weakening of the monsoon over continental south-central India during the Holocene, placing the onset of aridification at 6.5 ka BP, earlier than observed in marine records throughout the Indian Ocean. Since human colonization in this region, as suggested by archeological evidence, dates back to late Holocene (ca. 3.5/3.2 ka BP) a possible human influence on the observed vegetation change at 6.5 ka BP is unlikely. Despite the prevailing arid conditions in the region since 6.5 ka the availability of freshwater through perennial springs around the lake may have attracted human settlements close to the lake for grazing of animals or small-scale farming.

Experimental testing of Mackay's model for functional antagonism in the isolated costo-uterus of the rat.

PubMed Central

Henry, P. J.; Lulich, K. M.; Paterson, J. W.

1985-01-01

Several key predictions of a recently developed model for functional antagonism (Mackay, 1981) were experimentally tested using the rat isolated costo-uterine preparation. In the presence of the functional antagonist fenoterol (Fen), the functional constants (KAF) for carbachol and oxotremorine (Oxo) were respectively 9.9 and 3.4 fold greater than their corresponding affinity constants (KA). According to Mackay's model for functional antagonism, the higher KAF/KA ratio for carbachol indicates that this cholinoceptor agonist has a greater efficacy than Oxo. This was confirmed by using conventional pharmacological methods. As predicted from the model of functional antagonism, the plot of KAF/KA-1 against the fraction of cholinoceptors not irreversibly blocked by phenoxybenzamine (Pbz) was linear for both carbachol and Oxo and the lines of best fit crossed the axes at a point not significantly different from the origin. The value of 4.6 for the relative efficacy of carbachol to Oxo estimated from functional antagonism studies was comparable to the value of 5.6 calculated using the method of irreversible antagonism proposed by Furchgott (1966). PMID:3840396

Paying for hospital-based care of Kala-azar in Nepal: assessing catastrophic, impoverishment and economic consequences.

PubMed

Adhikari, Shiva R; Maskay, Nephil M; Sharma, Bishnu P

2009-03-01

Households obtaining health care services in developing countries incur substantial costs, despite services generally being provided free of charge by public health institutions. This constitutes an economic burden on low-income households, and contributes to deepening their level of poverty. In addition to the economic burden of obtaining health care, the method of financing these payments has implications for the distribution of household assets. This effect on resource-poor households is amplified since they have decreased access to health insurance. Recent literature, however, ignores the importance of the method of financing health care payments. This paper looks at the case of Nepal and highlights the impact on households of paying for hospital-based care of Kala-azar (KA) by analysing the catastrophic, impoverishment and economic consequences of their coping strategies. The paper utilizes micro-data on a random selection of 50% of the KA-affected households of Siraha and Saptari districts of Nepal. The empirical results suggest that direct costs of hospital-based treatment of KA are catastrophic since they consume 17% of annual household income. This expenditure causes more than 20% of KA-affected households to fall below the poverty line, with the remaining households being pushed into the category of marginal poor; the poverty gap ratio is more than 90%. Further, KA incidence can have prolonged and severe economic consequences for the household economy due to the mechanisms of informal sector financing to which households resort. A heavy burden of loan repayments can lead households on a downward spiral that eventually becomes a poverty trap. In other words, the method of financing health care payments is an important ingredient in understanding the economic burden of disease.

Fitful and protracted magma assembly leading to a giant eruption, Youngest Toba Tuff, Indonesia

USGS Publications Warehouse

Reid, Mary R; Vazquez, Jorge A.

2017-01-01

The paroxysmal eruption of the 74 ka Youngest Toba Tuff (YTT) of northern Sumatra produced an extraordinary 2800 km3 of non-welded to densely welded ignimbrite and co-ignimbrite ash-fall. We report insights into the duration of YTT magma assembly obtained from ion microprobe U-Th and U-Pb dates, including continuous age spectra over >50% of final zircon growth, for pumices and a welded tuff spanning the compositional range of the YTT. A relatively large subpopulation of zircon crystals nucleated before the penultimate caldera-related eruption at 501 ka, but most zircons yielded interior dates 100-300 ka thereafter. Zircon nucleation and growth was likely episodic and from diverse conditions over protracted time intervals of >100 to >500 ka. Final zircon growth is evident as thin rim plateaus that are in Th/U chemical equilibrium with hosts, and that give crystallization ages within tens of ka of eruption. The longevity and chemical characteristics of the YTT zircons, as well as evidence for intermittent zircon isolation and remobilization associated with magma recharge, is especially favored at the cool and wet eutectoid conditions that characterize at least half of the YTT, wherein heat fluxes could dissolve major phases but have only a minor effect on larger zircon crystals. Repeated magma recharge may have contributed to the development of compositional zoning in the YTT but, considered together with limited allanite, quartz, and other mineral dating and geospeedometry, regular perturbations to the magma reservoir over >400 ka did not lead to eruption until 74 ka ago.

Late Pleistocene paleoclimatic history documented by an oxygen isotope record from carbonate sediments in Qarhan Salt Lake, NE Qinghai-Tibetan Plateau

NASA Astrophysics Data System (ADS)

Fan, QiShun; Ma, HaiZhou; Wei, HaiCheng; Shan, FaShou; An, FuYuan; Xu, LiMing; Madsen, David B.

2014-05-01

Late Pleistocene paleoclimatic variability on the northeastern Qinghai-Tibetan Plateau (NE QTP) was reconstructed using a chronology based on AMS 14C and 230Th dating results and a stable oxygen isotopic record. These are derived from lake carbonates in a 102-m-long Qarhan sediment core (ISL1A) collected from the eastern Qaidam Basin. Previous research indicates that the δ18O values of lacustrine carbonates are mainly controlled by the isotopic composition of lake water, which in turn is a function of regional P/E balance and the proportion of precipitation that is monsoon-derived on the NE QTP. Modern isotopic observations indicate that the δ18O values of lake carbonates in hyper-arid Qaidam Basin are more positive during the warm and wet period. Due to strong evaporation and continental effect in this basin, the positive δ18O values in the arid region indicate drier climatic conditions. Based on this interpretation and the δ18O record of fine-grained lake carbonates and dating results in ISL1A, the results imply that drier climatic conditions in the Qarhan region occurred in three intervals, around 90-80 ka, 52-38 ka and 10-9 ka, which could correspond to late MIS 5, middle MIS 3 and early Holocene, respectively. These three phases were almost coincided with low lake level periods of Gahai, Toson and Qinghai Lakes (to the east of Qarhan Lake) influenced by ASM on the orbital timescales. Meanwhile, there was an episode of relatively high δ18O value during late MIS 3, suggesting that relatively dry climatic condition in this period, rather than “a uniform Qarhan mega-paleolake” spanning the ˜44 to 22 ka period. These results insight into the understanding of “the Greatest Lake Period” on the QTP.

Comparison of the KSC-ER Cloud-to-Ground Lightning Surveillance System (CGLSS) and the U.S. National Lightning Detection Network(TradeMark)(NLDN)

NASA Technical Reports Server (NTRS)

Ward, Jennifer G.; Cummins, Kenneth L.; Krider, E. Philip

2007-01-01

The NASA Kennedy Space Center (KSC) and Air Force Eastern Range (ER) use data from two cloud-to-ground lightning detection networks, CGLSS and NLDN, during ground and launch operations at the KSC-ER. For these applications, it is very important to understand the location accuracy and detection efficiency of each network near the KSC-ER. If a cloud-to-ground (CG) lightning strike is missed or mis-located by even a small amount, the result could have significant safety implications, require expensive retests, or create unnecessary delays or scrubs in launches. Therefore, it is important to understand the performance of each lightning detection system in considerable detail. To evaluate recent upgrades in the CGLSS sensors in 2000 and the entire NLDN in 2002- 2003, we have compared. measurements provided by these independent networks in the summers of 2005 and 2006. Our analyses have focused on the fraction of first strokes reported individually and in-common by each network (flash detection efficiency), the spatial separation between the strike points reported by both networks (relative location accuracy), and the values of the estimated peak current, Ip, reported by each network. The results within 100 km of the KSC-ER show that the networks produce very similar values of Ip (except for a small scaling difference) and that the relative location accuracy is consistent with model estimates that give median values of 200-300m for the CGLSS and 600-700m for the NLDN in the region of the KSC-ER. Because of differences in the network geometries and sensor gains, the NLDN does not report 10-20% of the flashes that have a low Ip (2 kA < |Ip| < 16 kA), both networks report 99 % of the flashes that have intermediate values of Ip (16< |Ip| < 50 kA), and the CGLSS fails to report 20-30% of the high-current events (|Ip| >=0 kA).

Physicochemical properties of hydroxylated polychlorinated biphenyls aid in predicting their interactions with rat sulfotransferase 1A1 (rSULT1A1)

PubMed Central

Liu, Yungang; Lehmler, Hans-Joachim; Robertson, Larry W.; Duffel, Michael W.

2010-01-01

Hydroxylated metabolites of polychlorinated biphenyls (OHPCBs) interact with rat sulfotransferase 1A1 (rSULT1A1) as substrates and inhibitors. Previous studies have shown that there are complex and incompletely understood structure-activity relationships governing the interaction of rSULT1A1 with these molecules. Furthermore, modification of the enzyme with glutathione disulfide (GSSG) results in the conversion of some OHPCBs from inhibitors to substrates. We have now examined estimated values for the acid-dissociation constant (Ka) and the octanol-water distribution coefficient (D), as well as experimentally determined dissociation constants for enzyme complexes, to assist in the prediction of interactions of OHPCBs with rSULT1A1. Under reducing conditions, initial velocities for rSULT1A1-catalyzed sulfation exhibited a positive correlation with pKa and a negative correlation with log D of the OHPCBs. IC50 values of inhibitory OHPCBs decreased with decreasing pKa values for both the glutathione (GSH)-pretreated and GSSG-pretreated forms of rSULT1A1. Comparison of GSH- and GSSG-pretreated forms of rSULT1A1 with respect to binding of OHPCB in the presence and absence of adenosine 3’,5’-diphosphate (PAP) revealed that the dissociation constants with the two redox states of the enzyme were similar for each OHPCB. Thus, pKa and log D values are useful in predicting the binding of OHPCBs to the two redox forms of rSULT1A1 as well as the rates of sulfation of those OHPCBs that are substrates. However, the differences in substrate specificity for OHPCBs that are seen with changes in redox status of the enzyme are not directly related to specific structural effects of individual OHPCBs within inhibitory enzyme-PAP-OHPCB complexes. PMID:21130751

Past climate variability between 97 and 7 ka reconstructed from a multi proxy speleothem record from Western Cuba

NASA Astrophysics Data System (ADS)

Winterhalder, Sophie; Scholz, Denis; Mangini, Augusto; Spötl, Christoph; Jochum, Klaus Peter; Pajón, Jesús M.

2016-04-01

The tropical hydrological cycle plays a key role in regulating global climate, mainly through the export of heat and moisture to higher latitudes, and is highly sensitive to climate change, for instance due to changes in the position of the Intertropical Convergence Zone (ITCZ). Previous work on Caribbean stalagmites suggests a strong connection of precipitation variability to North Atlantic (NA) sea surface temperatures on multidecadal to millenial timescales (Fensterer et al., 2012; Fensterer et al., 2013; Winter et al., 2011). Cold phases in the NA potentially lead to a southward shift of the ITCZ and thus drier conditions in Cuba. On orbital timescales, Cuban stalagmites suggest a relation of speleothem δ18O values with the δ18O value of Caribbean surface waters (Fensterer et al., 2013). Here we present an expansion of the Cuban speleothem record covering the whole last glacial period from the end of MIS5c (97 ka BP) until 7 ka with hiatuses between 93-80 ka, 37-35 ka and 13-10 ka. Stalagmite Cuba medio (CM) has been precisely dated with 60 230Th/U-ages, mainly performed by the MC-ICPMS technique. The δ18O and δ13C records are completed by a continuous, high resolution LA-ICPMS trace element profile. These data allow for the first time to establish a multi-proxy climate reconstruction for the North Western Caribbean at decadal to centennial resolution for this period. The long-term variability of the δ18O values probably reflects rainfall amount in Cuba. The response to some Dansgaard/Oeschger and Heinrich stadials confirms the previously observed correlation between Caribbean and NA climate variability. However, this connection is not clearly imprinted throughout the record. Furthermore, trace elements, such as Mg, do not proof without ambiguity drier conditions in Cuba during NA cold events, such as the Heinrich stadials. This suggests that climate variability in Cuba was more complex during the last 100ka, and that the NA was not the only driving factor. Due to the competing influence of the NA, the Gulf of Mexico and the Pacific Ocean, the proposed severe changes in the tropical hydrological cycle during that time (such as variations of the ITCZ, insolation and the thermohaline circulation (THC)) have potentially lead to significant changes in sources and trajectories of precipitation in Western Cuba. Our record, thus, provides an important contribution towards understanding and differentiating these parameters on Caribbean climate during glacial climate changes. References: Fensterer, C., Scholz, D., Hoffmann, D., Spötl, C., Pajón, J.M., Mangini, A., 2012. Cuban stalagmite suggests relationship between Caribbean precipitation and the Atlantic Multidecadal Oscillation during the past 1.3 ka. The Holocene, 0959683612449759. Fensterer, C., Scholz, D., Hoffmann, D.L., Spötl, C., Schröder-Ritzrau, A., Horn, C., Pajón, J.M., Mangini, A., 2013. Millennial-scale climate variability during the last 12.5 ka recorded in a Caribbean speleothem. Earth and Planetary Science Letters 361, 143-151. Winter, A., Miller, T., Kushnir, Y., Sinha, A., Timmermann, A., Jury, M.R., Gallup, C., Cheng, H., Edwards, R.L., 2011. Evidence for 800years of North Atlantic multi-decadal variability from a Puerto Rican speleothem. Earth and Planetary Science Letters 308, 23-28.

New K Ar age determinations of Kilimanjaro volcano in the North Tanzanian diverging rift, East Africa

NASA Astrophysics Data System (ADS)

Nonnotte, Philippe; Guillou, Hervé; Le Gall, Bernard; Benoit, Mathieu; Cotten, Joseph; Scaillet, Stéphane

2008-06-01

The Kilimanjaro is the African highest mountain and culminates at 5895 m high. This huge volcanic edifice is composed of three main centres along a N110°E-striking axis (Shira, Kibo and Mawenzi from W to E), and emplaced in a key area where a major N80°E-oriented volcanic lineament intersects a first-order NW-SE basement fault-like discontinuity. Seventeen K-Ar ages (on microcrystalline groundmass) acquired on lavas and intrusive facies from the three eruptive centres confirm that the Plio-Quaternary volcanicity of Kilimanjaro is clearly polyphased. The oldest phases of volcanic activity begun at ~ 2.5 Ma in the Shira vent and our data suggest that the latest important phases occurred around 1.9 Ma, just before the collapse of the Northern part of the edifice. Magmatic activity then shifted eastwards in the Mawenzi and Kibo twin centres where initial volcanism is dated at ~ 1 Ma. Two K-Ar ages obtained for the most recent Mawenzi rocks from the Neumann Tower-Mawenzi group (492 ka) and Mawenzi eruptive centre (448 ka), near the present summit, are linked to the final stage of edification for this centre. Whereas the eruptive activity ceased in the Mawenzi, it still continued on Kibo since sub-actual time. The oldest dated rocks from Kibo (482 ka) is obtained on a dyke from the Lava Tower group cropping out at 4600 m high. The main phase of magmatism on Kibo is recorded by two lava formations with a great spatial extension - the Rhomb Porphyry group and the Lent group - that have been emplaced in a short time interval at ~ 460-360 ka (including two erosive stages) and 359-337 ka, respectively. Based on the dating of Caldera rim group lavas, it is shown that the edification of the present cone was accomplished in a period ranging from 274 to 170 ka. The new ages obtained for the main episodes of volcanic activity on Kibo appear to roughly coincide with the oldest known Quaternary glaciations. The interaction between eruptive phenomena and the ice cover is assumed to have played an important role in triggering collapse processes and associated lahars deposits. The last volcanicity, around 200-150 ka, is marked by the formation of the present summit crater in Kibo and the development of linear parasitic volcanic belts, constituted by numerous Strombolian-type isolated cones on the NW and SE slopes of Kilimanjaro. These belts are likely to occur above deep-seated fractures that have guided the magma ascent, and the changes in their directions with time might be related to the rotation of recent local stress field.

The natural food colorant Peonidin from cranberries as a potential radical scavenger - A DFT based mechanistic analysis.

PubMed

Rajan, Vijisha K; Hasna, C K; Muraleedharan, K

2018-10-01

A theoretical evaluation of the antioxidant property of a natural food colorant Peonidin has been performed. The most suitable mechanism for explaining the radical scavenging capacity of Peonidin is the Hydrogen Atom Transfer and the most active site for radical formation is position 3 and is confirmed through Mulliken charge analysis, pKa value evaluation, Bond Dissociation Energy values, and Natural Bond Orbital analysis. Position 3 and 5 in Peonidin exists in blood as deprotonated as their pKa values are lower than the pH of blood. Peonidin is highly reactive than Quercetin and less stable than flavan-3-ols due to the small band gap. Global descriptor analysis shows that PN prefers to accept electrons than to donate. The effect of number of OH groups and the nature of substituents are well explained through this work. Copyright © 2018 Elsevier Ltd. All rights reserved.

Late Quaternary climate and environmental reconstruction based on leaf wax analyses in the loess sequence of Möhlin, Switzerland

NASA Astrophysics Data System (ADS)

Wüthrich, Lorenz; Bliedtner, Marcel; Kathrin Schäfer, Imke; Zech, Jana; Shajari, Fatemeh; Gaar, Dorian; Preusser, Frank; Salazar, Gary; Szidat, Sönke; Zech, Roland

2017-12-01

We present the results of leaf wax analyses (long-chain n-alkanes) from the 6.8 m deep loess sequence of Möhlin, Switzerland, spanning the last ˜ 70 kyr. Leaf waxes are well preserved and occur in sufficient amounts only down to 0.4 m and below 1.8 m depth, so no paleoenvironmental reconstructions can be done for marine isotope stage (MIS) 2. Compound-specific δ2Hwax analyses yielded similar values for late MIS 3 compared to the uppermost samples, indicating that various effects (e.g., more negative values due to lower temperatures, more positive values due to an enriched moisture source) cancel each other out. A pronounced ˜ 30 ‰ shift towards more negative values probably reflects more humid conditions before ˜ 32 ka. Radiocarbon dating of the n-alkanes corroborates the stratigraphic integrity of leaf waxes and their potential for dating loess-paleosol sequences (LPS) back to ˜ 30 ka.

Integrated geochronology of Acheulian sites from the southern Latium (central Italy): Insights on human-environment interaction and the technological innovations during the MIS 11-MIS 10 period

NASA Astrophysics Data System (ADS)

Pereira, Alison; Nomade, Sébastien; Moncel, Marie-Hélène; Voinchet, Pierre; Bahain, Jean-Jacques; Biddittu, Italo; Falguères, Christophe; Giaccio, Biagio; Manzi, Giorgio; Parenti, Fabio; Scardia, Giancarlo; Scao, Vincent; Sottili, Gianluca; Vietti, Amina

2018-05-01

We have explored the multimethod approach combining 40Ar/39Ar on single crystal, ESR on bleached quartz, and ESR/U-series on teeth to improve the age of four neighbours "Acheulian" sites of the Frosinone Province (Latium, Italy): Fontana Ranuccio, Cava Pompi (Pofi), Isoletta, and Lademagne. Ages obtained by the three methods are in mutual agreement and confirm the potential of dating with confidence Middle Pleistocene sites of Italy using these methods. At Fontana Ranuccio, the 40Ar/39Ar age (408 ± 10 ka, full external error at 2σ) obtained for the archaeological level (unit FR4) and geochemical analyses of glass shards performed on the Unit FR2a layer allow us to attribute the studied volcanic material to the Pozzolane Nere volcanic series, a well-known caldera-forming event originated from the Colli Albani volcanic district. These new data ascribe the Fontana Ranuccio site, as well as the eponym faunal unit, to the climatic optimum of Marine Isotope Stage (MIS) 11. Ages obtained for the Cava Pompi, Isoletta, and Lademagne sites cover a relatively short period of time between 408 ka and 375 ka, spanning MIS 11 climatic optimum to the MIS 11-10 transition. Analysis of small collections of lithic industries, bifacial tools, and small cores technologies from Isoletta, Lademagne, and the neighbour site of Ceprano-Campogrande shows common technical strategies for the period comprised between MIS 11 and MIS 9 (410-325 ka), such as the elaboration of flaked elephant bone industries found over the whole Latium region. However, some features found only in the Frosinone province area, like large-sized bifaces, suggest particular regional behaviours. The presence of one Levallois core in the oldest layer of Lademagne (i.e. > 405 ± 9 ka) suggests a punctual practice of this technology, also proposed as early as MIS 10/11 in the neighbour site of Guado San Nicola (Molise) in central Italy.

Mid-Holocene drying of the U.S. Great Basin recorded in Nevada speleothems

NASA Astrophysics Data System (ADS)

Steponaitis, Elena; Andrews, Alexandra; McGee, David; Quade, Jay; Hsieh, Yu-Te; Broecker, Wallace S.; Shuman, Bryan N.; Burns, Stephen J.; Cheng, Hai

2015-11-01

Lake level records point to dramatic changes in Great Basin water balance over the last 25 ka, but the timing and pace of Holocene drying in the region remains poorly documented. Here we present stable isotope and trace metal data from two Lehman Caves, NV speleothems that provide a well-dated record of latest Pleistocene to mid-Holocene hydroclimate in the U.S. Great Basin. Together the stalagmites span the interval between 16.4 ka and 3.8 ka, with a hiatus from 15.0 ka to 12.7 ka. Mg/Ca and δ13C covary throughout the records, consistent with control by the extent of degassing and prior calcite precipitation (PCP); measurements of modern cave and soil waters support PCP as the primary control on drip-water trace-element composition. We therefore interpret Mg/Ca and δ13C as reflecting infiltration rates, with higher values corresponding to drier periods. Both Mg/Ca and δ13C indicate a wet period at the beginning of the record (12.7-8.2 ka) followed by pronounced drying after 8.2 ka. This mid-Holocene drying is consistent with records from around the western United States, including a new compilation of Great Basin lake-level records. The strong temporal correspondence with the collapse of the Laurentide ice sheet over Hudson Bay suggests that this drying may have been triggered by northward movement of the winter storm track as a result of ice sheet retreat. However, we cannot rule out an alternative hypothesis that wet early Holocene conditions are related to equatorial Pacific sea-surface temperature. Regardless, our results suggest that Great Basin water balance in the early Holocene was driven by factors other than orbital changes.

Late Quaternary environmental dynamics in the Atacama Desert reconstructed from rodent midden pollen records

USGS Publications Warehouse

de Porras, M.E.; Maldonado, A.; De Pol-Holz, R.; Latorre, C.; Betancourt, Julio L.

2017-01-01

In the past two decades, much has been learned about the late Quaternary climate history of the Atacama Desert with some details still unclear about the seasonality, timing and extent of wet and dry phases. Modern climate studies reveal that, far from exhibiting a unique pattern, seasonal precipitation originates from many sources and mechanisms. For the last 16 ka, we attempt to sort out these complexities in pollen records from four fossil rodent midden series spanning 22°–25°S in northern Chile. Widespread wet conditions prevailed during the late Pleistocene and early Holocene, particularly between 13 and 9 ka, evidenced by <400 m lowering of pollen zones (plant communities) compared to today. Regional differences in the timing and magnitude of this displacement may be related to the prevailing source (tropical/extra‐tropical) or mode (NNW/SE) of tropical precipitation through time. Wet conditions persisted well into the early Holocene, lasting ∼1–1.5 ka longer than previously suggested. The pollen record suggests extreme drying ∼8 ka, possibly associated with a northward shift of the Inter Tropical Convergence Zone, tracking minimum insolation values at subtropical latitudes during the austral summer. The establishment of conditions similar to today happened ∼4 ka. 

Late quaternary changes in lakes, vegetation, and climate in the Bonneville Basin reconstructed from sediment cores from Great Salt Lake: Chapter 11

USGS Publications Warehouse

Thompson, Robert S.; Oviatt, Charles G.; Honke, Jeffrey S.; McGeehin, John

2016-01-01

Sediment cores from Great Salt Lake (GSL) provide the basis for reconstructing changes in lakes, vegetation, and climate for the last ~ 40 cal ka. Initially, the coring site was covered by a shallow saline lake and surrounded by Artemisia steppe or steppe-tundra under a cold and dry climate. As Lake Bonneville began to rise (from ~ 30 to 28 cal ka), Pinus and subalpine conifer pollen percentages increased and Artemisia declined, suggesting the onset of wetter conditions. Lake Bonneville oscillated near the Stansbury shoreline between ~ 26 and ~ 24 cal ka, rose to the Bonneville shoreline by ~ 18 cal ka, and then fell to the Provo shoreline, which it occupied until ~ 15 cal ka. Vegetation changed during this time span, albeit not always with the same direction or amplitude as the lake. The pollen percentages of Pinus and subalpine conifers were high from ~ 25 to 21.5 cal ka, indicating cool and moist conditions during the Stansbury oscillation and for much of the rise toward the Bonneville shoreline. Pinus percentages then decreased and Artemisia became codominant, suggesting drier and perhaps colder conditions from ~ 21 to ~ 15 cal ka, when Lake Bonneville was at or near its highest levels.Lake Bonneville declined to a low level by ~ 13 cal ka, while Pinus pollen percentages increased, indicating that conditions remained cooler and moister than today. During the Younger Dryas interval, the brief Gilbert episode rise in lake level was followed by a shallow lake with a stratified water column. This lake rise occurred as Pinus pollen percentages were declining and those of Artemisia were rising (reflecting increasingly dry conditions), after which Artemisia pollen was at very high levels (suggesting cold and dry conditions) for a brief period.Since ~ 10.6 cal ka lacustrine conditions have resembled those of present-day GSL. Pollen spectra for the period from ~ 10.6 to 7.2 cal ka have low levels of conifer pollen and high (for the Holocene) levels of desert and steppe taxa, suggesting generally dry conditions with maximum aridity occurring prior to the deposition of the Mazama tephra (~ 7.6 cal ka). After ~ 10.6 cal ka, Juniperus pollen percentages began to increase and by ~ 7.2 cal ka juniper woodlands were well established on lower mountain slopes. From ~ 7 to 4 cal ka, pollen percentages fluctuated near their mean values for the entire Holocene. The neopluvial (~ 4 to 2 cal ka) was the wettest part of the Holocene, with higher levels of Juniperus pollen and lower levels for steppe and desert taxa than in older Holocene sediments. Pollen percentages for the last ~ 2 cal ka are variable, but generally indicate a return to drier conditions.

Glacier extent in sub-Antarctic Kerguelen archipelago from MIS 3 period: Evidence from 36Cl dating

NASA Astrophysics Data System (ADS)

Jomelli, Vincent; Schimmelpfennig, Irene; Favier, Vincent; Mokadem, Fatima; Landais, Amaelle; Rinterknecht, Vincent; Brunstein, Daniel; Verfaillie, Deborah; Legentil, Claude; Aumaitre, Georges; Bourlès, Didier L.; Keddadouche, Karim

2018-03-01

Documenting sub-Antarctic glacier variations during the local last glacial maximum is of major interest to better understand their sensitivity to atmospheric and oceanic temperature changes in conjunction with Antarctic ice sheet changes. However, data are sparse because evidence of earlier glacier extents is for most sub-Antarctic islands located offshore making their observation complex. Here, we present 22 cosmogenic 36Cl surface exposure ages obtained from five sites at Kerguelen to document the glacial history. The 36Cl ages from roche moutonnee surfaces, erratics and boulders collected on moraines span from 41.9 ± 4.4 ka to 14.3 ± 1.1 ka. Ice began to retreat on the eastern part of the main island before 41.4 ± 4.4 ka. Slow deglaciation occurred from ∼41 to ∼29 ka. There is no evidence of advances between 29 ka and the Antarctic Cold Reversal (ACR) period (∼14.5-12.9 ka) period. During the ACR, however, the Bontemps and possibly Belvedere moraines were formed by the advance of a Cook Ice Cap outlet glacier and a local glacier on the Presque Ile Jeanne d'Arc, respectively. This glacier evolution differs partly from that of glaciers in New Zealand and in Patagonia. These asynchronous glacier changes in the sub-Antarctic region are however in agreement with sea surface temperature changes recorded around Antarctica, which suggest differences in the climate evolution of the Indo-Pacific and Atlantic sectors of Antarctica.

150 000 Years of Loess Deposition in Interior Alaska as Told by Magnetic Susceptibility

NASA Astrophysics Data System (ADS)

Jensen, B. J. L.; Evans, M. E.; Froese, D. G.; Kravchinsky, V. A.

2015-12-01

The Halfway House loess deposit in interior Alaska contains a well-studied and complex paleomagnetic and paleoenvironmental record. Unfortunately, a lack of chronologic control has made it difficult to interpret the results of these studies. Detailed reexamination of stratigraphy, paleomagnetics and tephrostratigraphy reveals a relatively complete marine isotope stage (MIS) 6 to Holocene record constrained by the Old Crow (124 ± 10 ka), VT (106 ± 10 ka), Sheep Creek-Klondike (ca. 80 ka), Dominion Creek (77 ± 8 ka) and Dawson (ca. 30.2 cal ka BP) tephras. Two well-developed paleosols are shown to have formed during Marine Isotope Stages (MIS) 5e and 5a, while MIS 5c and 5b are either poorly represented or absent. A magnetic excursion is identified as the post-Blake excursion (94.1 ± 7.8 ka) and provides independent age control while adding to an increasing body of evidence that Alaskan loess is a detailed recorder of variations of the Earth's magnetic field over time. High-resolution magnetic susceptibility profiles placed into this new chronostratigraphic framework help refine loess deposition models for the interior of Alaska, while providing a means to correlate to previous magnetic studies at this site. The profiles support the hypothesis that wind-intensity is the main variable controlling fluctuations in susceptibility, with the highest susceptibility during peak glacial times and the lowest values in paleosols representing interglacials. However, the correlation of the susceptibility record to global marine d18O records is complicated by highly variable accumulation rates. We find the lowest rates of accumulation during peak warm and cold stages, while abrupt increases are associated with periods of transition between marine isotope stages, represented by intermediate susceptibility values. Previous accumulation models for Alaska have emphasized the role of surface roughness as an important variable controlling loess accumulation. However our results suggest that while this may be the case during transitions and peak cold periods, the negligible accumulation during the peak warmth of MIS 5e and 5a suggests loess production was exceedingly low, negating the role of surface roughness.

Sedimentary Evolution of Marginal Ganga Foreland Basin during the Late Pleistocene

NASA Astrophysics Data System (ADS)

Ghosh, R.; Srivastava, P.; Shukla, U. K.

2017-12-01

Ganga foreland basin, an asymmetrical basin, was formed as result of plate-plate collision during middle Miocene. A major thrust event occurred during 500 ka when upper Siwalik sediments were uplifted and the modern Ganga foreland basin shifted towards craton, making a more wide and deep basin. The more distal part of this basin, south of axial river Yamuna, records fluvial sedimentary packages that helps to understand dynamics of peripheral bulge during the late Quaternary. Sedimentary architecture in conjunction with chemical index of alteration (CIA), paleocurrent direction and optically stimulated dating (OSL) from 19 stratigraphic sections helped reconstructing the variations in depositional environments vis-à-vis climate change and peripheral bulge tectonics. Three major units (i) paleosol; (ii) cratonic gravel; (iii) interfluve succession were identified. The lower unit-I showing CIA values close to 70-80 and micro-morphological features of moderately well-developed pedogenic unit that shows development of calcrete, rhizoliths, and mineralized organic matter in abundance. This is a regional paleosols unit and OSL age bracketed 200 ka. This is unconformably overlain by unit-II, a channelized gravel composed of sub-angular to sub-rounded clasts of granite, quartz, quartzite, limestone and calcrete. The gravel have low CIA value up to 55, rich in vertebrate fossil assemblages and mean paleocurrent vector direction is NE, which suggesting deposition by a fan of a river draining craton into foreland. This unit is dated between 100 ka and 54 ka. The top unit-III, interfluve succession of 10-15 m thick is composed of dark and light bands of sheet like deposit of silty clay to clayey silt comprises sand lenses of red to grey color and displaying top most OSL age is 12 ka. The basal mature paleosol signifies a humid climate developed under low subsidence rate at >100 ka. After a hiatus represented by pedogenic surface deposition of unit-II (gravel) suggests uplift and increased relief in the peripheral bulge region resulting into large flux of coarse sediments from craton. This was accompanied by humid climate and braided rivers forming a craton derived north propagating fans. Similar depositional setup at the base Siwalik is termed as peripheral bulge unconformity.

Monte Carlo determination of the conversion coefficients Hp(3)/Ka in a right cylinder phantom with 'PENELOPE' code. Comparison with 'MCNP' simulations.

PubMed

Daures, J; Gouriou, J; Bordy, J M

2011-03-01

This work has been performed within the frame of the European Union ORAMED project (Optimisation of RAdiation protection for MEDical staff). The main goal of the project is to improve standards of protection for medical staff for procedures resulting in potentially high exposures and to develop methodologies for better assessing and for reducing, exposures to medical staff. The Work Package WP2 is involved in the development of practical eye-lens dosimetry in interventional radiology. This study is complementary of the part of the ENEA report concerning the calculations with the MCNP-4C code of the conversion factors related to the operational quantity H(p)(3). In this study, a set of energy- and angular-dependent conversion coefficients (H(p)(3)/K(a)), in the newly proposed square cylindrical phantom made of ICRU tissue, have been calculated with the Monte-Carlo code PENELOPE and MCNP5. The H(p)(3) values have been determined in terms of absorbed dose, according to the definition of this quantity, and also with the kerma approximation as formerly reported in ICRU reports. At a low-photon energy (up to 1 MeV), the two results obtained with the two methods are consistent. Nevertheless, large differences are showed at a higher energy. This is mainly due to the lack of electronic equilibrium, especially for small angle incidences. The values of the conversion coefficients obtained with the MCNP-4C code published by ENEA quite agree with the kerma approximation calculations obtained with PENELOPE. We also performed the same calculations with the code MCNP5 with two types of tallies: F6 for kerma approximation and *F8 for estimating the absorbed dose that is, as known, due to secondary electrons. PENELOPE and MCNP5 results agree for the kerma approximation and for the absorbed dose calculation of H(p)(3) and prove that, for photon energies larger than 1 MeV, the transport of the secondary electrons has to be taken into account.

Current achievements and challenges of a multiple dating approach (14C, 230Th/U and 36Cl) to infer tsunami transport age(s) of reef-top boulders on Bonaire (Leeward Antilles)

NASA Astrophysics Data System (ADS)

Rixhon, Gilles; May, Simon Matthias; Engel, Max; Mechernich, Silke; Schroeder-Ritzrau, Andrea; Frank, Norbert; Fohlmeister, Jens; Boulvain, Frédéric; Dunai, Tibor; Brückner, Helmut

2017-04-01

The deposition of supratidal coarse-clast deposits is difficult to date, limiting their value for inferring frequency-magnitude patterns of high-energy wave events. On Bonaire (Leeward Antilles, Caribbean), these deposits form prominent landforms, and transport by one or several Holocene tsunamis is assumed at least for the largest clasts. Although a large dataset of 14C and electron spin resonance (ESR) ages is available for major coral rubble ridges and ramparts, it is still debated whether these data reflect the timing of major events, and how these datasets are biased by the reworking of coral fragments. As an attempt to overcome the current challenges for dating the dislocation of singular boulders, three distinct dating methods are implemented and compared: (i) 14C dating of boring bivalves attached to the boulders; (ii) 230Th/U dating of post-depositional, secondary calcite flowstone and subaerial microbialites at the underside of the boulders; and (iii) surface exposure dating of overturned boulders via 36Cl concentration measurements in corals. Approaches (ii) and (iii) have never been applied to coastal boulder deposits so far. The three 14C age estimates are older than 37 ka, i.e. most probably beyond the applicability of the method, which is attributed to post-depositional diagenetic processes, shedding doubt on the usefulness of this method in the local context. The remarkably convergent 230Th/U ages, all pointing to the Late Holocene period (1.0-1.6 ka), are minimum ages for the transport event(s). The microbialite sample yields an age of 1.23±0.23 ka and both flowstone samples are in stratigraphic order: the older (onset of carbonate precipitation) and younger flowstone layers yield ages of 1.59±0.03 and 1.23±0.03 ka, respectively. Four coral samples collected from the topside of overturned boulders yielded similar 36Cl concentration measurements. However, the computed ages are affected by large uncertainties, mostly due to the high natural chlorine concentration resulting in low AMS ratios. After correction for the inherited component and chemical denudation since platform emergence (inducing additional uncertainty), the calculated 36Cl ages cluster between 2.5±1.3 and 3.0±1.3 ka for three of four boulders whilst the fourth one yields an age of 6.1±1.8 ka, probably related to a higher inheritance. These 230Th/U and 36Cl age estimates are coherent with a suggested tsunami age of <3.3 ka obtained from the investigation of allochthonous shell horizons in sediment cores of northwestern Bonaire. While 230Th/U dating of post-depositional calcite flowstone appears to be the most robust and/or accurate approach, these results illustrate the potential and current limitations of the applied methods for dating the dislocation of supralittoral boulders in carbonate-reef settings.

Effect of the acid treatment conditions of kaolinite on etheramine adsorption: A comparative analysis using chemometric tools.

PubMed

Leal, Paulo Vitor Brandão; Magriotis, Zuy Maria; Sales, Priscila Ferreira de; Papini, Rísia Magriotis; Viana, Paulo Roberto de Magalhães

2017-07-15

The present work evaluated the effect of the acid treatment conditions of natural kaolinite (NK) regarding its efficiency in removing etheramine. The treatment was conducted using sulfuric acid at the concentrations of 1 mol L -1 (KA-01), 2 mol L -1 (KA-02) and 5 mol L -1 (KA-05) at 85 °C. The obtained adsorbents were characterized by X-ray fluorescence, X-ray diffraction, N 2 adsorption/desorption isotherms, zeta potential analysis and infrared spectroscopy. The Response Surface Method was used to optimize adsorption parameters (initial concentration of etheramine, adsorbent mass and pH of the solution). The results, described by means of a central composite design, were adjusted to the quadratic model. Results revealed that the adsorption was more efficient at the etheramine concentration of 400 mg L -1 , pH 10 and adsorbent mass of 0.1 g for NK and 0.2 g for KA-01, KA-02 and KA-05. The sample KA-02 presented a significant increase of etheramine removal compared to the NK sample. The adsorption kinetics conducted under optimized conditions showed that the system reached the equilibrium in approximately 30 min. The kinetic data were better adjusted to the pseudo-second order model. The isotherm data revealed that the Sips model was the most adequate one. The calculation of E ads allowed to infer that the mechanism for etheramine removal in all the evaluated samples was chemisorption. The reuse tests showed that, after four uses, the efficiency of adsorbents in removing etheramine did not suffer significant modifications, which makes the use of kaolinite to treat effluents from the reverse flotation of iron ore feasible. Copyright © 2017 Elsevier Ltd. All rights reserved.

Asynchronous marine-terrestrial signals of the last deglacial warming in East Asia associated with low- and high-latitude climate changes.

PubMed

Xu, Deke; Lu, Houyuan; Wu, Naiqin; Liu, Zhenxia; Li, Tiegang; Shen, Caiming; Wang, Luo

2013-06-11

A high-resolution multiproxy record, including pollen, foraminifera, and alkenone paleothermometry, obtained from a single core (DG9603) from the Okinawa Trough, East China Sea (ECS), provided unambiguous evidence for asynchronous climate change between the land and ocean over the past 40 ka. On land, the deglacial stage was characterized by rapid warming, as reflected by paleovegetation, and it began ca. 15 kaBP, consistent with the timing of the last deglacial warming in Greenland. However, sea surface temperature estimates from foraminifera and alkenone paleothermometry increased around 20-19 kaBP, as in the Western Pacific Warm Pool (WPWP). Sea surface temperatures in the Okinawa Trough were influenced mainly by heat transport from the tropical western Pacific Ocean by the Kuroshio Current, but the epicontinental vegetation of the ECS was influenced by atmospheric circulation linked to the northern high-latitude climate. Asynchronous terrestrial and marine signals of the last deglacial warming in East Asia were thus clearly related to ocean currents and atmospheric circulation. We argue that (i) early warming seawater of the WPWP, driven by low-latitude insolation and trade winds, moved northward via the Kuroshio Current and triggered marine warming along the ECS around 20-19 kaBP similar to that in the WPWP, and (ii) an almost complete shutdown of the Atlantic Meridional Overturning Circulation ca. 18-15 kaBP was associated with cold Heinrich stadial-1 and delayed terrestrial warming during the last deglacial warming until ca. 15 kaBP at northern high latitudes, and hence in East Asia. Terrestrial deglacial warming therefore lagged behind marine changes by ca. 3-4 ka.

Pollen-climate relationships in time (9 ka, 6 ka, 0 ka) and space (upland vs. lowland) in eastern continental Asia

NASA Astrophysics Data System (ADS)

Tian, Fang; Cao, Xianyong; Dallmeyer, Anne; Zhao, Yan; Ni, Jian; Herzschuh, Ulrike

2017-01-01

Temporal and spatial stability of the vegetation-climate relationship is a basic ecological assumption for pollen-based quantitative inferences of past climate change and for predicting future vegetation. We explore this assumption for the Holocene in eastern continental Asia (China, Mongolia). Boosted regression trees (BRT) between fossil pollen taxa percentages (Abies, Artemisia, Betula, Chenopodiaceae, Cyperaceae, Ephedra, Picea, Pinus, Poaceae and Quercus) and climate model outputs of mean annual precipitation (Pann) and mean temperature of the warmest month (Mtwa) for 9 and 6 ka (ka = thousand years before present) were set up and results compared to those obtained from relating modern pollen to modern climate. Overall, our results reveal only slight temporal differences in the pollen-climate relationships. Our analyses suggest that the importance of Pann compared with Mtwa for taxa distribution is higher today than it was at 6 ka and 9 ka. In particular, the relevance of Pann for Picea and Pinus increases and has become the main determinant. This change in the climate-tree pollen relationship parallels a widespread tree pollen decrease in north-central China and the eastern Tibetan Plateau. We assume that this is at least partly related to vegetation-climate disequilibrium originating from human impact. Increased atmospheric CO2 concentration may have permitted the expansion of moisture-loving herb taxa (Cyperaceae and Poaceae) during the late Holocene into arid/semi-arid areas. We furthermore find that the pollen-climate relationship between north-central China and the eastern Tibetan Plateau is generally similar, but that regional differences are larger than temporal differences. In summary, vegetation-climate relationships in China are generally stable in space and time, and pollen-based climate reconstructions can be applied to the Holocene. Regional differences imply the calibration-set should be restricted spatially.

Food safety knowledge on the Bt mutant protein Cry8Ka5 employed in the development of coleopteran-resistant transgenic cotton plants.

PubMed

Farias, Davi F; Peijnenburg, Ad A C M; Grossi-de-Sá, Maria F; Carvalho, Ana F U

2015-01-01

Insecticidal Cry proteins from Bacillus thuringiensis (Bt) have been exploited in the development of genetically modified (GM) crops for pest control. However, several pests are still difficult to control such as the coleopteran boll weevil Anthonomus grandis. By applying in vitro molecular evolution to the cry8Ka1 gene sequence, variants were generated with improved activity against A. grandis. Among them, Cry8Ka5 mutant protein showed coleoptericidal activity 3-fold higher (LC50 2.83 μg/mL) than that of the original protein (Cry8Ka1). Cry8Ka5 has been used in breeding programs in order to obtain coleopteran-resistant cotton plants. Nevertheless, there is some concern in relation to the food safety of transgenic crops, especially to the heterologously expressed proteins. In this context, our research group has performed risk assessment studies on Cry8Ka5, using the tests recommended by Codex as well as tests that we proposed as alternative and/or complementary approaches. Our results on the risk analysis of Cry8Ka5 taken together with those of other Cry proteins, point out that there is a high degree of certainty on their food safety. It is reasonable to emphasize that most safety studies on Cry proteins have essentially used the Codex approach. However, other methodologies would potentially provide additional information such as studies on the effects of Cry proteins and derived peptides on the indigenous gastrointestinal microbiota and on intestinal epithelial cells of humans. Additionally, emerging technologies such as toxicogenomics potentially will offer sensitive alternatives for some current approaches or methods.

Food safety knowledge on the Bt mutant protein Cry8Ka5 employed in the development of coleopteran-resistant transgenic cotton plants

PubMed Central

Farias, Davi F; Peijnenburg, Ad A C M; Grossi-de-Sá, Maria F; Carvalho, Ana F U

2015-01-01

Insecticidal Cry proteins from Bacillus thuringiensis (Bt) have been exploited in the development of genetically modified (GM) crops for pest control. However, several pests are still difficult to control such as the coleopteran boll weevil Anthonomus grandis. By applying in vitro molecular evolution to the cry8Ka1 gene sequence, variants were generated with improved activity against A. grandis. Among them, Cry8Ka5 mutant protein showed coleoptericidal activity 3-fold higher (LC50 2.83 μg/mL) than that of the original protein (Cry8Ka1). Cry8Ka5 has been used in breeding programs in order to obtain coleopteran-resistant cotton plants. Nevertheless, there is some concern in relation to the food safety of transgenic crops, especially to the heterologously expressed proteins. In this context, our research group has performed risk assessment studies on Cry8Ka5, using the tests recommended by Codex as well as tests that we proposed as alternative and/or complementary approaches. Our results on the risk analysis of Cry8Ka5 taken together with those of other Cry proteins, point out that there is a high degree of certainty on their food safety. It is reasonable to emphasize that most safety studies on Cry proteins have essentially used the Codex approach. However, other methodologies would potentially provide additional information such as studies on the effects of Cry proteins and derived peptides on the indigenous gastrointestinal microbiota and on intestinal epithelial cells of humans. Additionally, emerging technologies such as toxicogenomics potentially will offer sensitive alternatives for some current approaches or methods. PMID:26513483

Asynchronous marine-terrestrial signals of the last deglacial warming in East Asia associated with low- and high-latitude climate changes

PubMed Central

Xu, Deke; Lu, Houyuan; Wu, Naiqin; Liu, Zhenxia; Li, Tiegang; Shen, Caiming; Wang, Luo

2013-01-01

A high-resolution multiproxy record, including pollen, foraminifera, and alkenone paleothermometry, obtained from a single core (DG9603) from the Okinawa Trough, East China Sea (ECS), provided unambiguous evidence for asynchronous climate change between the land and ocean over the past 40 ka. On land, the deglacial stage was characterized by rapid warming, as reflected by paleovegetation, and it began ca. 15 kaBP, consistent with the timing of the last deglacial warming in Greenland. However, sea surface temperature estimates from foraminifera and alkenone paleothermometry increased around 20–19 kaBP, as in the Western Pacific Warm Pool (WPWP). Sea surface temperatures in the Okinawa Trough were influenced mainly by heat transport from the tropical western Pacific Ocean by the Kuroshio Current, but the epicontinental vegetation of the ECS was influenced by atmospheric circulation linked to the northern high-latitude climate. Asynchronous terrestrial and marine signals of the last deglacial warming in East Asia were thus clearly related to ocean currents and atmospheric circulation. We argue that (i) early warming seawater of the WPWP, driven by low-latitude insolation and trade winds, moved northward via the Kuroshio Current and triggered marine warming along the ECS around 20–19 kaBP similar to that in the WPWP, and (ii) an almost complete shutdown of the Atlantic Meridional Overturning Circulation ca. 18–15 kaBP was associated with cold Heinrich stadial-1 and delayed terrestrial warming during the last deglacial warming until ca. 15 kaBP at northern high latitudes, and hence in East Asia. Terrestrial deglacial warming therefore lagged behind marine changes by ca. 3–4 ka. PMID:23720306

Ultra-Compact Ka-Band Parabolic Deployable Antenna for RADAR and Interplanetary CubeSats

NASA Technical Reports Server (NTRS)

Sauder, Jonathan; Chahat, Nacer; Thomson, Mark; Hodges, Richard; Peral, Eva; Rahmat-Samii, Yahya

2015-01-01

Over the past several years, technology and launch opportunities for CubeSats have exploded, enabling a wide variety of missions. However, as instruments become more complex and CubeSats travel deeper into space, data communication rates become an issue. To solve this challenge, JPL has initiated a research and technology development effort to design a 0.5 meter Ka-band parabolic deployable antenna (KaPDA) which would stow in 1.5U (10 x 10 x 15 cu cm) and provide 42dB of gain (50% efficiency). A folding rib architecture and dual reflector Cassegrainian design was selected as it best balances RF gain and stowed size. The design implements an innovative telescoping waveguide and gas powered deployment. RF simulations show that after losses, the antenna would have over 42 dB gain, supported by preliminary test results. KaPDA would create opportunities for a host of new CubeSat missions by allowing high data rate communication which would enable using high fidelity instruments or venturing further into deep space, including potential interplanetary missions. Additionally KaPDA would provide a solution for other small antenna needs and the opportunity to obtain Earth science data. This paper discusses the design challenges encountered, the architecture of the solution, and the antennas expected performance capabilities.

Luminescence dating of the Zeketai loess section in the Ili Basin, northwestern China: Methodological considerations

NASA Astrophysics Data System (ADS)

Qin, Jintang; Zhou, Liping

2018-04-01

Loess deposits in Xinjiang, northwestern China are ideal archives for past environmental changes in the Westerlies-dominated central Asia. Among previous luminescence dating studies of loess in Xinjiang, few have attempted to systematically investigate the methodological aspects. In this study, we report results of a multiple-procedure luminescence dating of the Zeketai loess section in the Ili Basin, central Xinjiang. Optically stimulated luminescence (OSL) and post-infrared infrared stimulated luminescence (pIRIR) signals were used for quartz and polymineral grains of different sizes. The pIRIR ages obtained with two protocols agree well with each other and constrain the loess deposition between 50 ka and 88 ka. The OSL ages of fine-grained quartz are in stratigraphic order and range from 37 ka to 61 ka, but are ∼30% younger than the pIRIR295 ages of both fine and medium grained polyminerals. Although the causes of the discrepancy between the ages derived from different luminescence dating protocols are still to be understood, we stress that the quartz OSL ages of loess in this region are likely to be underestimated, especially for samples older than 40 ka. The polymineral or potassium feldspar pIRIR signal is recommended for dating loess in the Ili Basin, at least as an internal check.

Controls on aggradation and incision in the NE Negev, Israel, since the middle Pleistocene

DOE PAGES

Matmon, A.; Elfasi, S.; Hidy, A. J.; ...

2016-02-23

Here, we investigated the mid-Pleistocene to recent aggradation-incision pattern of two drainage systems (Nahal Peres and Nahal Tahmas) in the hyperarid north eastern Negev desert, southern Israel. Although these drainage systems drain into the tectonically active Dead Sea basin, lake level fluctuations cannot account for the aggradation-incision pattern as bedrock knickpoints disconnect the investigated parts of these drainage systems from base level influence. We applied geomorphic mapping, soil stratigraphy, optically stimulated luminescence (OSL) and cosmogenic (in situ 10Be) exposure dating to reconstruct cycles of aggradation and incision of alluvial terraces and to study their temporal association with regional periods ofmore » humidity and aridity and global glacial-interglacial cycles. The spatial and temporal relationships between the alluvial units suggest changes in the drainage system behavior since the middle Pleistocene, and show a pattern in which prolonged periods of sediment aggradation alternated with short periods of rapid and intense degradation through erosion and incision into sediment and bedrock. We obtain ages for several Pleistocene-Holocene periods of incision: ~ 1.1 Ma, ~ 300 ka, ~ 120 ka, ~ 20 ka, ~ 12 ka and ~ 2 ka. Although broadly synchronous, the Nahal Peres and Nahal Tahmas systems exhibit temporal differences in aggradation and incision.« less

Controls on aggradation and incision in the NE Negev, Israel, since the middle Pleistocene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matmon, A.; Elfasi, S.; Hidy, A. J.

Here, we investigated the mid-Pleistocene to recent aggradation-incision pattern of two drainage systems (Nahal Peres and Nahal Tahmas) in the hyperarid north eastern Negev desert, southern Israel. Although these drainage systems drain into the tectonically active Dead Sea basin, lake level fluctuations cannot account for the aggradation-incision pattern as bedrock knickpoints disconnect the investigated parts of these drainage systems from base level influence. We applied geomorphic mapping, soil stratigraphy, optically stimulated luminescence (OSL) and cosmogenic (in situ 10Be) exposure dating to reconstruct cycles of aggradation and incision of alluvial terraces and to study their temporal association with regional periods ofmore » humidity and aridity and global glacial-interglacial cycles. The spatial and temporal relationships between the alluvial units suggest changes in the drainage system behavior since the middle Pleistocene, and show a pattern in which prolonged periods of sediment aggradation alternated with short periods of rapid and intense degradation through erosion and incision into sediment and bedrock. We obtain ages for several Pleistocene-Holocene periods of incision: ~ 1.1 Ma, ~ 300 ka, ~ 120 ka, ~ 20 ka, ~ 12 ka and ~ 2 ka. Although broadly synchronous, the Nahal Peres and Nahal Tahmas systems exhibit temporal differences in aggradation and incision.« less

N-tuple topological/geometric cutoffs for 3D N-linear algebraic molecular codifications: variability, linear independence and QSAR analysis.

PubMed

García-Jacas, C R; Marrero-Ponce, Y; Barigye, S J; Hernández-Ortega, T; Cabrera-Leyva, L; Fernández-Castillo, A

2016-12-01

Novel N-tuple topological/geometric cutoffs to consider specific inter-atomic relations in the QuBiLS-MIDAS framework are introduced in this manuscript. These molecular cutoffs permit the taking into account of relations between more than two atoms by using (dis-)similarity multi-metrics and the concepts related with topological and Euclidean-geometric distances. To this end, the kth two-, three- and four-tuple topological and geometric neighbourhood quotient (NQ) total (or local-fragment) spatial-(dis)similarity matrices are defined, to represent 3D information corresponding to the relations between two, three and four atoms of the molecular structures that satisfy certain cutoff criteria. First, an analysis of a diverse chemical space for the most common values of topological/Euclidean-geometric distances, bond/dihedral angles, triangle/quadrilateral perimeters, triangle area and volume was performed in order to determine the intervals to take into account in the cutoff procedures. A variability analysis based on Shannon's entropy reveals that better distribution patterns are attained with the descriptors based on the cutoffs proposed (QuBiLS-MIDAS NQ-MDs) with regard to the results obtained when all inter-atomic relations are considered (QuBiLS-MIDAS KA-MDs - 'Keep All'). A principal component analysis shows that the novel molecular cutoffs codify chemical information captured by the respective QuBiLS-MIDAS KA-MDs, as well as information not captured by the latter. Lastly, a QSAR study to obtain deeper knowledge of the contribution of the proposed methods was carried out, using four molecular datasets (steroids (STER), angiotensin converting enzyme (ACE), thermolysin inhibitors (THER) and thrombin inhibitors (THR)) widely used as benchmarks in the evaluation of several methodologies. One to four variable QSAR models based on multiple linear regression were developed for each compound dataset following the original division into training and test sets. The results obtained reveal that the novel cutoff procedures yield superior performances relative to those of the QuBiLS-MIDAS KA-MDs in the prediction of the biological activities considered. From the results achieved, it can be suggested that the proposed N-tuple topological/geometric cutoffs constitute a relevant criteria for generating MDs codifying particular atomic relations, ultimately useful in enhancing the modelling capacity of the QuBiLS-MIDAS 3D-MDs.

Sea-level changes and shelf break prograding sequences during the last 400 ka in the Aegean margins: Subsidence rates and palaeogeographic implications

NASA Astrophysics Data System (ADS)

Lykousis, V.

2009-09-01

The subsidence rates of the Aegean margins during the Middle-Upper Pleistocene were evaluated based on new and historical seismic profiling data. High-resolution seismic profiling (AirGun, Sparker and 3.5 kHz) have shown that (at least) four major oblique prograding sequences can be traced below the Aegean marginal slopes at increasing subbottom depths. These palaeo-shelf break glacial delta sediments have been developed during successive low sea-level stands (LST prograding sequences), suggesting continuous and gradual subsidence of the Aegean margins during the last 400 ka. Subsidence rates of the Aegean margins were calculated from the vertical displacement of successive topset-to-foreset transitions (palaeo-shelf break) of the LST prograding sediment sequences. The estimated subsidence rates that were calculated in the active boundaries of the Aegean microplate (North Aegean margins, Gulfs of Patras and Corinth) are high and range from 0.7 to 1.88 m ka -1, while the lowest values (0.34-0.60 m ka -1) are related to the low tectonic and seismic activity margins like the margin of Cyclades plateau. Lower subsidence rates (0.34-0.90 m ka -1) were estimated for the period 146-18 ka BP (oxygen isotopic stages 6-2) and higher (1.46-1.88 m ka -1) for the period from 425 to 250 ka BP (oxygen isotopic stages 12/10-8). A decrease of about 50% of the subduction rates in the Aegean margins was observed during the last 400 ka. During the isotopic stages 8, 10, 11 and 12, almost the 50-60% of the present Aegean Sea was land with extensive drainage systems and delta plains and large lakes in the central and North Aegean. Marine transgression in the North Aegean was rather occurred during the isotopic 9 interglacial period. The estimated palaeomorphology should imply fan delta development and sediment failures in the steep escarpments of the North Aegean margins and high sedimentation rates and turbidite sediment accumulation in the basins. It is deduced that the Black Sea was isolated from the Mediterranean during the Pleistocene prior oxygen isotopic stage 5.

Spatial and temporal deformation along the northern San Jacinto fault, southern California: Implications for slip rates

USGS Publications Warehouse

Kendrick, K.J.; Morton, D.M.; Wells, S.G.; Simpson, R.W.

2002-01-01

The San Timoteo badlands is an area of uplift and erosional dissection that has formed as a result of late Quaternary uplift along a restraining bend in the San Jacinto fault, of the San Andreas fault system in southern California. This bend currently is located in a region where late Quaternary deposits and associated surfaces have formed in lower San Timoteo Canyon. We have used morphometric analysis of these surfaces, in conjunction with computer modeling of deformational patterns along the San Jacinto fault, to reconstruct spatial and temporal variations in uplift along the bend. Morphometric techniques used include envelope/subenvelope mapping, a gradient-length index along channels, and denudation values. Age control is determined using a combination of thermoluminescence (TL) and near infrared optical simulation luminescence dating (IROSL) and correlation of soil-development indices. These approaches are combined with an elastic half-space model used to determine the deformation associated with the fault bend. The region of modeled uplift has a similar distribution as that determined by morphometric techniques. Luminescence dates and soil-correlation age estimates generally agree. Based on soil development, surfaces within the study area were stabilized at approximately 300-700 ka for Q3, 43-67 ka for Q2, and 27.5-67 ka for Q1. Luminescence ages (both TL and IROSL) for the formation of the younger two surfaces are 58 to 94 ka for Q2 and 37 to 62 ka for Q1 (ages reported to 1?? uncertainty). Periods of uplift were determined for the surfaces in the study area, resulting in approximate uplift rates of 0.34 to 0.84 m/ka for the past 100 ka and 0.13 to 1.00 m/ka for the past 66 ka. Comparison of these rates of uplift to those generated by the model support a higher rate of lateral slip along the San Jacinto fault than commonly assumed (greater than 20 mm/yr, as compared to 8-12 mm/yr commonly cited). This higher slip rate supports the proposal that a greater amount of slip has transferred from the San Andreas fault to the San Jacinto fault than generally held. The San Jacinto fault may have accommodated a significant portion of the plate boundary slip during the past 100 ka.

Geomagnetic field intensity determination from Pleistocene trachytic lava flows in Jeju Geopark

NASA Astrophysics Data System (ADS)

Jeong, Doohee; Yu, Yongjae; Liu, Qingsong; Jiang, Zhaoxia; Koh, Gi Won; Koh, Dong-Chan

2014-03-01

A composite of 28 trachytic lava flows were recovered from the Jeju Geopark Drilling Project (JGDP) in Jeju Geopark, one of the new seven wonders of Nature declared by UNESCO in 2011. Each trachytic lava flow has a tendency to increase in magnetic grain size from the rapidly cooled brecciated margin and vesicle streaked zone downward into the massive crystalline flow interiors. The brecciated margin and vesicle streaked zone of individual trachytic lava flow contains exclusively fine-grained magnetite as inclusions in plagioclase. High-fidelity paleointensity determinations were obtained from 26 (out of 224 examined) samples from JGDP cores. Temporal variation of virtual axial dipole moments (VADMs) calculated from the absolute paleointensity estimates follows the trend of sint-800 data for the interval from ˜80 to ˜360 ka. High VADM from flow 21 possibly represents real intensity peak, as previously recognized high VADM in Japan at ˜336 ka, in Trans-Mexican volcanism ˜339, and in Hawaii ˜340-350 ka. Perhaps such a strong magnetic intensity near ˜325-350 ka might be smoothed out in relative paleointensity records.

Experimental demonstration of plasma startup by coaxial helicity injection

NASA Astrophysics Data System (ADS)

Raman, R.; Jarboe, T. R.; Nelson, B. A.; Hamp, W. T.; Izzo, V. A.; O'Neill, R. G.; Redd, A. J.; Sieck, P. E.; Smith, R. J.

2004-05-01

Experimental results on the transfer of a coaxial-helicity-injection (CHI) produced discharge to inductive operation are reported. CHI assisted plasma startup is more robust than inductive only operation and reduces volt-seconds consumption. After handoff to inductive operation, the initial 100 kA of CHI produced current drops to 50 kA, then ramps up to 180 kA, using only 30 mVs, about 40% higher than that produced by induction alone. Results show that initiation of CHI discharges at lower densities produce higher levels of coupling current. Coupling a CHI produced discharge to induction from a precharged central solenoid has produced record currents of 290 kA using only 52 mWb of central solenoid flux. CHI discharges can also be generated while the central transformer is in the process of being precharged, during which period it induces a negative loop voltage on the CHI discharge. These significant results were obtained on the Helicity Injected Torus-II (HIT-II) [T.R. Jarboe, Fusion Technol. 15, 7 (1989)] spherical torus experiment (major/minor radius of 0.3/0.2 m and elongation of 1.5).

Age and significance of former low-altitude corrie glaciers on Hoy, Orkney Islands

USGS Publications Warehouse

Ballantyne, C.K.; Hall, A.M.; Phillips, W.; Binnie, S.; Kubik, P.W.

2007-01-01

Geomorphological mapping provides evidence for two former low-level corrie glaciers on Hoy, both defined by end moraines. Five 10Be exposure ages obtained from sandstone boulders on moraine crests fall within the range 12.4??1.5 ka to 10.4??1.7 ka (weighted mean 11.7??0.6 ka), confirming that these glaciers developed during the Loch Lomond (Younger Dryas) Stade (LLS) of 12.9-11.5 cal. ka BP, and demonstrate the feasibility of using this approach to establish the age of LLS glacier limits. The equilibrium line altitude (ELA) of one of the glaciers (99 m) is the lowest recorded for any LLS glacier, and the area-weighted mean ELA for both (141 m) is consistent with a general northward ELA decrease along the west coast of Britain. The size of moraines fronting these small (???0.75 km2) glaciers implies that glacier termini remained at or close to their limits for a prolonged period. The apparent restriction of LLS glaciers to only two sites on Hoy probably reflects topographic favourability, and particularly the extent of snow-contributing areas.

Pharmacokinetics study of ferulic acid in rats after oral administration of γ-oryzanol under combined use of Tween 80 by LC/MS/MS.

PubMed

Pan, Y; Cai, L; He, S; Zhang, Z

2014-01-01

γ-oryzanol (OZ) is a rich source of commercially-important bioactive phytochemicals, most of them of interest in nutrition, pharmacy and cosmetics. However, the poor solubility of OZ limited the use. In the paper, ultraviolet-visible (UV-Vis) analysis was conducted to analysis the solubilization of OZ under combined use of Tween 80 in vitro. In addition, to further confirm the solubilizing effect of Tween 80, a pharmacokinetic study of ferulic acid (FA) in rats after oral administration of OZ 100 mg/kg under combined use of Tween 80 though LCMS/MS was carried out. Solubility enhancement as high as 100-fold is achieved using 1% Tween 80 in vitro. Following oral administration of OZ-Tween 80 100 mg/kg, the values of Tmax, Cmax, AUC0-∞, T1/2Ka and MRT0-∞ were 46.667 ± 39.328, 129.498 ± 27.025, 63738.28 ± 599, 14.274 ± 7.309 and 859.592 ± 108.780 respectively. The values of T1/2Ka, AUC0-∞, MRT0-t, and Tmax showed up to increase 16%, 58%, 44% and 47% while Cmax and CL/F decreased 22% and 12%, respectively. The decreased Cmax value indicated that Tween 80 can hardly enhance the absorption of FA in rats. However, T1/2Ka and Tmax values showed that the absorption of FA was extended, which resulted the increased values of AUC0-∞ and MRT0-∞. Our results reveal that Tween 80 improves solubility of OZ in vitro and could enhance the bioavailability of OZ by extending its absorption and elimination.

Study of the hydrolysis and ionization constants of Schiff base from pyridoxal 5'-phosphate and n-hexylamine in partially aqueous solvents. An application to phosphorylase b.

PubMed Central

Donoso, J; Muñoz, F; García Del Vado, A; Echevarría, G; García Blanco, F

1986-01-01

Formation and hydrolysis rate constants as well as equilibrium constants of the Schiff base derived from pyridoxal 5'-phosphate and n-hexylamine were determined between pH 3.5 and 7.5 in ethanol/water mixtures (3:17, v/v, and 49:1, v/v). The results indicate that solvent polarity scarcely alters the values of these constants but that they are dependent on the pH. Spectrophotometric titration of this Schiff base was also carried out. We found that a pKa value of 6.1, attributed in high-polarity media to protonation of the pyridine nitrogen atom, is independent of solvent polarity, whereas the pKa of the monoprotonated form of the imine falls from 12.5 in ethanol/water (3:17) to 11.3 in ethanol/water (49:1). Fitting of the experimental results for the hydrolysis to a theoretical model indicates the existence of a group with a pKa value of 6.1 that is crucial in the variation of kinetic constant of hydrolysis with pH. Studies of the reactivity of the coenzyme (pyridoxal 5'-phosphate) of glycogen phosphorylase b with hydroxylamine show that this reaction only occurs when the pH value of solution is below 6.5 and the hydrolysis of imine bond has started. We propose that the decrease in activity of phosphorylase b when the pH value is less than 6.2 must be caused by the cleavage of enzyme-coenzyme binding and that this may be related with protonation of the pyridine nitrogen atom of pyridoxal 5'-phosphate. PMID:3099764

PCE: web tools to compute protein continuum electrostatics

PubMed Central

Miteva, Maria A.; Tufféry, Pierre; Villoutreix, Bruno O.

2005-01-01

PCE (protein continuum electrostatics) is an online service for protein electrostatic computations presently based on the MEAD (macroscopic electrostatics with atomic detail) package initially developed by D. Bashford [(2004) Front Biosci., 9, 1082–1099]. This computer method uses a macroscopic electrostatic model for the calculation of protein electrostatic properties, such as pKa values of titratable groups and electrostatic potentials. The MEAD package generates electrostatic energies via finite difference solution to the Poisson–Boltzmann equation. Users submit a PDB file and PCE returns potentials and pKa values as well as color (static or animated) figures displaying electrostatic potentials mapped on the molecular surface. This service is intended to facilitate electrostatics analyses of proteins and thereby broaden the accessibility to continuum electrostatics to the biological community. PCE can be accessed at . PMID:15980492

Optical fiber sensor having an active core

NASA Technical Reports Server (NTRS)

Egalon, Claudio Oliveira (Inventor); Rogowski, Robert S. (Inventor)

1993-01-01

An optical fiber is provided. The fiber is comprised of an active fiber core which produces waves of light upon excitation. A factor ka is identified and increased until a desired improvement in power efficiency is obtained. The variable a is the radius of the active fiber core and k is defined as 2 pi/lambda wherein lambda is the wavelength of the light produced by the active fiber core. In one embodiment, the factor ka is increased until the power efficiency stabilizes. In addition to a bare fiber core embodiment, a two-stage fluorescent fiber is provided wherein an active cladding surrounds a portion of the active fiber core having an improved ka factor. The power efficiency of the embodiment is further improved by increasing a difference between the respective indices of refraction of the active cladding and the active fiber core.

Holocene paleoclimatic evidence and sedimentation rates from a core in southwestern Lake Michigan

USGS Publications Warehouse

Colman, Steven M.; Jones, Glenn A.; Forester, R.M.; Foster, D.S.

1990-01-01

Preliminary results of a multidisciplinary study of cores in southwestern Lake Michigan suggest that the materials in these cores can be interpreted in terms of both isostatically and climatically induced changes in lake level. Ostracodes and mollusks are well preserved in the Holocene sediments, and they provide paleolimnologic and paleoclimatic data, as well as biogenic carbonate for stable-isotope studies and radiocarbon dating. Pollen and diatom preservation in the cores is poor, which prevents comparison with regional vegetation records. New accelerator-mass spectrometer 14C ages, from both carbon and carbonate fractions, provide basin-wide correlations and appear to resolve the longstanding problem of anomalously old ages that result from detrital organic matter in Great Lakes sediments. Several cores contain a distinct unconformity associated with the abrupt fall in lake level that occurred about 10.3 ka when the isostatically depressed North Bay outlet was uncovered by the retreating Laurentide Ice Sheet. Below the unconformity, ostracode assemblages imply deep, cold water with very low total dissolved solids (TDS), and bivalves have ?? 18O (PDB) values as light as - 10 per mil. Samples from just above the unconformity contain littoral to sublittoral ostracode species that imply warmer, higher-TDS (though still dilute) water than that inferred below the unconformity. Above this zone, another interval with ?? 18O values more negative than - 10 occurs. The isotopic data suggest that two influxes of cold, isotopically light meltwater from Laurentide ice entered the lake, one shortly before 10.3 ka and the other about 9 ka. These influxes were separated by a period during which the lake was warmer, shallower, but still very low in dissolved solids. One or both of the meltwater influxes may be related to discharge from Lake Agassiz into the Great Lakes. Sedimentation rates appear to have been constant from about 10 ka to 5 ka. Bivalve shells formed between about 8 and 5 ka have ?? 18O values that range from-2.3 to-3.3 per mil and appear to decrease toward the end of the interval. The ostracode assemblages and the stable isotopes suggest changes that are climatically controlled, including fluctuating water levels and increasing dissolved solids, although the water remained relatively dilute (TDS < 300 mg/l). A dramatic decrease in sedimentation rates occurred at about 5 ka, about the time of the peak of the Nippissing high lake stage. This decrease in sedimentation rate may be associated with a large increase in effective wave base as the lake approached its present size and fetch. A dramatic reduction in ostracode and mollusk abundances during the late Holocene is probably due to this decrease in sedimentation rates, which would result in increased carbonate dissolution. Ostracode productivity may also have declined due to a reduction in bottom-water oxygen caused by increased epilimnion algal productivity. 

Branched GDGT-based paleotemperature reconstruction of the last 30,000 years in humid monsoon region of Southeast China

NASA Astrophysics Data System (ADS)

Wang, M.

2017-12-01

The use of bacterial branched glycerol dialkyl glycerol tetraethers (brGDGTs) to reconstruct mean annual air temperatures (MAATs) and environmental pH from soils has sparked significant interest in the terrestrial paleoclimate community. However, the reconstruction of these climate proxies from peat bogs is rare in monsoonal regions of the East Asia. This research was carried out on a core from the Shuizhuyang (SZY) peat bog located in Fujian Province. Branched GDGT (brGDGT) indexes were used for reconstructing the paleoclimate of the last 30 cal ka. The aim was to evaluate quantitatively the MAAT and pH values since the Last Glacial Maximum (LGM) in the subtropical zone of China. Results show that the CBT-MBT'-derived MAAT at MIS 3 is about 15.6 °C on average, which is followed by a significant fall at the LGM (11.7-12.1 °C). The temperature difference between the LGM and the present-day value is as high as 5.8 °C. The synchronous variation of biomarker and pollen proxies indicates that replacement of subtropical evergreen broadleaved forests by coldtolerant, deciduous broadleaved forests was driven by the significant drop in air temperature. Our results also indicate that the Younger Dryas event lasted from about 12.9 to about 11.3 cal ka, and cooling event at 3.2 cal ka in the late Holocene was detected, showing the sensitivity of peat bogs to rapid cooling. Our pH reconstructions indicate that the pH of the bog rose during Heinrich 1 and Bølling-Allerød periods, probably due to low precipitation, and were lowest in the Holocene thermal maximum between 8 ka and 2.5 ka, probably due to higher precipitation. The decoupling of reconstructed MAAT and pH during particularly deglaciation and YD periods supports the hypothesis that the variations in temperature and precipitation are not always synchronous.

Evaluation of the possibility of using the water of the Bystrytsya-Nadvirnyans'ka River in Cherniiv (Ukraine) to supply the population with drinking water

NASA Astrophysics Data System (ADS)

Pietrzak, D.; Mandryk, O.; Wątor, K.; Kmiecik, E.; Zelmanowych, A.

2018-02-01

The article presents the results of the research carried out in order to assess the possibility of using surface water of the Bystrytsya-Nadvirnyans'ka River in Cherniiv (western Ukraine), for the public supply of water intended for human consumption. For this purpose an existing database that contains the results of analyses of surface water samples collected in 1999, 2002, 2005, 2008, 2011 and 2014 was used. Each year, from 8 to 13 samples were collected from the Bystrytsya-Nadvirnyans'ka River in Cherniiv. Physicochemical analyses of the samples taken included the determination of pH value, temperature, TDS, alkalinity, hardness, dissolved oxygen, BOD5, COD, suspended solids and ions: Ca2+, Mg2+, Na+, K+, Fe2+, NH4+, Cu2+, Cl-, SO42-, PO43-, HCO3-, NO2-, NO3-. These chemical analyses were verified by calculation of errors based on the ionic balance. The results of the analyses were referred to the polish applicable requirements for surface water used for public supply of water intended for human consumption and to the regulation regarding the classification of the surface water status and environmental quality standards for priority substances. The results indicate that water of the Bystrytsya-Nadvirnyans'ka River in the area of Cherniiv was out of the class in the years 1999 and 2002 due to exceeding the limit values for category A3 for Cu2+. On the basis of incomplete assessment of the status of the Bystrytsya-Nadvirnyans'ka River water (due to the tests limitation to the physical and chemical components) determined that the water has a bad status because it exceeded the limits for class II for Cl-, SO42-, NO3- and TDS. In the samples collected in 1999 and 2002 it is also observed exceeding the maximum limit concentrations for Cu2+.

Constraining Resurgence through Lake Sediment Paleomagnetism on Resurgent Dome Samosir Island in Toba Caldera, Sumatra, Indonesia

NASA Astrophysics Data System (ADS)

Solada, K.; de Silva, S. L.; Stoner, J. S.; Mucek, A. E.; Reilly, B. T.; Hatfield, R. G.; Pratomo, I.; Bowers, J.; Jamil, R.; Setianto, B.

2017-12-01

Around 74 ka, a supervolcano, Toba Caldera in Sumatra, Indonesia erupted, producing the Youngest Toba Tuff and its associated caldera. After this catastrophic eruption, a lake filled the caldera, sedimentation within the lake occurred, and the process known as resurgence began. Today, the resurgent dome, Samosir Island, is uplifted 700 m above the lake with the upper 100 m composed of these post eruption lake sediments. These sediments and their ages offer insight to the resurgent uplift history. To constrain sediment chronology, we collected discrete paleomagnetic 8 cm3 cubes and 43 radiocarbon samples from 10 sites around the island. Bulk organic carbon 14C ages provide an initial chronostratigraphic framework, which is improved by correlating paleomagnetic signals between site sections. Additionally, nearby marine sediment paleomagnetic records show large amplitude changes in inclination over the past 74 ka, providing a good template to compare the sediment chronology. 27 radiocarbon samples have already been dated, with the oldest dating at 38 ka. However, our radiocarbon and paleomagnetic correlation suggest that this record extends even older. Natural and laboratory magnetizations on discrete samples were studied using alternating field (AF) demagnetization at the Oregon State University P-Mag Lab. Although there is variability in magnetic susceptibility between study sites and natural remanant magnetization intensities are often relatively low ( 10-4 (A/m)), AF demagnetization behavior suggests a primary magnetization is recorded. Characteristic remanent magnetizations are reasonably well-defined using a principal component analysis with maximum angular deviation values < 15°, though stronger samples typically have better resolved magnetizations. Data from 4 sites with 14C ages ranging from 23 ka to 38 ka, show low inclination values, averaging around -5° compared with geocentric axial dipole prediction for the site location of approximately 4°. This is consistent with the negative inclination anomaly associated with this region. These observations and similar patterns between sections suggest that a reliable record is preserved that is suitable for magnetic stratigraphy.

Authigenic 10Be/9Be ratio signatures of the cosmogenic nuclide production linked to geomagnetic dipole moment variation since the Brunhes/Matuyama boundary.

PubMed

Simon, Quentin; Thouveny, Nicolas; Bourlès, Didier L; Valet, Jean-Pierre; Bassinot, Franck; Ménabréaz, Lucie; Guillou, Valéry; Choy, Sandrine; Beaufort, Luc

2016-11-01

Geomagnetic dipole moment variations associated with polarity reversals and excursions are expressed by large changes of the cosmogenic nuclide beryllium-10 ( 10 Be) production rates. Authigenic 10 Be/ 9 Be ratios (proxy of atmospheric 10 Be production) from oceanic cores therefore complete the classical information derived from relative paleointensity (RPI) records. This study presents new authigenic 10 Be/ 9 Be ratio results obtained from cores MD05-2920 and MD05-2930 collected in the west equatorial Pacific Ocean. Be ratios from cores MD05-2920, MD05-2930 and MD90-0961 have been stacked and averaged. Variations of the authigenic 10 Be/ 9 Be ratio are analyzed and compared with the geomagnetic dipole low series reported from global RPI stacks. The largest 10 Be overproduction episodes are related to dipole field collapses (below a threshold of 2 × 10 22  Am 2 ) associated with the Brunhes/Matuyama reversal, the Laschamp (41 ka) excursion, and the Iceland Basin event (190 ka). Other significant 10 Be production peaks are correlated to geomagnetic excursions reported in literature. The record was then calibrated by using absolute dipole moment values drawn from the Geomagia and Pint paleointensity value databases. The 10 Be-derived geomagnetic dipole moment record, independent from sedimentary paleomagnetic data, covers the Brunhes-Matuyama transition and the whole Brunhes Chron. It provides new and complementary data on the amplitude and timing of millennial-scale geomagnetic dipole moment variations and particularly on dipole moment collapses triggering polarity instabilities.

Probing the mechanism of proton coupled electron transfer to dioxygen: the oxidative half-reaction of bovine serum amine oxidase.

PubMed

Su, Q; Klinman, J P

1998-09-08

Bovine serum amine oxidase (BSAO) catalyzes the oxidative deamination of primary amines, concomitant with the reduction of molecular oxygen to hydrogen peroxide via a ping-pong mechanism. A protocol has been developed for an analysis of chemical and kinetic mechanisms in the conversion of dioxygen to hydrogen peroxide. Steady-state kinetics show that two groups need to be deprotonated to facilitate the oxidative half-reaction. The pH dependence of Vmax/Km(O2) reveals pKa's of 6.2 +/- 0.3 and 7.0 +/- 0.2, respectively. A pKa of 7.2 +/- 0.1 has been obtained from a titration of anaerobically reduced BSAO using UV-vis spectrophotometry. The near identity of the pKa obtained from the reduced enzyme titration with the second pKa from steady-state kinetics suggests that this second pKa arises from the reduced cofactor. The assignment of pKa is supported by the observed pH dependence for formation of the cofactor semiquinone signal, detected by EPR spectroscopy under anaerobic conditions. To address the nature of rate-limiting steps in the oxidative half-reaction, the solvent isotope effect, viscosity effect, and O-18 isotope effect on Vmax/Km(O2) have been determined. The solvent isotope effect is indistinguishable from unity, ruling out a proton transfer as a rate-determining step. Use of glucose as a solvent viscosogen shows no viscosity effect, indicating that binding of oxygen is not in the rate-determining step. The O-18 kinetic isotope effect is independent of pH with an average value of 18(V/K) = 1.0097 +/- 0. 0010. This has been compared to calculated equilibrium O-18 isotope effects for various dioxygen intermediate species [Tian and Klinman (1993) J. Am. Chem. Soc. 115, 8891], leading to the conclusion that either the first electron transfer to dioxygen or the desorption of product peroxide from a Cu(II)-OOH complex could be the rate-limiting step. The distribution of steady-state enzyme species was, therefore, analyzed through a combination of stopped-flow experiments and analysis of DV and D(V/K) for benzylamine oxidation. We conclude that the major species accumulating in the steady state are the oxidized cofactor-substrate Schiff base complex and the reduced, aminoquinol form of cofactor. These data rule out a slow release of product hydroperoxide from the aminoquinone form of enzyme, leading to the conclusion that the first electron transfer from substrate-reduced cofactor to dioxygen is the rate-determining step in the oxidative half-reaction. This step is also estimated to be 40% rate-limiting in kcat. An important mechanistic conclusion from this study is that dioxygen binding is a separate step from the rate-limiting electron-transfer step to form superoxide. On the basis of a recently determined X-ray structure for the active form of a yeast amine oxidase from Hansenula polymorpha [Li et al. (1998) Structure 6, 293], a hydrophobic space has been identified near the O-2 position of reduced cofactor as the putative dioxygen binding site. Movement of superoxide from this site onto the Cu(II) at the active site may occur prior to further electron transfer from cofactor to superoxide.

Ostracods and sediment geochemistry as indicators of hydrologic and climatic variability in the central part of the Mexican Chihuahuan Desert over the last 27 ka cal BP

NASA Astrophysics Data System (ADS)

Chávez Lara, C. M.; Roy, P. D.; Lozano Santa Cruz, R.; López Balbiaux, N.

2013-12-01

The paleolake Santiaguillo (Durango State) is located in the central part of the Chihuahuan Desert (Mexico). The lacustrine basin covers an area of approximately 1,964 km2 and is surrounded by mountains up to ca. 2,700 masl. This basin was formed by tectonic processes and the basement is formed by volcanic felsic rocks of Tertiary age. Four sediment cores were obtained from central and western part of the basin to reconstruct hydrologic and climate variability during the late Pleistocene and Holocene. In this work, we present paleo-ecology of ostracods and sedimentary geochemistry from two sediment cores (300 cm and 200 cm long) collected from the western basin margin. The age model was constructed from 8 AMS radiocarbon dates and the longest profile represents the last 27 cal ka BP. The ostracode faunal content consists of 4 different species: Limnocythere bradburyi, Cadona patzcuaro, Cypridopsis vidua and Limnocythere ceriotuberosa (listed from highest to lowest abundance) and total abundance varies between 0 and 125 valves/g. Paleo-environmental conditions were reconstructed from the Total Organic Carbon (TOC), Total Inorganic Carbon (TIC), Carbon/Nitrogen ratios (C/N), Chemical Index of Alteration (CIA) and concentrations of Ti, Ca, Si and Al. The results were divided into two zones for interpretation. Zone 1 covers ca. 27-17 cal ka BP (300-191 cm) and is characterized by higher Ti concentrations and above average CIA values. This suggests greater interaction between water and sediment, lower evaporation and relatively higher lake level in the basin. During this interval of higher lakestand, the deposited organic matter was autochthonous (lacustrine origin) and ostracodes suggest presence of a warm and dilute water column (>13 °C and >100 ppm). Sediments of the last 17 cal ka BP (191-0 cm) (Zone 2) are characterized by below average water-sediment interaction, higher carbonate precipitation and deposition of allochthonous organic matter (terrestrial origin). During the shallow lake conditions, the ostracode assemblage suggests presence of a warm and saline water column (>13 °C and >400ppm).

A mathematical model of pH, based on the total stoichiometric concentration of acids, bases and ampholytes dissolved in water.

PubMed

Mioni, Roberto; Mioni, Giuseppe

2015-10-01

In chemistry and in acid-base physiology, the Henderson-Hasselbalch equation plays a pivotal role in studying the behaviour of the buffer solutions. However, it seems that the general function to calculate the valence of acids, bases and ampholytes, N = f(pH), at any pH, has only been provided by Kildeberg. This equation can be applied to strong acids and bases, pluriprotic weak acids, bases and ampholytes, with an arbitrary number of acid strength constants, pKA, including water. By differentiating this function with respect to pH, we obtain the general equation for the buffer value. In addition, by integrating the titration curve, TA, proposed by Kildeberg, and calculating its Legendre transform, we obtain the Gibbs free energy of pH (or pOH)-dependent titratable acid. Starting from the law of electroneutrality and applying suitable simplifications, it is possible to calculate the pH of the buffer solutions by numerical methods, available in software packages such as Excel. The concept of buffer capacity has also been clarified by Urbansky, but, at variance with our approach, not in an organic manner. In fact, for each set of monobasic, dibasic, tribasic acids, etc., various equations are presented which independently fit each individual acid-base category. Consequently, with the increase in acid groups (pKA), the equations become more and more difficult, both in practice and in theory. Some examples are proposed to highlight the boundary that exists between acid-base physiology and the thermodynamic concepts of energy, chemical potential, amount of substance and acid resistance.

The age of Homo naledi and associated sediments in the Rising Star Cave, South Africa

PubMed Central

Dirks, Paul HGM; Roberts, Eric M; Hilbert-Wolf, Hannah; Kramers, Jan D; Hawks, John; Dosseto, Anthony; Duval, Mathieu; Elliott, Marina; Evans, Mary; Grün, Rainer; Hellstrom, John; Herries, Andy IR; Joannes-Boyau, Renaud; Makhubela, Tebogo V; Placzek, Christa J; Robbins, Jessie; Spandler, Carl; Wiersma, Jelle; Woodhead, Jon; Berger, Lee R

2017-01-01

New ages for flowstone, sediments and fossil bones from the Dinaledi Chamber are presented. We combined optically stimulated luminescence dating of sediments with U-Th and palaeomagnetic analyses of flowstones to establish that all sediments containing Homo naledi fossils can be allocated to a single stratigraphic entity (sub-unit 3b), interpreted to be deposited between 236 ka and 414 ka. This result has been confirmed independently by dating three H. naledi teeth with combined U-series and electron spin resonance (US-ESR) dating. Two dating scenarios for the fossils were tested by varying the assumed levels of 222Rn loss in the encasing sediments: a maximum age scenario provides an average age for the two least altered fossil teeth of 253 +82/–70 ka, whilst a minimum age scenario yields an average age of 200 +70/–61 ka. We consider the maximum age scenario to more closely reflect conditions in the cave, and therefore, the true age of the fossils. By combining the US-ESR maximum age estimate obtained from the teeth, with the U-Th age for the oldest flowstone overlying Homo naledi fossils, we have constrained the depositional age of Homo naledi to a period between 236 ka and 335 ka. These age results demonstrate that a morphologically primitive hominin, Homo naledi, survived into the later parts of the Pleistocene in Africa, and indicate a much younger age for the Homo naledi fossils than have previously been hypothesized based on their morphology. DOI: http://dx.doi.org/10.7554/eLife.24231.001 PMID:28483040

Propagation experiment of COMETS Ka/Q-band communication link for future satellite cellular system

NASA Technical Reports Server (NTRS)

Hase, Yoshihiro

1995-01-01

Mobile/Personal Satellite Communication Systems in L/S-bands are going into the operational phase. In the future, they will be operated in much higher frequency bands, for example in Ka-band, because the available bandwidth in L-band is limited. Systems with large on-board antennas in higher frequencies allow the same configuration as terrestrial cellular radio systems, since the on-board antennas will have many small spot beams. This may be true especially in a low earth orbit system such as Teledesic, which will use Ka-band. The most important parameter of Satellite Cellular may be cell size, that is, a diameter of the spot beam. A system designer needs the local correlation data in a cell and the size of the correlative area. On the other hand, the most significant difficulty of Ka and higher band systems is the countermeasure to rain attenuation. Many-cell systems can manage the limited power of on-board transponders by controlling output power of each beam depending on the rain attenuation of each cell. If the cell size is equal to the correlative area, the system can probably achieve the maximum performance. Propagation data of Ka and higher band obtained in the past shows a long term cumulative feature and link availability, but do not indicate the correlative area. The Japanese COMETS satellite, which will be launched in February 1997, has transponders in Ka and Q-band. The CRL is planning to measure the correlative area using 21 GHz and 44 GHz CW transmissions from the COMETS.

Temperature and heat flux changes at the base of Laurentide ice sheet inferred from geothermal data (evidence from province of Alberta, Canada)

NASA Astrophysics Data System (ADS)

Demezhko, Dmitry; Gornostaeva, Anastasia; Majorowicz, Jacek; Šafanda, Jan

2018-01-01

Using a previously published temperature log of the 2363-m-deep borehole Hunt well (Alberta, Canada) and the results of its previous interpretation, the new reconstructions of ground surface temperature and surface heat flux histories for the last 30 ka have been obtained. Two ways to adjust the timescale of geothermal reconstructions are discussed, namely the traditional method based on the a priori data on thermal diffusivity value, and the alternative one including the orbital tuning of the surface heat flux and the Earth's insolation changes. It is shown that the second approach provides better agreement between geothermal reconstructions and proxy evidences of deglaciation chronology in the studied region.

Evidence for higher-than-average air temperatures after the 8.2 ka event provided by a Central European δ18O record

NASA Astrophysics Data System (ADS)

Andersen, Nils; Lauterbach, Stefan; Erlenkeuser, Helmut; Danielopol, Dan L.; Namiotko, Tadeusz; Hüls, Matthias; Belmecheri, Soumaya; Dulski, Peter; Nantke, Carla; Meyer, Hanno; Chapligin, Bernhard; von Grafenstein, Ulrich; Brauer, Achim

2017-09-01

The so-called 8.2 ka event represents one of the most prominent cold climate anomalies during the Holocene warm period. Accordingly, several studies have addressed its trigger mechanisms, absolute dating and regional characteristics so far. However, knowledge about subsequent climate recovery is still limited although this might be essential for the understanding of rapid climatic changes. Here we present a new sub-decadally resolved and precisely dated oxygen isotope (δ18O) record for the interval between 7.7 and 8.7 ka BP (103 calendar years before AD 1950), derived from the calcareous valves of benthic ostracods preserved in the varved lake sediments of pre-Alpine Mondsee (Austria). Besides a clear reflection of the 8.2 ka event, showing a good agreement in timing, duration and magnitude with other regional stable isotope records, the high-resolution Mondsee lake sediment record provides evidence for a 75-year-long interval of higher-than-average δ18O values directly after the 8.2 ka event, possibly reflecting increased air temperatures in Central Europe. This observation is consistent with evidence from other proxy records in the North Atlantic realm, thus most probably reflecting a hemispheric-scale climate signal rather than a local phenomenon. As a possible trigger we suggest an enhanced resumption of the Atlantic meridional overturning circulation (AMOC), supporting assumptions from climate model simulations.

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

PubMed

Falguères, Christophe; Bahain, Jean-Jacques; Bischoff, James L; Pérez-González, Alfredo; Ortega, Ana Isabel; Ollé, Andreu; Quiles, Anita; Ghaleb, Bassam; Moreno, Davinia; Dolo, Jean-Michel; Shao, Qingfeng; Vallverdú, Josep; Carbonell, Eudald; Bermúdez de Castro, Jose María; Arsuaga, Juan Luis

2013-08-01

The Sierra de Atapuerca, northern Spain, is known from many prehistoric and palaeontological sites documenting human prehistory in Europe. Three major sites, Gran Dolina, Galería and Sima del Elefante, range in age from the oldest hominin of Western Europe dated to 1.1 to 1.3 Ma (millions of years ago) at Sima del Elefante to c.a. 0.2 Ma on the top of the Galería archaeological sequence. Recently, a chronology based on luminescence methods (Thermoluminescence [TL] and Infrared Stimulated Luminescence [IRSL]) applied to cave sediments was published for the Gran Dolina and Galería sites. The authors proposed for Galería an age of 450 ka (thousands of years ago) for the units lower GIII and GII, suggesting that the human occupation there is younger than the hominid remains of Sima de los Huesos (>530 ka) around 1 km away. In this paper, we present new results obtained by combined Electron Spin Resonance/Uranium-series (ESR/U-series) dating on 20 herbivorous teeth from different levels at the Galería site. They are in agreement with the TL results for the upper part of the stratigraphic sequence (GIV and GIIIb), in the range of between 200 and 250 ka. But for the GIIIa to GIIb levels, the TL ages become abruptly older by 200 ka while ESR ages remain relatively constant. Finally, the TL and ESR data agree in the lowest part of the section (GIIa); both fall in the range of around 350-450 ka. Our results suggest a different interpretation for the GII, GIII and GIV units of Galería and the upper part of Gran Dolina (TD10 and TD11) than obtained by TL. The ESR/U-series results are supported by a Bayesian analysis, which allows a better integration between stratigraphic information and radiometric data. Copyright © 2013 Elsevier Ltd. All rights reserved.

An optimized multi-proxy, multi-site Antarctic ice and gas orbital chronology (AICC2012): 120-800 ka

NASA Astrophysics Data System (ADS)

Bazin, L.; Landais, A.; Lemieux-Dudon, B.; Toyé Mahamadou Kele, H.; Veres, D.; Parrenin, F.; Martinerie, P.; Ritz, C.; Capron, E.; Lipenkov, V.; Loutre, M.-F.; Raynaud, D.; Vinther, B.; Svensson, A.; Rasmussen, S. O.; Severi, M.; Blunier, T.; Leuenberger, M.; Fischer, H.; Masson-Delmotte, V.; Chappellaz, J.; Wolff, E.

2013-08-01

An accurate and coherent chronological framework is essential for the interpretation of climatic and environmental records obtained from deep polar ice cores. Until now, one common ice core age scale had been developed based on an inverse dating method (Datice), combining glaciological modelling with absolute and stratigraphic markers between 4 ice cores covering the last 50 ka (thousands of years before present) (Lemieux-Dudon et al., 2010). In this paper, together with the companion paper of Veres et al. (2013), we present an extension of this work back to 800 ka for the NGRIP, TALDICE, EDML, Vostok and EDC ice cores using an improved version of the Datice tool. The AICC2012 (Antarctic Ice Core Chronology 2012) chronology includes numerous new gas and ice stratigraphic links as well as improved evaluation of background and associated variance scenarios. This paper concentrates on the long timescales between 120-800 ka. In this framework, new measurements of δ18Oatm over Marine Isotope Stage (MIS) 11-12 on EDC and a complete δ18Oatm record of the TALDICE ice cores permit us to derive additional orbital gas age constraints. The coherency of the different orbitally deduced ages (from δ18Oatm, δO2/N2 and air content) has been verified before implementation in AICC2012. The new chronology is now independent of other archives and shows only small differences, most of the time within the original uncertainty range calculated by Datice, when compared with the previous ice core reference age scale EDC3, the Dome F chronology, or using a comparison between speleothems and methane. For instance, the largest deviation between AICC2012 and EDC3 (5.4 ka) is obtained around MIS 12. Despite significant modifications of the chronological constraints around MIS 5, now independent of speleothem records in AICC2012, the date of Termination II is very close to the EDC3 one.

An optimized multi-proxy, multi-site Antarctic ice and gas orbital chronology (AICC2012): 120-800 ka

NASA Astrophysics Data System (ADS)

Bazin, L.; Landais, A.; Lemieux-Dudon, B.; Toyé Mahamadou Kele, H.; Veres, D.; Parrenin, F.; Martinerie, P.; Ritz, C.; Capron, E.; Lipenkov, V.; Loutre, M.-F.; Raynaud, D.; Vinther, B.; Svensson, A.; Rasmussen, S. O.; Severi, M.; Blunier, T.; Leuenberger, M.; Fischer, H.; Masson-Delmotte, V.; Chappellaz, J.; Wolff, E.

2012-11-01

An accurate and coherent chronological framework is essential for the interpretation of climatic and environmental records obtained from deep polar ice cores. Until now, one common ice core age scale has been developed based on an inverse dating method (Datice) combining glaciological modelling with absolute and stratigraphic markers between 4 ice cores covering the last 50 ka (thousand of years before present) (Lemieux-Dudon et al., 2010). In this paper, together with the companion paper of Veres et al. (2012), we present an extension of this work back to 800 ka for the NGRIP, TALDICE, EDML, Vostok and EDC ice cores using an improved version of the Datice tool. The AICC2012 (Antarctic Ice Core Chronology 2012) chronology includes numerous new gas and ice stratigraphic links as well as improved evaluation of background and associated variance scenarios. This paper concentrates on the long timescales between 120-800 ka. In this frame, new measurements of δ18Oatm over Marine Isotope Stage (MIS) 11-12 on EDC and a complete δ18Oatm record of the TALDICE ice cores permit us to derive new orbital gas age constraints. The coherency of the different orbitally deduced ages (from δ18Oatm, δO2/N2 and air content) has been verified before implementation in AICC2012. The new chronology shows only small differences, well within the original uncertainty range, when compared with the previous ice core reference age scale EDC3. For instance, the duration of the last four interglacial periods is not affected by more than 5%. The largest deviation between AICC2012 and EDC3 (4.4 ka) is obtained around MIS 12. Despite significant modifications of the chronological constraints around MIS 5, now independent of speleothem records in AICC2012, the date of Termination II is very close to the EDC3 one.

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

USGS Publications Warehouse

Falguères, Christophe; Bahain, Jean-Jacques; Bischoff, James L.; Pérez-González, Alfredo; Ortega, Ana Isabel; Ollé, Andreu; Quilles, Anita; Ghaleb, Bassam; Moreno, Davinia; Dolo, Jean-Michel; Shao, Qingfeng; Vallverdú, Josep; Carbonell, Eudald; María Bermúdez de Castro, Jose; Arsuaga, Juan Luis

2013-01-01

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wesnousky, Steven G.; Briggs, Richard W.; Caffee, Marc W.

Deposits near Lamoille in the Ruby Mountains-East Humboldt Range of central Nevada and at Woodfords on the eastern edge of the Sierra Nevada each record two distinct glacial advances. In this paper, we compare independent assessments of terrestrial cosmogenic nuclide (TCN) surface exposure ages for glacial deposits that we have determined to those obtained by others at the two sites. At each site, TCN ages of boulders on moraines of the younger advance are between 15 and 30 ka and may be associated with marine oxygen isotope stage (MIS) 2. At Woodfords, TCN ages of boulders on the moraine ofmore » the older advance are younger than ~ 60 ka and possibly formed during MIS 4, whereas boulders on the correlative outwash surface show ages approaching 140 ka (~ MIS 6). The TCN ages of boulders on older glacial moraine at Woodfords thus appear to severely underestimate the true age of the glacial advance responsible for the deposit. The same is possibly true at Lamoille where clasts sampled from the moraine of the oldest advance have ages ranging between 20 and 40 ka with a single outlier age of ~ 80 ka. The underestimations are attributed to the degradation and denudation of older moraine crests. Noting that boulder ages on the older advances at each site overlap significantly with MIS 2. Finally, we speculate that erosion of the older moraines has been episodic, with a pulse of denudation accompanying the inception of MIS 2 glaciation.« less

Performance evolution of 60 kA HTS cable prototypes in the EDIPO test facility

NASA Astrophysics Data System (ADS)

Bykovsky, N.; Uglietti, D.; Sedlak, K.; Stepanov, B.; Wesche, R.; Bruzzone, P.

2016-08-01

During the first test campaign of the 60 kA HTS cable prototypes in the EDIPO test facility, the feasibility of a novel HTS fusion cable concept proposed at the EPFL Swiss Plasma Center (SPC) was successfully demonstrated. While the measured DC performance of the prototypes at magnetic fields from 8 T to 12 T and for currents from 30 kA to 70 kA was close to the expected one, an initial electromagnetic cycling test (1000 cycles) revealed progressive degradation of the performance in both the SuperPower and SuperOx conductors. Aiming to understand the reasons for the degradation, additional cycling (1000 cycles) and warm up-cool down tests were performed during the second test campaign. I c performance degradation of the SuperOx conductor reached ∼20% after about 2000 cycles, which was reason to continue with a visual inspection of the conductor and further tests at 77 K. AC tests were carried out at 0 and 2 T background fields without transport current and at 10 T/50 kA operating conditions. Results obtained in DC and AC tests of the second test campaign are presented and compared with appropriate data published recently. Concluding the first iteration of the HTS cable development program at SPC, a summary and recommendations for the next activity within the HTS fusion cable project are also reported.

Constraining Holocene hydrological changes in the Carpathian-Balkan region using speleothem δ18O and pollen-based temperature reconstructions

NASA Astrophysics Data System (ADS)

Drăguşin, V.; Staubwasser, M.; Hoffmann, D. L.; Ersek, V.; Onac, B. P.; Veres, D.

2014-07-01

Here we present a speleothem isotope record (POM2) from Ascunsă Cave (Romania) that provides new data on past climate changes in the Carpathian-Balkan region from 8.2 ka until the present. This paper describes an approach to constrain the effect of temperature changes on calcite δ18O values in stalagmite POM2 over the course of the middle Holocene (6-4 ka), and across the 8.2 and 3.2 ka rapid climate change events. Independent pollen temperature reconstructions are used to this purpose. The approach combines the temperature-dependent isotope fractionation of rain water during condensation and fractionation resulting from calcite precipitation at the given cave temperature. The only prior assumptions are that pollen-derived average annual temperature reflects average cave temperature, and that pollen-derived coldest and warmest month temperatures reflect the range of condensation temperatures of rain above the cave site. This approach constrains a range of values between which speleothem δ18O changes should be found if controlled only by surface temperature variations at the cave site. Deviations of the change in δ18Ocspel values from the calculated temperature-constrained range of change are interpreted towards large-scale variability of climate-hydrology. Following this approach, we show that an additional ∼0.6‰ enrichment of δ18Oc in the POM2 stalagmite was caused by changing hydrological patterns in SW Romania across the middle Holocene, most likely comprising local evaporation from the soil and an increase in Mediterranean moisture δ18O. Further, by extending the calculations to other speleothem records from around the entire Mediterranean basin, it appears that all eastern Mediterranean speleothems recorded a similar isotopic enrichment due to changing hydrology, whereas all changes recorded in speleothems from the western Mediterranean are fully explained by temperature variation alone. This highlights a different hydrological evolution between the two sides of the Mediterranean. Our results also demonstrate that during the 8.2 ka event, POM2 stable isotope data essentially fit the temperature-constrained isotopic variability. In the case of the 3.2 ka event, an additional climate-related hydrological factor is more evident. This implies a different rainfall pattern in the Southern Carpathian region during this event at the end of the Bronze Age.

40Ar/39Ar geochronology of submarine Mauna Loa volcano, Hawaii

NASA Astrophysics Data System (ADS)

Jicha, B.; Rhodes, J. M.; Singer, B. S.; Vollinger, M. J.; Garcia, M. O.

2009-12-01

A major impediment to our understanding of the nature and structure of the Hawaiian plume, and evaluating the competing plume models has been a lack of thick stratigraphic sections from which to obtain long temporal records of magmatic history. The Hawaii Scientific Drilling Project (HSDP) made a significant advance towards solving this problem by documenting the long-term magmatic evolution of Mauna Kea volcano on the Kea side of the plume. To evaluate comparable long-term magmatic history on the Loa side of the plume we collected a stratigraphically controlled sample suite using Jason and Pisces dives from three vertical transects of the 1.6 km high Kae Lae landslide scarp cut into Mauna Loa’s submarine southwest rift zone (SWR). We have undertaken an 40Ar/39Ar investigation of Mauna Loa’s growth history to integrate new geochronologic constraints with geochemical, and isotopic data, illuminating temporal trends within the Hawaiian plume. Obtaining precise 40Ar/39Ar ages from tholeiitic lavas younger than 500 ka containing only 0.2-0.6 wt.% K2O is challenging due to the extremely low radiogenic 40Ar contents. Furnace incremental heating experiments of groundmass separated from 15 submarine lavas have yielded four new age determinations (a 27% success rate). These four lavas give concordant age spectra with plateau and isochron ages that agree with stratigraphy. We also analyzed two previously-dated subaerial Mauna Kea tholeiites from the HSDP-2 drill core, to assess inter-laboratory reproducibility and calibrate our results to those obtained for the core. Two experiments on sample SR413-4.0 and one experiment from SR781-21.2 gave weighted mean plateau ages of 364 ± 95 ka and 473 ± 109, respectively, which are indistinguishable from the published 40Ar/39Ar ages of 390 ± 70 ka and 482 ± 67. Although Sharp and Renne (2005) preferred isochron ages for the submarine Mauna Kea tholeiites recovered from HSDP, we find that submarine Mauna Loa lavas contain trapped argon with a 40Ar/36Ar ratio that is indistinguishable from the atmospheric value of 295.5. Therefore, we consider the plateau ages to provide the most precise estimate of time elapsed since eruption. Lavas from 857, 1753, and 2112 mbsl give indistinguishable plateau ages of 473 ± 29, 463 ± 33, and 472 ± 107, respectively, implying an extraordinary period of lava accumulation. If correct, this implies that ~1300 m of lava was emplaced on the SWR at a rate far exceeding that proposed in previous accumulation models for Mauna Loa or Mauna Kea, possibly correlating with the peak of the shield-building stage. Three experiments from a more K-rich lava (0.67 wt. % K2O) near the top of the landslide scarp gave a weighted mean plateau age of 193 ± 16 ka, indicating a marked decline in eruption rates on this part of the SWR.

2H Kinetic Isotope Effects and pH Dependence of Catalysis as Mechanistic Probes of Rat Monoamine Oxidase A: Comparisons with the Human Enzyme‡

PubMed Central

Wang, Jin; Edmondson, Dale E.

2011-01-01

Monoamine oxidase A (MAO A) is a mitochondrial outer membrane-bound flavoenzyme important in the regulation of serotonin and dopamine levels. Since the rat is extensively used as an animal model in drug studies, it is important to understand how rat MAO A behaves in comparison with the more extensively studied human enzyme. For many reversible inhibitors, rat MAO A exhibits Ki values similar to those of human MAO A. The pH profile of kcat for rat MAO A shows a pKa of 8.2±0.1 for the benzylamine ES complex and pKa values of 7.5±0.1 and 7.6±0.1 for the respective ES complexes with p-CF3-1H and p-CF3-2H-benzylamine. In contrast to the human enzyme, the rat enzyme exhibits a single pKa value (8.3±0.1) with kcat/Km benzylamine vs. pH and pKa values of 7.8±0.1 and 8.1±0.2 are found for the ascending limbs, respectively, of kcat/Km vs. pH profiles for p-CF3-1H and p-CF3-2H-benzylamine and 9.3±0.1 and 9.1±0.2 for their respective descending limbs. The oxidation of para-substituted benzylamine substrate analogues by rat MAO A exhibit large deuterium kinetic isotope effects on kcat and on kcat/Km. These effects are pH-independent, and range from 7 to 14, demonstrating a rate-limiting α-C-H bond cleavage step in catalysis. Quantitative structure-activity correlations of log kcat with the electronic substituent parameter (σ) at pH 7.5 and at 9.0 show a dominant contribution with positive ρ values (+1.2 – 1.3) and a pH-independent negative contribution from the steric term. Quantitative structure-activity relationship analysis of the binding affinities of the para-substituted benzylamine analogues to rat MAO A show an increased van der Waals volumes (Vw) increases the affinity of the deprotonated amine for the enzyme. These results demonstrate that rat MAO A exhibits similar but not identical functional properties with the human enzyme and provide additional support for C-H bond cleavage via a polar nucleophilic mechanism. PMID:21819071

Younger-Dryas cooling and sea-ice feedbacks were prominent features of the Pleistocene-Holocene transition in Arctic Alaska

NASA Astrophysics Data System (ADS)

Gaglioti, Benjamin V.; Mann, Daniel H.; Wooller, Matthew J.; Jones, Benjamin M.; Wiles, Gregory C.; Groves, Pamela; Kunz, Michael L.; Baughman, Carson A.; Reanier, Richard E.

2017-08-01

Declining sea-ice extent is currently amplifying climate warming in the Arctic. Instrumental records at high latitudes are too short-term to provide sufficient historical context for these trends, so paleoclimate archives are needed to better understand the functioning of the sea ice-albedo feedback. Here we use the oxygen isotope values of wood cellulose in living and sub-fossil willow shrubs (δ18Owc) (Salix spp.) that have been radiocarbon-dated (14C) to produce a multi-millennial record of climatic change on Alaska's North Slope during the Pleistocene-Holocene transition (13,500-7500 calibrated 14C years before present; 13.5-7.5 ka). We first analyzed the spatial and temporal patterns of δ18Owc in living willows growing at upland sites and found that over the last 30 years δ18Owc values in individual growth rings correlate with local summer temperature and inter-annual variations in summer sea-ice extent. Deglacial δ18Owc values from 145 samples of subfossil willows clearly record the Allerød warm period (∼13.2 ka), the Younger Dryas cold period (12.9-11.7 ka), and the Holocene Thermal Maximum (11.7-9.0 ka). The magnitudes of isotopic changes over these rapid climate oscillations were ∼4.5‰, which is about 60% of the differences in δ18Owc between those willows growing during the last glacial period and today. Modeling of isotope-precipitation relationships based on Rayleigh distillation processes suggests that during the Younger Dryas these large shifts in δ18Owc values were caused by interactions between local temperature and changes in evaporative moisture sources, the latter controlled by sea ice extent in the Arctic Ocean and Bering Sea. Based on these results and on the effects that sea-ice have on climate today, we infer that ocean-derived feedbacks amplified temperature changes and enhanced precipitation in coastal regions of Arctic Alaska during warm times in the past. Today, isotope values in willows on the North Slope of Alaska are similar to those growing during the warmest times of the Pleistocene-Holocene transition, which were times of widespread permafrost thaw and striking ecological changes.

Relation Between the Adsorbed Quantity and the Immersion Enthalpy in Catechol Aqueous Solutions on Activated Carbons

PubMed Central

Moreno-Piraján, Juan Carlos; Blanco, Diego; Giraldo, Liliana

2012-01-01

An activated carbon, CarbochemTM—PS230, was modified by chemical and thermal treatment in flow of H2, in order to evaluate the influence of the activated carbon chemical characteristics in the adsorption of the catechol. The catechol adsorption in aqueous solution was studied along with the effect of the pH solution in the adsorption process of modified activated carbons and the variation of immersion enthalpy of activated carbons in the aqueous solutions of catechol. The interaction solid-solution is characterized by adsorption isotherms analysis, at 298 K and pH 7, 9 and 11 in order to evaluate the adsorption value above and below that of the catechol pKa. The adsorption capacity of carbons increases when the solution pH decreases. The retained amount increases slightly in the reduced carbon to maximum adsorption pH and diminishes in the oxidized carbon. Similar conclusions are obtained from the immersion enthalpies, whose values increase with the solute quantity retained. In granular activated carbon (CAG), the immersion enthalpies obtained are between 21.5 and 45.7 J·g−1 for catechol aqueous solutions in a range of 20 at 1500 mg·L−1. PMID:22312237

Metastable and equilibrium phase diagrams of unconjugated bilirubin IXα as functions of pH in model bile systems: Implications for pigment gallstone formation.

PubMed

Berman, Marvin D; Carey, Martin C

2015-01-01

Metastable and equilibrium phase diagrams for unconjugated bilirubin IXα (UCB) in bile are yet to be determined for understanding the physical chemistry of pigment gallstone formation. Also, UCB is a molecule of considerable biomedical importance because it is a potent antioxidant and an inhibitor of atherogenesis. We employed principally a titrimetric approach to obtain metastable and equilibrium UCB solubilities in model bile systems composed of taurine-conjugated bile salts, egg yolk lecithin (mixed long-chain phosphatidylcholines), and cholesterol as functions of total lipid concentration, biliary pH values, and CaCl2 plus NaCl concentrations. Metastable and equilibrium precipitation pH values were obtained, and average pKa values of the two carboxyl groups of UCB were calculated. Added lecithin and increased temperature decreased UCB solubility markedly, whereas increases in bile salt concentrations and molar levels of urea augmented solubility. A wide range of NaCl and cholesterol concentrations resulted in no specific effects, whereas added CaCl2 produced large decreases in UCB solubilities at alkaline pH values only. UV-visible absorption spectra were consistent with both hydrophobic and hydrophilic interactions between UCB and bile salts that were strongly influenced by pH. Reliable literature values for UCB compositions of native gallbladder biles revealed that biles from hemolytic mice and humans with black pigment gallstones are markedly supersaturated with UCB and exhibit more acidic pH values, whereas biles from nonstone control animals and patients with cholesterol gallstone are unsaturated with UCB. Copyright © 2015 the American Physiological Society.

Metastable and equilibrium phase diagrams of unconjugated bilirubin IXα as functions of pH in model bile systems: Implications for pigment gallstone formation

PubMed Central

Berman, Marvin D.

2014-01-01

Metastable and equilibrium phase diagrams for unconjugated bilirubin IXα (UCB) in bile are yet to be determined for understanding the physical chemistry of pigment gallstone formation. Also, UCB is a molecule of considerable biomedical importance because it is a potent antioxidant and an inhibitor of atherogenesis. We employed principally a titrimetric approach to obtain metastable and equilibrium UCB solubilities in model bile systems composed of taurine-conjugated bile salts, egg yolk lecithin (mixed long-chain phosphatidylcholines), and cholesterol as functions of total lipid concentration, biliary pH values, and CaCl2 plus NaCl concentrations. Metastable and equilibrium precipitation pH values were obtained, and average pKa values of the two carboxyl groups of UCB were calculated. Added lecithin and increased temperature decreased UCB solubility markedly, whereas increases in bile salt concentrations and molar levels of urea augmented solubility. A wide range of NaCl and cholesterol concentrations resulted in no specific effects, whereas added CaCl2 produced large decreases in UCB solubilities at alkaline pH values only. UV-visible absorption spectra were consistent with both hydrophobic and hydrophilic interactions between UCB and bile salts that were strongly influenced by pH. Reliable literature values for UCB compositions of native gallbladder biles revealed that biles from hemolytic mice and humans with black pigment gallstones are markedly supersaturated with UCB and exhibit more acidic pH values, whereas biles from nonstone control animals and patients with cholesterol gallstone are unsaturated with UCB. PMID:25359538

Electron Microprobe Analysis of Hf in Zircon: Suggestions for Improved Accuracy of a Difficult Measurement

NASA Astrophysics Data System (ADS)

Fournelle, J.; Hanchar, J. M.

2013-12-01

It is not commonly recognized as such, but the accurate measurement of Hf in zircon is not a trivial analytical issue. This is important to assess because Hf is often used as an internal standard for trace element analyses of zircon by LA-ICPMS. The issues pertaining to accuracy revolve around: (1) whether the Hf Ma or the La line is used; (2) what accelerating voltage is applied if Zr La is also measured, and (3) what standard for Hf is used. Weidenbach, et al.'s (2004) study of the 91500 zircon demonstrated the spread (in accuracy) of possible EPMA values for six EPMA labs, 2 of which used Hf Ma, 3 used Hf La, and one used Hf Lb, and standards ranged from HfO2, a ZrO2-HfO2 compound, Hf metal, and hafnon. Weidenbach, et al., used the ID-TIMS values as the correct value (0.695 wt.% Hf.), for which not one of the EPMA labs came close to that value (3 were low and 3 were high). Those data suggest: (1) that there is a systematic underestimation error of the 0.695 wt% Hf (ID-TIMS Hf) value if Hf Ma is used; most likely an issue with the matrix correction, as the analytical lines and absorption edges of Zr La, Si Ka and Hf Ma are rather tightly packed in the electromagnetic spectrum. Mass absorption coefficients are easily in error (e.g., Donovan's determination of the MAC of Hf by Si Ka of 5061 differs from the typically used Henke value of 5449 (Donovan et al, 2002); and (2) For utilization of the Hf La line, however, the second order Zr Ka line interferes with Hf La if the accelerating voltage is greater than 17.99 keV. If this higher keV is used and differential mode PHA is applied, only a portion of the interference is removed (e.g., removal of escape peaks), causing an overestimation of Hf content. Unfortunately, it is virtually impossible to apply an interference correction in this case, as it is impossible to locate Hf-free Zr probe standard. We have examined many of the combinations used by those six EPMA labs and concluded that the optimal EPMA is done with Hf La with the accelerating voltage under 18 keV (e.g. 17 keV is optimal), and also with synthetic stoichiometric hafnon as the standard. We have developed useful standards that are to be distributed to the community for those researchers working on this problem and can be obtained from the second author at jhanchar@mun.ca. The standards include synthetic stoichiometric undoped zircon and hafnon, and synthetic zircon doped with 2 wt. % Hf. Donovan et al. (2002) Probe for Windows: User's Guide and Reference Wiedenbeck, M., et al. (2004) Further characterisation of the 91500 zircon crystal. Geostandards and Geoanatytical Research, 28: 9-39.

Solenoid-free plasma startup in NSTX using transient CHI

NASA Astrophysics Data System (ADS)

Raman, R.; Jarboe, T. R.; Mueller, D.; Nelson, B. A.; Bell, M. G.; Bell, R.; Gates, D.; Gerhardt, S.; Hosea, J.; Kaita, R.; Kugel, H.; LeBlanc, B.; Maingi, R.; Maqueda, R.; Menard, J.; Nagata, M.; Ono, M.; Paul, S.; Roquemore, L.; Sabbagh, S.; Soukhanovskii, V.; Taylor, G.

2009-06-01

Experiments in NSTX have now demonstrated the coupling of toroidal plasmas produced by the technique of coaxial helicity injection (CHI) to inductive sustainment and ramp-up of the toroidal plasma current. In these discharges, the central Ohmic transformer was used to apply an inductive loop voltage to discharges with a toroidal current of about 100 kA created by CHI. The coupled discharges have ramped up to >700 kA and transitioned into an H-mode demonstrating compatibility of this startup method with conventional operation. The electron temperature in the coupled discharges reached over 800 eV and the resulting plasma had low inductance, which is preferred for long-pulse high-performance discharges. These results from NSTX in combination with the previously obtained record 160 kA non-inductively generated startup currents in an ST or tokamak in NSTX demonstrate that CHI is a viable solenoid-free plasma startup method for future STs and tokamaks.

A low-power, high-efficiency Ka-band TWTA

NASA Astrophysics Data System (ADS)

Curren, Arthur N.; Dayton, James A., Jr.; Palmer, Raymond W.; Force, Dale A.; Tamashiro, Rodney N.; Wilson, John F.; Dombro, Louis; Harvey, Wayne L.

1992-03-01

NASA has developed a new class of Ka-band TWT amplifiers (TWTAs) which achieve their high efficiency/low power performance goals by means of an advanced dynamic velocity taper (DVT). The DVT is characterized by a continuous, nonlinear reduction in helix pitch from its initial synchronous value in the output section of the TWT to near the end of the helix. Another efficiency-maximizing feature is the inclusion of a multistage depressed collector employing oxygen-free, high-conductivity Cu electrodes treated for secondary electron emission suppression by means of ion bombardment. An efficiency of 43 percent is expected to be reached.

Performance of a 10 kV, 625 kA, 85 kJ energy discharge module utilizing a solid dielectric switch

NASA Astrophysics Data System (ADS)

Richardson, R. A.; Cravey, W. R.; Goerz, D. A.

We have designed and tested an 87-kJ energy discharge system consisting of two 720-(mu)F, 11-kV capacitors discharged through parallel coaxial cables into a 250 nH load. Data will be presented on the current and voltage waveforms, with calculated values of the system inductance and resistance. The bank uses a solid dielectric switch punctured by an explosive bridge wire (EBW) to initiate the discharge. With the capacitors charged to 9 kV, a 625-kA peak current is sent through the load with a ringing frequency of 6.8 kHz. The coaxial cables used to transmit the current to the load are 3 m in length. Both RG-217 and YK-198 cable types were tested, which have an inductance of 74 nH/ft and 35 nH/ft respectively. Normal operation requires that each cable carry 52 kA. The cables were tested to 100 kA each by connecting fewer cables to the load, and gradually increasing the charge voltage. The solid dielectric switch was chosen for high reliability. Details of the switch will be describes and data on its performance will be presented.

A Targeted Mutation Identified through pKa Measurements Indicates a Postrecruitment Role for Fis1 in Yeast Mitochondrial Fission*

PubMed Central

Koppenol-Raab, Marijke; Harwig, Megan Cleland; Posey, Ammon E.; Egner, John M.; MacKenzie, Kevin R.; Hill, R. Blake

2016-01-01

The tail-anchored protein Fis1 is implicated as a passive tether in yeast mitochondrial fission. We probed the functional role of Fis1 Glu-78, whose elevated side chain pKa suggests participation in protein interactions. Fis1 binds partners Mdv1 or Dnm1 tightly, but mutation E78A weakens Fis1 interaction with Mdv1, alters mitochondrial morphology, and abolishes fission in a growth assay. In fis1Δ rescue experiments, Fis1-E78A causes a novel localization pattern in which Dnm1 uniformly coats the mitochondria. By contrast, Fis1-E78A at lower expression levels recruits Dnm1 into mitochondrial punctate structures but fails to support normal fission. Thus, Fis1 makes multiple interactions that support Dnm1 puncta formation and may be essential after this step, supporting a revised model for assembly of the mitochondrial fission machinery. The insights gained by mutating a residue with a perturbed pKa suggest that side chain pKa values inferred from routine NMR sample pH optimization could provide useful leads for functional investigations. PMID:27496949

DelPhiPKa web server: predicting pKa of proteins, RNAs and DNAs.

PubMed

Wang, Lin; Zhang, Min; Alexov, Emil

2016-02-15

A new pKa prediction web server is released, which implements DelPhi Gaussian dielectric function to calculate electrostatic potentials generated by charges of biomolecules. Topology parameters are extended to include atomic information of nucleotides of RNA and DNA, which extends the capability of pKa calculations beyond proteins. The web server allows the end-user to protonate the biomolecule at particular pH based on calculated pKa values and provides the downloadable file in PQR format. Several tests are performed to benchmark the accuracy and speed of the protocol. The web server follows a client-server architecture built on PHP and HTML and utilizes DelPhiPKa program. The computation is performed on the Palmetto supercomputer cluster and results/download links are given back to the end-user via http protocol. The web server takes advantage of MPI parallel implementation in DelPhiPKa and can run a single job on up to 24 CPUs. The DelPhiPKa web server is available at http://compbio.clemson.edu/pka_webserver. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Magma evolution as seen through zircon geochemistry: an example from the Southern Adamello Batholith, N. Italy

NASA Astrophysics Data System (ADS)

Broderick, C.; Schaltegger, U.; Gerdes, A.; Frick, D.; Guenther, D.; Brack, P.

2012-04-01

Zircon is an ubiquitous accessory mineral often used for U-Pb geochronology but is also an important recorder of geochemical information. The trace element and isotopic characteristics of zircon yield potential for tracking changes in an evolving magma through time. With recent advances in U-Pb zircon geochronology, 10-100 ka to Ma timescales are observed for incremental pluton construction (Michel et al., 2008, Schaltegger et al., 2009). In observed 100 ka timescales of zircon crystallization, can zircon record the processes that produce trace element variations in a magma? This study focuses on the Val Fredda Complex (VFC) in the southern tip of the 43 to 33 Ma Adamello batholith, N. Italy. The VFC displays complex relationships among mafic melts that were injected into solidifying felsic magmas. Single zircon crystals were dated using CA-ID-TIMS. With permil uncertainties on 206Pb/238U zircon dates, zircons reveal complexities within single populations. The mafic units crystallized potential autocrystic zircons over a duration of 100 - 150ka, whereas the felsic units record up to 200ka of zircon crystallization. In order to understand these complex zircon populations, we analyzed Hf isotopes and trace elements, on the same volume of zircon used for U-Pb dating, following the TIMS-TEA method (Schoene et al., 2010). This detailed zircon study will allow us to look at how magmas are evolving with time. Hf isotopes of VFC mafic zircons reveal distinct ɛHf values between the three mafic units and their ɛHf values remain consistent through time, whereas the VFC felsic units record more complexity in their ɛHf values. We observe changes such as increasing and slight decreases in ɛHf with time which suggest different processes are occurring to produce the different felsic units. Trace element ratios in zircon reveal differences which allow us to make distinctions between felsic and mafic units (e.g. Th/U, (Lu/Gd)N, REEs). The VFC records 200 ka of zircon crystallization and our data suggests that zircons do in fact reflect changes in isotopic and in trace element signatures on 100 ka timescales. Although we observe changes in our trace elements, the TIMS-TEA method provides an average of trace element concentrations from a zircon volume, dominated by more marginal growth zones. Therefore we will compare our data with in situ methods to determine how our trace element data compares with trace elements across zircon profiles. We acknowledge funding of FNS in the frame of ProDoc Adamello 4-D. Michel et al., 2008, Geol. 36 : 459-462 ; Schaltegger et al., 2009, Earth Planet. Sci.Lett. 286: 208-218; Schoene et al., 2010, Geochim. Cosmochim. Acta 74, 7144-7159.

Authigenic 10Be/9Be Ratio Signatures of the Cosmogenic Nuclide Production Linked to Geomagnetic Dipole Moment Variation During and Since the Brunhes/Matuyama Boundary

NASA Astrophysics Data System (ADS)

Simon, Q.; Thouveny, N.; Bourles, D. L.; Ménabréaz, L.; Valet, J. P.; Valery, G.; Choy, S.

2015-12-01

The atmospheric production rate of cosmogenic nuclides is linked to the geomagnetic dipole moment (GDM) by a non-linear inverse relationship. Large amplitude GDM variations associated with reversals and excursions can potentially be reconstructed using time variation of the cosmogenic beryllium-10 (10Be) production recorded in ocean sediments. Downcore profiles of authigenic 10Be/9Be ratios (proxy of atmospheric 10Be production) in oceanic cores provide independent and additional records of the evolution of the geomagnetic intensity and complete previous information derived from relative paleointensity (RPI). Here are presented new authigenic 10Be/9Be results obtained from cores MD05-2920 and from the top of core MD05-2930 collected in the West Equatorial Pacific Ocean. Completing data of Ménabréaz et al. (2012, 2014), these results provide the first continuous 10Be production rate sedimentary record covering the last 800 ka. Along these cores, authigenic 10Be/9Be ratio peaks are recorded - within methodological errors - at the stratigraphic level of RPI lows. High-resolution chronologies (δ18O-derived) lead to interpret these peaks as successive global 10Be overproduction events triggered by geomagnetic dipole lows present in the PISO-1500 and Sint-2000 stacks. The largest amplitude 10Be production enhancement is synchronous to the very large decrease of the dipole field associated with the last polarity reversal (772 ka). It is consistent in shape and duration with the peak recorded in core MD90-0961 from the Maldive area (Indian Ocean) (Valet et al. 2014). Two significant 10Be production enhancements are coeval with the Laschamp (41 ka) and Icelandic basin (190 ka) excursions, while 10Be production peaks of lower amplitude correlate to other recognized excursions such as the Blake (120 ka), Pringle-Falls (215 ka), Portuguese Margin (290 ka), Big Lost (540 ka) among others. This study provides new data on the amplitude and timing of dipole field variations, helping to understand the difference between paleosecular variation, excursions, aborted reversals and reversals regimes.

ACTS Ka-band Propagation Research in a Spatially Diversified Network with Two USAT Ground Stations

NASA Technical Reports Server (NTRS)

Kalu, Alex; Acousta, R.; Durand, S.; Emrich, Carol; Ventre, G.; Wilson, W.

1999-01-01

Congestion in the radio spectrum below 18 GHz is stimulating greater interest in the Ka (20/30 GHz) frequency band. Transmission at these shorter wavelengths is greatly influenced by rain resulting in signal attenuation and decreased link availability. The size and projected cost of Ultra Small Aperture Terminals (USATS) make site diversity methodology attractive for rain fade compensation. Separation distances between terminals must be small to be of interest commercially. This study measures diversity gain at a separation distance <5 km and investigates utilization of S-band weather radar reflectivity in predicting diversity gain. Two USAT ground stations, separated by 2.43 km for spatial diversity, received a continuous Ka-band tone sent from NASA Glenn Research Center via the Advanced Communications Technology Satellite (ACTS) steerable antenna beam. Received signal power and rainfall were measured, and Weather Surveillance Radar-1998 Doppler (WSR-88D) data were obtained as a measure of precipitation along the USAT-to-ACTS slant path. Signal attenuation was compared for the two sites, and diversity gain was calculated for fades measured on eleven days. Correlation of WSR-88D S-band reflectivity with measured Ka-band attenuation consisted of locating radar volume elements along each slant path, converting reflectivity to Ka-band attenuation with rain rate calculation as an intermediate step. Specific attenuation for each associated path segment was summed, resulting in total attenuation along the slant path. Derived Ka-band attenuation did not correlate closely with empirical data (r = 0.239), but a measured signal fade could be matched with an increase in radar reflectivity in all fade events. Applying a low pass filter to radar reflectivity prior to deriving Ka-band attenuation improved the correlation between measured and derived signal attenuation (r = 0.733). Results indicate that site diversity at small separation distances is a viable means of rain fade compensation, and that existing models underestimate diversity gain for a subtropical climate such as Florida. Also, filtered WSR-88D reflectivity can be used for optimizing diversity terminal placement by comparing derived Ka- band attenuation between the diversity sites.

Sunshine duration and its variability in the main ridge of the Karkonosze Mountains in relation to with atmospheric circulation

NASA Astrophysics Data System (ADS)

Urban, Grzegorz; Migała, Krzysztof; Pawliczek, Piotr

2018-02-01

Sunshine duration analysis was based on a series of measurements spanning the period from 1901 to 2014 for Śnieżka (1603 m a.s.l.) and from 1961 to 2000 for Szrenica (1362 m a.s.l.). The average annual sunshine duration (SD) on Śnieżka is 1423.0 h, which is among the lowest values in Poland. On average, the main ridge of the Karkonosze range receives 31% of potential sunshine duration in annual terms: from 25% in December to 36% in August and May. The changes in sunshine duration recorded on Śnieżka point to the existence of two cycles: a short one of approx. 2-4 years and a long one of approx. 60 years. The former most probably reflects the rhythm of atmospheric circulation in the North Atlantic (North Atlantic Oscillation), while the latter reflects the impact of ocean circulation associated with the AMO (Atlantic Multidecadal Oscillation) mechanism. Annual SD totals for the years 1901-2014 exhibit a slight trend to an increase of approx. 2.5 h/10 years, and the rate of increase during the winter quarter is many times higher than during the other seasons. Average monthly sunshine duration differences between Śnieżka and Szrenica are positive for all months of the year with the average monthly difference being 10 to 11 h. This means that the average radiation conditions on Śnieżka are more favourable than the main ridge of the Karkonosze range, which lies at an altitude 200 to 250 m lower. Average daily sunshine durations recorded on Śnieżka are only shorter than those on Szrenica for macro-types of atmospheric circulation with advection from the south.

Late quaternary temperature record from buried soils of the North American Great Plains

USGS Publications Warehouse

Nordt, L.; Von Fischer, J.; Tieszen, L.

2007-01-01

We present the first comprehensive late Quaternary record of North American Great Plains temperature by assessing the behavior of the stable isotopic composition (δ13C) of buried soils. After examining the relationship between the δ13C of topsoil organic matter and July temperature from 61 native prairies within a latitudinal range of 46°–38°N, we applied the resulting regression equation to 64 published δ13C values from buried soils of the same region to construct a temperature curve for the past 12 k.y. Estimated temperatures from 12 to 10 ka (1 k.y. = 1000 14C yr B.P.) fluctuated with a periodicity of ∼1 k.y. with two cool excursions between −4.5 and −3.5 °C and two warmer excursions between −1 and 0 °C, relative to modern. Early Holocene temperatures from ca. 10–7.5 ka were −1.0 to −2.0 °C before rising to +1.0 °C in the middle Holocene between 6.0 and 4.5 ka. After a cool interlude from 4.2 to 2.6 ka, when temperatures dropped to slightly below modern, another warm interval ensued from 2.6 to 1 ka as temperatures increased to ∼+0.5 °C. A final decline in temperature to below modern occurred beginning ca. 0.5 ka. Cooler than present temperatures in the Great Plains indicate telecommunications with cool-water episodes in the Gulf of Mexico and North Atlantic potentially governed by a combination of glacial meltwater pulses and low solar irradiance.

Quaternary displacement rates on the Meeman‐Shelby fault and Joiner ridge horst, eastern Arkansas: Results from coring Mississippi River alluvium

USGS Publications Warehouse

Ward, Alex; Counts, Ronald C.; Van Arsdale, Roy; Larsen, Daniel; Mahan, Shannon

2017-01-01

This research used coring and optically stimulated luminescence (OSL) dating of displaced, deeply buried Quaternary alluvium to determine vertical displacement rates for the Meeman‐Shelby fault and the Joiner ridge horst, two structures in northeastern Arkansas that have no modern seismicity associated with them. We drilled continuous cores of the entire alluvial section in the hanging wall of each structure, performed detailed core descriptions and analyses, and obtained three OSL ages from each core. The Meeman‐Shelby fault core consists of 36 m of 4.3–5.2‐ka Holocene alluvium overlying 4 m of 14.3‐ka Kennett alluvium that in turn overlies the upper part of Eocene Claiborne Group sediments at a depth of 41 m. Seismic reflection indicates that the basal (Kennett) alluvium at the Meeman‐Shelby fault is displaced ∼28  m across the Meeman‐Shelby fault, which equates to a time‐averaged vertical displacement rate of 2  mm/yr within the last 14.3 ka. The Joiner ridge horst core consists, in descending order, of 11 m of 6.3‐ka Holocene alluvium, 14 m of 11.5‐ka Morehouse alluvium, a paleosol, 6 m of Kennett alluvium, and 4 m of 20.3‐ka Sikeston alluvium that in turn overlies the upper part of Eocene Claiborne Group sediments at a depth of 36 m. Lignite exploration drilling conducted in the 1970s indicates that basal (Sikeston) alluvium is displaced ∼20  m across the eastern bounding fault of the Joiner ridge horst, resulting in a time‐averaged vertical displacement rate of ∼1  mm/yr within the last 20.3 ka. These late Quaternary displacement rates are comparable to time‐averaged displacement rates of faults within the active New Madrid seismic zone.

Deglaciation chronology in the Mérida Andes from cosmogenic 10Be dating, (Gavidia valley, Venezuela)

NASA Astrophysics Data System (ADS)

Angel, Isandra; Audemard M., Franck A.; Carcaillet, Julien; Carrillo, Eduardo; Beck, Christian; Audin, Laurence

2016-11-01

In the Mérida Andes, a detailed deglaciation history reconstruction is difficult to achieve due to scattered deglaciation chronologies available. This paper contributes with 24 exposure ages of glacial landforms sampled in the Gavidia valley. Exposure ages were obtained based on terrestrial cosmogenic nuclide 10Be dating. Results indicate deglaciation mainly occurred between ∼21 ka and 16.5 ka and the complete deglaciation occurred at ∼16.0 ka. The glacier retreated in two different phases. The oldest one occurred since the LGM until middle OtD or the local climate event El Caballo Stadial. The youngest phase occurred at ages younger than ∼16.5 ka until complete deglaciation. A combination of topographic features and changes in the paleoclimate conditions at the end of the El Caballo Stadial seems leaded the fastest former glacier extinction. The topographic feature which seems contributed to the fastest glacier extinction was the low valley bottom slopes. In addition, exposure ages of the Gavidia valley were integrated with deglaciation chronologies from the central Mérida Andes to compare deglaciation histories. Asynchronous deglaciation histories were observed. Local paleotemperatures and paleoprecipitations contrasts, different valleys aspects, insolation and catchments steepness could explain different deglaciation histories.

Comparative Study of Optical and Radio-Frequency Communication Systems for a Deep-Space Mission

NASA Technical Reports Server (NTRS)

Hemmati, H.; Wilson, K.; Sue, M. K.; Harcke, L. J.; Wilhelm, M.; Chen, C.-C.; Lesh, J.; Feria, Y.; Rascoe, D.; Lansing, F.

1997-01-01

We have performed a study on telecommunication systems for a hypothetical mission to Mars. The objective of the study was to evaluate and compare the benefits that microwave-X-band (8.4 GHz) and Ka-band (32 GHz) - and optical communications technologies a afford to future missions. The telecommunication systems were required to return data after launch and in orbit at 2.7 AU with daily data volumes of 0.1, 1.0, or 10.0 Gbits (Gb). Spacecraft terminals capable of delivering each of the three data volumes were proposed and characterized in terms of mass, power consumption, size, and cost. The estimated parameters for X-band, Ka-band, and optical frequencies are compared and presented here. For all cases, the optical light terminal exhibits about 60 percent of the mass of the corresponding radio frequency (RF) subsystem. Power consumption is comparable for all three technologies at a 0.1 Gb/day data volume, but the power required at either Ka-band or optical is less than half of the X-band requirement at 10 Gb/day. These benefits can be obtained only with a suitable investment in reception facilities for Ka-band or optical frequencies.

The Accuracy of New and Aged Mechanical Torque Devices Employed in Five Dental Implant Systems.

PubMed

Erdem, Mehmet Ali; Karatasli, Burcin; Dinçer Kose, Onur; Kose, Taha Emre; Çene, Erhan; Aydın Aya, Serhan; Cankaya, Abdulkadir Burak

2017-01-01

Friction-style and spring-style torque wrenches are used to tighten implant abutments and prosthetic screws. The mechanical stability of these torque wrenches is crucial for the implant-abutment connection. The purposes of this study were to assess the performance of five brands (Straumann, Zimmer, Implant KA, Bredent, and Biohorizons) of wrench and to evaluate possible changes in applied torque values of aged wrenches. Five new and aged wrenches that had been used approximately 250 times in a 1-year period were tested. The torque applied by friction- and spring-style wrenches was measured with a specially designed strain gauge indicator. Descriptive statistics, the one-sample t -test, and the independent-samples t -test were used to analyze values obtained from all torque wrenches. The accuracy of new and aged torque devices of all brands except Bredent differed significantly from the target values, but the mean values for aged and new wrenches did not differ significantly from each other ( p > 0.05). Values for the spring- and friction-type torque wrenches deviated from the target values by 11.6% and 10.2%, respectively. The accuracy of aged torque wrenches is adequate for prosthetic screw tightening, but that of new torque wrenches is unsatisfactory and must be examined carefully before delivery.

Spectroscopy of Ncncs at the Canadian Light Source: the Far-Infrared Spectrum of the ν_7 Region from 60-140 wn

NASA Astrophysics Data System (ADS)

Tokaryk, Dennis; Ross, Stephen Cary; Winnewisser, Brenda P.; Winnewisser, Manfred; De Lucia, Frank C.; Billinghurst, Brant E.

2014-06-01

We report on the analysis of our spectrum from 60-140 wn of the ν_7 bending fundamental and associated hot band sequence of NCNCS, obtained on the far-infrared beamline at the Canadian Light Source synchrotron. The data were collected in May 2013, building upon what we learned conducting experiments in May 2011 and 2012 on this molecule. Calculations indicated that the ν_7 system was very weak (one of the four weakest fundamental bands, all of comparable strength), but its spectrum became evident when 30 mTorr of NCNCS was admitted into the 2-m-long sample cell, through which the synchrotron beam passed 40 times. The best spectrum so far has been obtained with 121 mTorr of gas. Loomis-Wood plots reveal many branches, some of which were unambiguously assignable to Δ ν_7 = +1 subbands for ν_7" = 0, 1, 2, 3 and for K_a = 0, 1,2 with Δ K_a = 0 (a-type subbands) by comparison of lower-state combination differences with those obtained from the published pure-rotational data. We will continue the analysis by assigning as many a-type subbands as possible and by searching for b-type subbands with Δ K_a = ± 1 so that the connections between K_a-stacks can be measured. Finally, we will simultaneously fit the infrared and rotational data with a generalized semi-rigid bender Hamiltonian.

Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model

USGS Publications Warehouse

Tonkin, J.W.; Balistrieri, L.S.; Murray, J.W.

2004-01-01

Manganese oxides are important scavengers of trace metals and other contaminants in the environment. The inclusion of Mn oxides in predictive models, however, has been difficult due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), and the discrepancies between published sorption data and predictions using the available models. The authors have compiled a set of surface complexation reactions for synthetic hydrous Mn oxide (HMO) using a two surface site model and the diffuse double layer SCM which complements databases developed for hydrous Fe (III) oxide, goethite and crystalline Al oxide. This compilation encompasses a range of data observed in the literature for the complex HMO surface and provides an error envelope for predictions not well defined by fitting parameters for single or limited data sets. Data describing surface characteristics and cation sorption were compiled from the literature for the synthetic HMO phases birnessite, vernadite and ??-MnO2. A specific surface area of 746 m2g-1 and a surface site density of 2.1 mmol g-1 were determined from crystallographic data and considered fixed parameters in the model. Potentiometric titration data sets were adjusted to a pH1EP value of 2.2. Two site types (???XOH and ???YOH) were used. The fraction of total sites attributed to ???XOH (??) and pKa2 were optimized for each of 7 published potentiometric titration data sets using the computer program FITEQL3.2. pKa2 values of 2.35??0.077 (???XOH) and 6.06??0.040 (???YOH) were determined at the 95% confidence level. The calculated average ?? value was 0.64, with high and low values ranging from 1.0 to 0.24, respectively. pKa2 and ?? values and published cation sorption data were used subsequently to determine equilibrium surface complexation constants for Ba2+, Ca2+, Cd 2+, Co2+, Cu2+, Mg2+, Mn 2+, Ni2+, Pb2+, Sr2+ and Zn 2+. In addition, average model parameters were used to predict additional sorption data for which complementary titration data were not available. The two-site model accounts for variability in the titration data and most metal sorption data are fit well using the pKa2 and ?? values reported above. A linear free energy relationship (LFER) appears to exist for some of the metals; however, redox and cation exchange reactions may limit the prediction of surface complexation constants for additional metals using the LFER. ?? 2003 Elsevier Ltd. All rights reserved.

Simulation and measurement of a Ka-band HTS MMIC Josephson junction mixer

NASA Astrophysics Data System (ADS)

Zhang, Ting; Pegrum, Colin; Du, Jia; Guo, Yingjie Jay

2017-01-01

We report modeling and simulation results for a Ka band high-temperature superconducting (HTS) monolithic microwave integrated circuit (MMIC) Josephson junction mixer. A Verilog-A model of a Josephson junction is established and imported into the system simulator to realize a full HTS MMIC circuit simulation containing the HTS passive circuit models. Impedance matching optimization between the junction and passive devices is investigated. Junction DC I-V characteristics, current and local oscillator bias conditions and mixing performance are simulated and compared with the experimental results. Good agreement is obtained between the simulation and measurement results.

Concentration-related response potentiometric titrations to study the interaction of small molecules with large biomolecules.

PubMed

Hamidi-Asl, Ezat; Daems, Devin; De Wael, Karolien; Van Camp, Guy; Nagels, Luc J

2014-12-16

In the present paper, the utility of a special potentiometric titration approach for recognition and calculation of biomolecule/small-molecule interactions is reported. This approach is fast, sensitive, reproducible, and inexpensive in comparison to the other methods for the determination of the association constant values (Ka) and the interaction energies (ΔG). The potentiometric titration measurement is based on the use of a classical polymeric membrane indicator electrode in a solution of the small-molecule ligand. The biomolecule is used as a titrant. The potential is measured versus a reference electrode and transformed into a concentration-related signal over the entire concentration interval, also at low concentrations, where the millivolt (y-axis) versus log canalyte (x-axis) potentiometric calibration curve is not linear. In the procedure, Ka is calculated for the interaction of cocaine with a cocaine binding aptamer and with an anticocaine antibody. To study the selectivity and cross-reactivity, other oligonucleotides and aptamers are tested, as well as other small ligand molecules such as tetrakis(4-chlorophenyl)borate, metergoline, lidocaine, and bromhexine. The calculated Ka compared favorably to the value reported in the literature using surface plasmon resonance. The potentiometric titration approach called "concentration-related response potentiometry" is used to study molecular interaction for seven macromolecular target molecules and four small-molecule ligands.

Climate variability during the deglaciation and Holocene in a high-altitude alpine lake deduced from the sedimentary record from Laguna Seca, Sierra Nevada, southern Iberian Peninsula

NASA Astrophysics Data System (ADS)

Camuera, Jon; Jiménez-Moreno, Gonzalo; José Ramos-Román, María; García-Alix, Antonio; Jiménez-Espejo, Francisco; Anderson, R. Scott

2017-04-01

High-resolution X-ray fluorescence (XRF), magnetic susceptibility (MS), color and lithological analyses have been carried out on a 3.6 m-long sediment core from Laguna Seca, a high-elevation dry lake from Sierra Nevada mountain range, southern Spain. This is the longest sedimentary record retrieved from an alpine lake in southern Iberian Peninsula. Besides, alpine lakes are very sensitive environments to climate changes and previous studies showed that Laguna Seca could provide an excellent record to identify millennial-scale climate variations during deglaciation and the whole Holocene. XRF analyses, in particular high calcium and low K/Ca ratios, show aridity phases, very well represented during Last Glacial Maximum (LGM) and the Younger Dryas (YD). Arid events are also shown at ca. 8.1 ka BP, ca. 4.4 ka BP and the latest Holocene. On the other hand, negative values in calcium and positive values in K/Ca appear in the Bølling-Allerød (BA) and during the early Holocene until ca. 6 ka BP, indicating more humidity and higher run-off. A progressive aridification trend is also observed in the Holocene, changing from more humid conditions during the early Holocene to more aridity during the late Holocene.

Abiotic association of PAEs with humic substances and its influence on the fate of PAEs in landfill leachate.

PubMed

Xiaoli, Chai; Rong, Ji; Jun, Wu; Huanhuan, Tong; Youcai, Zhao

2010-03-01

An equilibrium dialysis combined with a (14)C-labeling method was used to study the abiotic association of phthalic acid esters (PAEs) with dissolved humic substances (HS) and its influence on the fate of PAEs in landfill leachate. Elemental analysis and FTIR spectral analysis were carried out on the humic acid (HA) and fulvic acid (FA) components of HS to examine the relationship between the structure of HS and the intensity of the association of the PAEs with HS (K(A)). The results show that the association intensity of HS with PAEs depends greatly on both the properties of the PAEs and the source of HS. The HS have a strong association reaction with dibutyl phthalic acid, which might explain the higher concentration of dibutyl phthalic acid detected in landfill leachate. The pH value strongly affects the K(A) of HS, and it decreases radically when the pH increase from 3.0 to 9.0. The non-specific hydrophobic interaction between HS and PAEs plays a more important role in the abiotic association of HS with PAEs. Elemental analysis and FTIR spectra suggest that the high K(A) values are related to the high aromatic content and larger molecular weight of HS. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

[Traditional Chinese medicine pairs (III)--effect of extract of Ginseng Radix et Rhizoma and Puerariae Lobatae Radix on intestinal absorption in rats].

PubMed

Chen, Yi-hang; Li, Meng-xuan; Meng, Zhao-qing; Yang, Jiao-jiao; Huang, Wen-zhe; Wang, Zhen-zhong; Wang, Yue-sheng; Xiao, Wei

2015-08-01

This study focused on the intestinal absorption of traditional Chinese medicines (TCM) to reveal the scientific connotation of the compatibility of TCM pairs. The single pass intestinal perfusion (SPIP) was used in rats to compare the absorption of single extracts from Puerariae Lobatae Radix, single extracts from Ginseng Radix et Rhizoma, combined extracts from Puerariae Lobatae Radix and Ginseng Radix et Rhizoma and Puerariae Lobatae Radix and Ginseng Radix et Rhizoma mixture in rats. The content of puerarin, ginsenoside Rg1, ginsenoside Re and ginsenoside Rb1 in liquid were tested by HPLC. The speed constant (Ka) and apparent permeability coefficients (Papp) were calculated and compared. Specifically, the order of puerarin Ka and Papp values from high to low was Ginseng Radix et Rhizoma and Puerariae Lobatae Radix mixture > single extracts from Puerariae Lobatae Radix > combined extracts from Ginseng Radix et Rhizoma and Puerariae Lobatae Radix; the order of ginsenosides Ka and Papp values from high to low was Ginseng Radix et Rhizoma and Puerariae Lobatae Radix mixture > single extracts from Ginseng Radix et Rhizoma > combined extracts from Ginseng Radix et Rhizoma and Puerariae Lobatae Radix. The combined administration of Ginseng Radix et Rhizoma and Puerariae Lobatae Radix may improve the absorption in the intestinal tract.

No surface breaking on the Ecemiş Fault, central Turkey, since Late Pleistocene (~ 64.5 ka); new geomorphic and geochronologic data from cosmogenic dating of offset alluvial fans

NASA Astrophysics Data System (ADS)

Sarıkaya, M. A.; Yıldırım, C.; Çiner, A.

2015-05-01

The Ecemiş Fault Zone (EF) has been recognized as a major left lateral strike-slip fault in the Central Anatolian Fault Zone (CAFZ) of Turkey. However, its Quaternary slip-rate has been challenging to determine due to the difficulty of dating offset markers. Using high-precision offset measurements and 36Cl cosmogenic nuclide dating, we present the first geochronologically determined Late Quaternary slip-rate for the EF. Our study focuses on the excellent exposures of offset alluvial fan surfaces, originating from the Aladağlar, a Late Quaternary glaciated mountain. Analysis of airborne orthophotogrametry and GNSS (Global Navigation Satellite System) surveys indicates 168 ± 2 m left lateral and 31 ± 1 m vertical displacements. In-situ terrestrial cosmogenic 36Cl geochronology obtained from eleven surface boulders provides a minimum abandonment/incision age of 104.2 ± 16.5 ka for the oldest offset alluvial fan surface. Our geomorphic observations together with Self-potential geophysical surveys revealed the presence of an unfaulted alluvial fan terrace, which allows us to constrain the timing of deformation. The abandonment/incision age of this fan is 64.5 ± 5.6 ka based on thirteen 36Cl depth profile samples. Accordingly, we obtained a geologic fault slip-rate of 4.2 ± 1.9 mm a- 1 horizontally and 0.8 ± 0.3 mm a- 1 vertically for the time frame between 104.2 ± 16.5 ka and 64.5 ± 5.6 ka. Our analysis indicates that the EF has not been producing a major surface breaking earthquake on the main strand at least since 64.5 ± 5.6 ka (mid-Late Pleistocene). This could be the result of abandonment of the main strand and accommodation of deformation by other faults within the EF. Nevertheless, a recently occurred (30 September 2011) low magnitude (ML: 4.3) left lateral strike-slip earthquake indicates recent seismic activity of the EF. Comparison of the recent GPS velocity field with the longer slip history along the CAFZ indicates a constant but low strain release without surface breaking and very long large earthquake recurrence intervals.

Ligand- and cell-dependent determinants of internalization and cAMP modulation by delta opioid receptor (DOR) agonists

PubMed Central

Charfi, Iness; Nagi, Karim; Mnie-Filali, Ouissame; Thibault, Dominic; Balboni, Gianfranco; Schiller, Peter W.; Trudeau, Louis-Eric

2014-01-01

Signaling bias refers to G protein-coupled receptor ligand ability to preferentially activate one type of signal over another. Bias to evoke signaling as opposed to sequestration has been proposed as a predictor of opioid ligand potential for generating tolerance. Here we measured whether delta opioid receptor agonists preferentially inhibited cyclase activity over internalization in HEK cells. Efficacy (τ) and affinity (KA) values were estimated from functional data and bias was calculated from efficiency coefficients (log τ/KA). This approach better represented the data as compared to alternative methods that estimate bias exclusively from τ values. Log (τ/KA) coefficients indicated that SNC-80 and UFP-512 promoted cyclase inhibition more efficiently than DOR internalization as compared to DPDPE (bias factor for SNC-80: 50 and for UFP-512: 132). Molecular determinants of internalization were different in HEK293 cells and neurons with βarrs contributing to internalization in both cell types, while PKC and GRK2 activities were only involved in neurons. Rank orders of ligand ability to engage different internalization mechanisms in neurons were compared to rank order of Emax values for cyclase assays in HEK cells. Comparison revealed a significant reversal in rank order for cyclase Emax values and βarr-dependent internalization in neurons, indicating that these responses were ligand-specific. Despite this evidence, and because kinases involved in internalization were not the same across cellular backgrounds, it is not possible to assert if the magnitude and nature of bias revealed by rank orders of maximal responses is the same as the one measured in HEK cells. PMID:24022593

Dichroic Filter for Separating W-Band and Ka-Band

NASA Technical Reports Server (NTRS)

Epp, Larry W.; Durden, Stephen L.; Jamnejad, Vahraz; Long, Ezra M.; Sosnowski, John B.; Higuera, Raymond J.; Chen, Jacqueline C.

2012-01-01

The proposed Aerosol/Cloud/Ecosystems (ACEs) mission development would advance cloud profiling radar from that used in CloudSat by adding a 35-GHz (Ka-band) channel to the 94-GHz (W-band) channel used in CloudSat. In order to illuminate a single antenna, and use CloudSat-like quasi-optical transmission lines, a spatial diplexer is needed to add the Ka-band channel. A dichroic filter separates Ka-band from W-band by employing advances in electrical discharge machining (EDM) and mode-matching analysis techniques developed and validated for designing dichroics for the Deep Space Network (DSN), to develop a preliminary design that both met the requirements of frequency separation and mechanical strength. First, a mechanical prototype was built using an approximately 102-micron-diameter EDM process, and tolerances of the hole dimensions, wall thickness, radius, and dichroic filter thickness measured. The prototype validated the manufacturing needed to design a dichroic filter for a higher-frequency usage than previously used in the DSN. The initial design was based on a Ka-band design, but thicker walls are required for mechanical rigidity than one obtains by simply scaling the Ka-band dichroic filter. The resulting trade of hole dimensions for mechanical rigidity (wall thickness) required electrical redesign of the hole dimensions. Updates to existing codes in the linear solver decreased the analysis time using mode-matching, enabling the electrical design to be realized quickly. This work is applicable to missions and instruments that seek to extend W-band cloud profiling measurements to other frequencies. By demonstrating a dichroic filter that passes W-band, but reflects a lower frequency, this opens up the development of instruments that both compare to and enhance CloudSat.

Mechanistic Studies of Human Spermine Oxidase: Kinetic Mechanism and pH Effects†

PubMed Central

Adachi, Maria S.; Juarez, Paul R.; Fitzpatrick, Paul F.

2009-01-01

In mammalian cells, the flavoprotein spermine oxidase (SMO) catalyzes the oxidation of spermine to spermidine and 3-aminopropanal. Mechanistic studies have been carried out with the recombinant human enzyme. The initial velocity pattern when the ratio between the concentrations of spermine and oxygen is kept constant establishes the steady-state kinetic pattern as ping-pong. Reduction of SMO by spermine in the absence of oxygen is biphasic. The rate constant for the rapid phase varies with the substrate concentration, with a limiting value (k3) of 49 s−1 and an apparent Kd value of 48 µM at pH 8.3. The rate constant for the slow step is independent of the spermine concentration, with a value of 5.5 s−1, comparable to the kcat value of 6.6 s−1. The kinetics of the oxidative half-reaction depend on the aging time after spermine and enzyme are mixed in a double mixing experiment. At an aging time of 6 s the reaction is monophasic with a second order rate constant of 4.2 mM−1 s−1. At an aging time of 0.3 s the reaction is biphasic with two second order constants equal to 4.0 and 40 mM−1 s−1. Neither is equal to the kcat/KO2 value of 13 mM−1s−1. These results establish the existence of more than one pathway for the reaction of the reduced flavin intermediate with oxygen. The kcat/KM value for spermine exhibits a bell-shaped pH-profile, with an average pKa value of 8.3. This profile is consistent with the active form of spermine having three charged nitrogens. The pH profile for k3 shows a pKa value of 7.4 for a group that must be unprotonated. The pKi-pH profiles for the competitive inhibitors N,N’-dibenzylbutane-1,4-diamine and spermidine show that the fully protonated forms of the inhibitors and the unprotonated form of an amino acid residue with a pKa of about 7.4 in the active site are preferred for binding. PMID:20000632

Pyroclastic chronology of the Sancy stratovolcano (Mont-Dore, French Massif Central): New high-precision 40Ar/39Ar constraints

NASA Astrophysics Data System (ADS)

Nomade, Sébastien; Scaillet, Stéphane; Pastre, Jean-François; Nehlig, Pierre

2012-05-01

The Sancy (16 km2) is the youngest of the two stratovolcanoes that constitute the Mont-Dore Massif (Massif Central, France). The restricted number of high precision radio-isotopic ages currently limits our knowledge of the pyroclastic chronology of this edifice which is the source of many tephra layers detected in middle Pleistocene sequences in southeast Europe. To improve our knowledge of the building phases of this stratovolcano, we collected thirteen pyroclastic units covering the entire proximal record. We present 40Ar/39Ar single grain laser dating performed in the facility hosted at the LSCE (Gif-sur-Yvette, France). The 40Ar/39Ar ages range from 1101 ± 11 ka to 392 ± 7 ka (1σ external). Four pyroclastic cycles lasting on average 100 ka were identified (C. I to C. IV). C. I corresponds to the earlier explosive phase between 1101 ka and 1000 ka and starts about 100 ka earlier than previously thought. The second pyroclastic cycle (C. II) is the main pyroclastic episode spanning from 818 to 685 ka. This cycle is constituted of a minimum of 8 major pyroclastic eruptions and includes a major event that corresponds to a large plinian eruption at 719 ± 10 ka (1σ external) and recorded as a 1.4 m thick layer 60 km south-east of the Sancy volcano. The link between this large eruption and formation of a caldera stays however, hypothetical. The third pyroclastic cycle (C. III) found in the northeastern part of the Sancy (Mont-Dore valley) spanned from 642 to 537 ka. Finally, the youngest pyroclastic cycle (C. IV) starts at 392 ka and probably ends around 280 ka. The age versus geographic location of each pyroclastic cycle indicates three preferential directions of channeling of the pyroclastic events and/or collapse of the volcanic edifice: northwest to west (C. I), southeast (C. II) and finally north to northeast (C. III and IV). The new high precision 40Ar/39Ar age for the Queureuilh bas pyroclastic unit (642 ± 9 ka) is identical within error with the U/Pb age obtained by Cocherie et al. (2009) [Geochimica et Cosmochimica Acta, 73, 1095-1108] and suggests a short residence time of the magma in a shallow, short-lived, small magmatic chamber. Finally, the source of the t21d tephra layer found in the Piànico Séllere varved sequence (Northern Italy) is not the Rivaux pumice flow as proposed by Brauer et al. (2007) [Journal of Quaternary Science 22, 85-96] and neither one of the C. II pyroclastic units as suggested by Roulleau et al. (2009) [Quaternary International 204, 31-43]. Accordingly, the source for the t21d layer has yet to be found at Sancy or elsewhere.

ARM KAZR-ARSCL Value Added Product

DOE Data Explorer

Jensen, Michael

2012-09-28

The Ka-band ARM Zenith Radars (KAZRs) have replaced the long-serving Millimeter Cloud Radars, or MMCRs. Accordingly, the primary MMCR Value Added Product (VAP), the Active Remote Sensing of CLouds (ARSCL) product, is being replaced by a KAZR-based version, the KAZR-ARSCL VAP. KAZR-ARSCL provides cloud boundaries and best-estimate time-height fields of radar moments.

Sedimentary record on the Indian Summer Monsoon since the Last Glacial Maximum: Evidence from the southeastern Andaman Sea

NASA Astrophysics Data System (ADS)

Shi, Xuefa; Liu, Shengfa; Cao, Peng; Khokiattiwong, Somkiat; Kornkanitnan, Narumol

2016-04-01

The Indian Summer Monsoon (ISM) generated by across-equatorial pressure gradient between the Asian continent and the southern Indian Ocean is a major component of the Asian monsoon system and establishes interactions among the ocean, land and atmosphere. Provenance and paleoclimate changes in the Andaman Sea during the last 26 ka were reconstructed from high-resolution records of grain-size, major elements and Sr-Nd isotopes in core ADM-9. The values of ɛNd(0) and 87Sr/86Sr were in good agreement with those of Irrawaddy River sediments, indicating a common source of origin. Two sensitive grain-size intervals (3.4-7.5 and 16.8-21.2 μm) were identified; the former was controlled primarily by sea-level change, whereas the latter was related to Irrawaddy River discharge and South-west Current transport driven by the ISM. Proxies of chemical weathering (K/Al) and terrigenous input (Ti/Ca) coupled with sensitive grain-size interval (16.8-21.2 μm population) revealed that the ISM was weak during ~15-26 ka BP and then strengthened gradually to a maximum during ~7-9 ka BP; subsequently, the ISM exhibited a generally declining trend to ~2 ka BP. The variation of the ISM recorded in this work is consistent with ISM variations observed in an open area in the northern Indian Ocean and in adjacent continents, implying the evolution of the Asia summer monsoon since 26 ka.

New Constraints on the Geometry and Kinematics of Matter Surrounding the Accretion Flow in X-Ray Binaries from Chandra High-Energy Transmission Grating X-Ray Spectroscopy

NASA Technical Reports Server (NTRS)

Tzanavaris, P.; Yaqoob, T.

2018-01-01

The narrow, neutral Fe Ka fluorescence emission line in X-ray binaries (XRBs) is a powerful probe of the geometry, kinematics, and Fe abundance of matter around the accretion flow. In a recent study it has been claimed, using Chandra High-Energy Transmission Grating (HETG) spectra for a sample of XRBs, that the circumnuclear material is consistent with a solar-abundance, uniform, spherical distribution. It was also claimed that the Fe Ka line was unresolved in all cases by the HETG. However, these conclusions were based on ad hoc models that did not attempt to relate the global column density to the Fe Ka line emission. We revisit the sample and test a self-consistent model of a uniform, spherical X-ray reprocessor against HETG spectra from 56 observations of 14 Galactic XRBs. We find that the model is ruled out in 13/14 sources because a variable Fe abundance is required. In two sources a spherical distribution is viable, but with nonsolar Fe abundance. We also applied a solar-abundance Compton-thick reflection model, which can account for the spectra that are inconsistent with a spherical model, but spectra with a broader bandpass are required to better constrain model parameters. We also robustly measured the velocity width of the Fe Ka line and found FWHM values of up to approx. 5000 km/s. Only in some spectra was the Fe Ka line unresolved by the HETG.

Age-related changes in with-the-rule and oblique corneal astigmatism.

PubMed

Naeser, Kristian; Savini, Giacomo; Bregnhøj, Jesper Flethøj

2018-01-25

To describe the age-related changes in with-the-rule (WTR) and oblique keratometric astigmatism (KA), posterior corneal astigmatism (PCA) and total corneal astigmatism (TCA). We used a Pentacam HR (high-resolution) rotating Scheimpflug camera to determine the KA, PCA and TCA in the right eyes of 710 patients, aged from 20 to 88 years. The age-related changes along the vertical, horizontal and oblique meridians were analyzed with Naeser's polar value method in a cross-sectional study. In the whole group, all meridional astigmatic powers and polar values were stable in the age groups from 20 to 49 years, followed by a 1.0 dioptre (D) against-the-rule (ATR) change in KA and TCA, and a 0.12 D reduction in against-the-rule PCA. A nasal rotation of the steep meridian in KA and TCA was noted in the 70-88 years old. The PCA averaged approximately 0.25 D ATR in all age groups. Females displayed the same early astigmatic stability as in the whole group, while male eyes demonstrated a linear decay from 1.5 D WTR at 20 years to 0.5 D ATR astigmatism for the oldest patients. Corneal astigmatism is stable until the age of 50 years; thereafter both keratometric and total corneal astigmatism show a 0.25 D ATR change per 10 years. The average 0.25 D ATR PCA compensates the predominant keratometric WTR astigmatism in the younger patients and increases the TCA in the elderly with keratometric ATR astigmatism. The gender-based differences in age-related astigmatism require further studies. © 2018 Acta Ophthalmologica Scandinavica Foundation. Published by John Wiley & Sons Ltd.

Evidence for an Elevated Aspartate pKa in the Active Site of Human Aromatase*

PubMed Central

Di Nardo, Giovanna; Breitner, Maximilian; Bandino, Andrea; Ghosh, Debashis; Jennings, Gareth K.; Hackett, John C.; Gilardi, Gianfranco

2015-01-01

Aromatase (CYP19A1), the enzyme that converts androgens to estrogens, is of significant mechanistic and therapeutic interest. Crystal structures and computational studies of this enzyme shed light on the critical role of Asp309 in substrate binding and catalysis. These studies predicted an elevated pKa for Asp309 and proposed that protonation of this residue was required for function. In this study, UV-visible absorption, circular dichroism, resonance Raman spectroscopy, and enzyme kinetics were used to study the impact of pH on aromatase structure and androstenedione binding. Spectroscopic studies demonstrate that androstenedione binding is pH-dependent, whereas, in contrast, the D309N mutant retains its ability to bind to androstenedione across the entire pH range studied. Neither pH nor mutation perturbed the secondary structure or heme environment. The origin of the observed pH dependence was further narrowed to the protonation equilibria of Asp309 with a parallel set of spectroscopic studies using exemestane and anastrozole. Because exemestane interacts with Asp309 based on its co-crystal structure with the enzyme, its binding is pH-dependent. Aromatase binding to anastrozole is pH-independent, consistent with the hypothesis that this ligand exploits a distinct set of interactions in the active site. In summary, we assign the apparent pKa of 8.2 observed for androstenedione binding to the side chain of Asp309. To our knowledge, this work represents the first experimental assignment of a pKa value to a residue in a cytochrome P450. This value is in agreement with theoretical calculations (7.7–8.1) despite the reliance of the computational methods on the conformational snapshots provided by crystal structures. PMID:25425647

Population Pharmacokinetics of Oral Topotecan in Infants and Very Young Children with Brain Tumors Demonstrates a Role of ABCG2 rs4148157 on the Absorption Rate Constant

PubMed Central

Roberts, Jessica K.; Birg, Anna V.; Lin, Tong; Daryani, Vinay M.; Panetta, John C.; Broniscer, Alberto; Robinson, Giles W.; Gajjar, Amar J.

2016-01-01

For infants and very young children with brain tumors, chemotherapy after surgical resection is the main treatment due to neurologic and neuroendocrine adverse effects from whole brain irradiation. Topotecan, an anticancer drug with antitumor activity against pediatric brain tumors, can be given intravenous or orally. However, high interpatient variability in oral drug bioavailability is common in children less than 3 years old. Therefore, this study aimed to determine the population pharmacokinetics of oral topotecan in infants and very young children, specifically evaluating the effects of age and ABCG2 and ABCB1 on the absorption rate constant (Ka), as well as other covariate effects on all pharmacokinetic parameters. A nonlinear mixed effects model was implemented in Monolix 4.3.2 (Lixoft, Orsay, France). A one-compartment model with first-order input and first-order elimination was found to adequately characterize topotecan lactone concentrations with population estimates as [mean (S.E.)]; Ka = 0.61 (0.11) h−1, apparent volume of distribution (V/F) = 40.2 (7.0) l, and apparent clearance (CL/F) = 40.0 (2.9) l/h. After including the body surface area in the V/F and CL/F as a power model centered on the population median, the ABCG2 rs4148157 allele was found to play a significant role in the value of Ka. Patients homozygous or heterozygous for G>A demonstrated a Ka value 2-fold higher than their GG counterparts, complemented with a 2-fold higher maximal concentration as well. These results demonstrate a possible role for the ABCG2 rs4148157 allele in the pharmacokinetics of oral topotecan in infants and very young children, and warrants further investigation. PMID:27052877

A chronology for glacial Lake Agassiz shorelines along Upham's namesake transect

NASA Astrophysics Data System (ADS)

Lepper, Kenneth; Buell, Alex W.; Fisher, Timothy G.; Lowell, Thomas V.

2013-07-01

Four traditionally recognized strandline complexes in the southern basin of glacial Lake Agassiz are the Herman, Norcross, Tintah and Campbell, whose names correspond to towns in west-central Minnesota that lie on a linear transect defined by the Great Northern railroad grade; the active corridor for commerce at the time when Warren Upham was mapping and naming the shorelines of Lake Agassiz (ca.1880-1895). Because shorelines represent static water planes, their extension around the lake margin establishes time-synchronous lake levels. Transitions between shoreline positions represent significant water-level fluctuations. However, geologic ages have never been obtained from sites near the namesake towns in the vicinity of the southern outlet. Here we report the first geologic ages for Lake Agassiz shorelines obtained at field sites along the namesake transect, and evaluate the emerging chronology in light of other paleoclimate records. Our current work from 11 sampling sites has yielded 16 independent ages. These results combined with a growing OSL age data set for Lake Agassiz's southern basin provide robust age constraints for the Herman, Norcross and Campbell strandlines with averages and standard deviations of 14.1 ± 0.3 ka, 13.6 ± 0.2 ka, and 10.5 ± 0.3 ka, respectively.

Geochemical and sedimentological properties of Heinrich layers H2 and H1 off the Hudson Strait ice-surging source areas: ice-rafting vs water-laid down depositional mechanisms

NASA Astrophysics Data System (ADS)

Nuttin, L.; Hillaire-Marcel, C.

2012-12-01

The ~9 m-long core HU08-029-004PC was raised from the lower Labrador Sea slope (2674 m water-depth), approximately 180 km off Hudson Strait shelf edge. It yielded a high resolution record spanning the last 35 ka. The sequence includes layers with abundant detrital carbonates produced by glacial erosion of Paleozoic rocks and released into the Labrador Sea through ice streaming processes in Hudson Strait and Ungava Bay. These layers are assigned to 'Heinrich events' 3 (at core bottom), 2 and 1. Sedimentological properties and U and Th isotope measurements are used to document depositional mechanisms and durations of these layers. Data suggest: i) intense ice-rafting deposition (IRD) due to iceberg calving at the ice-stream edge, as illustrated by the coarse fraction content of the layers, and ii) sub-glacial meltwater flushing over the Hudson Strait sill, carrying fine silt-size, carbonate-rich glacial flour to the shelf-edge. Such suspended sediment pulses led to the spreading of turbidites mostly into the deep Labrador Sea, through the NAMOC system. Others late-glacial events, such as the ~ 8.2 ka final drainage of Lake Agassiz, are also recorded in the study core, whereas the H0 layer, exclusively observed in the western Labrador Sea is missing. CAT-scan images, mineralogical data, carbonate abundance, %>106 μm fraction (mostly IRD here), U-Th isotope data and 14C ages of planktic foraminifera assemblages (Neogloboquadrina pachyderma, l.) are used to further document H2 (760 to 700 cm) and H1 (588 to 488 cm). The H-layers contain up to 60% of fine detrital carbonates (about 2/3 calcite, 1/3 dolomite). Whereas the fine calcitic material points to sediment sources (basal till/water-laid glacial sediments) in the Hudson Strait and Ungava Bay, i.e., originating from the glacial erosion of Paleozoic carbonates from the area, the dolomitic component might have several origins (from Proterozoic and Paleozoic limestones in the Hudson Bay and Strait, to northwestern Baffin Island Paleozoic dolomite sources). The carbonate-rich layers are characterized by 234U/238U activity ratio <1 and more importantly, by very low initial 230Th excesses (230Thxs)0. Such low values indicate extremely fast deposition. An inventory of the (230Thxs)0 has been made based on 13 calibrated 14C ages and then used for interpolating duration ages for the H2 and H1. Estimated of 1.34 and 2.02 ka (vs 1.64 and 2.03 ka 14C), were respectively obtained. Another rapidly deposited layer of fine detrital carbonates-rich sediment yielded an age of about 8.3 ka, suggesting an assignment to the final drainage age of Lake Agassiz. Above this layer, high (230Thxs)0 values, but low (230Thxs)0-fluxes point to much reduced sedimentation rates and possibly focussing deeper slope during the Holocene.

Reverberation Mapping of the Kepler-Field AGN KA1858+4850

NASA Technical Reports Server (NTRS)

Pei, Liuyi; Barth, Aaron J.; Aldering, Greg S.; Briley, Michael M.; Carroll, Carla J.; Carson, Daniel J.; Cenko, S., Bradley; Clubb, Kelsey I.; Cohen, Daniel P.; Cucchiara, Antonino;

Reverberation Mapping of the KEPLER Field AGN KA1858+4850

NASA Astrophysics Data System (ADS)

Pei, Liuyi; Barth, Aaron J.; Aldering, Greg S.; Briley, Michael M.; Carroll, Carla J.; Carson, Daniel J.; Cenko, S. Bradley; Clubb, Kelsey I.; Cohen, Daniel P.; Cucchiara, Antonino; Desjardins, Tyler D.; Edelson, Rick; Fang, Jerome J.; Fedrow, Joseph M.; Filippenko, Alexei V.; Fox, Ori D.; Furniss, Amy; Gates, Elinor L.; Gregg, Michael; Gustafson, Scott; Horst, J. Chuck; Joner, Michael D.; Kelly, Patrick L.; Lacy, Mark; Laney, C. David; Leonard, Douglas C.; Li, Weidong; Malkan, Matthew A.; Margon, Bruce; Neeleman, Marcel; Nguyen, My L.; Prochaska, J. Xavier; Ross, Nathaniel R.; Sand, David J.; Searcy, Kinchen J.; Shivvers, Isaac S.; Silverman, Jeffrey M.; Smith, Graeme H.; Suzuki, Nao; Smith, Krista Lynne; Tytler, David; Werk, Jessica K.; Worseck, Gábor

2014-11-01

KA1858+4850 is a narrow-line Seyfert 1 galaxy at redshift 0.078 and is among the brightest active galaxies monitored by the Kepler mission. We have carried out a reverberation mapping campaign designed to measure the broad-line region size and estimate the mass of the black hole in this galaxy. We obtained 74 epochs of spectroscopic data using the Kast Spectrograph at the Lick 3 m telescope from 2012 February to November, and obtained complementary V-band images from five other ground-based telescopes. We measured the Hβ light curve lag with respect to the V-band continuum light curve using both cross-correlation techniques (CCF) and continuum light curve variability modeling with the JAVELIN method and found rest-frame lags of τ CCF = 13.53+2.03-2.32 days and τ JAVELIN = 13.15+1.08-1.00 days. The Hβ rms line profile has a width of σline = 770 ± 49 km s-1. Combining these two results and assuming a virial scale factor of f = 5.13, we obtained a virial estimate of M{BH} = 8.06+1.59-1.72 × 106 {M}⊙ for the mass of the central black hole and an Eddington ratio of L/L Edd ≈ 0.2. We also obtained consistent but slightly shorter emission-line lags with respect to the Kepler light curve. Thanks to the Kepler mission, the light curve of KA1858+4850 has among the highest cadences and signal-to-noise ratios ever measured for an active galactic nucleus; thus, our black hole mass measurement will serve as a reference point for relations between black hole mass and continuum variability characteristics in active galactic nuclei.

Assessing backscatter change due to backscatter gradient over the Greenland ice sheet using Envisat and SARAL altimetry

NASA Astrophysics Data System (ADS)

Su, Xiaoli; Luo, Zhicai; Zhou, Zebing

2018-06-01

Knowledge of backscatter change is important to accurately retrieve elevation change time series from satellite radar altimetry over continental ice sheets. Previously, backscatter coefficients generated in two cases, namely with and without accounting for backscatter gradient (BG), are used. However, the difference between backscatter time series obtained separately in these two cases and its impact on retrieving elevation change are not well known. Here we first compare the mean profiles of the Ku and Ka band backscatter over the Greenland ice sheet (GrIS), with results illustrating that the Ku-band backscatter is 3 ∼ 5 dB larger than that of the Ka band. We then conduct statistic analysis about time series of backscatter formed separately in the above two cases for both Ku and Ka bands over two regions in the GrIS. It is found that the standard deviation of backscatter time series becomes slightly smaller after removing the BG effect, which suggests that the method for the BG correction is effective. Furthermore, the impact on elevation change from backscatter change due to the BG effect is separately assessed for both Ku and Ka bands over the GrIS. We conclude that Ka band altimetry would benefit from a BG induced backscatter analysis (∼10% over region 2). This study may provide a reference to form backscatter time series towards refining elevation change time series from satellite radar altimetry over ice sheets using repeat-track analysis.

Reconstruction of past climate variability in SE Spain between 14 and 8 ka

NASA Astrophysics Data System (ADS)

Budsky, Alexander; Scholz, Denis; Mertz-Kraus, Regina; Christoph, Spötl; Gibert, Luis; Jochum, Klaus Peter; Andreae, Meinrat O.

2016-04-01

In comparison to the large climatic oscillations during the Pleistocene, Holocene climate only underwent minor changes. Nevertheless, cyclic climate changes also occurred during the Holocene. The Bond events, represented by the presence of cold, ice-bearing waters from the north of Iceland as far south as the latitude of Britain, occurred at a cyclicity of about 1500 a and were particularly pronounced during the Early Holocene. However, their climatic impact on the terrestrial realm was not consistent over Europe, in particular with respect to changes in precipitation. Here we present a precisely dated high-resolution flowstone record from Cueva Victoria, SE Spain, a site well suited to study the competing influence of the Atlantic and Mediterranean Sea on the southern Iberian Peninsula. We sampled several flowstones with a thickness of up to 60 cm. 230Th/U-dating has shown that these deposits mainly formed during relatively warm climate intervals of the Middle and Late Pleistocene, i.e. interglacials and interstadials (Budsky et al., 2015; Gibert et al., 2016). Here we focus on a short (11 cm) flowstone sequence from the Holocene with a high temporal resolution (centennial for stable isotopes and annual for trace elements). The flowstone grew between 14 and ca. 8 ka b2k. The decreasing trend of the δ18O and δ13C values as well as of several trace elements between 12 and 11 ka b2k reflects an increase in temperature and precipitation at the beginning of the Holocene. In particular, Sr and Mg show a trend towards low and stable values. Subsequently, from 10.5 to 8 ka b2k, the δ13C values show a high variability (-11 to -4), whereas the δ18O values are rather stable (between -6 and -7). Maxima in δ13C are interpreted as drier conditions in response to Bond events. These events possibly led to a change of the atmospheric circulation, affecting the vegetation in SE Spain, which evolved towards an open C3 vegetation at ca. 8 ka b2k concomitant with drier conditions. Budsky, A., Scholz, D., Gibert, L., Mertz-Kraus, R., 2015. 230Th/U-dating of the Cueva Victoria flowstone sequence: Preliminary results and paleoclimate implications, in: Gibert, L., Ferràndez-Canadell, C. (Eds.), Geology and Paleontology of Cueva Victoria. Mastia 11-13, Cartagena, pp. 101-109. Gibert, L., Scott, G.R., Scholz, D., Budsky, A., Ferràndez, C., Ribot, F., Martin, R.A., Lería, M., 2016. Chronology for the Cueva Victoria fossil site (SE Spain): Evidence for Early Pleistocene Afro-Iberian dispersals. Journal of Human Evolution 90, 183-197.

Constant-pH Molecular Dynamics Study of Kyotorphin in an Explicit Bilayer

PubMed Central

Magalhães, Pedro R.; Machuqueiro, Miguel; Baptista, António M.

2015-01-01

To our knowledge, we present the first constant-pH molecular dynamics study of the neuropeptide kyotorphin in the presence of an explicit lipid bilayer. The overall conformation freedom of the peptide was found to be affected by the interaction with the membrane, in accordance with previous results using different methodologies. Analysis of the interactions between the N-terminus amine group of the peptide and several lipid atoms shows that the membrane is able to stabilize both ionized and neutral forms of kyotorphin, resulting in a pKa value that is similar to the one obtained in water. This illustrates how a detailed molecular model of the membrane leads to rather different results than would be expected from simply regarding it as a low-dielectric slab. PMID:25954885

Uranium-series coral ages from the US Atlantic Coastal Plain-the "80 ka problem" revisited

USGS Publications Warehouse

Wehmiller, J. F.; Simmons, K.R.; Cheng, H.; Edwards, R. Lawrence; Martin-McNaughton, J.; York, L.L.; Krantz, D.E.; Shen, C.-C.

2004-01-01

Uranium series coral ages for emergent units from the passive continental margin US Atlantic Coastal Plain (ACP) suggest sea level above present levels at the end of marine oxygen isotope stage (MIS) 5, contradicting age-elevation relations based on marine isotopic or coral reef models of ice equivalent sea level. We have reexamined this problem by obtaining high precision 230Th/238U and 231Pa/235U thermal ionization mass spectrometric ages for recently collected and carefully cleaned ACP corals, many in situ. We recognize samples that show no evidence for diagenesis on the basis of uranium isotopic composition and age concordance. Combining new and earlier data, among those ages close to or within the age range of MIS 5, over 85% cluster between 65 and 85 ka BP. Of the corals that we have analyzed, those that show the least evidence for diagenesis on the basis of uranium isotopic composition and age concordance have ages between 80 and 85 ka BP, consistent with a MIS 5a correlation. The units from which these samples have been collected are all emergent and have elevations within ???3-5m of those few units where early stage 5 (???125,000 ka BP) coral ages have been obtained. The ACP appears to record an unusual history of relative sea level throughout MIS 5, a history that is also apparent in the dated coral record for Bermuda. We speculate that this history is related to the regional (near-to intermediate-field) effects of ancestral Laurentide Ice sheets on last interglacial shorelines of the western North Atlantic. ?? 2004 Elsevier Ltd and INQUA. All rights reserved.

The glacial/deglacial history of sedimentation in Bear Lake, Utah and Idaho

USGS Publications Warehouse

Rosenbaum, J.G.; Heil, C.W.

2009-01-01

Bear Lake, in northeastern Utah and southern Idaho, lies in a large valley formed by an active half-graben. Bear River, the largest river in the Great Basin, enters Bear Lake Valley ???15 km north of the lake. Two 4-m-long cores provide a lake sediment record extending back ???26 cal k.y. The penetrated section can be divided into a lower unit composed of quartz-rich clastic sediments and an upper unit composed largely of endogenic carbonate. Data from modern fluvial sediments provide the basis for interpreting changes in provenance of detrital material in the lake cores. Sediments from small streams draining elevated topography on the east and west sides of the lake are characterized by abundant dolomite, high magnetic susceptibility (MS) related to eolian magnetite, and low values of hard isothermal remanent magnetization (HIRM, indicative of hematite content). In contrast, sediments from the headwaters of the Bear River in the Uinta Mountains lack carbonate and have high HIRM and low MS. Sediments from lower reaches of the Bear River contain calcite but little dolomite and have low values of MS and HIRM. These contrasts in catchment properties allow interpretation of the following sequence from variations in properties of the lake sediment: (1) ca. 26 cal ka-onset of glaciation; (2) ca. 26-20 cal ka-quasicyclical, millennial-scale variations in the concentrations of hematite-rich glacial fl our derived from the Uinta Mountains, and dolomite- and magnetite-rich material derived from the local Bear Lake catchment (reflecting variations in glacial extent); (3) ca. 20-19 cal ka-maximum content of glacial fl our; (4) ca. 19-17 cal ka-constant content of Bear River sediment but declining content of glacial fl our from the Uinta Mountains; (5) ca. 17-15.5 cal ka-decline in Bear River sediment and increase in content of sediment from the local catchment; and (6) ca. 15.5-14.5 cal ka-increase in content of endogenic calcite at the expense of detrital material. The onset of glaciation indicated in the Bear Lake record postdates the initial rise of Lake Bonneville and roughly corresponds to the Stansbury shoreline. The lake record indicates that maximum glaciation occurred as Lake Bonneville reached its maximum extent ca. 20 cal ka and that deglaciation was under way while Lake Bonneville remained at its peak. The transition from siliciclastic to carbonate sedimentation probably indicates increasingly evaporative conditions and may coincide with the climatically driven fall of Lake Bonneville from the Provo shoreline. Although lake levels fluctuated during the Younger Dryas, the Bear Lake record for this period is more consistent with drier conditions, rather than cooler, moister conditions interpreted from many studies from western North America. Copyright ?? 2009 The Geological Society of America.

Authigenic 10Be/9Be ratio signatures of the cosmogenic nuclide production linked to geomagnetic dipole moment variation since the Brunhes/Matuyama boundary

PubMed Central

Thouveny, Nicolas; Bourlès, Didier L.; Valet, Jean‐Pierre; Bassinot, Franck; Ménabréaz, Lucie; Guillou, Valéry; Choy, Sandrine; Beaufort, Luc

2016-01-01

Abstract Geomagnetic dipole moment variations associated with polarity reversals and excursions are expressed by large changes of the cosmogenic nuclide beryllium‐10 (10Be) production rates. Authigenic 10Be/9Be ratios (proxy of atmospheric 10Be production) from oceanic cores therefore complete the classical information derived from relative paleointensity (RPI) records. This study presents new authigenic 10Be/9Be ratio results obtained from cores MD05‐2920 and MD05‐2930 collected in the west equatorial Pacific Ocean. Be ratios from cores MD05‐2920, MD05‐2930 and MD90‐0961 have been stacked and averaged. Variations of the authigenic 10Be/9Be ratio are analyzed and compared with the geomagnetic dipole low series reported from global RPI stacks. The largest 10Be overproduction episodes are related to dipole field collapses (below a threshold of 2 × 1022 Am2) associated with the Brunhes/Matuyama reversal, the Laschamp (41 ka) excursion, and the Iceland Basin event (190 ka). Other significant 10Be production peaks are correlated to geomagnetic excursions reported in literature. The record was then calibrated by using absolute dipole moment values drawn from the Geomagia and Pint paleointensity value databases. The 10Be‐derived geomagnetic dipole moment record, independent from sedimentary paleomagnetic data, covers the Brunhes‐Matuyama transition and the whole Brunhes Chron. It provides new and complementary data on the amplitude and timing of millennial‐scale geomagnetic dipole moment variations and particularly on dipole moment collapses triggering polarity instabilities. PMID:28163989

Towards the definition of Institutional diagnostic reference levels in paediatric interventional cardiology procedures in Greece.

PubMed

Kottou, S; Kollaros, N; Plemmenos, C; Mastorakou, I; Apostolopoulou, S C; Tsapaki, V

2018-02-01

This study aimed to evaluate paediatric radiation doses in a dedicated cardiology hospital, with the objective of characterising patterns in dose variation. The ultimate purpose was to define Local (Institutional) Diagnostic Reference Levels (LDRLs) for different types of paediatric cardiac interventional procedures (IC), according to patient age. From a total of 710 cases performed during three consecutive years, by operators with more than 15 years of experience, the age was noted in only 477 IC procedures. The median values obtained for Fluoroscopy Time (FT), Number of Frames (N) and Kerma Area Product (P KA ) by age range were 5.8 min, 1322 and 2.0 Gy.cm 2 for <1 y; 6.5 min, 1403 and 3.0 Gy.cm 2 for 1 to <5 y; 5.9 min, 950 and 7.0 Gy.cm 2 for 5 to <10 y; 5.7 min, 940 and 14.0 Gy.cm 2 for 10 to <16 y, respectively. A large range of patient dose data is observed, depending greatly on procedure type and patient age. In all age groups the range of median FT, N and P KA values was 3.1-15.8 min, 579-1779 and 1.0-20.8 Gy.cm 2 respectively. Consequently, the definition of LDRLs presents challenges mainly due to the multiple clinical and technical factors affecting the outcome. On the other hand the lack of paediatric IC DRLs makes the identification of good practices more difficult. A consensus is needed on IC procedures nomenclature and grouping in order to allow a common assessment and comparison of doses. Copyright © 2018 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

Advancements in cosmogenic 38Ar exposure dating of terrestrial rocks

NASA Astrophysics Data System (ADS)

Oostingh, K. F.; Jourdan, F.; Danišík, M.; Evans, N. J.

2017-11-01

Cosmogenic exposure dating of Ca-rich minerals using 38Ar on terrestrial rocks could be a valuable new dating tool to determine timescales of geological surface processes on Earth. Here, we show that advancement in analytical precision, using the new generation multi-collector ARGUSVI mass spectrometer on irradiated pyroxene and apatite samples, allows determination of cosmogenic 38Ar abundances above background values, as well as discrimination of 38Ar/36Ar ratios (1σ absolute precision of ±0.3%) from the non-cosmogenic background value. Four statistically significant cosmochron (38Ar/36Ar vs37Ar/36Ar) diagrams could be constructed for southeast Australian pyroxene samples from the Mt Elephant scoria cone for which a combined apparent exposure age of 313 ± 179 ka (2σ) was obtained when using a 38Ar production rate (Ca) of 250 atoms /g Ca/ yr. This exposure age overlaps within error with the known 40Ar/39Ar eruption age of 184 ± 15 ka (2σ). Although apatite shows much larger 38Ar abundances than pyroxene, our modelling and analyses of unirradiated apatite suggest that apatite suffers from both natural and reactor-derived chlorogenic as well as natural nucleogenic contributions of 38Ar. Hence, we suggest that cosmogenic 38Ar exposure dating on irradiated Ca-rich (and eventually K-rich), but Cl-free, terrestrial minerals is a potential valuable and accessible tool to determine geological surface processes on timescales of a few Ma. Calculations show that with the new generation multi-collector mass spectrometers an analytical uncertainty better than 5% (2σ) can be achieved on samples with expected exposure ages of >4 Ma.

Biochemical and kinetic analysis of the GH3 family beta-xylosidase from Aspergillus awamori X-100.

PubMed

Eneyskaya, Elena V; Ivanen, Dina R; Bobrov, Kirill S; Isaeva-Ivanova, Lyudmila S; Shabalin, Konstantin A; Savel'ev, Andrew N; Golubev, Alexander M; Kulminskaya, Anna A

2007-01-15

The beta-xylosidase from Aspergillus awamori X-100 belonging to the family 3 glycoside hydrolase revealed a distinctive transglycosylating ability to produce xylooligosaccharides with degree of polymerization more than 7. In order to explain this fact, the enzyme has been subjected to the detailed biochemical study. The enzymatic hydrolysis of p-nitrophenyl beta-D-xylopyranoside was found to occur with overall retention of substrate anomeric configuration suggesting cleavage of xylosidic bonds through a double-displacement mechanism. Kinetic study with aryl beta-xylopyranosides substrates, in which leaving group pK(a)s were in the range of 3.96-10.32, revealed monotonic function of log(k(cat)) and no correlation of log(k(cat)/Km) versus pKa values indicating deglycosylation as a rate-limiting step for the enzymatic hydrolysis. The classical bell-shaped pH dependence of k(cat)/Km indicated two ionizable groups in the beta-xylosidase active site with apparent pKa values of 2.2 and 6.4. The kinetic parameters of hydrolysis, Km and k(cat), of p-nitrophenyl beta-D-1,4-xylooligosaccharides were very close to those for hydrolysis of p-nitrophenyl-beta-D-xylopyranoside. Increase of p-nitrophenyl-beta-D-xylopyranoside concentration up to 80 mM led to increasing of the reaction velocity resulting in k(cat)(app)=81 s(-1). Addition of alpha-methyl D-xylopyranoside to the reaction mixture at high concentration of p-nitrophenyl-beta-D-xylopyranoside (50 mM) caused an acceleration of the beta-xylosidase-catalyzed reactions and appearance of a new transglycosylation product, alpha-methyl D-xylopyranosyl-1,4-beta-D-xylopyranoside, that was identified by 1H NMR spectroscopy. The kinetic model suggested for the enzymatic reaction was consistent with the results obtained.

A 600,000 year long continental pollen record from Lake Van, eastern Turkey

NASA Astrophysics Data System (ADS)

Litt, T.; Pickarski, N.; Heumann, G.

2014-12-01

Lake Van is the fourth largest terminal lake in the world (38.5°N, 43 °E, volume 607 km3, area 3570 km2, maximum water depth 460 m), extending for 130 km WSW-ENE on the Eastern Anatolian High Plateau, Turkey. The sedimentary record of Lake Van, partly laminated, obtains a long and continuous continental sequence that covers multiple interglacial-glacial cycles. Promoted by the potential of the sedimentary sequence for reconstructing the paleoecological and paleoclimate development of the Near East, a deep drilling operation was carried out in 2010 supported by the International Continental Scientific Drilling Program (ICDP). The 119 m long continental record is based on a well-dated composite profile drilled on the so-called Ahlat Ridge in water depth of 360 m encompassing the last 600,000 years. It contains the longest continuous continental pollen record of the Quaternary in the entire Near East and central Asia obtained to date. It documents glacial and interglacial stages as well as pronounced interstadials encompassing the entire 600 ka of the sedimentary record. The cold-adapted vegetation in the Lake Van region during glacial stages and stadial substages can be described as dwarf-shrub steppe and desert steppe very similar to each other. The climax vegetation of the interglacial stages in the Lake Van region is characterized by an oak steppe-forest with pistachio and juniper. It is interesting to note that, in contrast to the atmospheric CO2 concentration from Antarctic ice cores or marine isotope values based on benthic foraminifera, there is no clear subdivision in the Lake Van pollen record between low-amplitude interglacials (cooler cycles) prior the mid-Brunhes event (MBE) at 430 ka and high-amplitude, post MBE interglacials. Lower CO2 concentrations in the atmosphere might be compensated by stronger insolation forcing during Marine Isotope Stages (MIS) 13a and 15a. A similar pattern can be observed during the triplicate interglacial complex MIS 7 when AP and oak values reach maximum values during MIS 7c instead of MIS 7e. This underlines the different environmental response to global climate change in the continental Lake Van region compared to the global ice volume and/or greenhouse-gas amounts.

Instantaneous axial force of a high-order Bessel vortex beam of acoustic waves incident upon a rigid movable sphere.

PubMed

Mitri, F G; Fellah, Z E A

2011-08-01

The present investigation examines the instantaneous force resulting from the interaction of an acoustical high-order Bessel vortex beam (HOBVB) with a rigid sphere. The rigid sphere case is important in fluid dynamics applications because it perfectly simulates the interaction of instantaneous sound waves in a reduced gravity environment with a levitated spherical liquid soft drop in air. Here, a closed-form solution for the instantaneous force involving the total pressure field as well as the Bessel beam parameters is obtained for the case of progressive, stationary and quasi-stationary waves. Instantaneous force examples for progressive waves are computed for both a fixed and a movable rigid sphere. The results show how the instantaneous force per unit cross-sectional surface and unit pressure varies versus the dimensionless frequency ka (k is the wave number in the fluid medium and a is the sphere's radius), the half-cone angle β and the order m of the HOBVB. It is demonstrated here that the instantaneous force is determined only for (m,n) = (0,1) (where n is the partial-wave number), and vanishes for m>0 because of symmetry. In addition, the instantaneous force and normalized amplitude velocity results are computed and compared with those of a rigid immovable (fixed) sphere. It is shown that they differ significantly for ka values below 5. The proposed analysis may be of interest in the analysis of instantaneous forces on spherical particles for particle manipulation, filtering, trapping and drug delivery. The presented solutions may also serve as a method for comparison to other solutions obtained by strictly numerical or asymptotic approaches. Copyright © 2011 Elsevier B.V. All rights reserved.

The eddy current probe array for Keda Torus eXperiment.

PubMed

Li, Zichao; Li, Hong; Tu, Cui; Hu, Jintong; You, Wei; Luo, Bing; Tan, Mingsheng; Adil, Yolbarsop; Wu, Yanqi; Shen, Biao; Xiao, Bingjia; Zhang, Ping; Mao, Wenzhe; Wang, Hai; Wen, Xiaohui; Zhou, Haiyang; Xie, Jinlin; Lan, Tao; Liu, Adi; Ding, Weixing; Xiao, Chijin; Liu, Wandong

2016-11-01

In a reversed field pinch device, the conductive shell is placed as close as possible to the plasma so as to balance the plasma during discharge. Plasma instabilities such as the resistive wall mode and certain tearing modes, which restrain the plasma high parameter operation, respond closely with conditions in the wall, in essence the eddy current present. Also, the effect of eddy currents induced by the external coils cannot be ignored when active control is applied to control instabilities. One diagnostic tool, an eddy current probe array, detects the eddy current in the composite shell. Magnetic probes measuring differences between the inner and outer magnetic fields enable estimates of the amplitude and angle of these eddy currents. Along with measurements of currents through the copper bolts connecting the poloidal shield copper shells, we can obtain the eddy currents over the entire shell. Magnetic field and eddy current resolutions approach 2 G and 6 A, respectively. Additionally, the vortex electric field can be obtained by eddy current probes. As the conductivity of the composite shell is high, the eddy current probe array is very sensitive to the electric field and has a resolution of 0.2 mV/cm. In a bench test experiment using a 1/4 vacuum vessel, measurements of the induced eddy currents are compared with simulation results based on a 3D electromagnetic model. The preliminary data of the eddy currents have been detected during discharges in a Keda Torus eXperiment device. The typical value of toroidal and poloidal eddy currents across the magnetic probe coverage rectangular area could reach 3.0 kA and 1.3 kA, respectively.

A detailed 2,000-year late holocene pollen record from lower Pahranagat Lake, Southern Nevada, USA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hemphill, M L; Wigand, P E

Preliminary analysis of 128 pollen samples and seven radiocarbon dates from a 5-meter long, 10-cm diameter sediment core retrieved from Lower Pahranagat Lake (elevation - 975 in), Lincoln County, Nevada, gives us a rare, continuous, record of vegetation change at an interval of every 14 years over the last 2,000 years. During this period increasing Pinus (pine) pollen values with respect to Juniperus Ouniper pollen values reflect the increasing dominance of pinyon in southern Nevada woodlands during the last 2,000 years. Today Pinus pollen values indicate that pinyon pine is more frequent in the southern Great Basin since the endmore » of the Neoglacial 2,000 years ago. During the same time frame, a general decrease in Poaceae (grass) pollen values with respect to Artemisia (sagebrush) pollen values reflect the general trend of increasing dominance of steppe and desert scrub species with respect to grasses. Variations in these two species reflect not only the generally more xeric nature of climate during the last 2,000 years, but also periods of summer shifted rainfall - 1,500 years ago that encouraged both a period of grass and pinyon expansion. The ratio of aquatic to littoral pollen types indicates generally deeper water conditions 2 to 1 ka and more variable, but predominately more marshy, conditions at the site during most of the last 1 ka. Investigation of ostracodes from the same record being conducted by Dr. R. Forester at the USGS corroborate the pollen record by evidencing shifts between open and closed hydrologic systems including lake, marsh and even stream habitats. Analysis of an additional 10 meters of core recovered in the summer of 1994 with a basal date of 5.6 ka promises to provide the best record of middle through late Holocene vegetation and climate history for southern Nevada.« less

Flowstones from SE Spain document a close relationship between North Atlantic temperature and precipitation in the Western Mediterranean between 7 and 112 ka

NASA Astrophysics Data System (ADS)

Budsky, Alexander; Scholz, Denis; Mertz-Kraus, Regina; Spötl, Christoph; Gibert, Luis; Jochum, Klaus Peter

2017-04-01

Here we present three flowstone records from Cueva Victoria, SE Spain, covering the period between Marine Isotope Stage (MIS) 5 and MIS 3, the Late Glacial and the Holocene. The flowstones were precisely dated by the MC-ICPMS 230Th/U-method. In addition, stable oxygen and carbon isotope ratios as well as trace element concentrations were determined at high resolution (centennial to decadal scale). Present-day climate of SE Spain is classified as semi-arid with dry summer months (<10 mm/month precipitation) and sparsely developed vegetation. A large dataset of 230Th/U ages on several flowstones from Cueva Victoria indicates preferential flowstone growth during warm phases (i.e., interglacials as well as warm interstadials), whereas flowstone growth is interrupted during glacial phases (Budsky et al., 2015). One of the drill cores shows more or less continuous flowstone growth between the Last Interglacial (MIS 5) and MIS 3 (112 - 46 ka). A flowstone from another part of the cave only records the time span from 86 to 50 ka including several growth interruptions. However, both flowstones cover the transition from MIS 4 to 3 including D/O events 17 to 13 at high resolution. Each D/O event is reflected by a remarkable decrease in both δ18O and δ13C values (both up to 3‰ ) accompanied by decreasing concentrations of Mg and Sr. In particular, longer D/O events, lasting several thousands of years (e.g., D/O 14, 19, 20 and 21), are well represented in the δ18O and δ13C records. The timing is in good agreement with the NGRIP ice core and sea-surface temperatures from the Iberian margin. δ18O values are around -3.5 ‰ and decrease to -5 to -6 ‰ during D/O events, while δ13C values are around -9 ‰ and decrease to -10 to -11 ‰ ) during D/O events. We interpret these changes as more humid conditions during D/O events, with elevated sea-surface temperatures in the North Atlantic and the Mediterranean Sea leading to increased moisture transport and precipitation on the SE Iberian Peninsula. As a consequence, vegetation density increased, which is reflected by the decrease in δ13C values and Mg and Sr concentrations and an increase in P content. In the Holocene, the flowstone grew continuously from the Bølling/Allerød to the mid-Holocene (7 ka). Stable isotopes record a trend of increasing temperatures with decreasing values towards the mid-Holocene (δ18O ≈ - 6.4 ‰ , δ13C ≈ -11 ‰ ). However, δ13C values record a significant excursion with elevated values (up to -3.8 ‰ ) during a period from 9.5 to 7.7 ka related to cold Bond-events in the North Atlantic, which is interpreted as a dry period in SE Spain. Budsky, A., Scholz, D., Gibert, L., Mertz-Kraus, R., 2015. 230Th/U-dating of the Cueva Victoria flowstone sequence: Preliminary results and paleoclimate implications, in: Gibert, L., Ferràndez-Canadell, C. (Eds.), Geology and Paleontology of Cueva Victoria. Mastia 11-13, Cartagena, pp. 101-109.

Everything you always wanted to know about black dye (but were afraid to ask): a DFT/TDDFT investigation.

PubMed

Fantacci, Simona; Lobello, Maria G; De Angelis, Filippo

2013-01-01

We report an exhaustive theoretical and computational investigation of the electronic, optical, redox and acid-base properties, along with the adsorption mode on TiO2, of Black Dye (BD), the prototypical panchromatic dye for solar cell applications. We investigated in detail the variation of the relevant dye properties as a function of the solution pH, corresponding to the stepwise deprotonation of the carboxylic groups. Our results reproduced the expected blue-shift of the optical absorption spectrum and the experimental trend of oxidation potentials by increasing pH, which turned both out to be in excellent agreement with experimental values. Also, our calculated excited state oxidation potential is in good agreement with available experimental data. We then looked at the pKa of the various deprotonation steps, finding lowest pKa values for the stepwise dissociation of three protons of 2.71, 3.69 and 5.20, in excellent agreement with experimental pKa values of 3 and 5, for two and one protons dissociation, respectively. We finally investigated the adsorption of BD on TiO2, finding the most stable adsorption to occur via two dissociated monodentate carboxylic groups. Inspection of the electronic structure and alignment of energy levels for N719 and BD revealed a reduced driving force for electron injection in the latter dye, which could possibly lead to energetically unfavorable electron transfer from the excited dye to the TiO2 conduction band. Our results may constitute a reference study for future investigations and optimization of BD-based dye-sensitized solar cells.

Magnetization and anisotropy of cobalt ferrite thin films

NASA Astrophysics Data System (ADS)

Eskandari, F.; Porter, S. B.; Venkatesan, M.; Kameli, P.; Rode, K.; Coey, J. M. D.

2017-12-01

The magnetization of thin films of cobalt ferrite frequently falls far below the bulk value of 455 kA m-1 , which corresponds to an inverse cation distribution in the spinel structure with a significant orbital moment of about 0.6 μB that is associated with the octahedrally coordinated Co2+ ions. The orbital moment is responsible for the magnetostriction and magnetocrystalline anisotropy and its sensitivity to imposed strain. We have systematically investigated the structure and magnetism of films produced by pulsed-laser deposition on different substrates (Ti O2 , MgO, MgA l2O4 , SrTi O3 , LSAT, LaAl O3 ) and as a function of temperature (500 -700 °C) and oxygen pressure (10-4-10 Pa ) . Magnetization at room-temperature ranges from 60 to 440 kA m-1 , and uniaxial substrate-induced anisotropy ranges from +220 kJ m-3 for films on deposited on MgO (100) to -2100 kJ m-3 for films deposited on MgA l2O4 (100), where the room-temperature anisotropy field reaches 14 T. No rearrangement of high-spin Fe3+ and Co2+ cations on tetrahedral and octahedral sites can reduce the magnetization below the bulk value, but a switch from Fe3+ and Co2+ to Fe2+ and low-spin Co3+ on octahedral sites will reduce the low-temperature magnetization to 120 kA m-1 , and a consequent reduction of Curie temperature can bring the room-temperature value to near zero. Possible reasons for the appearance of low-spin cobalt in the thin films are discussed.

The age of the meteorite recovery surfaces of Roosevelt County, New Mexico, USA

NASA Technical Reports Server (NTRS)

Zolensky, Michael E.; Rendell, Helen M.; Wilson, Ivan; Wells, Gordon L.

1992-01-01

We have obtained minimum age estimates for the sand units underlying the two largest meteorite deflation surfaces in Roosevelt County, New Mexico, USA, using thermoluminescence dating techniques. The dates obtained ranged from 53.5 (+/- 5.4) to 95.2 (+/- 9.5) ka, and must be considered lower limits for the terrestrial ages of the meteorites found within these specific deflation surfaces. These ages greatly exceed previous measurements from adjacent meteorite-producing deflation basins. We find that Roosevelt County meteorites are probably terrestrial contemporaries of the meteorites found at most accumulation zones in Antarctica. The apparent high meteorite accumulation rate reported for Roosevelt County by Zolensky et al. (1990) is incorrect, as it used an age of 16 ka for all Roosevelt County recovery surfaces. We conclude that the extreme variability of terrestrial ages of the Roosevelt County deflation surfaces effectively precludes their use for calculations of the meteorite accumulation rate at the Earth's surface.

Volcanic evolution of central Basse-Terre Island revisited on the basis of new geochronology and geomorphology data

NASA Astrophysics Data System (ADS)

Ricci, J.; Quidelleur, X.; Lahitte, P.

2015-10-01

Twenty-six new and seven previous K-Ar ages obtained on groundmass separates for samples from the Axial Chain massif (Guadeloupe, F.W.I.), associated with geomorphological investigations, allow us to propose a new model of the volcanic evolution of the central part of Basse-Terre Island. The Axial Chain is composed of four edifices, Moustique, Matéliane, Capesterre, and Icaque mounts, showing coeval activity from 681 ± 12 to 509 ± 10 ka, which contradicts a previous hypothesis that flank collapse affected them successively. Our geomorphological reconstruction shows that the Axial Chain can be considered as a single large volcano, named the Southern Axial Chain volcano (SCA), rather than a succession of several smaller volcanoes. It raises questions regarding the formation of a large depression within the SCA volcano, prior to the construction of the Sans-Toucher volcano between 451 ± 13 and 412 ± 8 ka. Given presently available evidence, a slump affecting the western part of the SCA volcano is the most probable scenario to reconcile the complete age dataset and the present-day morphology of central Basse-Terre. Finally, our study shows that the SCA volcano had a post-activity volume of 90 km3, implying a construction rate of 0.5 km3/kyr. This value strongly constrains interpretations of magma generation processes throughout the Lesser Antilles arc.

The Molecular Structure of a Phosphatidylserine Bilayer Determined by Scattering and Molecular Dynamics Simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Jianjun; Cheng, Xiaolin; Monticelli, Luca

2014-01-01

Phosphatidylserine (PS) lipids play essential roles in biological processes, including enzyme activation and apoptosis. We report on the molecular structure and atomic scale interactions of a fluid bilayer composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylserine (POPS). A scattering density profile model, aided by molecular dynamics (MD) simulations, was developed to jointly refine different contrast small-angle neutron and X-ray scattering data, which yielded a lipid area of 62.7 A2 at 25 C. MD simulations with POPS lipid area constrained at different values were also performed using all-atom and aliphatic united-atom models. The optimal simulated bilayer was obtained using a model-free comparison approach. Examination of themore » simulated bilayer, which agrees best with the experimental scattering data, reveals a preferential interaction between Na+ ions and the terminal serine and phosphate moieties. Long-range inter-lipid interactions were identified, primarily between the positively charged ammonium, and the negatively charged carboxylic and phosphate oxygens. The area compressibility modulus KA of the POPS bilayer was derived by quantifying lipid area as a function of surface tension from area-constrained MD simulations. It was found that POPS bilayers possess a much larger KA than that of neutral phosphatidylcholine lipid bilayers. We propose that the unique molecular features of POPS bilayers may play an important role in certain physiological functions.« less

Mechanistic and Structural Analyses of the Role of His67 in the Yeast Polyamine Oxidase Fms1†

PubMed Central

Adachi, Mariya S.; Taylor, Alexander B.; Hart, P. John; Fitzpatrick, Paul F.

2012-01-01

The flavoprotein oxidase Fms1 from Saccharomyces cerevisiae catalyzes the oxidation of spermine and N1-acetylspermine to spermidine and 3-aminopropanal or N-acetyl-3-aminopropanal. Within the active site of Fms1, His67 is positioned to form hydrogen bonds with the polyamine substrate. This residue is also conserved in other polyamine oxidases. The catalytic properties of H67Q, H67N, and H67A Fms1 have been characterized to evaluate the role of this residue in catalysis. With both spermine and N1-acetylspermine as the amine substrate, the value of the first-order rate constant for flavin reduction decreases 2–3 orders of magnitude, with the H67Q mutation having the smallest effect and H67N the largest. The kcat/KO2 value changes very little upon mutation with N1-acetylspermine as the amine substrate and decreases only an order of magnitude with spermine. The kcat/KM-pH profiles with N1-acetylspermine are bell-shaped for all the mutants; the similarity to the profile of the wild-type enzyme rules out His67 as being responsible for either of the pKa values. The pH profiles for the rate constant for flavin reduction for all the mutant enzymes similarly show the same pKa as wild-type Fms1, about ~7.4; this pKa is assigned to the substrate N4. The kcat/KO2-pH profiles for wild-type Fms1 and the H67A enzyme both show a pKa of about ~6.9; this suggests His67 is not responsible for this pH behaviour. With the H67Q, H67N, and H67A enzymes the kcat value decreases when a single residue is protonated, as is the case with the wild-type enzyme. The structure of H67Q Fms1 has been determined at a resolution of 2.4 Å. The structure shows that the mutation disrupts a hydrogen bond network in the active site, suggesting that His67 is important both for direct interactions with the substrate and to maintain the overall active site structure. PMID:22642831

Productivity and sedimentary δ15N variability for the last 17,000 years along the northern Gulf of Alaska continental slope

USGS Publications Warehouse

Addison, Jason A.; Finney, Bruce P.; Dean, Walter E.; Davies, Maureen H.; Mix, Alan C.; Jaeger, John M.

2012-01-01

Biogenic opal, organic carbon, organic matter stable isotope, and trace metal data from a well-dated, high-resolution jumbo piston core (EW0408–85JC; 59° 33.3′N, 144° 9.21′W, 682 m water depth) recovered from the northern Gulf of Alaska continental slope reveal changes in productivity and nutrient utilization over the last 17,000 years. Maximum values of opal concentration (∼10%) occur during the deglacial Bølling-Allerød (B-A) interval and earliest Holocene (11.2 to 10.8 cal ka BP), moderate values (∼6%) occur during the Younger Dryas (13.0 to 11.2 cal ka BP) and Holocene, and minimum values (∼3.5%) occur during the Late Glacial Interval (LGI). When converted to opal mass accumulation rates, the highest values (∼5000 g cm−2 kyr−1) occur during the LGI prior to 16.7 cal ka BP, which points to a strong influence by LGI glacimarine sedimentation regimes. Similar patterns are also observed in total organic carbon and cadmium paleoproductivity proxies. Mid-Holocene peaks in the terrestrial organic matter fraction at 5.5, 4.7, 3.5, and 1.2 cal ka BP indicate periods of enhanced delivery of glaciomarine sediments by the Alaska Coastal Current. The B-A and earliest Holocene intervals are laminated, and enrichments of redox-sensitive elements suggest dysoxic-to-anoxic conditions in the water column. The laminations are also associated with mildly enriched sedimentary δ15N ratios, indicating a link between productivity, nitrogen cycle dynamics, and sedimentary anoxia. After applying a correction for terrestrial δ15N contributions based on end-member mixing models of terrestrial and marine organic matter, the resulting B-A marine δ15N (6.3 ± 0.4 ‰) ratios are consistent with either mild denitrification, or increased nitrate utilization. These findings can be explained by increased micronutrient (Fe) availability during episodes of rapid rising sea level that released iron from the previously subaerial coastal plain; iron input from enhanced terrestrial runoff; and/or the intermittent presence of seasonal sea ice resulting from altered ocean/atmospheric circulation during the B-A in the Gulf of Alaska.

Productivity and sedimentary δ15N variability for the last 17,000 years along the northern Gulf of Alaska continental slope

USGS Publications Warehouse

Addison, Jason A.; Finney, Bruce P.; Dean, Walter E.; Davies, Maureen H.; Mix, Alan C.; Stoner, Joseph S.; Jaeger, John M.

2012-01-01

Biogenic opal, organic carbon, organic matter stable isotope, and trace metal data from a well-dated, high-resolution jumbo piston core (EW0408–85JC; 59° 33.3′N, 144° 9.21′W, 682 m water depth) recovered from the northern Gulf of Alaska continental slope reveal changes in productivity and nutrient utilization over the last 17,000 years. Maximum values of opal concentration (∼10%) occur during the deglacial Bølling-Allerød (B-A) interval and earliest Holocene (11.2 to 10.8 cal ka BP), moderate values (∼6%) occur during the Younger Dryas (13.0 to 11.2 cal ka BP) and Holocene, and minimum values (∼3.5%) occur during the Late Glacial Interval (LGI). When converted to opal mass accumulation rates, the highest values (∼5000 g cm−2 kyr−1) occur during the LGI prior to 16.7 cal ka BP, which points to a strong influence by LGI glacimarine sedimentation regimes. Similar patterns are also observed in total organic carbon and cadmium paleoproductivity proxies. Mid-Holocene peaks in the terrestrial organic matter fraction at 5.5, 4.7, 3.5, and 1.2 cal ka BP indicate periods of enhanced delivery of glaciomarine sediments by the Alaska Coastal Current. The B-A and earliest Holocene intervals are laminated, and enrichments of redox-sensitive elements suggest dysoxic-to-anoxic conditions in the water column. The laminations are also associated with mildly enriched sedimentary δ15N ratios, indicating a link between productivity, nitrogen cycle dynamics, and sedimentary anoxia. After applying a correction for terrestrial δ15N contributions based on end-member mixing models of terrestrial and marine organic matter, the resulting B-A marine δ15N (6.3 ± 0.4 ‰) ratios are consistent with either mild denitrification, or increased nitrate utilization. These findings can be explained by increased micronutrient (Fe) availability during episodes of rapid rising sea level that released iron from the previously subaerial coastal plain; iron input from enhanced terrestrial runoff; and/or the intermittent presence of seasonal sea ice resulting from altered ocean/atmospheric circulation during the B-A in the Gulf of Alaska.

Younger-Dryas cooling and sea-ice feedbacks were prominent features of the Pleistocene-Holocene transition in Arctic Alaska

USGS Publications Warehouse

Gaglioti, Benjamin V.; Mann, Daniel H.; Wooller, Matthew J.; Jones, Benjamin M.; Wiles, Gregory C.; Groves, Pamela; Kunz, Michael L.; Baughman, Carson; Reanier, Richard E.

2017-01-01

Declining sea-ice extent is currently amplifying climate warming in the Arctic. Instrumental records at high latitudes are too short-term to provide sufficient historical context for these trends, so paleoclimate archives are needed to better understand the functioning of the sea ice-albedo feedback. Here we use the oxygen isotope values of wood cellulose in living and sub-fossil willow shrubs (δ18Owc) (Salix spp.) that have been radiocarbon-dated (14C) to produce a multi-millennial record of climatic change on Alaska's North Slope during the Pleistocene-Holocene transition (13,500–7500 calibrated 14C years before present; 13.5–7.5 ka). We first analyzed the spatial and temporal patterns of δ18Owc in living willows growing at upland sites and found that over the last 30 years δ18Owc values in individual growth rings correlate with local summer temperature and inter-annual variations in summer sea-ice extent. Deglacial δ18Owcvalues from 145 samples of subfossil willows clearly record the Allerød warm period (∼13.2 ka), the Younger Dryas cold period (12.9–11.7 ka), and the Holocene Thermal Maximum (11.7–9.0 ka). The magnitudes of isotopic changes over these rapid climate oscillations were ∼4.5‰, which is about 60% of the differences in δ18Owc between those willows growing during the last glacial period and today. Modeling of isotope-precipitation relationships based on Rayleigh distillation processes suggests that during the Younger Dryas these large shifts in δ18Owc values were caused by interactions between local temperature and changes in evaporative moisture sources, the latter controlled by seaice extent in the Arctic Ocean and Bering Sea. Based on these results and on the effects that sea-ice have on climate today, we infer that ocean-derived feedbacks amplified temperature changes and enhanced precipitation in coastal regions of Arctic Alaska during warm times in the past. Today, isotope values in willows on the North Slope of Alaska are similar to those growing during the warmest times of the Pleistocene-Holocene transition, which were times of widespread permafrost thaw and striking ecological changes.

Towards symbiosis in knowledge representation and natural language processing for structuring clinical practice guidelines.

PubMed

Weng, Chunhua; Payne, Philip R O; Velez, Mark; Johnson, Stephen B; Bakken, Suzanne

2014-01-01

The successful adoption by clinicians of evidence-based clinical practice guidelines (CPGs) contained in clinical information systems requires efficient translation of free-text guidelines into computable formats. Natural language processing (NLP) has the potential to improve the efficiency of such translation. However, it is laborious to develop NLP to structure free-text CPGs using existing formal knowledge representations (KR). In response to this challenge, this vision paper discusses the value and feasibility of supporting symbiosis in text-based knowledge acquisition (KA) and KR. We compare two ontologies: (1) an ontology manually created by domain experts for CPG eligibility criteria and (2) an upper-level ontology derived from a semantic pattern-based approach for automatic KA from CPG eligibility criteria text. Then we discuss the strengths and limitations of interweaving KA and NLP for KR purposes and important considerations for achieving the symbiosis of KR and NLP for structuring CPGs to achieve evidence-based clinical practice.

Intensified summer monsoon and the urbanization of Indus Civilization in northwest India.

PubMed

Dixit, Yama; Hodell, David A; Giesche, Alena; Tandon, Sampat K; Gázquez, Fernando; Saini, Hari S; Skinner, Luke C; Mujtaba, Syed A I; Pawar, Vikas; Singh, Ravindra N; Petrie, Cameron A

2018-03-09

Today the desert margins of northwest India are dry and unable to support large populations, but were densely occupied by the populations of the Indus Civilization during the middle to late Holocene. The hydroclimatic conditions under which Indus urbanization took place, which was marked by a period of expanded settlement into the Thar Desert margins, remains poorly understood. We measured the isotopic values (δ 18 O and δD) of gypsum hydration water in paleolake Karsandi sediments in northern Rajasthan to infer past changes in lake hydrology, which is sensitive to changing amounts of precipitation and evaporation. Our record reveals that relatively wet conditions prevailed at the northern edge of Rajasthan from ~5.1 ± 0.2 ka BP, during the beginning of the agricultural-based Early Harappan phase of the Indus Civilization. Monsoon rainfall intensified further between 5.0 and 4.4 ka BP, during the period when Indus urban centres developed in the western Thar Desert margin and on the plains of Haryana to its north. Drier conditions set in sometime after 4.4 ka BP, and by ~3.9 ka BP an eastward shift of populations had occurred. Our findings provide evidence that climate change was associated with both the expansion and contraction of Indus urbanism along the desert margin in northwest India.

A diatom record of climate and hydrology for the past 200 KA from Owens Lake, California with comparison to other Breat Basin records

USGS Publications Warehouse

Bradbury, J.P.

1997-01-01

Diatoms from lake sediments beneath Owens Lake playa, Inyo County, California, document a nearly continuous paleolimnological record of climate and hydrologic change since the penultimate glacial-interglacial cycle based on a chronology established by radiocarbon, tephrochronology, and paleomagnetic control. Freshwater planktic diatoms (especially species of Stephanodiscus), plagioclase feldspar-rich sediments with high magnetic susceptibility, and Juniperus-type pollen characterized the penultimate glaciation at Owens Lake. Saline diatoms dominated in the following interglacial period, and there are several episodes during which freshwater planktic diatoms became abundant between 100 and 50 ka that may represent interstadial climatic conditions. Saline diatoms fell to low values after 50 ka, but warm-season Aulacoseira species indicate episodes of significant summer precipitation in the hydrologic balance of Owens Lake prior to the last glacial maximum. By 25 ka, glacial environments were again characterized by abundant Juniperus, plagioclase feldspar, and Stephanodiscus species. Generally and Holocene climates were recorded in Owens Lake by short-term fluctuations of saline and freshwater diatoms, desiccation, and oolitic sediments barren of diatoms. Comparison to paleoclimate records both north and south of Owens Lake suggest a southerly displacement of storm tracks originating from the Aleutian Low during glacial episodes.

Humans permanently occupied the Andean highlands by at least 7 ka

PubMed Central

Stefanescu, Ioana C.; Garcia-Putnam, Alexander; Aldenderfer, Mark S.; Clementz, Mark T.; Murphy, Melissa S.; Llave, Carlos Viviano; Watson, James T.

2017-01-01

High-elevation environments above 2500 metres above sea level (m.a.s.l.) were among the planet's last frontiers of human colonization. Research on the speed and tempo of this colonization process is active and holds implications for understanding rates of genetic, physiological and cultural adaptation in our species. Permanent occupation of high-elevation environments in the Andes Mountains of South America tentatively began with hunter–gatherers around 9 ka according to current archaeological estimates, though the timing is currently debated. Recent observations on the archaeological site of Soro Mik'aya Patjxa (8.0–6.5 ka), located at 3800 m.a.s.l. in the Andean Altiplano, offer an opportunity to independently test hypotheses for early permanent use of the region. This study observes low oxygen (δ18O) and high carbon (δ13C) isotope values in human bone, long travel distances to low-elevation zones, variable age and sex structure in the human population and an absence of non-local lithic materials. These independent lines of evidence converge to support a model of permanent occupation of high elevations and refute logistical and seasonal use models. The results constitute the strongest empirical support to date for permanent human occupation of the Andean highlands by hunter–gatherers before 7 ka. PMID:28680685

Structure and interactions of fully hydrated dioleoylphosphatidylcholine bilayers.

PubMed Central

Tristram-Nagle, S; Petrache, H I; Nagle, J F

1998-01-01

This study focuses on dioleoylphosphatidylcholine (DOPC) bilayers near full hydration. Volumetric data and high-resolution synchrotron x-ray data are used in a method that compares DOPC with well determined gel phase dipalmitoylphosphatidylcholine (DPPC). The key structural quantity obtained is fully hydrated area/lipid A0 = 72.2 +/- 1.1 A2 at 30 degrees C, from which other quantities such as thickness of the bilayer are obtained. Data for samples over osmotic pressures from 0 to 56 atmospheres give an estimate for the area compressibility of KA = 188 dyn/cm. Obtaining the continuous scattering transform and electron density profiles requires correction for liquid crystal fluctuations. Quantitation of these fluctuations opens an experimental window on the fluctuation pressure, the primary repulsive interaction near full hydration. The fluctuation pressure decays exponentially with water spacing, in agreement with analytical results for soft confinement. However, the ratio of decay length lambda(fl) = 5.8 A to hydration pressure decay length lambda = 2.2 A is significantly larger than the value of 2 predicted by analytical theory and close to the ratio obtained in recent simulations. We also obtain the traditional osmotic pressure versus water spacing data. Our analysis of these data shows that estimates of the Hamaker parameter H and the bending modulus Kc are strongly coupled. PMID:9675192

Timing of maximum glacial extent and deglaciation from HualcaHualca volcano (southern Peru), obtained with cosmogenic 36Cl.

NASA Astrophysics Data System (ADS)

Alcalá, Jesus; Palacios, David; Vazquez, Lorenzo; Juan Zamorano, Jose

2015-04-01

Andean glacial deposits are key records of climate fluctuations in the southern hemisphere. During the last decades, in situ cosmogenic nuclides have provided fresh and significant dates to determine past glacier behavior in this region. But still there are many important discrepancies such as the impact of Last Glacial Maximum or the influence of Late Glacial climatic events on glacial mass balances. Furthermore, glacial chronologies from many sites are still missing, such as HualcaHualca (15° 43' S; 71° 52' W; 6,025 masl), a high volcano of the Peruvian Andes located 70 km northwest of Arequipa. The goal of this study is to establish the age of the Maximum Glacier Extent (MGE) and deglaciation at HualcaHualca volcano. To achieve this objetive, we focused in four valleys (Huayuray, Pujro Huayjo, Mollebaya and Mucurca) characterized by a well-preserved sequence of moraines and roches moutonnées. The method is based on geomorphological analysis supported by cosmogenic 36Cl surface exposure dating. 36Cl ages have been estimated with the CHLOE calculator and were compared with other central Andean glacial chronologies as well as paleoclimatological proxies. In Huayuray valley, exposure ages indicates that MGE occurred ~ 18 - 16 ka. Later, the ice mass gradually retreated but this process was interrupted by at least two readvances; the last one has been dated at ~ 12 ka. In the other hand, 36Cl result reflects a MGE age of ~ 13 ka in Mollebaya valley. Also, two samples obtained in Pujro-Huayjo and Mucurca valleys associated with MGE have an exposure age of 10-9 ka, but likely are moraine boulders affected by exhumation or erosion processes. Deglaciation in HualcaHualca volcano began abruptly ~ 11.5 ka ago according to a 36Cl age from a polished and striated bedrock in Pujro Huayjo valley, presumably as a result of reduced precipitation as well as a global increase of temperatures. The glacier evolution at HualcaHualca volcano presents a high correlation with precipitation cycles of the Altiplano (Tauca / Coipasa phases) and Heinrich 1 / Younger Dryas cold climatic events. Research funded by Cryocrisis project (CGL2012-35858), Government of Spain

Cosmogenic exposure-age chronologies of Pinedale and Bull Lake glaciations in greater Yellowstone and the Teton Range, USA

USGS Publications Warehouse

Licciardi, J.M.; Pierce, K.L.

2008-01-01

We have obtained 69 new cosmogenic 10Be surface exposure ages from boulders on moraines deposited by glaciers of the greater Yellowstone glacial system and Teton Range during the middle and late Pleistocene. These new data, combined with 43 previously obtained 3He and 10Be ages from deposits of the northern Yellowstone outlet glacier, establish a high-resolution chronology for the Yellowstone-Teton mountain glacier complexes. Boulders deposited at the southern limit of the penultimate ice advance of the Yellowstone glacial system yield a mean age of 136??13 10Be ka and oldest ages of ???151-157 10Be ka. These ages support a correlation with the Bull Lake of West Yellowstone, with the type Bull Lake of the Wind River Range, and with Marine Isotope Stage (MIS) 6. End moraines marking the maximum Pinedale positions of outlet glaciers around the periphery of the Yellowstone glacial system range in age from 18.8??0.9 to 16.5??1.4 10Be ka, and possibly as young as 14.6??0.7 10Be ka, suggesting differences in response times of the various ice-cap source regions. Moreover, all dated Pinedale terminal moraines in the greater Yellowstone glacial system post-date the Pinedale maximum in the Wind River Range by ???4-6 kyr, indicating a significant phase relationship between glacial maxima in these adjacent ranges. Boulders on the outermost set and an inner set of Pinedale end moraines enclosing Jenny Lake on the eastern Teton front yield mean ages of 14.6??0.7 and 13.5??1.1 10Be ka, respectively. The outer Jenny Lake moraines are partially buried by outwash from ice on the Yellowstone Plateau, hence their age indicates a major standstill of an expanded valley glacier in the Teton Range prior to the Younger Dryas, followed closely by deglaciation of the Yellowstone Plateau. These new glacial chronologies are indicative of spatially variable regional climate forcing and temporally complex patterns of glacier responses in this region of the Rocky Mountains during the Pleistocene. ?? 2008 Elsevier Ltd. All rights reserved.

Slotted Polyimide-Aerogel-Filled-Waveguide Arrays

NASA Technical Reports Server (NTRS)

Rodriguez-Solis, Rafael A.; Pacheco, Hector L.; Miranda, Felix A.; Meador, Mary Ann B.

2013-01-01

Polyimide aerogels were considered to serve as a filling for millimeter-wave waveguides. While these waveguides present a slightly higher loss than hollow waveguides, they have less losses than Duroid substrate integrated waveguides (less than 0.15 dB at Ka-band, in a 20 mm section), and exhibit an order of magnitude of mass reduction when compared to commercial waveguides. A Ka-band slotted aerogel-filled-waveguide array was designed, which provided the same gain (9 dBi) as its standard waveguide counterpart, and a slotted aerogel-filled-waveguide array using folded-slots was designed for comparison, obtaining a gain of 9 dB and a bandwidth of 590 MHz.

An in vitro study of enhanced H+ diffusion by urease action on urea. Implications for Helicobacter pylori-associated peptic ulceration.

PubMed

Desai, M A; Vadgama, P M

1993-10-01

The in vitro effect of urea and hydrolysis of urea by urease on mucus H+ permeability is reported here. The effective DHCl values indicate a strong pH dependence for H+ diffusion in both water and mucus layers, with no apparent trend at concentrations between 1 and 50 mM urea. However, the estimated DHCl at near-neutral and alkaline pH are 4- to 10-fold lower through mucus than through aqueous films. Moreover, the pKa values of HCO3- and NH3 (generated by urease action on urea) had a profound effect on measured DHCl. These in vitro studies suggest that a high local concentration of NH3 and HCO3- within the mucus layer, generated by the action of Helicobacter pylori urease on endogenous intragastric urea, could greatly accelerate proton flux to the surface epithelium by operation of a buffer shuttle. This results in enhanced H+ permeability, particularly at pKa values of HCO3- and NH3, and in extreme circumstances it may result in gastric ulcer formation.

Glacial and volcanic evolution on Nevado Coropuna (Tropical Andes) based on cosmogenic 36Cl surface exposure dating

NASA Astrophysics Data System (ADS)

Úbeda, J.; Palacios, D.; Vázquez-Selém, L.

2012-04-01

We have reconstructed the evolution of the paleo-glaciers of the volcanic complex Nevado Coropuna (15°S, 72°W; 6377 m asl) through the interpretation and dating of geomorphological evidences. Surface exposure dating (SED) based on the accumulation of 36Cl on the surface of moraine boulders, polished bedrock and lava flows allowed: 1) to confirm that the presence of ice masses in the region dates back to >80ka; 2) to produce chronologies of glacial and volcanic phases for the last ~21 ka; and 3) to obtain evidences of the reactivation of volcanic activity after the Last Glacial Maximum. Bromley et al. (2009) presented 3He SED ages of 21 ka for moraine boulders on the Mapa Mayo valley, to the North of Nevado Coropuna. Our 36Cl SED SED for moraine boulders from the valleys on the NE sector of the volcanic complex suggest a maximum initial advance between 20 and 16 ka, followed by another expansion of similar extent at 12-11 ka. On the Southern slope of Nevado Coropuna, the 36Cl ages show a maximum initial advance that reaches to the level of the Altiplano at 14 ka, and a re-advance at ~10-9 ka BP. Other data show minor re-advances at 9 ka on the Northern slope and at 6 ka to the South of the volcanic complex. These minor positive pulses interrupted a fast deglaciation process during the Holocene as shown by two series of 36Cl SED from polished rock surfaces on successively higher altitudes along the valleys of rivers Blanco and Cospanja, to the SW and SE. Despite the global warming occuring since 20 ka, deduced from the record of sea surface paleo-temperature of the Galapago Islands (Lea et al, 2006), the evolution of the fresh-water plankton from Lake Titicaca (Fritz et al, 2007) is consistent with sustained glacial conditions until 10-9 ka as suggested by the present work. Exposure ages of three lava flows indicate a reactivation of the magmatic system as the paleo-glaciers abandonned the slopes. The eruptive activity migrated from the West, where we found a lava flow of 6 ka, to the East, where we dated two units similar to the previous one at 2 and <1ka. Bromley, G.R. et al., 2009. Relative timing of last glacial maximum and late-glacial events in the central tropical Andes. Quaternary Science Reviews, 1-13. Bromley, R.M. et al., 2011. Glacier fluctuations in the southern Peruvian Andes during the late-glacial period, constrained with cosmogenic 3He. Journal of Quaternary Science, 26 (1): 37-43. Fritz, S.C. et al., 2007. Lake Titicaca 370KYr LT01-2B Sediment Database. Lake Titicaca 370KYr LT01-2B Sediment Data. IGBP PAGES/World Data Center-A for Paleoclimatology Data Contribution Series # 92-008. NOAA/NGDC Paleoclimatology Program. Boulder (EEUU). Lea, D.W. et al., 2006. Galápagos TR163-22 Foraminiferal ^18O and Mg/Ca Data and SST Reconstruction. IGBP PAGES/World Data Center for Paleoclimatology Data Contribution Series # 2006-090. NOAA/NCDC Paleoclimatology Program, Boulder (EEUU). Research funded by CGL2009-7343 project, Government of Spain.

Paleoenvironmental events during the last 13,000 years in the central Red Sea as recorded by pteropoda

NASA Astrophysics Data System (ADS)

Almogi-Labin, Ahuva; Hemleben, Christoph; Meischner, Dieter; Erlenkeuser, Helmut

1991-02-01

A high-resolution record was obtained by investigating a sedimentary sequence from two cores taken in the central Red Sea (R/V Meteor cruise 5, leg 2). The numerical variations between nonmigratory and migratory pteropods and their stable isotopic record were studied together with variations in the carbonate and total organic carbon content in order to estimate changes in the structure of the water column during the last 13 kyr. The results indicate the existence of a highly stratified water column during deglaciation and early Holocene (13-8.5 ka). During this period the depth of the mixed layer varied between less than 50-100 m at most, and productivity was markedly reduced in comparison to the recent situation. The intermediate and deep water were constantly highly depleted in oxygen. A pronounced Younger Dryas event was recognized at 10.4 ka which coincides with an arid phase on the border land. The oxygenation of the intermediate water improved remarkably after 7.5 ka and peaked during the period between 4.6 and 2.0 ka. During this period the mixed layer reached its present depth and the productivity which was maximal during middle Holocene attained present level during the last 4.6 kyr.

Full Ka Band Waveguide-to-Microstrip Inline Transition Design

NASA Astrophysics Data System (ADS)

Li, Jianxing; Li, Lei; Qiao, Yu; Chen, Juan; Chen, Jianzhong; Zhang, Anxue

2018-05-01

In this paper, a compact and broadband inline waveguide-to-microstrip transition is proposed to cover the full Ka band. The transition can be segmented from the electric point of view into three building blocks, comprising a microstrip line to rectangular coaxial line, a wedged rectangular coaxial line to ridged waveguide, and a final tapered ridged waveguide impedance transformer to standard waveguide. Both good electrical performance and simple modular assembly without any soldering have been simultaneously obtained. The validation of the design concept has been conducted by numerical simulations and experimental measurements. The experimental results of a fabricated back-to-back transition prototype coincide with the simulated results. It shows that the proposed transition achieves good return loss of lower than 15.5 dB and low insertion loss with a fluctuation between 0.23 to 0.60 dB across the entire Ka band. Details of design considerations and operation mechanism as well as simulation and measurement results are presented.

Authigenic carbonates from newly discovered active cold seeps on the northwestern slope of the South China Sea: Constraints on fluid sources, formation environments, and seepage dynamics

NASA Astrophysics Data System (ADS)

Liang, Qianyong; Hu, Yu; Feng, Dong; Peckmann, Jörn; Chen, Linying; Yang, Shengxiong; Liang, Jinqiang; Tao, Jun; Chen, Duofu

2017-06-01

Authigenic carbonates recovered from two newly discovered active cold seeps on the northwestern slope of the South China Sea have been studied using petrography, mineralogy, stable carbon and oxygen isotopic, as well as trace element compositions, together with AMS 14C ages of shells of seep-dwelling bivalves to unravel fluid sources, formation conditions, and seepage dynamics. The two seeps (ROV1 and ROV2), referred to as 'Haima seeps' herein, are approximately 7 kilometers apart, and are typified by abundant carbonate rocks represented bycrusts and nodules. Aragonite and high-Mg calcite are the main carbonate minerals. Based on low δ13Ccarbonate values ranging from -43.0‰ to -27.5‰ (V-PDB) methane is apparently the predominant carbon source of seep carbonates. The corresponding δ18O values, varying from 2.5‰ to 5.8‰ (V-PDB), mostly are higher than calculated values representing precipitation in equilibrium with seawater (2.5‰ to 3.8‰), which probably reflects past destabilization of locally abundant gas hydrates. In addition, we found that carbonates with bivalve shells are generally aragonite-dominated, and bear no barium enrichment but uranium enrichments, reflecting shallow formation depths close to the seafloor. In contrast, carbonate crusts without bivalve shells and nodules contain more calcite, and are characterized by major molybdenum enrichment and different degrees of barium enrichment, agreeing with precipitation at greater depth under strictly anoxic conditions. AMS 14C ages suggest that a major episode of carbonate precipitation occurred between 6.1 ka and 5.1 ka BP at the Haima seeps, followed by a possibly subordinate episode from approximately 3.9 ka to 2.9 ka BP. The common occurrence of dead bivalves at both sites indicates that chemosynthesis-based communities flourished to a greater extent in the past, probably reflecting a decline of seepage activity in recent times. Overall, these results confirm that authigenic carbonates from gas hydrate-bearing areas can provide insight into long-term seepage dynamics and the genesis and fate of marine gas hydrate reservoirs.

ESR and mass-spectrometric uranium-series dating studies of a mammoth tooth from stanton harcourt, Oxfordshire, England

NASA Astrophysics Data System (ADS)

Zhou, L. P.; McDermott, F.; Rhodes, E. J.; Marseglia, E. A.; Mellars, P. A.

The age of the Channel Deposits at Stanton Harcourt, Oxfordshire, England, has been a topic of debate with important implications for British Pleistocene stratigraphy. Recent excavations led by K. Scott reveal ample evidence for ancient environmental conditions characteristic of an interglacial. However, the question remains on the assignment of its age. At present it is thought to represent an interglacial corresponding to either marine OI Stage 7 or 5e. In an attempt to constrain the chronology of the site, and to assess the techniques' reliability, we have made electron spin resonance (ESR) measurements on enamel and mass-spectrometric U-series measurements on both enamel and dentine from a mammoth tooth buried in the Channel Deposits at Stanton Harcourt. Four dentine samples gave U-series dates between 65.4±0.4 and 146.5±1.0 ka and two enamel samples between these dentine layers were dated to 53.3±0.2 and 61.1±0.6 ka. The corresponding ESR age estimates for the enamel samples are 59±6 and 62±4 ka (early U-uptake, EU) and 95±11 and 98±7 ka (linear U-uptake, LU). The recent U-uptake (RU) dates are 245±38 and 238±31 ka, but in light of the U-series data we would not expect these to represent realistic age estimates. Similar ESR results were obtained from two other adjacent enamel samples. The effect of the large size of the mammoth tooth on the external gamma dose, and the internal gamma contribution from the high U content of the dentine, are considered. While the recent uptake ESR dates appear to coincide with OI Stage 7, all the early and linear uptake ESR and mass-spectrometric U-series dates are younger than the expected age estimation based on recent geological interpretation and amino acid racemisation measurements (>200 ka) and optical dating studies (200-450 ka). Possible causes of the unexpected dating results are discussed. We conclude that our mass-spectrometric U-series and EU and LU ESR measurements represent minimum age estimates for the tooth analysed. Our results seem to suggest that the tooth and hence the Channel Deposits are at least 147 ka in age. i.e. predating the last interglacial.

Acidicapsa borealis gen. nov., sp. nov. and Acidicapsa ligni sp. nov., subdivision 1 Acidobacteria from Sphagnum peat and decaying wood.

PubMed

Kulichevskaya, Irina S; Kostina, Lilia A; Valásková, Vendula; Rijpstra, W Irene C; Damsté, Jaap S Sinninghe; de Boer, Wietse; Dedysh, Svetlana N

2012-07-01

Two strains of subdivision 1 Acidobacteria, a pink-pigmented bacterium KA1(T) and a colourless isolate WH120(T), were obtained from acidic Sphagnum peat and wood under decay by the white-rot fungus Hyploma fasciculare, respectively. Cells of these isolates were Gram-negative-staining, non-motile, short rods, which were covered by large polysaccharide capsules and occurred singly, in pairs, or in short chains. Strains KA1(T) and WH120(T) were strictly aerobic mesophiles that grew between 10 and 33 °C, with an optimum at 22-28 °C. Both isolates developed under acidic conditions, but strain WH120(T) was more acidophilic (pH growth range 3.5-6.4; optimum, 4.0-4.5) than strain KA1(T) (pH growth range 3.5-7.3; optimum , 5.0-5.5). The preferred growth substrates were sugars. In addition, the wood-derived isolate WH120(T) grew on oxalate, lactate and xylan, while the peat-inhabiting acidobacterium strain KA1(T) utilized galacturonate, glucuronate and pectin. The major fatty acids were iso-C(15:0) and iso-C(17:1)ω8c; the cells also contained significant amounts of 13,16-dimethyl octacosanedioic acid. The quinone was MK-8. The DNA G+C contents of strains KA1(T) and WH120(T) were 54.1 and 51.7 mol%, respectively. Strains KA1(T) and WH120(T) displayed 97.8% 16S rRNA gene sequence similarity to each other. The closest recognized relatives were Acidobacterium capsulatum and Telmatobacter bradus (93.4-94.3% 16S rRNA gene sequence similarity). These species differed from strains KA1(T) and WH120(T) by their ability to grow under anoxic conditions, the absence of capsules, presence of cell motility and differing fatty acid composition. Based on these differences, the two new isolates are proposed as representing a novel genus, Acidicapsa gen. nov., and two novel species. Acidicapsa borealis gen. nov., sp. nov. is the type species for the new genus with strain KA1(T) (=DSM 23886(T)=LMG 25897(T)=VKM B-2678(T)) as the type strain. The name Acidicapsa ligni sp. nov. is proposed for strain WH120(T) (=LMG 26244(T)=VKM B-2677(T)=NCCB 100371(T)).

Sedimentary constraints on late Quaternary lake-level fluctuations at Bear Lake, Utah and Idaho

USGS Publications Warehouse

Smoot, J.P.; Rosenbaum, J.G.

2009-01-01

A variety of sedimentological evidence was used to construct the lake-level history for Bear Lake, Utah and Idaho, for the past ???25,000 years. Shorelines provide evidence of precise lake levels, but they are infrequently preserved and are poorly dated. For cored sediment similar to that in the modern lake, grain-size distributions provide estimates of past lake depths. Sedimentary textures provide a highly sensitive, continuous record of lake-level changes, but the modern distribution of fabrics is poorly constrained, and many ancient features have no modern analog. Combining the three types of data yields a more robust lake-level history than can be obtained from any one type alone. When smooth age-depth models are used, lake-level curves from multiple cores contain inconsistent intervals (i.e., one record indicates a rising lake level while another record indicates a falling lake level). These discrepancies were removed and the multiple records were combined into a single lake-level curve by developing age-depth relations that contain changes in deposition rate (i.e., gaps) where indicated by sedimentological evidence. The resultant curve shows that, prior to 18 ka, lake level was stable near the modern level, probably because the lake was overflowing. Between ca. 17.5 and 15.5 ka, lake level was ???40 m below the modern level, then fluctuated rapidly throughout the post-glacial interval. Following a brief rise centered ca. 15 ka ( = Raspberry Square phase), lake level lowered again to 15-20 m below modern from ca. 14.8-11.8 ka. This regression culminated in a lowstand to 40 m below modern ca. 12.5 ka, before a rapid rise to levels above modern ca. 11.5 ka. Lake level was typically lower than present throughout the Holocene, with pronounced lowstands 15-20 m below the modern level ca. 10-9, 7.0, 6.5-4.5, 3.5, 3.0-2.5, 2.0, and 1.5 ka. High lake levels near or above the modern lake occurred ca. 8.5-8.0, 7.0-6.5, 4.5-3.5, 2.5, and 0.7 ka. This lake-level history is more similar to records from Pyramid Lake, Nevada, and Owens Lake, California, than to those from Lake Bonneville, Utah. Copyright ?? 2009 The Geological Society of America.

Solvent kinetic isotope effects of human placental alkaline phosphatase in reverse micelles.

PubMed Central

Huang, T M; Hung, H C; Chang, T C; Chang, G G

1998-01-01

Human placental alkaline phosphatase was embedded in a reverse micellar system prepared by dissolving the surfactant sodium bis(2-ethylhexyl) sulphosuccinate (Aerosol-OT) in 2,2, 4-trimethylpentane. This microemulsion system provides a convenient instrumental tool to study the possible kinetic properties of the membranous enzyme in an immobilized form. The pL (pH/p2H) dependence of hydrolysis of 4-nitrophenyl phosphate has been examined over a pL range of 8.5-12.5 in both aqueous and reverse micellar systems. Profiles of log V versus pL were Ha-bell shaped in the acidic region but reached a plateau in the basic region in which two pKa values of 9.01-9.71 and 9.86-10.48, respectively, were observed in reverse micelles. However, only one pKa value of 9.78-10.27 in aqueous solution was detected. Profiles of log V/K versus pL were bell-shaped in the acidic region. However, they were wave-shaped in the basic region in which a residue of pKa 9.10-9.44 in aqueous solution and 8.07-8.78 in reverse micelles must be dehydronated for the reaction to reach an optimum. The V/K value shifted to a lower value upon dehydronation of a pKa value of 9.80-10.62 in aqueous solution and 11.23-12.17 in reverse micelles. Solvent kinetic isotope effects were measured at three pL values. At pL 9.5, the observed isotope effect was a product of equilibrium isotope effect and a kinetic isotope effect; at pL 10.4, the log V/K value was identical in water and deuterium. The deuterium kinetic isotope effect on V/K was 1.14 in an aqueous solution and 1.16 in reverse micelles. At pL 11.0 at which the log V values reached a plateau in either solvent system, the deuterium kinetic isotope effect on V was 2.08 in an aqueous solution and 0.62 in reverse micelles. Results from a proton inventory experiment suggested that a hydron transfer step is involved in the transition state of the catalytic reaction. The isotopic fractionation factor (pi) for deuterium for the transition state (piT) increased when the pH of the solution was raised. At pL 11.0, the piT was 1.07 in reverse micelles, which corresponds to the inverse-isotope effect of the reaction in this solvent system. Normal viscosity effects on kcat and kcat/Km were observed in aqueous solution, corresponding to a diffusional controlled physical step as the rate-limiting step. We propose that the rate-limiting step of the hydrolytic reaction changes from phosphate releasing in aqueous solution to a covalent phosphorylation or dephosphorylation step in reverse micelles. PMID:9461520

Solvent kinetic isotope effects of human placental alkaline phosphatase in reverse micelles.

PubMed

Huang, T M; Hung, H C; Chang, T C; Chang, G G

1998-02-15

Human placental alkaline phosphatase was embedded in a reverse micellar system prepared by dissolving the surfactant sodium bis(2-ethylhexyl) sulphosuccinate (Aerosol-OT) in 2,2, 4-trimethylpentane. This microemulsion system provides a convenient instrumental tool to study the possible kinetic properties of the membranous enzyme in an immobilized form. The pL (pH/p2H) dependence of hydrolysis of 4-nitrophenyl phosphate has been examined over a pL range of 8.5-12.5 in both aqueous and reverse micellar systems. Profiles of log V versus pL were Ha-bell shaped in the acidic region but reached a plateau in the basic region in which two pKa values of 9.01-9.71 and 9.86-10.48, respectively, were observed in reverse micelles. However, only one pKa value of 9.78-10.27 in aqueous solution was detected. Profiles of log V/K versus pL were bell-shaped in the acidic region. However, they were wave-shaped in the basic region in which a residue of pKa 9.10-9.44 in aqueous solution and 8.07-8.78 in reverse micelles must be dehydronated for the reaction to reach an optimum. The V/K value shifted to a lower value upon dehydronation of a pKa value of 9.80-10.62 in aqueous solution and 11.23-12.17 in reverse micelles. Solvent kinetic isotope effects were measured at three pL values. At pL 9.5, the observed isotope effect was a product of equilibrium isotope effect and a kinetic isotope effect; at pL 10.4, the log V/K value was identical in water and deuterium. The deuterium kinetic isotope effect on V/K was 1.14 in an aqueous solution and 1.16 in reverse micelles. At pL 11.0 at which the log V values reached a plateau in either solvent system, the deuterium kinetic isotope effect on V was 2.08 in an aqueous solution and 0.62 in reverse micelles. Results from a proton inventory experiment suggested that a hydron transfer step is involved in the transition state of the catalytic reaction. The isotopic fractionation factor (pi) for deuterium for the transition state (piT) increased when the pH of the solution was raised. At pL 11.0, the piT was 1.07 in reverse micelles, which corresponds to the inverse-isotope effect of the reaction in this solvent system. Normal viscosity effects on kcat and kcat/Km were observed in aqueous solution, corresponding to a diffusional controlled physical step as the rate-limiting step. We propose that the rate-limiting step of the hydrolytic reaction changes from phosphate releasing in aqueous solution to a covalent phosphorylation or dephosphorylation step in reverse micelles.

The new math of ownership.

PubMed

Gross, B

1998-01-01

In 1994, when the software maker Knowledge Adventure decided to spin out a new venture--Worlds, Incorporated--founder Bill Gross expected the worst. He had argued with the board that it was in KA's best interests to maintain a controlling ownership stake in Worlds, whose powerful new software technology had enormous revenue potential. But the board prevailed, and KA took only a 20% ownership in the new company, giving the rest to Worlds' employees. Within a year, the company's performance had surpassed all expectations, and instead of owning 80% of a $5 million business, KA owned 20% of a $77 million business. The arithmetic may have been counterintuitive, but the lesson was clear. When KA let go of Worlds and gave its employees near total ownership, the company unleashed a new level of employee performance. That, in turn, led to the creation of economic value that more than made up for the equity KA had surrendered. So compelling was this "new math of ownership" that Gross founded a new company, Idealab, on this principle. The company, which develops ideas for Internet-based businesses and seeds the most promising ones, takes no more than a 49% equity stake in the new ventures and gives at least 1% of ownership to each employee. For Gross, this radical approach to ownership is the key to inspiring stellar performances. In part, employee-owners are motivated by their potential to earn great financial reward. But the drama of ownership, he argues, is even more important. In that drama, employees become personally involved in the struggle to outdo the competition and emerge victorious.

Late-surviving megafauna in Tasmania, Australia, implicate human involvement in their extinction.

PubMed

Turney, Chris S M; Flannery, Timothy F; Roberts, Richard G; Reid, Craig; Fifield, L Keith; Higham, Tom F G; Jacobs, Zenobia; Kemp, Noel; Colhoun, Eric A; Kalin, Robert M; Ogle, Neil

2008-08-26

Establishing the cause of past extinctions is critical if we are to understand better what might trigger future occurrences and how to prevent them. The mechanisms of continental late Pleistocene megafaunal extinction, however, are still fiercely contested. Potential factors contributing to their demise include climatic change, human impact, or some combination. On the Australian mainland, 90% of the megafauna became extinct by approximately 46 thousand years (ka) ago, soon after the first archaeological evidence for human colonization of the continent. Yet, on the neighboring island of Tasmania (which was connected to the mainland when sea levels were lower), megafaunal extinction appears to have taken place before the initial human arrival between 43 and 40 ka, which would seem to exonerate people as a contributing factor in the extirpation of the island megafauna. Age estimates for the last megafauna, however, are poorly constrained. Here, we show, by direct dating of fossil remains and their associated sediments, that some Tasmanian megafauna survived until at least 41 ka (i.e., after their extinction on the Australian mainland) and thus overlapped with humans. Furthermore, a vegetation record for Tasmania spanning the last 130 ka shows that no significant regional climatic or environmental change occurred between 43 and 37 ka, when a land bridge existed between Tasmania and the mainland. Our results are consistent with a model of human-induced extinction for the Tasmanian megafauna, most probably driven by hunting, and they reaffirm the value of islands adjacent to continental landmasses as tests of competing hypotheses for late Quaternary megafaunal extinctions.

Late-surviving megafauna in Tasmania, Australia, implicate human involvement in their extinction

PubMed Central

Turney, Chris S. M.; Flannery, Timothy F.; Roberts, Richard G.; Reid, Craig; Fifield, L. Keith; Higham, Tom F. G.; Jacobs, Zenobia; Kemp, Noel; Colhoun, Eric A.; Kalin, Robert M.; Ogle, Neil

2008-01-01

Establishing the cause of past extinctions is critical if we are to understand better what might trigger future occurrences and how to prevent them. The mechanisms of continental late Pleistocene megafaunal extinction, however, are still fiercely contested. Potential factors contributing to their demise include climatic change, human impact, or some combination. On the Australian mainland, 90% of the megafauna became extinct by ≈46 thousand years (ka) ago, soon after the first archaeological evidence for human colonization of the continent. Yet, on the neighboring island of Tasmania (which was connected to the mainland when sea levels were lower), megafaunal extinction appears to have taken place before the initial human arrival between 43 and 40 ka, which would seem to exonerate people as a contributing factor in the extirpation of the island megafauna. Age estimates for the last megafauna, however, are poorly constrained. Here, we show, by direct dating of fossil remains and their associated sediments, that some Tasmanian megafauna survived until at least 41 ka (i.e., after their extinction on the Australian mainland) and thus overlapped with humans. Furthermore, a vegetation record for Tasmania spanning the last 130 ka shows that no significant regional climatic or environmental change occurred between 43 and 37 ka, when a land bridge existed between Tasmania and the mainland. Our results are consistent with a model of human-induced extinction for the Tasmanian megafauna, most probably driven by hunting, and they reaffirm the value of islands adjacent to continental landmasses as tests of competing hypotheses for late Quaternary megafaunal extinctions. PMID:18719103

Incompressibility in finite nuclei and nuclear matter

NASA Astrophysics Data System (ADS)

Stone, J. R.; Stone, N. J.; Moszkowski, S. A.

2014-04-01

The incompressibility (compression modulus) K0 of infinite symmetric nuclear matter at saturation density has become one of the major constraints on mean-field models of nuclear many-body systems as well as of models of high density matter in astrophysical objects and heavy-ion collisions. It is usually extracted from data on the giant monopole resonance (GMR) or calculated using theoretical models. We present a comprehensive reanalysis of recent data on GMR energies in even-even 112-124Sn and 106,100-116Cd and earlier data on 58≤A≤208 nuclei. The incompressibility of finite nuclei KA is calculated from experimental GMR energies and expressed in terms of A-1/3 and the asymmetry parameter β =(N-Z)/A as a leptodermous expansion with volume, surface, isospin, and Coulomb coefficients Kvol, Ksurf, Kτ, and KCoul. Only data consistent with the scaling approximation, leading to a fast converging leptodermous expansion, with negligible higher-order-term contributions to KA, were used in the present analysis. Assuming that the volume coefficient Kvol is identified with K0, the KCoul=-(5.2±0.7) MeV and the contribution from the curvature term KcurvA-2/3 in the expansion is neglected, compelling evidence is found for K0 to be in the range 250

Co-solvent effects on reaction rate and reaction equilibrium of an enzymatic peptide hydrolysis.

PubMed

Wangler, A; Canales, R; Held, C; Luong, T Q; Winter, R; Zaitsau, D H; Verevkin, S P; Sadowski, G

2018-04-25

This work presents an approach that expresses the Michaelis constant KaM and the equilibrium constant Kth of an enzymatic peptide hydrolysis based on thermodynamic activities instead of concentrations. This provides KaM and Kth values that are independent of any co-solvent. To this end, the hydrolysis reaction of N-succinyl-l-phenylalanine-p-nitroanilide catalysed by the enzyme α-chymotrypsin was studied in pure buffer and in the presence of the co-solvents dimethyl sulfoxide, trimethylamine-N-oxide, urea, and two salts. A strong influence of the co-solvents on the measured Michaelis constant (KM) and equilibrium constant (Kx) was observed, which was found to be caused by molecular interactions expressed as activity coefficients. Substrate and product activity coefficients were used to calculate the activity-based values KaM and Kth for the co-solvent free reaction. Based on these constants, the co-solvent effect on KM and Kx was predicted in almost quantitative agreement with the experimental data. The approach presented here does not only reveal the importance of understanding the thermodynamic non-ideality of reactions taking place in biological solutions and in many technological applications, it also provides a framework for interpreting and quantifying the multifaceted co-solvent effects on enzyme-catalysed reactions that are known and have been observed experimentally for a long time.

An Improved MUSIC Model for Gibbsite Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mitchell, Scott C.; Bickmore, Barry R.; Tadanier, Christopher J.

2004-06-01

Here we use gibbsite as a model system with which to test a recently published, bond-valence method for predicting intrinsic pKa values for surface functional groups on oxides. At issue is whether the method is adequate when valence parameters for the functional groups are derived from ab initio structure optimization of surfaces terminated by vacuum. If not, ab initio molecular dynamics (AIMD) simulations of solvated surfaces (which are much more computationally expensive) will have to be used. To do this, we had to evaluate extant gibbsite potentiometric titration data that where some estimate of edge and basal surface area wasmore » available. Applying BET and recently developed atomic force microscopy methods, we found that most of these data sets were flawed, in that their surface area estimates were probably wrong. Similarly, there may have been problems with many of the titration procedures. However, one data set was adequate on both counts, and we applied our method of surface pKa int prediction to fitting a MUSIC model to this data with considerable success—several features of the titration data were predicted well. However, the model fit was certainly not perfect, and we experienced some difficulties optimizing highly charged, vacuum-terminated surfaces. Therefore, we conclude that we probably need to do AIMD simulations of solvated surfaces to adequately predict intrinsic pKa values for surface functional groups.« less

Time Evolution of the Basse Terre Island (Guadeloupe, French West Indies) Effusive Volcanism from New K-Ar Cassignol-Gillot Ages.

NASA Astrophysics Data System (ADS)

Samper, A.; Quidelleur, X.; Mollex, D.; Komorowski, J. C.; Boudon, G.

2004-12-01

Radiometric dating and geochemistry of effusive volcanics have been combined with geomorphological observations in order to provide a general evolution model of the volcanic island of Basse Terre, Guadeloupe (French West Indies). More than forty new Cassignol-Gillot K-Ar ages distributed within the entire island, together with the twenty ages (Blanc, 1983; Carlut et al., 2000) previously obtained with the same technique, makes the Guadeloupe Island the best place to study the evolution of volcanic processes within the Lesser Antilles Arc. Dating was performed on the carefully separated groundmass in order to avoid K loss due to weathering and excess argon carried by mafic minerals. Ages obtained are relatively younger than previously thought on Basse Terre and range from a few ka to 2.79+-0.04 Ma. When available, the paleomagnetic polarity of the dated flows agree with the GPTS and a very good coherence of ages is observed for each massif. Our results demonstrate the general north to south migration of volcanism through time. It correlates with the main volcanic stages previously identified. The 2.75 Ma Basal Complex, the 1.81+-0.03 _ 1.15+-0.02 Ma Septentrional Chain, the 1.02+-0.02 Ma _ 0.606+-0.02 Ma Axial Chain, the 442+-6 _ 207+-28 ka Mateliane _ Sans Toucher Complex and the < 200 ka Complex of La Grande Decouverte, which outlines a relative continuity in the Basse Terre magmatism. Lavas are mainly basaltic andesites and andesites although a few basalt and dacite have also been dated. All of them are characterized by low MgO values (< 6 %), tholeiitic to calc-alkaline REE chondrite-normalized patterns and are of both low K and medium K affinity. Lavas display geochemical characteristics similar to that of the central islands of the Lesser Antilles arc. Within Basse Terre, geochemical characteristics are relatively constant through time, indicating no major change of volcanic processes during the whole subaerial activity. Finally the detailed chronological framework now available provides new constraints for estimating rates of edification and destruction at the island scale and, more generally, to help better understand the evolution of the still active Guadeloupe island Soufriere volcano.

Pore geometry effects on intrapore viscous to inertial flows and on effective hydraulic parameters

NASA Astrophysics Data System (ADS)

Chaudhary, Kuldeep; Cardenas, M. Bayani; Deng, Wen; Bennett, Philip C.

2013-02-01

In this article, the effects of different diverging-converging pore geometries were investigated, and the microscale fluid flow and effective hydraulic properties from these pores were compared with that of a pipe from viscous to inertial laminar flow regimes. The flow fields are obtained using computational fluid dynamics, and the comparative analysis is based on a new dimensionless hydraulic shape factor β, which is the "specific surface" scaled by the length of pores. Results from all diverging-converging pores show an inverse pattern in velocity and vorticity distributions relative to the pipe flow. The hydraulic conductivity K of all pores is dependent on and can be predicted from β with a power function with an exponent of 3/2. The differences in K are due to the differences in distribution of local friction drag on the pore walls. At Reynolds number (Re) ˜ 0 flows, viscous eddies are found to exist almost in all pores in different sizes, but not in the pipe. Eddies grow when Re → 1 and leads to the failure of Darcy's law. During non-Darcy or Forchheimer flows, the apparent hydraulic conductivity Ka decreases due to the growth of eddies, which constricts the bulk flow region. At Re > 1, the rate of decrease in Ka increases, and at Re >> 1, it decreases to where the change in Ka ≈ 0, and flows once again exhibits a Darcy-type relationship. The degree of nonlinearity during non-Darcy flow decreases for pores with increasing β. The nonlinear flow behavior becomes weaker as β increases to its maximum value in the pipe, which shows no nonlinearity in the flow; in essence, Darcy's law stays valid in the pipe at all laminar flow conditions. The diverging-converging geometry in pores plays a critical role in modifying the intrapore fluid flow, implying that this property should be incorporated in effective larger-scale models, e.g., pore-network models.

New Insights into the 8.2 ka Cold Event and Subsequent Climate Recovery in Central Europe Provided by a Precisely Dated Ostracod δ18O Record from Mondsee (Austria)

NASA Astrophysics Data System (ADS)

Lauterbach, S.; Andersen, N.; Brauer, A.; Erlenkeuser, H.; Danielopol, D. L.; Namiotko, T.; Huels, M.; Belmecheri, S.; Nantke, C.; Meyer, H.; Chapligin, B.; von Grafenstein, U.

2015-12-01

As evidenced by numerous palaeoclimate records worldwide, the Holocene warm period has been interrupted by several short, low-amplitude cold episodes. Among these, the so-called 8.2 ka cold event is the most prominent Holocene climate perturbation but despite extensive studies, knowledge about its synchrony in different areas and particularly about the dynamics of subsequent climate recovery is still limited. As this is of crucial importance for understanding the complex mechanisms that trigger rapid climate fluctuations and for testing the performance of climate models, new data on the 8.2 ka cold event are needed. Here we present a new sub-decadally resolved, precisely dated oxygen isotope (δ18O) record for the interval 7.7-8.7 ka BP obtained from benthic ostracods preserved in the varved lake sediments of Mondsee (Austria), providing new insights into climate development around the 8.2 ka cold event in Central Europe. The new high-resolution δ18O data set reveals the occurrence of a pronounced cold spell around 8.2 ka BP, whose amplitude (~1.0 ‰, equivalent to a 1.5-2.0 °C cooling), total duration (151 a) and absolute dating (8231-8080 a BP, i.e. calendar years before AD 1950) perfectly agree with results from other Northern Hemisphere palaeoclimate archives, e.g. the precisely dated Greenland ice cores. In addition, the Mondsee δ18O record also indicates a 75-year-long air temperature overshoot of ~0.7 °C directly after the 8.2 ka event (between 8080 and 8005 a BP), which is so far only poorly documented in the mid-latitudes. However, this observation is consistent with results from coupled climate models and high-latitude proxy records, thus likely reflecting a hemispheric-scale climate signal driven by enhanced resumption of the Atlantic meridional overturning circulation (AMOC), which apparently also caused synchronous migrations of atmospheric and oceanic front systems in the North Atlantic realm.

A 400-ka tephrochronological framework for Central America from Lake Petén Itzá (Guatemala) sediments

NASA Astrophysics Data System (ADS)

Kutterolf, S.; Schindlbeck, J. C.; Anselmetti, F. S.; Ariztegui, D.; Brenner, M.; Curtis, J.; Schmid, D.; Hodell, D. A.; Mueller, A.; Pérez, L.; Pérez, W.; Schwalb, A.; Frische, M.; Wang, K.-L.

2016-10-01

Lake Petén Itzá, northern Guatemala, lies within a hydrologically closed basin in the south-central area of the Yucatán Peninsula, and was drilled under the auspices of the International Continental Scientific Drilling Program (ICDP) in 2006. At 16°55‧N latitude, the lake is ideally located for study of past climate and environmental conditions in the Neotropical lowlands. Because of its great depth (>160 m), Lake Petén Itzá has a record of continuous sediment accumulation that extends well into the late Pleistocene. A key obstacle to obtaining long climate records from the region is the difficulty of establishing a robust chronology beyond ∼40 ka, the limit of 14C dating. Tephra layers within the Lake Petén Itzá sediments, however, enable development of age/depth relations beyond 40 ka. Ash beds from large-magnitude, Pleistocene-to-Holocene silicic eruptions of caldera volcanoes along the Central American Volcanic Arc (CAVA) were found throughout drill cores collected from Lake Petén Itzá. These ash beds were used to establish a robust chronology extending back 400 ka. We used major- and trace-element glass composition to establish 12 well-constrained correlations between the lacustrine tephra layers in Lake Petén Itzá sediments and dated deposits at the CAVA source volcanoes, and with their marine equivalents in eastern Pacific Ocean sediments. The data also enabled revision of eight previous determinations of erupted volumes and masses, and initial estimates for another four eruptions, as well as the designation of source areas for 14 previously unknown eruptions. The new and revised sedimentation rates for the older sediment successions identify the interglacial of MIS5a between 84 and 72 ka, followed by a stadial between 72 and 59 ka that corresponds to MIS4. We modified the age models for the Lake Petén Itzá sediment sequences, extended the paleoclimate and paleoecological record for this Neotropical region to ∼400 ka, and determined the magnitude and timing of CAVA eruptions.

Terrestrial cosmogenic surface exposure dating of glacial and associated landforms in the Ruby Mountains-East Humboldt Range of central Nevada and along the northeastern flank of the Sierra Nevada

DOE PAGES

Wesnousky, Steven G.; Briggs, Richard W.; Caffee, Marc W.; ...

2016-05-07

Deposits near Lamoille in the Ruby Mountains-East Humboldt Range of central Nevada and at Woodfords on the eastern edge of the Sierra Nevada each record two distinct glacial advances. In this paper, we compare independent assessments of terrestrial cosmogenic nuclide (TCN) surface exposure ages for glacial deposits that we have determined to those obtained by others at the two sites. At each site, TCN ages of boulders on moraines of the younger advance are between 15 and 30 ka and may be associated with marine oxygen isotope stage (MIS) 2. At Woodfords, TCN ages of boulders on the moraine ofmore » the older advance are younger than ~ 60 ka and possibly formed during MIS 4, whereas boulders on the correlative outwash surface show ages approaching 140 ka (~ MIS 6). The TCN ages of boulders on older glacial moraine at Woodfords thus appear to severely underestimate the true age of the glacial advance responsible for the deposit. The same is possibly true at Lamoille where clasts sampled from the moraine of the oldest advance have ages ranging between 20 and 40 ka with a single outlier age of ~ 80 ka. The underestimations are attributed to the degradation and denudation of older moraine crests. Noting that boulder ages on the older advances at each site overlap significantly with MIS 2. Finally, we speculate that erosion of the older moraines has been episodic, with a pulse of denudation accompanying the inception of MIS 2 glaciation.« less

Terrestrial cosmogenic surface exposure dating of glacial and associated landforms in the Ruby Mountains-East Humboldt Range of central Nevada and along the northeastern flank of the Sierra Nevada

USGS Publications Warehouse

Wesnousky, Steven G.; Briggs, Richard; Caffee, Marc W.; Ryerson, Rick J.; Finkel, Robert C.; Owen, Lewis A.

2016-01-01

Deposits near Lamoille in the Ruby Mountains-East Humboldt Range of central Nevada and at Woodfords on the eastern edge of the Sierra Nevada each record two distinct glacial advances. We compare independent assessments of terrestrial cosmogenic nuclide (TCN) surface exposure ages for glacial deposits that we have determined to those obtained by others at the two sites. At each site, TCN ages of boulders on moraines of the younger advance are between 15 and 30 ka and may be associated with marine oxygen isotope stage (MIS) 2. At Woodfords, TCN ages of boulders on the moraine of the older advance are younger than ~ 60 ka and possibly formed during MIS 4, whereas boulders on the correlative outwash surface show ages approaching 140 ka (~ MIS 6). The TCN ages of boulders on older glacial moraine at Woodfords thus appear to severely underestimate the true age of the glacial advance responsible for the deposit. The same is possibly true at Lamoille where clasts sampled from the moraine of the oldest advance have ages ranging between 20 and 40 ka with a single outlier age of ~ 80 ka. The underestimations are attributed to the degradation and denudation of older moraine crests. Noting that boulder ages on the older advances at each site overlap significantly with MIS 2. We speculate that erosion of the older moraines has been episodic, with a pulse of denudation accompanying the inception of MIS 2 glaciation.

New ages for Middle and Later Stone Age deposits at Mumba rockshelter, Tanzania: optically stimulated luminescence dating of quartz and feldspar grains.

PubMed

Gliganic, Luke A; Jacobs, Zenobia; Roberts, Richard G; Domínguez-Rodrigo, Manuel; Mabulla, Audax Z P

2012-04-01

The archaeological deposits at Mumba rockshelter, northern Tanzania, have been excavated for more than 70 years, starting with Margit and Ludwig Köhl-Larsen in the 1930s. The assemblages of Middle Stone Age (MSA) and Later Stone Age (LSA) artefacts collected from this site constitute the type sequences for these cultural phases in East Africa. Despite its archaeological importance, however, the chronology of the site is poorly constrained, despite the application since the 1980s of several dating methods (radiocarbon, uranium-series and amino acid racemisation) to a variety of materials recovered from the deposits. Here, we review these previous chronologies for Mumba and report new ages obtained from optically stimulated luminescence (OSL) and infrared stimulated luminescence (IRSL) measurements on single grains of quartz and multi-grain aliquots of potassium (K) feldspar from the MSA and LSA deposits. Measurements of single grains of quartz allowed the rejection of unrepresentative grains and the application of appropriate statistical models to obtain the most reliable age estimates, while measurements of K-feldspars allowed the chronology to be extended to older deposits. The seven quartz ages and four K-feldspar ages provide improved temporal constraints on the archaeological sequence at Mumba. The deposits associated with the latest Kisele Industry (Bed VI-A) and the earliest Mumba Industry (Bed V) are dated to 63.4 ± 5.7 and 56.9 ± 4.8 ka (thousands of years ago), respectively, thus constraining the time of transition between these two archaeological phases to ~60 ka. An age of 49.1 ± 4.3 ka has been obtained for the latest deposits associated with the Mumba Industry, which show no evidence for post-depositional mixing and contain ostrich eggshell (OES) beads and abundant microlithics. The Nasera Industry deposits (Bed III) contain large quantities of OES beads and date to 36.8 ± 3.4 ka. We compare the luminescence ages with the previous chronologies for Mumba, and briefly discuss how the revised chronology fits in the context of existing archaeological records and palaeoclimatic reconstructions for East Africa. Copyright © 2012 Elsevier Ltd. All rights reserved.

Increased production of cosmogenic 10Be recorded in oceanic sediment sequences: Information on the age, duration, and amplitude of the geomagnetic dipole moment minimum over the Matuyama-Brunhes transition

NASA Astrophysics Data System (ADS)

Simon, Quentin; Thouveny, Nicolas; Bourlès, Didier L.; Bassinot, Franck; Savranskaia, Tatiana; Valet, Jean-Pierre; Aster Team

2018-05-01

New high-resolution authigenic 10Be/9Be ratio (Be-ratio) records covering the last geomagnetic reversal, i.e. the Matuyama-Brunhes transition (MBT), have been obtained and set on a time scale using benthic δ18O (Cibicides wuellerstorfi) records. The geographic distribution of the four studied sites allows global comparison between the North Atlantic, Indian and Pacific Oceans. All Be-ratio records contain a two-fold increase triggered by the geomagnetic dipole moment (GDM) collapse associated with the MBT. The stratigraphic position of the Be-ratio spike, relative to marine isotope stages, allows establishment of a robust astrochronological framework for the MBT, anchoring its age between 778 and 766 ka (average mid-peaks at 772 ka), which is consistent with all other available 10Be-proxy records from marine, ice and loess archives. The global 10Be atmospheric production doubling represents an increase of more than 300 atoms m-2 s-1 that is compatible with the increased magnitude of atmospheric 10Be production obtained by simulations between the present GDM and a null-GDM. The minimum 10Be-derived GDM average computed for the 776-771 ka interval is 1.7 ± 0.4 ×1022 Am2, in agreement with model simulations and absolute paleointensities of transitional lava flows.

Spectroscopic analysis of the interaction between thiazolo[2,3-b]pyrimidine analogues and bovine serum albumin.

PubMed

Yu, Xianyong; Yang, Ying; Yao, Qing; Tao, Hongwen; Lu, Shiyu; Xie, Jian; Zhou, Hu; Yi, Pinggui

2012-10-01

The interaction between thiazolo[2,3-b]pyrimidine (TZPM) analogues and bovine serum albumin (BSA) was investigated by fluorescence spectroscopy and UV-Vis spectroscopy at two different temperatures (299 and 307K) under imitated physiological conditions. The results indicate that both static quenching and dynamic quenching contribute to the fluorescence quenching of BSA by TZPM. The binding constant (K(a)) and binding sites (n) were calculated from the obtained spectra. Based on the Förster non-radiation energy transfer theory, the average binding distance between BSA and TZPM was estimated. The synchronous fluorescence spectra indicate that the conformation of BSA has been changed. The comparison of binding potency of TZPM and BSA suggests that the substituents on the benzene ring enhance the binding affinity of TZPM and BSA. We investigated the possible sub-domains on BSA that bind TZPM by displacement experiments. Furthermore, to explore the effect of molecular structure on the binding, a study on quantitative structure-property relationship (QSPR) was performed, the quantitative relationship equation of R(0), r and K(a) were obtained. We observed that R(0), r and K(a) between BSA and TZPM is connected with the margin of the highest and the lowest occupied orbital energy (ΔE), dipole moment (μ), Molar Volume (V(m)), Mole Mass (M). Copyright © 2012 Elsevier B.V. All rights reserved.

The Accuracy of New and Aged Mechanical Torque Devices Employed in Five Dental Implant Systems

PubMed Central

Karatasli, Burcin; Dinçer Kose, Onur; Kose, Taha Emre; Çene, Erhan; Aydın Aya, Serhan

2017-01-01

Purpose Friction-style and spring-style torque wrenches are used to tighten implant abutments and prosthetic screws. The mechanical stability of these torque wrenches is crucial for the implant–abutment connection. The purposes of this study were to assess the performance of five brands (Straumann, Zimmer, Implant KA, Bredent, and Biohorizons) of wrench and to evaluate possible changes in applied torque values of aged wrenches. Materials and Methods Five new and aged wrenches that had been used approximately 250 times in a 1-year period were tested. The torque applied by friction- and spring-style wrenches was measured with a specially designed strain gauge indicator. Descriptive statistics, the one-sample t-test, and the independent-samples t-test were used to analyze values obtained from all torque wrenches. Results The accuracy of new and aged torque devices of all brands except Bredent differed significantly from the target values, but the mean values for aged and new wrenches did not differ significantly from each other (p > 0.05). Values for the spring- and friction-type torque wrenches deviated from the target values by 11.6% and 10.2%, respectively. Conclusion The accuracy of aged torque wrenches is adequate for prosthetic screw tightening, but that of new torque wrenches is unsatisfactory and must be examined carefully before delivery. PMID:29238725

Salubrious effect of Kalpaamruthaa, a modified indigenous preparation in adjuvant-induced arthritis in rats--a biochemical approach.

PubMed

Mythilypriya, Rajendran; Shanthi, Palanivelu; Sachdanandam, Panchanadam

2008-05-28

Interactions between the phytochemicals and drugs and their combinations are capable of providing longer remissions and perhaps a complete cure for many diseases including rheumatoid arthritis (RA). In addition to articular manifestations in RA, extra-articular signs involving reticuloendothelial and hepatic systems are an indication of more severe disease and thus, have prognostic value. The present study was designed to illustrate the beneficial outcome of the drug Kalpaamruthaa (constituting Semecarpus anacardium nut milk extract, fresh dried powder of Emblica officinalis fruit and honey) in adjuvant-induced arthritic rat model with respect to the changes in extra-articular manifestation involving hematological and cellular constituents. Levels of hematological parameters, cellular constituents, activities of marker enzymes and the level of DNA damage were assessed in control, arthritis-induced, SA, KA and drug control treated rats. Significant decrease (p<0.005) in the levels of Hb, RBC, PCV, total protein, albumin, A/G ratio, plasma uric acid, urinary urea, uric acid, creatinine, FFA, HDL and significant increase (p<0.05) in the levels of WBC, platelet count, ESR, globulin, plasma creatinine, blood glucose, urea, AST, ALT, ALP, TC, FC, TG, PL, LDL and VLDL were observed in arthritic rats. No other significant change was observed in tissue DNA and RNA levels of control and experimental animals. On the contrary an increase in DNA damage was observed in arthritic rats when compared to control animals. The above said derangements were brought back to near normal levels upon SA and KA treatments and KA revealed a profound beneficial effect than SA. The enhanced effect of KA might be attributed to the combined effects of phytoconstituents such as flavonoids, tannins and other compounds such as vitamin C present in KA. Thus KA via this preliminary protective effect might contribute to the amelioration of the disease process.

Luminescence and Radiocarbon dating of roman time harbour sediments from Cologne - A comparison of different methods

NASA Astrophysics Data System (ADS)

Lauer, Tobias; Frechen, Manfred; Fuchs, Magret C.; Trier, Marcus; Tsukamoto, Sumiko

2010-05-01

Optically stimulated luminescence (OSL) dating was applied to fluvial and colluvial deposits which were taken from a roman time harbour basin in Cologne. Hence, independent age control was given by roman artefacts (coins, bricks) of known age and by three radiocarbon data. For one sample (well sorted fluvial sand), a single aliquot regenerative (SAR) protocol was applied to coarse grain quartz. A large number of equivalent doses (80) were collected and after De-measurements, different statistical approaches were tested. The results show, that calculating the age by using the Mean or Median of all accepted De-values yields OSL ages of 3.5 ± 0.3 ka and 2.8 ± 0.3 ka, respectively, what would be significantly too old. The application of the Leading Edge Method (Lepper & McKeever 2002), the statistical approach after Fuchs & Lang (2001) or the Minimum Age Method (MAM3) after Galbraith et al. (1999) yield OSL age estimates of 2.0 ± 0.1 ka, 2.1 ± 0.1 ka and 1.7 ± 0.6 ka, respectively. Those ages fit very well to the 14C-ages and are in better agreement with the known archaeological background. For the colluvial sample, the quartz OSL signal was effected by feldspar impurities. For this sample, different methodological approaches were tested to see which one has the best potential to minimize the feldspar contribution. Therefore the post-IR blue stimulated quartz luminescence was recorded. The quartz signal was measured using continuous wave (CW) and pulsed OSL (POSL). For the CW measurements, it was tested if a prior IR-bleach @ 50°C or @ 225°C has better potential for minimizing the feldspar signal. In this case, an IR-bleach @ 225°C (Buylaert et al. in press) was the most effective way to obtain a higher purity of the quartz OSL signal. Buylaert, J.P., Murray, A.S., Thomsen, K.J., Jain, M.: The effect of preheating on the IRSL signal from feldspar. In press. - Radiat. Meas., special issue, LED08. Fuchs, M. & Lang, A. (2001): OSL dating of coarse-grain fluvial quartz using single-aliquot protocols on sediments from NE Peloponnese, Greece. - Quaternary Science Reviews, 20: 783-787. Galbraith, R. F., Roberts, R. G., Laslett, G. M., Yoshida, H. & Olley, J. M. (1999): Optical dating of single and multiple grains of quartz from Jinmium Rock Shelter, northern Australia: Part 1, experimental design and statistical models. - Archaeometry, 41: 339-364. Lepper, K. & McKeever, S.W.S. (2002): An objective methodology for dose distribution analysis. Radiation Protection Dosimetry. - Solid State Dosimetry, 101: 349-352.

High Throughput pharmacokinetic modeling using computationally predicted parameter values: dissociation constants (TDS)

EPA Science Inventory

Estimates of the ionization association and dissociation constant (pKa) are vital to modeling the pharmacokinetic behavior of chemicals in vivo. Methodologies for the prediction of compound sequestration in specific tissues using partition coefficients require a parameter that ch...

Schmidt-hammer exposure-age dating (SHD) of Lateglacial rock glacier systems near the eastern margin of the European Alps

NASA Astrophysics Data System (ADS)

Kellerer-Pirklbauer, Andreas

2016-04-01

Rock glaciers are widespread permafrost landforms in Austria. Various rock glacier inventories list more than 4500 rock glaciers in the country; some 30-40% of them are intact. Relict (permafrost free) and pseudo-relict rock glaciers (sporadic and isolated permafrost particularly near the root zone) prevail in number. Rock glaciers are commonly formed over a period of several ka. Dating such landforms helps to understand palaeoclimatic conditions. In this study three rock glaciers consisting of gneiss were dated applying the Schmidt-hammer exposure-age dating (SHD) method. The rock glaciers are located at three neighbouring cirques in the Seckauer Tauern Range named Reichart Rock Glacier (RRG, area 1.26 km², length 1800 m, elevation range 1520-1940 m a.s.l.), Schöneben Rock Glacier (SRG, 0.11 km², 750 m, 1715-1905 m a.s.l.), and Dürrtal Rock Glacier (DRG, 0.08 km², 850 m, 1750-1980 m a.s.l.). RRG is one of the largest rock glaciers in Austria. All three landforms are influenced by lenses of permafrost at present (as indicated by ERT). During the LGM the Seckauer Tauern were covered by valley glaciers and deglaciation occurred presumably already early in the Alpine Lateglacial period. An analogue N-type Schmidt-hammer (proceq) was used for measuring the surface strength of stable blocks at the rock glacier surface by recording a rebound value (R-value) of a spring-loaded bolt. The R-value gives a relative measure of the surface hardness and hence time since exposure to weathering. Eight (RRG) or six (SRG, DRG) Schmidt-hammer measurement sites (with 50-100 individual readings) aligned along longitudinal transects (=former central flow line) between a talus slope (with relatively fresh boulders) in the root zone and the frontal ridge were measured. Mean R-value differences of 30.5 at RRG, 25.1 at SRG, and 20.7 at DRG were revealed along the three transects. The differences between the lowest and the highest R-value at the rock glaciers itself were 19.0 at RRG, 15.2 at SRG, and 10.5 at DRG. The differences in R-values between the talus slopes and the uppermost Schmidt-hammer site at the rock glacier were 11.5 at RRG, 9.9 at SRG, and 10.2 at DRG. No high-quality age control points are available at the studied rock glacier. Therefore, an age-calibration curve cannot be established. An age-calibration curve for gneiss has been established previously for a rock glacier c.110 km west of the study area yielding a mean decrease of 1.46 R/1 ka. This allows the estimate that the rock glacier formation period in the study area stretched over a period of several ka. Not unlikely, the formation of the rock glaciers was initiated already during the Gschnitz stadial (Heinrich 1 ice rafting event) dated to 15.4 ka BP or even earlier. SRG is the oldest rock glacier possibly starting to form during the later part of the Lateglacial ice decay-phase. At least 7-8 ka ago the stabilisation of the uppermost part of the three rock glaciers was accomplished. This rather late stabilisation might be also related to the thermally inert response of coarse rock glacier systems.

VizieR Online Data Catalog: Spectral Classes in Kapteyn areas 92-115 (Kharadze+, 2003)

NASA Astrophysics Data System (ADS)

Kharadze, E. K.; Bartaya, R. A.; Chargeishvili, K. B.

2014-07-01

The present catalogue is the last one of the four catalogues published according to programme of Abastumani Astrophysical Observatory of a massive two-dimensional MK classification of stars in 115 kapteyn Select Areas (KA) of Northen Sky. The catalogue lists the spectral types and luminosity classes for 3880 stars in 23 Kapteyn areas 92-115 through the declination circle of 0°. KA 95 was skipped because of poor quality of observational data. The catalogue is compiled on the basis of the spectral data obtained with the 70-cm meniscus telescope of Abastumani Astrophysical Observatory using the 8° objective prism (dispersion 166Å/mm near Hγ; in the short-wave region, the spectrum extends up to 3500Å). The field of the meniscus telescope is 4.5°x4.5°. The photo material is taken on Kodak IIa-O, hyper-sensitized Kodak IIIa-J and in order to detect also Hα emission stars and M, S, C type stars in the surveyed KA's, hyper-sensitized Kodak IIIa-F plates were also taken. A limiting apparent magnitude in V for stars in question is 12.5 photographic mag. and for M ones - 15.0mag. The data for all KA's are uniform not only in the sense of classification accuracy (the whole classification is done by one person - the author of the present catalogue), but also in the sense of penetration. The errors of our determinations are: ±0.6 for spectral subtype and ±0.5 for luminosity class. The stars in the KA's are arranged in the Catalogue by increasing right ascension. The stars are numbered according to zones of 1° in declination. The printed catalogue is provided with suitable stellar charts for separate KA's reproduced from the Lick Catalogue. The reference system on the charts refers to 1950 epoch and it is plotted according to the Smithsonian Astrophysical Observatory (SAO) catalogue. (1 data file).

Mechanical properties of lipid bilayers from molecular dynamics simulation

PubMed Central

Venable, Richard M.; Brown, Frank L.H.; Pastor, Richard W.

2015-01-01

Lipid areas (Aℓ), bilayer area compressibilities (KA), bilayer bending constants (KC), and monolayer spontaneous curvatures (c0) from simulations using the CHARMM36 force field are reported for 12 representative homogenous lipid bilayers. Aℓ (or their surrogate, the average deuterium order parameter in the “plateau region” of the chain) agree very well with experiment, as do the KA. Simulated KC are in near quantitative agreement with vesicle flicker experiments, but are somewhat larger than KC from x-ray, pipette aspiration, and neutron spin echo for saturated lipids. Spontaneous curvatures of bilayer leaflets from the simulations are approximately 30% smaller than experimental values of monolayers in the inverse hexagonal phase. PMID:26238099

Study on the interaction mechanism between aromatic amino acids and quercetin

NASA Astrophysics Data System (ADS)

Gou, Xingxing; Pu, Xiaohua; Li, Zongxiao

2017-11-01

In this paper, we selected quercetin and aromatic amino acids (tryptophan, tyrosine, phenylalanine) as the research objects to investigate the change rules in the reaction process. The thermodynamic functions (Ka, Δ G, and Δ S) of the interactions between quercetin and aromatic amino acids (tryptophan, tyrosine, phenylalanine) were measured by isothermal titration calorimetry. The values of binding constant (Ka) reached maximum at 25°C; the entropies and Gibbs free energies were both negative at different temperatures. The kinetic parameters of quercetin and amino acids in the interaction process was determined by microcalorimetry. The results inferred that the driving force of the reaction was hydrogen bond or van der Waals force.

Submicrosecond characteristics of lightning return-stroke currents

NASA Technical Reports Server (NTRS)

Leteinturier, Christiane; Hamelin, Joel H.; Eybert-Berard, Andre

1991-01-01

The authors describe the experimental results obtained during 1987 and 1988 triggered-lightning experiments in Florida. Seventy-four simultaneous submicrosecond time-resolved measurements of triggered return-stroke current (I) and current derivative (dI/dt) were made in Florida in 1987 and 1988. Peak currents ranged from about 5 to 76 kA, peak dI/dt amplitude from 13 to 411 kA/microsec and rise time from 90 to 1000 ns. The mean peak dI/dt values of 110 kA/microsec were 2-3 times higher than data from instrumented towers and peak I and dI/dt appear to be positively correlated. These data confirm previous experiments and conclusions supported by forty measurements. They are important in order to define, for example, standards for lightning protection. Present standards give a dI/dt maximum of 140 kA/microsec.

Experimental Study of the Richtmyer-Meshkov Instability of Incompressible Fluids

NASA Technical Reports Server (NTRS)

Niederhaus, Charles; Jacobs, Jeffrey W.

2002-01-01

The Richtmyer-Meshkov instability of a low Atwood number, miscible, two-liquid system is investigated experimentally. The initially stratified fluids are contained within a rectangular tank mounted to a sled that rides on a vertical set of rails. The instability is generated by dropping the sled onto a coil spring, producing a nearly impulsive upward acceleration. The subsequent freefall that occurs as the container travels upward and then downward on the rails allows the instability to evolve in the absence of gravity. The interface separating the two liquids initially has a well-defined, sinusoidal perturbation that quickly inverts and then grows in amplitude after undergoing the impulsive acceleration. Disturbance amplitudes are measured and compared to theoretical predictions. Linear stability theory gives excellent agreement with the measured initial growth rate, a(sub 0), for single-mode perturbations with the predicted amplitudes differing by less than 10% from experimental measurements up to a nondimensional time ka(sub 0)t = 0.7, where k is the wavenumber. Linear stability theory also provides excellent agreement for the individual mode amplitudes of multi-mode initial perturbations up until the interface becomes multi-valued. Comparison with previously published weakly nonlinear single-mode models shows good agreement up to ka(sub 0)t = 3, while published nonlinear single-mode models provide good agreement up to ka(sub 0)t = 30. The effects of Reynolds number on the vortex core evolution and overall growth rate of the interface are also investigated. Measurements of the overall amplitude are found to be unaffected by the Reynolds number for the range of values studied here. However, experiments carried out at lower values of Reynolds numbers were found to have decreased vortex core rotation rates. In addition, an instability in the vortex cores is observed.

A 120 ka record of reconstructed paleoprecipitation signals at Lake El'gygytgyn, NE Russia derived from compound-specific δD analysis of terrestrial biomarkers

NASA Astrophysics Data System (ADS)

Wilkie, K. M.; Chapligin, B.; Burns, S. J.; Petsch, S.; Meyer, H.; Brigham-Grette, J.

2011-12-01

Sediment cores recovered from Lake El'gygytgyn, NE Russia extend back to 3.6Ma, representing the longest time-continuous sediment record of past climate change in the terrestrial Arctic. Comparison of the stable isotope composition of modern precipitation and compound-specific isotopic analyses of modern vegetation and sedimentary lipids from the last 120ka allows reconstruction of past hydrological conditions, thereby providing a powerful tool for reconstructing past Arctic climate changes. The stable isotopic composition of modern precipitation, streams, and lake water are presented and used to constrain isotope systematics of the Lake El'gygytgyn Basin hydrology. The hydrogen isotopic compositions (δD) of alkanoic acids from modern vegetation are compared with modern precipitation and lake core top sediments. Multi-species net fractionation values between source water and leaf wax lipid δD values (-113 ± 13%) agree with previous results in arid environments and provide a basis for applying this proxy further downcore. δD measurements of sedimentary alkanoic acids representing terrestrial sources (e.g. δDTER: nC30) show significant variation (up to 70%) over the past 120 ka. Interglacial periods are characterized by isotopic enrichment while the most negative δDTER values occur during glacial conditions (i.e. the Last Glacial Maximum and MIS 4). Preliminary reconstruction of the isotopic composition of past precipitation from the δDTER record correlates strongly with the δ18Ocalcite record from Sanbao and Hulu caves1 (China) and the δDvostok record2 (Antarctica) suggesting global teleconnections and 'circum-Pacific' coherence to paleo-precipitation archives. 1 Wang et al. (2005), Science 308, 854-857. 2 Petit et al. (1999), Nature 399, 429-436.

Seasonal variations measured by TDR and GPR on an anthropogenic sandy soil and the implications for utility detection

NASA Astrophysics Data System (ADS)

Curioni, Giulio; Chapman, David N.; Metje, Nicole

2017-06-01

The electromagnetic (EM) soil properties are dynamic variables that can change considerably over time, and they fundamentally affect the performance of Ground Penetrating Radar (GPR). However, long-term field studies are remarkably rare and records of the EM soil properties and their seasonal variation are largely absent from the literature. This research explores the extent of the seasonal variation of the apparent permittivity (Ka) and bulk electrical conductivity (BEC) measured by Time Domain Reflectometry (TDR) and their impact on GPR results, with a particularly important application to utility detection. A bespoke TDR field monitoring station was specifically developed and installed in an anthropogenic sandy soil in the UK for 22 months. The relationship between the temporal variation of the EM soil properties and GPR performance has been qualitatively assessed, highlighting notably degradation of the GPR images during wet periods and a few days after significant rainfall events following dry periods. Significantly, it was shown that by assuming arbitrary average values (i.e. not extreme values) of Ka and BEC which do not often reflect the typical conditions of the soil, it can lead to significant inaccuracies in the estimation of the depth of buried targets, with errors potentially up to approximately 30% even over a depth of 0.50 m (where GPR is expected to be most accurate). It is therefore recommended to measure or assess the soil conditions during GPR surveys, and if this is not possible to use typical wet and dry Ka values reported in the literature for the soil expected at the site, to improve confidence in estimations of target depths.

Substituent effects and pH profiles for stability constants of arylboronic acid diol esters.

PubMed

Martínez-Aguirre, Mayte A; Villamil-Ramos, Raul; Guerrero-Alvarez, Jorge A; Yatsimirsky, Anatoly K

2013-05-17

Stability constants of boronic acid diol esters in aqueous solution have been determined potentiometrically for a series of meta-, para-substituted phenylboronic acids and diols of variable acidity. The constants β(11-1) for reactions between neutral forms of reactants producing the anionic ester plus proton follow the Hammett equation with ρ depending on pKa of diol and varying from 2.0 for glucose to 1.29 for 4-nitrocatechol. Observed stability constants (K(obs)) measured by UV-vis and fluorometric titrations at variable pH for esters of 4,5-dihydroxy-1,3-benzenedisulfonate (Tiron) generally agree with those expected on the basis of β(11-1) values, but the direct fitting of K(obs) vs pH profiles gives shifted pKa values both for boronic acids and diol as a result of significant interdependence of fitting parameters. The subsituent effects on absorption and fluorescence spectra of Tiron arylboronate esters are characterized. The K(obs) for Tiron determined by (11)B NMR titrations are approximately 1 order of magnitude smaller than those determined by UV-vis titrations under identical conditions. A general equation, which makes possible an estimate of β(11-1) for any pair of boronic acid and diol from their pKa values, is proposed on the basis of established Brönsted-type correlation of Hammett parameters for β(11-1) with acidity of diols. The equation allows one to calculate stability constants expected only on basis of acid-base properties of the components, thus permitting more strict evaluation of contributions of additional factors such as steric or charge effects to the ester stability.

Intrinsically disordered inhibitor of glutamine synthetase is a functional protein with random-coil-like pKa values.

PubMed

Cozza, Concetta; Neira, José L; Florencio, Francisco J; Muro-Pastor, M Isabel; Rizzuti, Bruno

2017-06-01

The sequential action of glutamine synthetase (GS) and glutamate synthase (GOGAT) in cyanobacteria allows the incorporation of ammonium into carbon skeletons. In the cyanobacterium Synechocystis sp. PCC 6803, the activity of GS is modulated by the interaction with proteins, which include a 65-residue-long intrinsically disordered protein (IDP), the inactivating factor IF7. This interaction is regulated by the presence of charged residues in both IF7 and GS. To understand how charged amino acids can affect the binding of an IDP with its target and to provide clues on electrostatic interactions in disordered states of proteins, we measured the pK a values of all IF7 acidic groups (Glu32, Glu36, Glu38, Asp40, Asp58, and Ser65, the backbone C-terminus) at 100 mM NaCl concentration, by using NMR spectroscopy. We also obtained solution structures of IF7 through molecular dynamics simulation, validated them on the basis of previous experiments, and used them to obtain theoretical estimates of the pK a values. Titration values for the two Asp and three Glu residues of IF7 were similar to those reported for random-coil models, suggesting the lack of electrostatic interactions around these residues. Furthermore, our results suggest the presence of helical structure at the N-terminus of the protein and of conformational changes at acidic pH values. The overall experimental and in silico findings suggest that local interactions and conformational equilibria do not play a role in determining the electrostatic features of the acidic residues of IF7. © 2017 The Protein Society.

Quaternary magnetic excursions recorded in marine sediments.

NASA Astrophysics Data System (ADS)

Channell, J. E. T.

2017-12-01

This year is the golden (50th) anniversary of the first documentation of a magnetic excursion, the Laschamp excursion in volcanics from the Chaine des Puys (Bonhommet and Babkine, 1967). The first recording of an excursion in sediments was from the Blake Outer Ridge (Smith and Foster, 1969). Magnetic excursions are directional aberrations of the geomagnetic field apparently involving short-lived reversal of the main dipole field. They have durations of a few kyrs, and are therefore rarely recorded in sediments with mean sedimentation rates <10 cm/kyr. Certain Brunhes-aged excursions are now well documented having been recorded in both marine sediments and in lavas (Laschamp excursion, 41 ka). Other excursions have not been adequately recorded in lavas, but have been widely recorded in marine and lake sediments (Iceland Basin excursion, 190 ka). The recording of excursions is fortuitous both in lava sequences and in marine sediments due to their millennial/centennial-scale duration, however, the global recording of the Laschamp and Iceland Basin excursions imply that excursions involve the main dipole field, are recorded synchronously over the globe, and are therefore important in stratigraphic correlation. The marine sediment record includes magnetic excursions at 26 ka (Rockall), 32 ka (Mono Lake), 41 ka (Laschamp), 115 ka (Blake), 190 ka (Iceland Basin), 238 ka (Pringle Falls?), 286 ka (Portuguese Orphan), 495 ka (Bermuda), 540 ka (Big Lost), 590 ka (La Palma), and 670 ka (Osaka Bay), implying at least 11 excursions in the Brunhes Chron. For the Matuyama Chron, excursions have been recorded in marine sediments at 868 ka (Kamikatsura?), 932 ka (Santa Rosa), 1051 ka (Intra-Jaramillo), 1115 ka (Punaruu), 1255 ka (Bjorn), 1476 ka (Gardar), 1580 ka (Gilsa), and 2737 ka (Porcupine). Excursions coincide with minima in relative paleointensity (RPI) records. Ages are from correlation of excursion records to oxygen isotope records in the same cores, and ice-volume calibration of the oxygen isotope template. The marine sediment record of excursions, combined with independent documentation of excursions in lavas with Ar/Ar age control, is progressively strengthening our knowledge of the excursion inventory in the Quaternary, and enhancing the importance of excursions and RPI in Quaternary stratigraphy.

High resolution sedimentary record from the Cocos Ridge: evidence of land-ocean linkages in the Eastern Equatorial Pacific over the last 70 ka

NASA Astrophysics Data System (ADS)

Murdmaa, I.; Ivanova, E.; Leduc, G.; Beaufort, L.; Peresypkin, V.; Vidal, L.; Ovsepyan, E.; Alekhina, G.; Kravtsov, V.; Vasileva, V.

2009-04-01

We analyzed n-alkanes spectra, TOC content, and C/N ratio in the upper 12 m of the giant IMAGES Core MD02-2529 from the Cocos Ridge (08°12.33'N; 84°07.32'W; 1619 m w.d.) to estimate terrestrial organic matter (TOM) and marine organic matter (MOM) contribution to the total organic matter budget in sediments. Multi-proxy studies of nannofossils, benthic and planktic foraminifers reveal productivity variations during the time interval of the last ~ 70 ka recovered by the upper part of the core according to the age model based on AMS-14C dates and benthic oxygen isotope record. According to the shipboard core description, the slightly calcareous hemipelagic mud recovered by Core MD02-2529 contains a considerable admixture of terrestrial plant remains. This is confirmed by optical microscopic and SEM studies which reveal a strong pyritization of the particular terrestrial organic matter. As estimated by the proportion of the mainly terrestrial long-molecular alkanes (C23 - C38) relative to mainly planktic short-molecular ones (C10 - C22), the TOM input largely controls variations in the TOC content throughout the studied core interval, possibly except for the Upper Holocene, where higher TOC values correspond to relatively increased MOM content. TOM strongly dominates over the MOM content in sediments of the beginning of Termination 1, most enriched in total organic matter (up to 3.4% TOC). High content of the TOM is also fixed by n-alkane data over the Younger Dryas and H-events. Mass accumulation rates (MAR) of TOC, as well as terrestrial and marine organic matter, generally support the data on percentages, but show that the MOM flux was considerable even during the maximum TOM input at the beginning of Termination I. We suggest that this abundant TOM flux was related to the glacioeustatic sea level lowstand at the LGM, during which the emerged shelf became a vegetated coastal plain affected by seasonally humid tropical monsoon climate. The terrestrial organic debris was most intensely washed off the coastal plain at the beginning of post-glacial transgression ~17 cal. ka BP. Glacioeustatic sea level oscillations, along with climate and river runoff changes, controlled variations in the TOM flux throughout the studied interval. The MOM commonly prevails in intervals with a low TOC content, although its relatively high MAR values may also coincide with TOC maxima, as at the beginning of Termination I. The MOM contribution to the total organic matter increased in the Early Holocene, at ~ 8 cal. ka, and especially at ~ 60 cal. ka (possibly coeval with the H-6 event). Relatively low and less variable accumulation rates of MOM, as compared to those of TOM may be explained by the location of the site MD02-2529 between the two high-productivity areas associated with coastal upwellings in the Panama Bight and Gulf of Papagayo. The paleoproductivity estimates based on coccolithophoride counts show a short-term variability with the extremal values during the Termination I. This high-productivity event corresponds to the highest planktic foraminiferal abundance and the maximum values of foraminiferal productivity index. The productivity increase at 16-14 cal ka BP might result from the nutrient rearrangement related to reorganization of the thermohaline circulation over the termination. However, high total abundance of benthic foraminifera and maximum values of several productivity-related benthic species are found at MIS 2, from ~ 25 to 22 cal ka BP. MOM export from the upper continental slope by the bottom nepheloid layer during the LGM sea level lowstand might serve as the food source for this benthic production pulse. Meanwhile, calcareous phytoplankton production seems to remain rather high through the late MIS3 - Termination I and decreased during the Holocene. The low total abundance of planktic foraminifera and an enhanced content of oligotrophic mixed-layer dwelling planktic foraminiferal species in the Holocene sediments confirm the productivity decrease. The low productivity might result from a pycnocline deepening due to abundant moisture supply from the Caribbean and corresponding surface water freshening at site MD02-2529.

Equilibrium Line Altitudes and paleotemperature reconstructions from Nevado Hualcán (9°S) and Nevado Coropuna (15°S), Tropical Andes (Peru).

NASA Astrophysics Data System (ADS)

Úbeda, J.; Giráldez, C.; Palacios, D.

2012-04-01

We have reconstructed the Equilibrium Line Altitude (ELA) in seven valleys on the SW slope of Nevado Hualcán (9°S, 77°W; 6122 m asl) and on the SE slope of Nevado Coropuna (15°S, 72°W; 6377masl) using the Area x Altitude Balance Ratio method (Osmaston 2005). We have also deduced the paleotemperatures using the following equation: ΔT=ATLR•ΔELA; being ΔT (°C) the paleotemperature depression; ATLR (°C/m) the Atmospheric Temperature Lapse Rate; and ΔELA (m) the ELA depression. The ATLR for Coropuna was deduced through the use of data loggers. For Hualcán we used the value ATLR =0.0065°C/m, valid for the tropics (Kaser and Osmaston, 2002). We obtained the following results: 1) Hualcán: a) ELAs: 5124m (2003); 5018m (1962); 4994m during the Little Ice Age (LIA); and 4652m during the last studied maximum advance considered to be the Younger Dryas (YD, ~13-11ka) by correlation with nearby mountains (Glasser et al., 2009). b) ΔELAs: 106m (1962); 130m (LIA); and 199m (YD). c) ΔT: -0.69°C (1962); -0.85°C (LIA); -3.07°C (YD). 2) Coropuna: a) ELAs: 5862m (2007); 5853m (1986); 5787m (1955); 5776 (LIA); and 4951m in the 13-1136Cl ka phase (Ubeda, 2011). b) ΔELA: 9m (1986); 66m (1955); 86m (LIA); and 911m in 13-1136Cl ka. C) ΔT: -0.20°C (1986); -0.71°C (1955); and -7.65°C (13-1136Cl ka). The values ΔT during LIA in Hualcán and Coropuna (0.85 and 0.72°C) are consistent with the global warming considered to be 0,74°C between 1906 and 2005 (IPCC, 2007). During the mid XXth century and the LIA, ΔT is higher in Hualcán (0.69°C and 0.85°C) than in Coropuna (0.55°C and 0.72°C), with a regional gradient of -0.02°C per degree of latitude (°C/°). However, during the YD (13-1136Cl ka), ΔT was higher in Coropuna (7.65°C) than in Hualcán (3.07°C), with a gradient of 0.76°C/°. Although other evidences exist of a pantropical cooling of >5°C during the last glaciation, in Coropuna this cooling was strengthened by the retro-alimentation of its glacial system which in 13-1136Cl ka had a surface of >400 km2 (Ubeda, 2011). Glasser, N.F., Clemmens, S., Schnabel, C., Fenton, C.R. and McHargue, L., 2009. Tropical glacier fluctuations in the Cordillera Blanca, Peru between 12.5 and 7.6 ka from cosmogenic 10Be dating. Quaternary Science Reviews, 28: 3448-3458. IPCC, 2007: Climate Change 2007: Synthesis Report. Contribution of Working Groups I, II and III to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change [Core Writing Team, Pachauri, R.K and Reisinger, A. (eds.)]. IPCC, Geneva, Switzerland, 104 pp. Kaser, G. and Osmaston, H., 2002. Tropical Glaciers. International Hydrology Series. Cambridge University Press, Cambridge (U.K.), 207 pp. Osmaston, H., 2005. Estimates of glacier equilibrium line altitudes by the Area x Altitude, the Area x Altitude Balance Ratio and the Area x Altitude Balance Index methods and their validation. Quaternary International, 22-31: 138-139. Úbeda, J., 2011. El impacto del cambio climático en los glaciares del complejo volcánico Nevado Coropuna (cordillera occidental de los Andes, Sur del Perú). PhD Thesis. Universidad Complutense de Madrid, (Spain), 558 pp. Available online: http://eprints.ucm.es/12076/ Research funded by CGL2009-7343 project, Government of Spain.

Exploring 3D structural influences of aliphatic and aromatic chemicals on α-cyclodextrin binding.

PubMed

Linden, Lukas; Goss, Kai-Uwe; Endo, Satoshi

2016-04-15

Binding of solutes to macromolecules is often influenced by steric effects caused by the 3D structures of both binding partners. In this study, the 1:1 α-cyclodextrin (αCD) binding constants (Ka1) for 70 organic chemicals were determined to explore the solute-structural effects on the αCD binding. Ka1 was measured using a three-part partitioning system with either a headspace or a passive sampler serving as the reference phase. The Ka1 values ranged from 1.08 to 4.97 log units. The results show that longer linear aliphatic chemicals form more stable complexes than shorter ones, and that the position of the functional group has a strong influence on Ka1, even stronger than the type of the functional group. Comparison of linear and variously branched aliphatic chemicals indicates that having a sterically unhindered alkyl chain is favorable for binding. These results suggest that only one alkyl chain can enter the binding cavity. Relatively small aromatic chemicals such as 1,3-dichlorobenzene bind to αCD well, while larger ones like tetrachlorobenzene and 3-ring aromatic chemicals show only a weak interaction with αCD, which can be explained by cavity exclusion. The findings of this study help interpret cyclodextrin binding data and facilitate the understanding of binding processes to macromolecules. Copyright © 2016 Elsevier Inc. All rights reserved.

Quantitative summer and winter temperature reconstructions from pollen and chironomid data in the Baltic-Belarus area

NASA Astrophysics Data System (ADS)

Veski, Siim; Seppä, Heikki; Stančikaitė, Migle; Zernitskaya, Valentina; Reitalu, Triin; Gryguc, Gražyna; Heinsalu, Atko; Stivrins, Normunds; Amon, Leeli; Vassiljev, Jüri; Heiri, Oliver

2015-04-01

Quantitative reconstructions based on fossil pollen and chironomids are widely used and useful for long-term climate variability estimations. The Lateglacial and early Holocene period (15-8 ka BP) in the Baltic-Belarus (BB) area between 60°-51° N was characterized by sudden shifts in climate due to various climate forcings affecting the climate of the northern hemisphere and North Atlantic, including the proximity of receding ice sheets. Climate variations in BB during the LG were eminent as the southern part of the region was ice free during the Last Glacial Maximum over 19 ka BP, whereas northern Estonia became ice free no sooner than 13 ka BP. New pollen based reconstructions of summer (May-to-August) and winter (December-to-February) temperatures between 15-8 ka BP along a S-N transect in the BB area display trends in temporal and spatial changes in climate variability. These results are completed by two chironomid-based July mean temperature reconstructions (Heiri et al. 2014). The magnitude of change compared with modern temperatures was more prominent in the northern part of BB area than in the southern part. The 4 °C winter and 2 °C summer warming at the start of GI-1 was delayed in the BB area and Lateglacial maximum temperatures were reached at ca 13.6 ka BP, being 4 °C colder than the modern mean. The Younger Dryas cooling in the area was 5 °C colder than present as inferred by all proxies (Veski et al. in press). In addition, our analyses show an early Holocene divergence in winter temperature trends with modern values reaching 1 ka earlier (10 ka BP) in southern BB compared to the northern part of the region (9 ka BP). Heiri, O., Brooks, S.J., Renssen, H., Bedford, A., Hazekamp, M., Ilyashuk, B., Jeffers, E.S., Lang, B., Kirilova, E., Kuiper, S., Millet, L., Samartin, S., Toth, M., Verbruggen, F., Watson, J.E., van Asch, N., Lammertsma, E., Amon, L., Birks, H.H., Birks, J.B., Mortensen, M.F., Hoek, W.Z., Magyari, E., Muñoz Sobrino, C., Seppä, H., Tinner, W., Tonkov, S., Veski, S., Lotter, A.F., 2014. Validation of climate model-inferred regional temperature change for late-glacial Europe. Nature Communications 5:4914, doi: 10.1038/ncomms5914 Veski, S., Seppä, H., Stančikaitė, M., Zernitskaya, V., Reitalu, T., Gryguc, G., Heinsalu, A., Stivrins, N., Amon, L., Vassiljev, J., Heiri, O. (in press). Quantitative summer and winter temperature reconstructions from pollen and chironomid data between 15 and 8 ka BP in the Baltic-Belarus area. Quaternary International. doi: 10.1016/j.quaint.2014.10.059

Bromine release during Plinian eruptions along the Central American Volcanic Arc

NASA Astrophysics Data System (ADS)

Hansteen, T. H.; Kutterolf, S.; Appel, K.; Freundt, A.; Perez-Fernandez, W.; Wehrmann, H.

2010-12-01

Volcanoes of the Central American Volcanic Arc (CAVA) have produced at least 72 highly explosive eruptions within the last 200 ka. The eruption columns of all these “Plinian” eruptions reached well into the stratosphere such that their released volatiles may have influenced atmospheric chemistry and climate. While previous research has focussed on the sulfur and chlorine emissions during such large eruptions, we here present measurements of the heavy halogen bromine by means of synchrotron radiation induced micro-XRF microanalysis (SR-XRF) with typical detection limits at 0.3 ppm (in Fe rich standard basalt ML3B glass). Spot analyses of pre-eruptive glass inclusions trapped in minerals formed in magma reservoirs were compared with those in matrix glasses of the tephras, which represent the post-eruptive, degassed concentrations. The concentration difference between inclusions and matrix glasses, multiplied by erupted magma mass determined by extensive field mapping, yields estimates of the degassed mass of bromine. Br is probably hundreds of times more effective in destroying ozone than Cl, and can accumulate in the stratosphere over significant time scales. Melt inclusions representing deposits of 22 large eruptions along the CAVA have Br contents between 0.5 and 13 ppm. Br concentrations in matrix glasses are nearly constant at 0.4 to 1.5 ppm. However, Br concentrations and Cl/Br ratios vary along the CAVA. The highest values of Br contents (>8 ppm) and lowest Cl/Br ratios (170 to 600) in melt inclusions occur across central Nicaragua and southern El Salvador, and correlate with bulk-rock compositions of high Ba/La > 85 as well as low La/Yb <5. Thus we observe the maximum magmatic Br-concentrations in the segements of the arc. where the input of sediment and water into the subduction system is largest and the melting column is longest. The largest eruptive emissions of Br into the atmosphere, however, occurred in Guatemala due to the large magnitude of eruptions. The most prominent example is the 84 ka Los Chocoyos eruption from Atitlán Caldera, which discharged 700 kilotons of Br. On average, each of the remaining 21 CAVA eruptions studied have discharged c.100 kilotons of bromine. During the past 200 ka, CAVA volcanoes have emitted a cumulative mass of 3.2 Mt of Br through highly explosive eruptions. There are six periods in the past (c. 2ka, 6ka, 25ka, 40ka, 60ka, 75ka) when up to four larger eruptions occurred within only several hundred years. The heavy halogen release of these eruptions may have had a cumulative effect on the atmosphere which is presently investigated by climate/atmosphere models based on our analyses as input data.

Post-collapse evolution of a coastal caldera system: Insights from a 3D multichannel seismic survey from the Campi Flegrei caldera (Italy)

NASA Astrophysics Data System (ADS)

Steinmann, Lena; Spiess, Volkhard; Sacchi, Marco

2018-01-01

In this study we present the first 3D high-resolution multichannel seismic dataset from a (partly) submerged caldera setting, the Campi Flegrei caldera (CFc). Our work aims at examining the spatial and temporal evolution of the CFc since the last caldera-forming event, the Neapolitan Yellow Tuff (NYT, 15 ka) eruption. The main objectives are to investigate the caldera's shallow (< 200 m) subsurface structure and post-NYT-collapse (< 15 ka) deformational processes, the manifestation of magmatic and hydrothermal processes in the subsurface, as well as the volume, dispersal and explosivity of coastal post-collapse eruptions, thereby significantly advancing our current knowledge of the CFc. Our findings confirm the existence of a nested-caldera system comprising two caldera depressions bordered by an inner and a deeper (> 200 m) outer caldera ring-fault zone. The seismic data revealed that the NYT collapse occurred exclusively along the inner caldera ring-fault and that the related NYT caldera depression is filled with on average 61 m of sediment deposited between 15 and 8.6 ka. The geometry of the inner ring-fault, consisting of four fault segments, seems to be strongly influenced by regional NW-SE and NE SW-trending faults. Furthermore, we found that the ring-faults have acted as pathway for the recent (< 3.7 ka) ascent of fluids (gases and liquids) and the emplacement of intrusions. We propose that the outer ring-fault zone, which likely formed in the course of the Campanian Ignimbrite (CI, 39 ka) eruption, has had the main control on the release and ascent of fluids. Overall, the caldera ring-faults represent key locations for the interconnection between the magmatic-hydrothermal systems and the surface and, thus, potentially represent future eruption sites as well as important fluid pathways during the recent unrest episodes. Furthermore, we reassessed the volume, dispersal, and explosivity of the post-collapse Nisida Bank (10.3-9.5 ka), Nisida Island ( 3.98 ka), and Capo Miseno (3.7 ka) eruptions, yielding DRE values of 0.15 km3, 0.1 km3, and 0.08 km3, respectively, and an explosive magnitude of at least moderate-large scale (VEI 3). Our findings highlight that eruption volumes may be underestimated by 3 to 4 times if the submerged portion of a (partly) submerged caldera is not considered, implying severe consequences for the hazard and risk evaluation. The spatial response of the post-collapse (< 15 ka) depositional environment to volcanic activity, deformational processes and sea-level variations is presented in a comprehensive 3D evolutionary model.

A chemical model of seawater including dissolved ammonia and the stoichiometric dissociation constant of ammonia in estuarine water and seawater from -2 to 40°C

NASA Astrophysics Data System (ADS)

Clegg, Simon L.; Whitfield, Michael

1995-06-01

The calculation of the percentage of un-ionised ammonia in estuarine water and seawater requires values of the stoichiometric dissociation constant of ammonia, defined by: K*a/mol kg -1 = mNH 3mH +/ mNH +4, where m denotes molality. A thermodynamic model of seawater, including dissolved NH 3 and NH +4, is developed using an extended Pitzer formalism parameterised from available data. The model is validated using emf measurements for cells containing artificial seawater with added HCl, and NH 4Cl, and NH 3 over a range of temperatures and salinities. Calculated values of K*a are tabulated from 0 to 40 ppt salinity and -2 to 40°C, on both a free ( mH +) and total ( mH + + mHSO -4) hydrogen ion basis for use with pH measurements made on the corresponding scales. Accuracy (in K*a) is likely to be better than 5% at all temperatures and salinities.

Design and evaluation of 66 kV-class HTS power cable using REBCO wires

NASA Astrophysics Data System (ADS)

Ohya, M.; Yumura, H.; Masuda, T.; Amemiya, N.; Ishiyama, A.; Ohkuma, T.

2011-11-01

Sumitomo Electric (SEI) has been involved in the development of 66 kV-class HTS cables using REBCO wires. One of the technical targets in this project is to reduce the AC loss to less than 2 W/m/phase at 5 kA. SEI has developed a clad-type of textured metal substrate with lower magnetization loss compared with a conventional NiW substrate. In addition, 30 mm-wide REBCO tapes were slit into 4 mm-wide strips, and these strips were wound spirally on a former with small gaps. The AC loss of a manufactured 4-layer cable conductor was 1.5 W/m at 5 kA at 64 K. Given that the AC loss in a shield layer is supposed to be one-fourth of a whole cable core loss, our cables are expected to achieve the AC loss target of less than 2 W/m/phase at 5 kA. Another important target is to manage a fault current. A cable core was designed and fabricated based on the simulation findings, and over-current tests (max. 31.5 kA, 2 s) were conducted to check its performance. The critical current value of the cable cores were measured before and after the over-current tests and verified its soundness. A 5 kA-class current lead for the cable terminations was also developed. The current loading tests were conducted for the developed current leads. The temperature distribution of the current leads reached to the steady-state within less than 12 h, and it was confirmed that the developed current lead has enough capacity of 5 kA loading.

A high-resolution Holocene speleothem record from NE Romania: the nexus of Arctic and North Atlantic atmospheric circulations

NASA Astrophysics Data System (ADS)

Constantin, S.; Pourmand, A.; Moldovan, O.; Sharifi, A.; Mehterian, S.; Swart, P. K.

2017-12-01

The Romanian Carpathians act as a geomorphological barrier between different atmospheric circulation systems over Central and Eastern Europe; the NW of Romania lies under the remote influence of the North Atlantic oscillation, while the NE is influenced by the Arctic climate. In NW Romania, previous stable isotope studies of speleothems have not yielded a clear account of abrupt climate oscillations during the Holocene. Here we present results from a stalagmite collected from the Tauşoare Cave, located in NE Carpathians. The chronology of stalagmite T141 is based on 15 high-precision Th/U dates ranging between 32 and 1.1 ka with a continuous growth between 13.3 and 1.1 ka. The portion of the record within the Holocene was analyzed for δ18O and δ13C at a resolution ranging between 15 to 200 years/sample. The resulting δ18O record captures the Younger Dryas (YD) event centered at 12.9 ka, with δ18O values about 4 ‰ more depleted than those corresponding to the Holocene Climatic Optimum. The 8.2 ka event appears to be also captured in the record, although less prominent. The T141 isotope record is significantly different when compared to coeval records measured in speleothems from NW Carpathians, which do not exhibit marked changes during the YD or 8.2 ka events. This is likely due to the contrasting effect of temperature and atmospheric transport on δ18O signal in NW Romania. Within a distance of 200 km to the east, on the eastern flank of the Carpathian range, the δ18O signal of the Arctic circulation appears to be more prominent and clearly exhibits a positive relationship with temperature changes.

Proton storage site in bacteriorhodopsin: new insights from QM/MM simulations of microscopic pKa and infrared spectra

PubMed Central

Goyal, Puja; Ghosh, Nilanjan; Phatak, Prasad; Clemens, Maike; Gaus, Michael; Elstner, Marcus; Cui, Qiang

2011-01-01

Identifying the group that acts as the proton storage/loading site is a challenging but important problem for understanding the mechanism of proton pumping in biomolecular proton pumps, such as bacteriorhodopsin (bR) and cytochrome c oxidase. Recent experimental studies of bR propelled the idea that the proton storage/release group (PRG) in bR is not an amino acid but a water cluster embedded in the protein. We argue that this idea is at odds with our knowledge of protein electrostatics, since invoking the water cluster as PRG would require the protein to raise the pKa of a hydronium by almost 11 pKa units, which is difficult considering known cases of pKa shifts in proteins. Our recent QM/MM simulations suggested an alternative “intermolecular proton bond” model in which the stored proton is shared between two conserved Glu residues (194 and 204). Here we show that this model leads to microscopic pKa values consistent with available experimental data and the functional requirement of a PRG. Extensive QM/MM simulations also show that, independent of a number of technical issues, such as the influence of QM region size, starting x-ray structure and nuclear quantum effects, the “intermolecular proton bond” model is qualitatively consistent with available spectroscopic data. Potential of mean force calculations show explicitly that the stored proton strongly prefers the pair of Glu residues over the water cluster. The results and analyses help highlight the importance of considering protein electrostatics and provide arguments for why the “intermolecular proton bond” model is likely applicable to PRG in biomolecular proton pumps in general. PMID:21761868

Automatized sspKa measurements of dihydrogen phosphate and Tris(hydroxymethyl) aminomethane in acetonitrile/water mixtures from 20 to 60°C.

PubMed

Acquaviva, A; Tascon, M; Padró, J M; Gagliardi, L G; Castells, C B

2014-09-01

We measured pKa values of Tris(hydroxymethyl)aminomethane and dihydrogen phosphate; both are commonly used to prepare buffers for reverse-phase liquid chromatography (RPLC), in acetonitrile/water mixtures from 0% to 70% (v/v) (64.6% (w/w)) acetonitrile and at 20, 30, 40, 50, and 60°C. The procedure is based on potentiometric measurements of pH of buffer solutions of variable solvent compositions using a glass electrode and a novel automated system. The method consists in the controlled additions of small volumes of a thermostated solution from an automatic buret into another isothermal solution containing exactly the same buffer-component concentrations, but a different solvent composition. The continuous changes in the solvent composition induce changes in the potentials. Thus, only two sequences of additions are needed: increasing the amount of acetonitrile from pure water and decreasing the content of acetonitrile from 70% (v/v) (64.6% (w/w)). In the procedure with homemade apparatus, times for additions, stirring, homogenization, and data acquisition are entirely controlled by software programmed for this specific routine. This rapid, fully automated method was applied to acquire more than 40 potential data covering the whole composition range (at each temperature) in about two hours and allowed a systematic study of the effect of temperature and acetonitrile composition on acid-base equilibria of two widely used substances to control pH close to 7. The experimental pKa results were fitted to empirical functions between pKa and temperature and acetonitrile composition. These equations allowed predictions of pKa to estimate the pH of mixtures at any composition and temperature, which would be very useful, for instance, during chromatographic method development. Copyright © 2014 Elsevier B.V. All rights reserved.

From contact angle titration to chemical force microscopy: a new route to assess the pH-dependent character of the stratum corneum.

PubMed

Wagner, Matthieu; Mavon, Alain; Haidara, Hamidou; Vallat, Marie-France; Duplan, Hélène; Roucoules, Vincent

2012-02-01

Despite of its complex multicomponent organization and its compact architecture, the Stratum corneum (SC) is not completely impermeable to substances directly applied on the skin surface. A huge number of works have been dedicated to the understanding of the mechanisms involved in substance permeation by exploring deeper layers than the SC itself. Surprisingly, there is a poor interest in studies relating to interactions which may occur in the near-surface region (i.e. approximately 1 nm depth) of the SC. In this work, equilibrium proton-transfer reactions have been used as probes to define in a fundamental point of view the nature of the SC interactions with its environment. Such titration curves are investigated on 'in vitro' SC (isolated SC from abdominal skin tissue) and on 'in vivo' volar forearm (a sebum poor area). The results are discussed in term of work of adhesion and surface pKa values. Because SC can 'reconstruct' under heating, influence of the temperature on titration curves is investigated and the role of the different components is discussed. Different sigmoidal transitions were observed. Two common pKa values (pKa(1) = 4 and pKa(2) = 11.5) were clearly identified in both cases and associated to an acid-base character. By playing with the temperature of 'in vitro' SC, the 'accessibility' of polar functions was increased, thus refining the results by revealing an amphoteric character with an acid-to-base transition at pH 3.5 and two acid transitions at pH = 6.5 and pH = 11.5. Adhesion forces between an Atomic Force Microscopy (AFM) tip and a single isolated corneocyte through buffered liquid media were also investigated to better understand the role of the individual corneocytes. © 2011 The Authors. ICS © 2011 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Increased thyrotropin binding in hyperfunctioning thyroid nodules.

PubMed

Müller-Gärtner, H W; Schneider, C; Bay, V; Tadt, A; Rehpenning, W; de Heer, K; Jessel, M

1987-08-01

The object of this study was to investigate TSH receptors in hyperfunctioning thyroid nodules (HFN). In HFN, obtained from seven patients, 125-I-TSH binding as determined by equilibrium binding analysis on particulate membrane preparations, was found to be significantly increased as compared with normal thyroid tissues (five patients; P less than 0.001). Scatchard analysis of TSH-binding revealed two kinds of binding sites for both normal thyroid tissue and HFN, and displayed significantly increased association constants of high- and low-affinity binding sites in HFN (Ka = 11.75 +/- 6.8 10(9) M-1, P less than 0.001 and Ka = 2.1 +/- 1.0 10(7) M-1, P less than 0.025; x +/- SEM) as compared with normal thyroid tissue (Ka = 0.25 +/- 0.06 10(9) M-1, Ka = 0.14 +/- 0.03 10(7) M-1; x +/- SEM). The capacity of the high-affinity binding sites in HFN was found to be decreased (1.8 +/- 1.1 pmol/mg protein, x +/- SEM) in comparison with normal thyroid tissue (4.26 +/- 1.27 pmol/mg protein; x +/- SEM). TSH-receptor autoradiography applied to cryostatic tissue sections confirmed increased TSH binding of the follicular epithelium in HFN. These data suggest that an increased affinity of TSH-receptor sites in HFN in iodine deficient areas may be an important event in thyroid autonomy.

Sequence preservation of osteocalcin protein and mitochondrial DNA in bison bones older than 55 ka

NASA Astrophysics Data System (ADS)

Nielsen-Marsh, Christina M.; Ostrom, Peggy H.; Gandhi, Hasand; Shapiro, Beth; Cooper, Alan; Hauschka, Peter V.; Collins, Matthew J.

2002-12-01

We report the first complete sequences of the protein osteocalcin from small amounts (20 mg) of two bison bone (Bison priscus) dated to older than 55.6 ka and older than 58.9 ka. Osteocalcin was purified using new gravity columns (never exposed to protein) followed by microbore reversed-phase high-performance liquid chromatography. Sequencing of osteocalcin employed two methods of matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS): peptide mass mapping (PMM) and post-source decay (PSD). The PMM shows that ancient and modern bison osteocalcin have the same mass to charge (m/z) distribution, indicating an identical protein sequence and absence of diagenetic products. This was confirmed by PSD of the m/z 2066 tryptic peptide (residues 1 19); the mass spectra from ancient and modern peptides were identical. The 129 mass unit difference in the molecular ion between cow (Bos taurus) and bison is caused by a single amino-acid substitution between the taxa (Trp in cow is replaced by Gly in bison at residue 5). Bison mitochondrial control region DNA sequences were obtained from the older than 55.6 ka fossil. These results suggest that DNA and protein sequences can be used to directly investigate molecular phylogenies over a considerable time period, the absolute limit of which is yet to be determined.

Measurement of the affinity and phosphorylation constants governing irreversible inhibition of cholinesterases by di-isopropyl phosphorofluoridate

PubMed Central

Main, A. R.; Iverson, F.

1966-01-01

1. A procedure is described for determining the affinity constant Ka and the phosphorylation constant kp for the inhibition by di-isopropyl phosphorofluoridate of erythrocyte acetylcholinesterase and serum cholinesterase. The procedure depends on the use of a specially designed reaction vessel with which incubation times as short as 1·2sec. could be obtained at any convenient temperature. 2. The Ka of acetylcholinesterase decreased from 1·58 (±0·22)×10−3m at 5° to 1·17 (±0·10)×10−3m at 25° and the associated change in enthalpy was 2980 cal. 3. The kp of acetylcholinesterase increased from 11·9 (±0·7)min.−1 at 5° to 40·7 (±1·4)min.−1 at 25°, indicating an activational energy of 9600 cal. The change in entropy associated with Ka was 23·5 cal. degree−1 at 25°. 4. At 5°, the Ka and kp of serum cholinesterase were 9·95 (±1·10)×10−6m and 11·2 (±0·63)min.−1 respectively. 5. The 150-fold difference in the inhibitory power of di-isopropyl phosphorofluoridate for the two cholinesterases was attributed entirely to differences in affinity. PMID:5968549

New Progress in Paleoearthquake Studies of the East Sertengshan Piedmont Fault, Inner Mongolia, China

NASA Astrophysics Data System (ADS)

He, Zhongtai

2017-04-01

The two eastern segments of the Sertengshan piedmont fault have moved considerably since the Holocene. Several paleoseismic events have occurred along the fault since 30 ka BP. Paleoearthquake studies have been advanced by digging new trenches and combining the results with the findings of previous studies. Comprehensive analyses of the trenches revealed that 6 paleoseismic events have occurred on the Kuoluebulong segment since approximately 30 ka BP within the following successive time periods: 19.01-37.56 ka, 18.73 ka, 15.03-15.86 ka, 10.96 ka, 5.77-6.48 ka and 2.32 ka BP. The analyses also revealed that 6 paleoseismic events have occurred on the Dashetai segment since approximately 30 ka BP, and the successive occurrence times are 29.07 ka, 19.12-28.23 ka, 13.92-15.22 ka, 9.38-9.83 ka, 6.08-8.36 ka and 3.59 ka BP. The results indicate that quasi-periodic recurrences occurred along the two segments with an approximate 4000 a mean recurrence interval. The consistent timing of the 6 events between the two segments indicates that the segments might conform to the cascade rupturing model between the two segments of the Sertengshan piedmont fault. The latest event on the Kuoluebulong segment of the Sertengshan piedmont fault is the historical M8 earthquake that occurred on November 11, 7 BC, which was recorded by a large number of Chinese historical texts.

AV3V lesions attenuate the cardiovascular responses produced by blood-borne excitatory amino acid analogs

NASA Technical Reports Server (NTRS)

Whalen, E. J.; Beltz, T. G.; Lewis, S. J.; Johnson, A. K.

1999-01-01

Systemic injections of the excitatory amino acid (EAA) analogs, kainic acid (KA) and N-methyl-D-aspartate (NMDA), produce a pressor response in conscious rats that is caused by a centrally mediated activation of sympathetic drive and the release of arginine vasopressin (AVP). This study tested the hypothesis that the tissue surrounding the anteroventral part of the third ventricle (AV3V) plays a role in the expression of the pressor responses produced by systemically injected EAA analogs. Specifically, we examined whether prior electrolytic ablation of the AV3V region would affect the pressor responses to KA and NMDA (1 mg/kg iv) in conscious rats. The KA-induced pressor response was smaller in AV3V-lesioned than in sham-lesioned rats (11 +/- 2 vs. 29 +/- 2 mmHg; P < 0.05). After ganglion blockade, KA produced a pressor response in sham-lesioned but not AV3V-lesioned rats (+27 +/- 3 vs. +1 +/- 2 mmHg; P < 0.05). The KA-induced pressor response in ganglion-blocked sham-lesioned rats was abolished by a vasopressin V1-receptor antagonist. Similar results were obtained with NMDA. The pressor response to AVP (10 ng/kg iv) was slightly smaller in AV3V-lesioned than in sham-lesioned ganglion-blocked rats (45 +/- 3 vs. 57 +/- 4 mmHg; P < 0.05). This study demonstrates that the pressor responses to systemically injected EAA analogs are smaller in AV3V-lesioned rats. The EAA analogs may produce pressor responses by stimulation of EAA receptors in the AV3V region, or the AV3V region may play an important role in the expression of these responses.

Toward an integrated ice core chronology using relative and orbital tie-points

NASA Astrophysics Data System (ADS)

Bazin, L.; Landais, A.; Lemieux-Dudon, B.; Toyé Mahamadou Kele, H.; Blunier, T.; Capron, E.; Chappellaz, J.; Fischer, H.; Leuenberger, M.; Lipenkov, V.; Loutre, M.-F.; Martinerie, P.; Parrenin, F.; Prié, F.; Raynaud, D.; Veres, D.; Wolff, E.

2012-04-01

Precise ice cores chronologies are essential to better understand the mechanisms linking climate change to orbital and greenhouse gases concentration forcing. A tool for ice core dating (DATICE [developed by Lemieux-Dudon et al., 2010] permits to generate a common time-scale integrating relative and absolute dating constraints on different ice cores, using an inverse method. Nevertheless, this method has only been applied for a 4-ice cores scenario and for the 0-50 kyr time period. Here, we present the bases for an extension of this work back to 800 ka using (1) a compilation of published and new relative and orbital tie-points obtained from measurements of air trapped in ice cores and (2) an adaptation of the DATICE inputs to 5 ice cores for the last 800 ka. We first present new measurements of δ18Oatm and δO2/N2 on the Talos Dome and EPICA Dome C (EDC) ice cores with a particular focus on Marine Isotopic Stages (MIS) 5, and 11. Then, we show two tie-points compilations. The first one is based on new and published CH4 and δ18Oatm measurements on 5 ice cores (NorthGRIP, EPICA Dronning Maud Land, EDC, Talos Dome and Vostok) in order to produce a table of relative gas tie-points over the last 400 ka. The second one is based on new and published records of δO2/N2, δ18Oatm and air content to provide a table of orbital tie-points over the last 800 ka. Finally, we integrate the different dating constraints presented above in the DATICE tool adapted to 5 ice cores to cover the last 800 ka and show how these constraints compare with the established gas chronologies of each ice core.

Development of a Species-Specific PCR Assay for Detection of Leishmania donovani in Clinical Samples from Patients with Kala-Azar and Post-Kala-Azar Dermal Leishmaniasis

PubMed Central

Salotra, Poonam; Sreenivas, G.; Pogue, Gregory P.; Lee, Nancy; Nakhasi, Hira L.; Ramesh, V.; Negi, N. S.

2001-01-01

We have developed a PCR assay that is capable of amplifying kinetoplast DNA (kDNA) of Leishmania donovani in a species-specific manner among Old World leishmanias. With Indian strains and isolates of L. donovani the assay was sensitive enough to detect kDNA in an amount equivalent to a single parasite or less. The extreme sensitivity of the assay was reflected in its ability to detect parasite DNA from small volumes of peripheral blood of patients with kala-azar (KA) and from skin lesions from patients with post-KA dermal leishmaniasis (PKDL). A total of 107 clinical leishmaniasis samples were analyzed. Of these 102 (95.3%) were positive by PCR. The test provided a diagnosis of KA with 96% sensitivity using patient whole-blood samples instead of bone marrow or spleen aspirates that are obtained by invasive procedures. The assay was also successful in the diagnosis of 45 of 48 PKDL cases (93.8%). Cross-reactions with pathogens prevalent in the area of endemicity, viz., Mycobacterium tuberculosis, Mycobacterium leprae, and Plasmodium spp., could be ruled out. Eighty-one control samples, including dermal scrapings from healthy portions of skin from patients with PKDL were all negative. Two of twenty controls from the area of endemicity were found positive by PCR assay; however, there was a good possibility that these two were asymptomatic carriers since they were serologically positive for KA. Thus, this PCR assay represents a tool for the diagnosis of KA and PKDL in Indian patients in a noninvasive manner, with simultaneous species identification of parasites in clinical samples. PMID:11230394

Effects of administration of beta-carotene, ascorbic acid, persimmons, and pods on antioxidative ability in UV-irradiated ODS rats.

PubMed

Hosotani, Keisuke; Yoshida, Minoru; Kitagawa, Masahiro

2005-07-01

To evaluate the effects of supplementing diets with carotenoid and ascorbic acid (AsA) on the antioxidative ability of Osteogenic Disorder-Shionogi (ODS) rats, we added synthetic beta-carotene (betaC), AsA, and powders of persimmon (Ka) and pods (Po) containing betaC and AsA to the diet and obtained the following results. The urinary 8-hydroxydeoxyguanosine (8-OHdG) concentration was low in the -betaC.AsA and +AsA groups but high in the +betaC.AsA, +Ka, and +Po groups. The thiobarbituric acid-reactive substances (TBARS) in both the liver and skin were higher in the -betaC.AsA group than in the +betaC.AsA group and were low in the +Ka and +Po groups. As antioxidant enzymes, glutathione peroxidase (GSH-Px) activity was high in the +betaC.AsA group, low in the -beta3C.AsA group in both the skin and liver, and also high in the + Ka and +Po group in the liver. Superoxide dismutase (SOD) activity was high in the -betaC.AsA group and low in the +betaC.AsA and +Ka groups in both the skin and liver. Catalase (CAT) activity in the liver was low in the -betaC.AsA, +AsA, and +betaC groups and high in the +betaC.AsA and +Po groups. These results confirmed that the administration of betaC, AsA, and persimmons and pods increases antioxidative ability in the skin and liver of ultraviolet-b(UV-B)-irradiated ODS rats.

Evaluation of the duration of thromboembolic prophylaxis after high-risk orthopaedic surgery: the ETHOS observational study.

PubMed

Bergqvist, David; Arcelus, Juan I; Felicissimo, Paulo

2012-02-01

Real-life data on post-discharge venous thromboembolism (VTE) prophylaxis practices and treatments are lacking. We assessed post-operative VTE prophylaxis prescribed and received in a prospective registry, compared with the 2004 American College of Chest Physicians (ACCP) guidelines in high-risk orthopaedic surgery patients. Consecutive patients undergoing total hip arthroplasty (THA), hip fracture surgery (HFS), or knee arthroplasty (KA) were enrolled at discharge from 161 centres in 17 European countries if they had received in-hospital VTE prophylaxis that was considered in accordance with the ACCP guidelines by the treating physician. Data on prescribed and actual prophylaxis were obtained from hospital charts and patient post-discharge diaries. Post-operative prophylaxis prescribed and actual prophylaxis received were considered adherent or adequate, respectively, if recommended therapies were used for ≥28 days (HFS and THA) or ≥10 days (KA). Among 4,388 patients, 69.9% were prescribed ACCP-adherent VTE prophylaxis (THA: 1,411/2,217 [63.6%]; HFS: 701/1,112 [63.0%]; KA: 955/1,059 [90.2%]). Actual prophylaxis received was described in 3,939 patients with an available diary after discharge (non-evaluability rate of 10%). Mean actual durations of pharmacological prophylaxis from surgery were: 28.4 ± 13.7 (THA), 29.3 ± 13.9 (HFS), and 28.7 ± 14.1 days (KA). ACCP-adequate VTE prophylaxis was received by 66.5% of patients (60.9% THA, 55.4% HFS, and 88.7% KA). Prophylaxis inadequacies were mainly due to inadequate prescription, non-recommended prophylaxis prescription at discharge, or too short prophylaxis prescribed. In high-risk orthopaedic surgery patients with hospital-initiated prophylaxis, there is a gap between ACCP recommendations, prescribed and actual prophylaxis received, mainly due to inadequate prescription at discharge.

Infrared-Vacuum Ultraviolet Pulsed Field Ionization-Photoelectron Study of C₂H₄ + Using a High-Resolution Infrared Laser

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xing, Xi; Reed, Beth; Bahng, Mi-Kyung

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The infrared (IR)-vacuum ultraviolet (VUV)-pulsed field ionization-photoelectron (IR-VUV-PFI-PE) spectrum for C₂H₄(X 1A g, V 11 = 1, N' Ka' Kc'=3₀₃) in the VUV range of 83 000-84 800 cm -1 obtained using a single mode infrared laser revealed 24 rotationally resolved vibrational bands for the ion C₂H₄ +(X 2B 3u) ground state. The frequencies and symmetry of the vibrational bandsmore » thus determined, together with the anharmonic frequency predictions calculated at the CCSD(T)/aug-cc-pVQZ level, have allowed the unambiguous assignment of these vibrational bands. These bands are mostly combination bands. The measured frequencies of these bands yield the fundamental frequencies for V 8 + ) 1103± ( 10 cm -1 and V 10 + ) 813 ( 10 cm -1 of C₂H₄ +(X 2B 3u), which have not been determined previously. The present IR-VUV-PFI-PE study also provides truly rovibrationally selected and resolved state-to-state cross sections for the photoionization transitions C₂H₄(X~ 1A g; V 11, N' Ka' Kc') → C₂H₄ +(X ~ 2B 3u; V i +, N + Ka + Kc +), where N' Ka' Kc' denotes the rotational level of C₂H₄(X ~ 1Ag; V 11), and V i + and N + Ka + Kc + represent the vibrational and rotational states of the cation.« less

RFP tags for labeling secretory pathway proteins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Liyang; Zhao, Yanhua; Zhang, Xi

2014-05-09

Highlights: • Membrane protein Orai1 can be used to report the fusion properties of RFPs. • Artificial puncta are affected by dissociation constant as well as pKa of RFPs. • Among tested RFPs mOrange2 is the best choice for secretory protein labeling. - Abstract: Red fluorescent proteins (RFPs) are useful tools for live cell and multi-color imaging in biological studies. However, when labeling proteins in secretory pathway, many RFPs are prone to form artificial puncta, which may severely impede their further uses. Here we report a fast and easy method to evaluate RFPs fusion properties by attaching RFPs to anmore » environment sensitive membrane protein Orai1. In addition, we revealed that intracellular artificial puncta are actually colocalized with lysosome, thus besides monomeric properties, pKa value of RFPs is also a key factor for forming intracellular artificial puncta. In summary, our current study provides a useful guide for choosing appropriate RFP for labeling secretory membrane proteins. Among RFPs tested, mOrange2 is highly recommended based on excellent monomeric property, appropriate pKa and high brightness.« less

pH-Triggered Molecular Alignment for Reproducible SERS Detection via an AuNP/Nanocellulose Platform

PubMed Central

Wei, Haoran; Vikesland, Peter J.

2015-01-01

The low affinity of neutral and hydrophobic molecules towards noble metal surfaces hinders their detection by surface-enhanced Raman spectroscopy (SERS). Herein, we present a method to enhance gold nanoparticle (AuNP) surface affinity by lowering the suspension pH below the analyte pKa. We developed an AuNP/bacterial cellulose (BC) nanocomposite platform and applied it to two common pollutants, carbamazepine (CBZ) and atrazine (ATZ) with pKa values of 2.3 and 1.7, respectively. Simple mixing of the analytes with AuNP/BC at pH < pKa resulted in consistent electrostatic alignment of the CBZ and ATZ molecules across the nanocomposite and highly reproducible SERS spectra. Limits of detection of 3 nM and 11 nM for CBZ and ATZ, respectively, were attained. Tests with additional analytes (melamine, 2,4-dichloroaniline, 4-chloroaniline, 3-bromoaniline, and 3-nitroaniline) further illustrate that the AuNP/BC platform provides reproducible analyte detection and quantification while avoiding the uncontrolled aggregation and flocculation of AuNPs that often hinder low pH detection. PMID:26658696

pH-Triggered Molecular Alignment for Reproducible SERS Detection via an AuNP/Nanocellulose Platform

NASA Astrophysics Data System (ADS)

Wei, Haoran; Vikesland, Peter J.

2015-12-01

The low affinity of neutral and hydrophobic molecules towards noble metal surfaces hinders their detection by surface-enhanced Raman spectroscopy (SERS). Herein, we present a method to enhance gold nanoparticle (AuNP) surface affinity by lowering the suspension pH below the analyte pKa. We developed an AuNP/bacterial cellulose (BC) nanocomposite platform and applied it to two common pollutants, carbamazepine (CBZ) and atrazine (ATZ) with pKa values of 2.3 and 1.7, respectively. Simple mixing of the analytes with AuNP/BC at pH < pKa resulted in consistent electrostatic alignment of the CBZ and ATZ molecules across the nanocomposite and highly reproducible SERS spectra. Limits of detection of 3 nM and 11 nM for CBZ and ATZ, respectively, were attained. Tests with additional analytes (melamine, 2,4-dichloroaniline, 4-chloroaniline, 3-bromoaniline, and 3-nitroaniline) further illustrate that the AuNP/BC platform provides reproducible analyte detection and quantification while avoiding the uncontrolled aggregation and flocculation of AuNPs that often hinder low pH detection.

Individual organic compounds in water extracts from podzolic soils of the Komi Republic

NASA Astrophysics Data System (ADS)

Shamrikova, E. V.; Punegov, V. V.; Gruzdev, I. V.; Vanchikova, E. V.; Vetoshkina, A. A.

2012-10-01

The contents of organic compounds in water extracts from organic horizons of loamy soils with different water contents from the medium taiga zone of the Komi Republic were determined by gas-liquid chromatography and chromatography-mass spectrometry. The mass concentration of organic carbon in the extracts was in the range of 290-330 mg/dm3; the mass fraction of the carbon from the identified compounds was 0.5-1.9%. Hydrocarbons made up about 60% of the total identified compounds; acids and their derivatives composed less than 40%. Most of the acids (40-70%) were aliphatic hydroxy acids. The tendencies in the formation of different classes of organic compounds were revealed depending on the degree of the soil hydromorphism. The acid properties of the water-soluble compounds were studied by pK spectroscopy. Five groups of compounds containing acid groups with similar pKa values were revealed. The compounds containing groups with pKa < 4.0 were predominant. The increase in the surface wetting favored the formation of compounds with pKa 3.2-4.0 and 7.4-8.4.

Paleomagnetic record determined in cores from deep research wells in the Quaternary Santa Clara basin, California

USGS Publications Warehouse

Mankinen, Edward A.; Wentworth, Carl M.

2016-01-01

The Mono Lake (ca. 32 ka), Pringle Falls (ca. 210 ka), and Big Lost (ca. 565 ka) geomagnetic excursions all seem to be represented in the Santa Clara Valley wells. Possible correlations to the Laschamp (ca. 40 ka) and Blake (ca. 110 ka) excursions are also noted. Three additional excursions that have apparently not been previously reported from western North America occur within cycle 6 (between 536 and 433 ka), near the base of cycle 5 (after 433 ka), and near the middle of cycle 2 (before ca. 75 ka).

Late Pleistocene deglaciation and paleo-environment in the Retezat Mountains, Southern Carpathians

NASA Astrophysics Data System (ADS)

Ruszkiczay-Rüdiger, Zsófia; Madarász, Balázs; Kern, Zoltán; Urdea, Petru; Braucher, Régis; Aster Team

2017-04-01

This study aims to use in situ produced 10Be based Cosmic Ray Exposure (CRE) ages to reconstruct glacier evolution in the Retezat Mts, the Southern Carpathians most glaciated area with peak elevations up to 2509 m asl. In the study area currently devoid of glaciers, the calculated theoretical ELA is at ˜2860 m asl. The paleo-Equilibrium Line Altitudes (ELAs) were calculated over the ˜21 to ˜13 ka time period based on the reconstructed glacial stillstands or re-advances geometries using the ssAAR method [1, 2]. Regarding the Northern side of the Retezat Mts, new and re-evaluated 10Be CRE ages (n=34) [3] were used while regarding the Southern side, they all result from a new sampling (n=25). According to the data, the most extended glaciation occurred during the LGM, down to ˜1050 m asl. on both sides of the Retezat Mts with most probable 10Be CRE ages of 21.0 -1.5+0.8 ka and 20.7 -1.0+0.9 ka. The reconstructed ELA depression in the North was ˜1010 m while it was ˜1190 m, in the South where the valleys glacial system (Lăpuşnicu - Judele) was significantly larger with longer glacier tongues. At the beginning of the Lateglacial (˜17-18 ka) the glaciers withdrew and the North-South difference between the ELA depression was decreased (˜885 m and ˜945 m, respectively). The ELA differences further reduced and vanished for the ˜15.3 ka glacial event - the last cold stage before the abrupt Bölling/Alleröd warming - with ELA depressions of ˜728 m and ˜712 m, respectively. The last glacial phase in the area characterized by small cirque glaciers occurred at 13.5 -0.6+0.6 ka in the North and 13.9 -0.4+0.9 ka in the South. By this time, the ELA depression was reduced to ˜660-680 m. Due to the small glacier size this value may have been influenced by local topoclimatic factors. So far, no data support Younger Dryas or Holocene glaciation of the Retezat Mts. The elevation difference of the ELAs suggests more precipitation on the Southern side of the Retezat Mts during the LGM. This may indicate a southerly wind regime at this part of Europe, which subsequently gave place to the westerly winds during the warming climate of the Lateglacial. Using a Chironomidae-based summer temperature (T) reconstruction from the area [4], T and mean annual precipitation (P) at the ELA were calculated for the ˜15.3 ka stage. Based on Ohmura et al. [5] a ˜4.5-4.9 ˚ C decrease of T and a ˜10-15% increase of P compared to the present values were calculated. Thanks to OTKA PD83610, PD104899; NKM-96/2014, NKM-31/2015; OMAA 90öu17; LP2012-27/2012, INSU/CNRS, the ANR through the program "EQUIPEX Investissement d'Avenir", IRD and CEA. References: [1] Pellitero et al. 2015 Computers & Gerosciences 82: 55-62 [2] Kern and László, 2010. Quat. Sci. Rev. 29, 2781-2787. [3] Ruszkiczay-Rüdiger et al. 2016 Quat. Int. 415. 216-229. [4] Tóth et al., 2012. Quat. Res. 77. 122-131. [5] Ohmura et al. 1992. J. of Glaciology, 38. 397-411.

Asian dust deposition rendered volcanic-ash-soils the ability to retain radiocesium in Japan

NASA Astrophysics Data System (ADS)

Nakao, A.; Uno, S.; Tanaka, R.; Yanai, J.; Kosaki, T.; Kubotera, H.

2017-12-01

Although mineral dusts are known to contribute greatly to marine and terrestrial biogeochemical cycles, their role in increasing the retention of radio-Cs in soil is less clear. Fine-mica, which is one of the main component of Asian dust, has a specific adsorption site for radio-Cs. Therefore, historical deposition of Asian dust may have rendered soils in Japan capable of retaining radio-Cs. This effect may be particularly important for volcanic-ash derived soils since they originally contain only small amounts of fine-mica. To test this hypothesis, we investigated 47 soils in volcanic ash-fall layers at four sites (Site 1, 2, 3, 4) with a different distance from volcanic crater of Mt. Aso, Japan, which is 10, 14, 16, and 32 km, respectively. Soils were collected from surface to the volcanic layer with 7.3 ka in Site 1 and 2, whereas from surface to the layer with 30 ka in Site 3 and 4. Ages of key layers were confirmed by tephrochronology and 14C dating method. Oxygen isotopic ratio (d18O) value of fine-quartz was used as a fingerprint of Asian dust in each volcanic layer. Average d18O value for fine-quartz from Site 3 and 4 was 16.0 ± 0.4‰, which was homogeneous and very close to those of fine-quartz in Gobi Desert, while clearly different from those of SiO2 in volcanic rocks. Fine-quartz and fine-mica contents were larger with increased distance from the volcanic crater and showed a linear relationship. Cumulative amount of fine-mica in the layers deposited during the last glacial period (i.e. 10 ka to 30 ka) was about five times larger than those deposited during the postglacial period (i.e. < 10 ka). These results clearly indicated that fine-mica in the volcanic ash-fall layers are mostly derived from Asian dust. Since radio-Cs adsorption experiment revealed that the ability to retain radio-Cs increased linearly as soils contained larger amount of fine-mica, we concluded that the inclusion rate of Asian dust to volcanic ash determine the ability to retain radio-Cs in volcanic-ash soils in Japan and probably any other soil influenced by these aeolian materials.

South Atlantic intermediate water advances into the North-east Atlantic with reduced Atlantic meridional overturning circulation during the last glacial period

NASA Astrophysics Data System (ADS)

Dubois-Dauphin, Quentin; Bonneau, Lucile; Colin, Christophe; Montero-Serrano, Jean-Carlos; Montagna, Paolo; Blamart, Dominique; Hebbeln, Dierk; Van Rooij, David; Pons-Branchu, Edwige; Hemsing, Freya; Wefing, Anne-Marie; Frank, Norbert

2016-06-01

The Nd isotopic composition (ɛNd) of seawater and cold-water coral (CWC) samples from the Gulf of Cádiz and the Alboran Sea, at a depth of 280-827 m were investigated in order to constrain middepth water mass dynamics within the Gulf of Cádiz over the past 40 ka. ɛNd of glacial and Holocene CWC from the Alboran Sea and the northern Gulf of Cádiz reveals relatively constant values (-8.6 to -9.0 and -9.5 to -10.4, respectively). Such values are similar to those of the surrounding present-day middepth waters from the Mediterranean Outflow Water (MOW; ɛNd ˜ -9.4) and Mediterranean Sea Water (MSW; ɛNd ˜ -9.9). In contrast, glacial ɛNd values for CWC collected at thermocline depth (550-827 m) in the southern Gulf of Cádiz display a higher average value (-8.9 ± 0.4) compared to the present-day value (-11.7 ± 0.3). This implies a higher relative contribution of water masses of Mediterranean (MSW) or South Atlantic origin (East Antarctic Intermediate Water, EAAIW). Our study has produced the first evidence of significant radiogenic ɛNd values (˜ -8) at 19, 23-24, and 27 ka, which are coeval with increasing iceberg discharges and a weakening of Atlantic Meridional Overturning Circulation (AMOC). Since MOW ɛNd values remained stable during the last glacial period, it is suggested that these radiogenic ɛNd values most likely reflect an enhanced northward propagation of glacial EAAIW into the eastern Atlantic Basin.

Formation of M-Like Intermediates in Proteorhodopsin in Alkali Solutions (pH ≥ ∼8.5) Where the Proton Release Occurs First in Contrast to the Sequence at Lower pH.

PubMed

Tamogami, Jun; Sato, Keitaro; Kurokawa, Sukuna; Yamada, Takumi; Nara, Toshifumi; Demura, Makoto; Miyauchi, Seiji; Kikukawa, Takashi; Muneyuki, Eiro; Kamo, Naoki

2016-02-23

Proteorhodopsin (PR) is an outward light-driven proton pump observed in marine eubacteria. Despite many structural and functional similarities to bacteriorhodopsin (BR) in archaea, which also acts as an outward proton pump, the mechanism of the photoinduced proton release and uptake is different between two H(+)-pumps. In this study, we investigated the pH dependence of the photocycle and proton transfer in PR reconstituted with the phospholipid membrane under alkaline conditions. Under these conditions, as the medium pH increased, a blue-shifted photoproduct (defined as Ma), which is different from M, with a pKa of ca. 9.2 was produced. The sequence of the photoinduced proton uptake and release during the photocycle was inverted with the increase in pH. A pKa value of ca. 9.5 was estimated for this inversion and was in good agreement with the pKa value of the formation of Ma (∼ 9.2). In addition, we measured the photoelectric current generated by PRs attached to a thin polymer film at varying pH. Interestingly, increases in the medium pH evoked bidirectional photocurrents, which may imply a possible reversal of the direction of the proton movement at alkaline pH. On the basis of these findings, a putative photocycle and proton transfer scheme in PR under alkaline pH conditions was proposed.

Origin of increased terrigenous supply to the NE South American continental margin during Heinrich Stadial 1 and the Younger Dryas

NASA Astrophysics Data System (ADS)

Zhang, Yancheng; Chiessi, Cristiano M.; Mulitza, Stefan; Zabel, Matthias; Trindade, Ricardo I. F.; Hollanda, Maria Helena B. M.; Dantas, Elton L.; Govin, Aline; Tiedemann, Ralf; Wefer, Gerold

2015-12-01

We investigate the redistribution of terrigenous materials in the northeastern (NE) South American continental margin during slowdown events of the Atlantic Meridional Overturning Circulation (AMOC). The compilation of stratigraphic data from 108 marine sediment cores collected across the western tropical Atlantic shows an extreme rise in sedimentation rates off the Parnaíba River mouth (about 2°S) during Heinrich Stadial 1 (HS1, 18-15 ka). Sediment core GeoB16206-1, raised offshore the Parnaíba River mouth, documents relatively constant 143Nd/144Nd values (expressed as εNd(0)) throughout the last 30 ka. Whereas the homogeneous εNd(0) data support the input of fluvial sediments by the Parnaíba River from the same source area directly onshore, the increases in Fe/Ca, Al/Si and Rb/Sr during HS1 indicate a marked intensification of fluvial erosion in the Parnaíba River drainage basin. In contrast, the εNd(0) values from sediment core GeoB16224-1 collected off French Guiana (about 7°N) suggest Amazon-sourced materials within the last 30 ka. We attribute the extremely high volume of terrigenous sediments deposited offshore the Parnaíba River mouth during HS1 to (i) an enhanced precipitation in the catchment region and (ii) a reduced North Brazil Current, which are both associated with a weakened AMOC.

A 220 ka terrestrial δ18O and deuterium excess biomarker record from an eolian permafrost paleosol sequence, NE-Siberia

NASA Astrophysics Data System (ADS)

Tuthorn, Mario; Zech, Michael; Detsch, Florian; Rozanski, Kazimierz; Zech, Roland; Zöller, Ludwig; Zech, Wolfgang; Glaser, Bruno

2013-04-01

The natural abundances of stable oxygen (18O/16O) and hydrogen isotopes (D/H) are valuable proxies of climate changes in the past. Yet, to date no continuous δ18O and only few δD records are available from loess-paleosol sequences. Taking advantage of a recently developed method based on compound-specific δ18O analyzes of hemicellulose sugar biomarkers in soils (Zech and Glaser, 2009), we here present a first terrestrial δ18O biomarker record from an eolian permafrost paleosol sequence in NE-Siberia that covers the last ~220 ka. The δ18O values of the hemicellulose biomarkers arabinose and xylose range from 22.5 to 32.8‰ and from 21.3 to 31.9‰, respectively, and reveal systematic glacial - interglacial shifts. The modern topsoil and the interglacial paleosols exhibit more positive δ18O values, whereas the glacial paleosols are characterized by more negative δ18O values. This is in agreement with the δD record obtained for sedimentary n-alkane leaf wax biomarkers. We present a conceptual model for interpreting the combined δ18O and δD biomarker record. Based on this model, we suggest that both our δ18O and the δD record primarily reflect the temperature-controlled isotopic composition of paleoprecipitation modified by evaporative isotope enrichment of leaf water during transpiration. Considering fractionation factors during sugar and n-alkane biomarker biosynthesis allows reconstructing the leaf water isotopic composition and the deuterium excess of the leaf water. The deuterium excess may serve as proxy for evaporative enrichment and allows calculating relative humidity using a Craig-Gordon model. Accordingly, relative humidity in NE-Siberia was higher during marine isotope stage (MIS) 6 compared to MIS 2, 4 and 5d and thus could help explaining the much larger extent of the Late Saalian glaciation compared to the Weichselian glaciations. Using the Craig-Gordon model, we also calculated δ18O of the plant source water (δ18Osource water), which can be assumed to primarily reflect δ18O of paleoprecipitation. Our 220 ka δ18Osource water record is well in agreement with the δ18Odiatom record from Crater Lake El'gygytgyn in NE-Siberia and enables a regional paleoclimate reconstruction and interpretation. Accordingly, summer temperature was periodically warmer than at present during the Weichselian glacial period and there is a strong July insolation forcing of the summer temperature in the extremely continental study area. Overall, our study highlights the great potential of the novel hemicellulose biomarker δ18O method for paleoclimate reconstructions, especially when combined with δD analyzes of n-alkane lipid biomarkers.

Competitive adsorption/desorption of tetracycline, oxytetracycline and chlortetracycline on two acid soils: Stirred flow chamber experiments.

PubMed

Fernández-Calviño, David; Bermúdez-Couso, Alipio; Arias-Estévez, Manuel; Nóvoa-Muñoz, Juan Carlos; Fernández-Sanjurjo, Maria J; Álvarez-Rodríguez, Esperanza; Núñez-Delgado, Avelino

2015-09-01

The objective of this work was to study the competitive adsorption/desorption of tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC) on two acid soils. We used the stirred flow chamber technique to obtain experimental data on rapid kinetic processes affecting the retention/release of the antibiotics. Both adsorption and desorption were higher on soil 1 (which showed the highest carbon, clay and Al and Fe oxides content) than on soil 2. Moreover, hysteresis affected the adsorption/desorption processes. Experimental data were fitted to a pseudo-first order equation, resulting qamax (adsorption maximum) values that were higher for soil 1 than for soil 2, and indicating that CTC competed with TC more intensely than OTC in soil 1. Regarding soil 2, the values corresponding to the adsorption kinetics constants (ka) and desorption kinetics constants for fast sites (kd1), followed a trend inverse to qamax and qdmax respectively. In conclusion, competition affected adsorption/desorption kinetics for the three antibiotics assayed, and thus retention/release and subsequent transport processes in soil and water environments. Copyright © 2015 Elsevier Ltd. All rights reserved.

Simulation of weak polyelectrolytes: a comparison between the constant pH and the reaction ensemble method

NASA Astrophysics Data System (ADS)

Landsgesell, Jonas; Holm, Christian; Smiatek, Jens

2017-03-01

The reaction ensemble and the constant pH method are well-known chemical equilibrium approaches to simulate protonation and deprotonation reactions in classical molecular dynamics and Monte Carlo simulations. In this article, we demonstrate the similarity between both methods under certain conditions. We perform molecular dynamics simulations of a weak polyelectrolyte in order to compare the titration curves obtained by both approaches. Our findings reveal a good agreement between the methods when the reaction ensemble is used to sweep the reaction constant. Pronounced differences between the reaction ensemble and the constant pH method can be observed for stronger acids and bases in terms of adaptive pH values. These deviations are due to the presence of explicit protons in the reaction ensemble method which induce a screening of electrostatic interactions between the charged titrable groups of the polyelectrolyte. The outcomes of our simulation hint to a better applicability of the reaction ensemble method for systems in confined geometries and titrable groups in polyelectrolytes with different pKa values.

High-resolution stratigraphy and multiple luminescence dating techniques to reveal the paleoseismic history of the central Dead Sea fault (Yammouneh fault, Lebanon)

NASA Astrophysics Data System (ADS)

Le Béon, Maryline; Tseng, Ya-Chu; Klinger, Yann; Elias, Ata; Kunz, Alexander; Sursock, Alexandre; Daëron, Mathieu; Tapponnier, Paul; Jomaa, Rachid

2018-07-01

Continuous sedimentation and detailed stratigraphy are key parameters for a complete paleo-earthquake record. Here, we present a new paleoseismological study across the main strike-slip fault branch of the Dead Sea fault in Lebanon. We aim to expand the current knowledge on local paleoseismicity and seismic behavior of strike-slip plate boundary faults and to explore the limitations of paleoseismology and dating methods. The trench, dug in the Jbab el-Homr basin, reveals a succession of remarkable, very thin (0.1 to 5 cm) palustrine and lacustrine layers, ruptured by at least 17 earthquakes. Absolute ages of 4 samples are obtained from three luminescence-dating techniques targeting fine-grain minerals. Blue-green stimulated luminescence (BGSL) on quartz and post-infrared infrared-stimulated luminescence at 225 °C on polymineral aliquots led to consistent ages, while ages from infrared-stimulated luminescence at 50 °C on polymineral aliquots appeared underestimated. The quartz BGSL ages are 26.9 ± 2.3 ka at 0.50 m depth and 30.8 ± 2.9 ka at 3.65 m depth. During this time period of 3.9 ka ([0; 9.1 ka]), 14 surface-rupturing events occurred with a mean return time of 280 years ([0; 650 years]) and probable clustering. This return time is much shorter than the 1127 ± 135 years return time previously determined at the Yammouneh site, located 30 km south. Although fault segmentation and temporal variations in the earthquake cycle remain possible causes for such different records, we argue that the high-resolution stratigraphy in Jbab is the main factor, enabling us to record small deformations related to smaller-magnitude events that may have been missed in the rougher strata of Yammouneh. Indeed, focusing only on larger events of Jbab, we obtain a mean return time of 720 years ([0; 1670 years]) that is compatible with the Yammouneh record.

10Be exposure age chronology of the last glaciation of the Roháčská Valley in the Western Tatra Mountains, central Europe

NASA Astrophysics Data System (ADS)

Engel, Zbyněk; Mentlík, Pavel; Braucher, Régis; Křížek, Marek; Pluháčková, Markéta; Arnold, Maurice; Aumaître, Georges; Bourlès, Didier; Keddadouche, Karim; Aster Team; Arnold, Maurice; Aumaître, Georges; Bourlès, Didier; Keddadouche, Karim

2017-09-01

10Be exposure ages from moraines and bedrock sites in the Roháčská Valley provide chronology of the last glaciation in the largest valley of the Western Tatra Mts., the Western Carpathians. The minimum apparent exposure age of 19.4 ± 2.1 ka obtained for the oldest sampled boulder and the mean age of 18.0 ± 0.8 ka calculated for the terminal moraine indicate that the oldest preserved moraine was probably deposited at the time of the global Last Glacial Maximum (LGM). The age of this moraine coincides with the termination of the maximum glacier expansion in other central European ranges, including the adjacent High Tatra Mts. and the Alps. The equilibrium line altitude (ELA) of the LGM glacier in the Roháčská Valley, estimated at 1400-1410 m a.s.l., was 50-80 m lower than in the eastern part of the range, indicating a positive ELA gradient from west to east among the north-facing glaciers in the Tatra Mts. Lateglacial glacier expansion occurred no later than 13.4 ± 0.5 ka and 11.9 ± 0.5 ka, as indicated by the mean exposure ages calculated for re-advance moraines. This timing is consistent with the exposure age chronology of the last Lateglacial re-advance in the High Tatra Mts., Alps and lower mountain ranges in central Europe. The ELA in the Roháčská Valley estimated at 1690-1770 m a.s.l. in this period was located 130-300 m lower than in the north-facing valleys in the High Tatra Mts. 10Be exposure ages obtained for a rock glacier constrains the timing of this landform stabilization in the Salatínska Valley and provides the first chronological evidence for the Lateglacial activity of rock glaciers in the Carpathians.

Benzimidazole acrylonitriles as multifunctional push-pull chromophores: Spectral characterisation, protonation equilibria and nanoaggregation in aqueous solutions

NASA Astrophysics Data System (ADS)

Horak, Ema; Vianello, Robert; Hranjec, Marijana; Krištafor, Svjetlana; Zamola, Grace Karminski; Steinberg, Ivana Murković

2017-05-01

Heterocyclic donor-π-acceptor molecular systems based on an N,N-dimethylamino phenylacrylonitrile benzimidazole skeleton have been characterised and are proposed for potential use in sensing applications. The benzimidazole moiety introduces a broad spectrum of useful multifunctional properties to the system including electron accepting ability, pH sensitivity and compatibility with biomolecules. The photophysical characterisation of the prototropic forms of these chromophores has been carried out in both solution and on immobilisation in polymer films. The experimental results are further supported by computational determination of pKa values. It is noticed that compound 3 forms nanoaggregates in aqueous solutions with aggregation-induced emission (AIE) at 600 nm. All the systems demonstrate spectral pH sensitivity in acidic media which shifts towards near-neutral values upon immobilisation in polymer films or upon aggregation in an aqueous environment (compound 3). The structure-property relationships of these functional chromophores, involving their spectral characteristics, acid-base equilibria, pKa values and aggregation effects have been determined. Potential applications of the molecules as pH and biomolecular sensors are proposed based on their pH sensitivity and AIE properties.

Comparative Study of Optical and RF Communication Systems for a Mars Mission - Part II. Unified Value Metrics

NASA Technical Reports Server (NTRS)

Hemmati, H.; Layland, J.; Lesh, J.; Wilson, K.; Sue, M.; Rascoe, D.; Lansing, F.; Wilhelm, M.; Harcke, L.; Chen, C.;

A 16 MJ compact pulsed power system for electromagnetic launch

NASA Astrophysics Data System (ADS)

Dai, Ling; Zhang, Qin; Zhong, Heqing; Lin, Fuchang; Li, Hua; Wang, Yan; Su, Cheng; Huang, Qinghua; Chen, Xu

2015-07-01

This paper has established a compact pulsed power system (PPS) of 16 MJ for electromagnetic rail gun. The PPS consists of pulsed forming network (PFN), chargers, monitoring system, and current junction. The PFN is composed of 156 pulse forming units (PFUs). Every PFU can be triggered simultaneously or sequentially in order to obtain different total current waveforms. The whole device except general control table is divided into two frameworks with size of 7.5 m × 2.2 m × 2.3 m. It is important to estimate the discharge current of PFU accurately for the design of the whole electromagnetic launch system. In this paper, the on-state characteristics of pulse thyristor have been researched to improve the estimation accuracy. The on-state characteristics of pulse thyristor are expressed as a logarithmic function based on experimental data. The circuit current waveform of the single PFU agrees with the simulating one. On the other hand, the coaxial discharge cable is a quick wear part in PFU because the discharge current will be up to dozens of kA even hundreds of kA. In this article, the electromagnetic field existing in the coaxial cable is calculated by finite element method. On basis of the calculation results, the structure of cable is optimized in order to improve the limit current value of the cable. At the end of the paper, the experiment current wave of the PPS with the load of rail gun is provided.

Improved H mode with flat central q profile on EAST

NASA Astrophysics Data System (ADS)

Liu, Haiqing; Yang, Yao; Gao, Xiang; Zeng, Long; Qian, Jinping; Gong, Xianzu; Wan, Baonian; Ding, Weixing; Brower, David Lyn; EAST Team

2017-10-01

High betaN ( 1.8) plasma with good confinement (H98y2 1.1) on EAST tokamak has been reported recently. These ELMy H-mode plasmas with Bt = 1.6T, Ip = 400 kA and q95 4.5 were heated by lower hybrid wave and neutral beam injection. The internal transport barrier (ITB) and edge transport barrier (ETB) are both observed with m/n =1/1 fishbone, which were identified to clamp central q at values close to unity. Implying an improved H-mode with flat central q profile and absence of sawteeth, like other devices. Accurate q profile, key profile for developing scenarios aim at high performance H mode, were derived by Polarimeter-interferometer (POINT) measurement as constraint. Base on the optimized current profile, better confinement (H98y2 1.4) with an electron ITB was obtained also with flat central q profile and absence of sawteeth at high betaP ( 2) regime with Bt = 2.5T, Ip = 400 kA. Both high betaN regime and high betaP regime H mode, are characterized by a stationary flat central q profile q0 >=1, but typically close to 1, absence of sawteeth, H98(y,2) >1 and simultaneously, with ITB. This work is supported by the National Magnetic Confinement Fusion Program of China with Contract No. 2014GB106002 and partly supported by the US D.O.E. contract DESC0010469.

A 16 MJ compact pulsed power system for electromagnetic launch.

PubMed

Dai, Ling; Zhang, Qin; Zhong, Heqing; Lin, Fuchang; Li, Hua; Wang, Yan; Su, Cheng; Huang, Qinghua; Chen, Xu

2015-07-01

This paper has established a compact pulsed power system (PPS) of 16 MJ for electromagnetic rail gun. The PPS consists of pulsed forming network (PFN), chargers, monitoring system, and current junction. The PFN is composed of 156 pulse forming units (PFUs). Every PFU can be triggered simultaneously or sequentially in order to obtain different total current waveforms. The whole device except general control table is divided into two frameworks with size of 7.5 m × 2.2 m × 2.3 m. It is important to estimate the discharge current of PFU accurately for the design of the whole electromagnetic launch system. In this paper, the on-state characteristics of pulse thyristor have been researched to improve the estimation accuracy. The on-state characteristics of pulse thyristor are expressed as a logarithmic function based on experimental data. The circuit current waveform of the single PFU agrees with the simulating one. On the other hand, the coaxial discharge cable is a quick wear part in PFU because the discharge current will be up to dozens of kA even hundreds of kA. In this article, the electromagnetic field existing in the coaxial cable is calculated by finite element method. On basis of the calculation results, the structure of cable is optimized in order to improve the limit current value of the cable. At the end of the paper, the experiment current wave of the PPS with the load of rail gun is provided.

Production and characterization of recombinant scFv against digoxin by phage display technology.

PubMed

Alirezapour, Behruz; Rajabibazl, Masoumeh; Rasaee, Mohhamad Javad; Omidfar, Kobra

2013-06-01

The cardiac glycoside digoxin is widely used for the treatment of congestive heart failure and cardiac arrhythmias. Digoxin is a highly toxic drug and consequently is routinely measured in sera of treated patients. In such cases, antibodies are required against digoxin for detection as well as detoxification purposes. To obtain recombinant single chain antibody against digoxin, RNA was extracted from spleen of BALB/c mice immunized with digoxin-BSA and converted to cDNA. The gene fragment corresponding to the variable regions of the repertoire of antibody genes were amplified by PCR. ScFv construct was generated by randomly joining individual heavy- and light-chain variable domains through gene splicing by overlapping extension PCR. Recombinant phage library expressing scFv polypeptides were produced. Phages with higher affinity toward digoxin were selected in the biopanning process. Sensitivity of produced recombinant MAb (AR85) was determined to be about 100 pg/well, while intact MAb (BBA) produced by hybridoma technology (data not shown) was reported to be around 100 pg/well too. The saturation value for recombinant scFv MAb was found to be 1000 ng/well while that for hybridoma MAb was reported to be 10 ng/well. The affinity constant of recombinant MAb (AR85) towards digoxin was also found to be around ka=3.8×10(7) M(-1) while that for hybridoma MAb (BBA) was reported to be ka=2.6×10(8) M(-1).

Plasma current start-up using the lower hybrid wave on the TST-2 spherical tokamak

NASA Astrophysics Data System (ADS)

Takase, Y.; Ejiri, A.; Inada, T.; Moeller, C. P.; Shinya, T.; Tsujii, N.; Yajima, S.; Furui, H.; Homma, H.; Imamura, K.; Nakamura, K.; Nakamura, K.; Sonehara, M.; Takeuchi, T.; Togashi, H.; Tsuda, S.; Yoshida, Y.

2015-12-01

Non-inductive plasma current start-up, ramp-up and sustainment by waves in the lower hybrid wave (LHW) frequency range at 200 MHz were investigated on the TST-2 spherical tokamak (R0 ≤ 0.38 m, a ≤ 0.25 m, Bt0 ≤ 0.3T, Ip ≤ 0.14 MA). Experimental results obtained using three types of antenna were compared. Both the highest plasma current (Ip = 18 kA) and the highest current drive figure of merit ηCD≡n¯eIpR0/PRF=1.4 ×1017 A/W/m2 were achieved using the capacitively-coupled combline (CCC) antenna, designed to excite the LHW with a sharp and highly directional wavenumber spectrum. For Ip greater than about 5 kA, high energy electrons accelerated by the LHW become the dominant carrier of plasma current. The low value of ηCD observed so far are believed to be caused by a rapid loss of energetic electrons and parasitic losses of the LHW energy in the plasma periphery. ηCD is expected to improve by an order of magnitude by increasing the plasma current to improve energetic electron confinement. In addition, edge power losses are expected to be reduced by increasing the toroidal magnetic field to improve wave accessibility to the plasma core, and by launching the LHW from the inboard upper region of the torus to achieve better single-pass absorption.

Neodymium Isotope Variations in Late Quaternary Carbonate Lake Sediments, Owens Valley, Eastern California.

NASA Astrophysics Data System (ADS)

Minervini, J. M.; Stewart, B. W.

2001-12-01

Owens Lake is situated in a mostly-closed basin fed by water and sediments derived primarily from the eastern Sierra Nevada range. Chemical and sedimentological variations in USGS Owens Lake Core OL-92, which extends back 800 ka, have been shown to be sensitive tracers of Great Basin paleoclimate. Here we report preliminary neodymium (Nd) isotope data from core OL-92 to investigate sediment provenance, the chemical behavior of rare earth elements (REE) in non-marine systems, and possible climate-related shifts in weathering patterns of the eastern Sierra Nevada during the last glacial-interglacial transition. Neodymium isotopic analyses were carried out on the carbonate fraction of sediment samples ranging in age from 16.8 to 6.9 ka from Owens Lake core OL-92. Samples were treated with ammonium acetate to remove exchangeable cations from coexisting silicate material, and subsequently leached with 8% acetic acid to dissolve carbonate minerals. Based on the mass of sediment leached with acetic acid, the fraction of carbonate (relative to clastic silicate material) increases from 6.6 to 66.5% over the 10 ka period represented by these samples. This increase in carbonate reflects desiccation of the Owens Lake basin; as streamwater flow is reduced, the lake spends a greater proportion of its time saturated in carbonate minerals, and clastic input might also be reduced. Concentrations of Nd in Owens Lake carbonate range from 7 to 170 ppm, values that are 2-1000 times higher than marine planktonic foraminifera (e.g., Vance and Burton, 1999, EPSL 173, 365). In general, high concentrations of Nd in Owens Lake carbonate are associated with older sediment samples with lower carbonate fractions. The decrease in Nd concentration over this time period could be a result of extraction of Nd from lake waters by precipitation of carbonate as desiccation proceeded. Epsilon-Nd values of Owens Lake carbonate range from -5.3 to -6.5, and are consistent with eastern Sierra Nevada granitic bedrock values. A slight shift from higher to lower epsilon-Nd values occurs between about 14 and 9 ka, and could be due to variations in sediment source regions associated with the retreat of alpine glaciers along the eastern flank of the Sierra Nevada. With ongoing studies to assess the relationship between clastic and carbonate sources, neodymium isotope data can potentially provide detailed information about the relationship between chemical and mechanical weathering processes in a well-constrained continental setting.

Using resonance light scattering and UV/vis absorption spectroscopy to study the interaction between gliclazide and bovine serum albumin.

PubMed

Zhang, Qiu-Ju; Liu, Bao-Sheng; Li, Gai-Xia; Han, Rong

2016-08-01

At different temperatures (298, 310 and 318 K), the interaction between gliclazide and bovine serum albumin (BSA) was investigated using fluorescence quenching spectroscopy, resonance light scattering spectroscopy and UV/vis absorption spectroscopy. The first method studied changes in the fluorescence of BSA on addition of gliclazide, and the latter two methods studied the spectral change in gliclazide while BSA was being added. The results indicated that the quenching mechanism between BSA and gliclazide was static. The binding constant (Ka ), number of binding sites (n), thermodynamic parameters, binding forces and Hill's coefficient were calculated at three temperatures. Values for the binding constant obtained using resonance light scattering and UV/vis absorption spectroscopy were much greater than those obtained from fluorescence quenching spectroscopy, indicating that methods monitoring gliclazide were more accurate and reasonable. In addition, the results suggest that other residues are involved in the reaction and the mode 'point to surface' existed in the interaction between BSA and gliclazide. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

[A correlation between diffusion kurtosis imaging and the proliferative activity of brain glioma].

PubMed

Tonoyan, A S; Pronin, I N; Pitshelauri, D I; Shishkina, L V; Fadeeva, L M; Pogosbekyan, E L; Zakharova, N E; Shults, E I; Khachanova, N V; Kornienko, V N; Potapov, A A

2015-01-01

The aim of the study was to assess the capabilities of diffusion kurtosis imaging (DKI) in diagnosis of the glioma proliferative activity and to evaluate a relationship between the glioma proliferative activity index and diffusion parameters of the contralateral normal appearing white matter (CNAWM). The study included 47 patients with newly diagnosed brain gliomas (23 low grade, 13 grade III, and 11 grade IV gliomas). We determined a relationship between absolute and normalized parameters of the diffusion tensor (mean (MD), axial (AD), and radial (RD) diffusivities; fractional (FA) and relative (RA) anisotropies) and diffusion kurtosis (mean (MK), axial (AK), and radial (RK) kurtosis; kurtosis anisotropy (KA)) and the proliferative activity index in the most malignant glioma parts (p<0.05). We also established a relationship between the tensor and kurtosis parameters of CNAWM and the glioma proliferative activity index (p<0.05). The correlation between all the absolute and normalized diffusion parameters and the glioma proliferative activity index, except absolute and normalized FA and RA values, was found to be statistically significant (p<0.05). Kurtosis (MK, AK, and RK) and anisotropy (KA, FA, RA) values increased, and diffusivity (MD, AD, RD) values decreased as the glioma proliferative activity index increased. A strong correlation between the proliferative activity index and absolute RK (r=0,71; p=0.000001) and normalized values of MK (r=0.8; p=0.000001), AK (r=0.71; p=0.000001), RK (r=0.81; p=0.000001), and RD (r=-0.71; p=0.000001) was found. A weak, but statistically significant correlation between the glioma proliferative activity index and diffusion values RK (r=-0.36; p=0.014), KA (r=-0.39; p=0.007), RD (r=0.35; p=0.017), FA (r=-0.42; p=0.003), and RA (r=-0.41; p=0.004) of CNAWM was found. DKI has good capabilities to detect immunohistochemical changes in gliomas. DKI demonstrated a high sensitivity in detection of microstructural changes in the contralateral normal appearing white matter in patients with brain gliomas.

Mars Global Surveyor Ka-Band Frequency Data Analysis

NASA Astrophysics Data System (ADS)

Morabito, D.; Butman, S.; Shambayati, S.

2000-01-01

The Mars Global Surveyor (MGS) spacecraft, launched on November 7, 1996, carries an experimental space-to-ground telecommunications link at Ka-band (32 GHz) along with the primary X-band (8.4 GHz) downlink. The signals are simultaneously transmitted from a 1.5-in diameter parabolic high gain antenna (HGA) on MGS and received by a beam-waveguide (BWG) R&D 34-meter antenna located in NASA's Goldstone Deep Space Network (DSN) complex near Barstow, California. The projected 5-dB link advantage of Ka-band relative to X-band was confirmed in previous reports using measurements of MGS signal strength data acquired during the first two years of the link experiment from December 1996 to December 1998. Analysis of X-band and Ka-band frequency data and difference frequency (fx-fka)/3.8 data will be presented here. On board the spacecraft, a low-power sample of the X-band downlink from the transponder is upconverted to 32 GHz, the Ka-band frequency, amplified to I-W using a Solid State Power Amplifier, and radiated from the dual X/Ka HGA. The X-band signal is amplified by one of two 25 W TWTAs. An upconverter first downconverts the 8.42 GHz X-band signal to 8 GHz and then multiplies using a X4 multiplier producing the 32 GHz Ka-band frequency. The frequency source selection is performed by an RF switch which can be commanded to select a VCO (Voltage Controlled Oscillator) or USO (Ultra-Stable Oscillator) reference. The Ka-band frequency can be either coherent with the X-band downlink reference or a hybrid combination of the USO and VCO derived frequencies. The data in this study were chosen such that the Ka-band signal is purely coherent with the X-band signal, that is the downconverter is driven by the same frequency source as the X-band downlink). The ground station used to acquire the data is DSS-13, a 34-meter BWG antenna which incorporates a series of mirrors inside beam waveguide tubes which guide the energy to a subterranean pedestal room, providing a stable environment for the feed and electronics equipment. A dichroic plate is used to reflect the X-band energy and pass the Ka-band energy to another mirror. The RF energy for each band is then focused onto a feed horn and low-noise amplifier package. After amplification and RF/IF downconversion, the IF signals are sent to the Experimental Tone Tracker (ETT), a digital phase-lock-loop receiver, which simultaneously tracks both X-band and Ka-band carrier signals. Once a signal is detected, the ETT outputs estimates of the SNR in a I -Hz bandwidth (Pc/No), baseband phase and frequency of the signals every I -sec. Between December 1996 and December 1998, the Ka-band and X-band signals from MGS were tracked on a regular basis using the ETT. The Ka-band downlink frequencies described here were referenced to the spacecraft's on-board USO which was also the X-band frequency reference (fka= 3.8 fx). The ETT estimates of baseband phase at I -second sampled time tags were converted to sky frequency estimates. Frequency residuals were then generated for each band by removing a model frequency from each observable frequency at each time tag. The model included Doppler and other effects derived from spacecraft trajectory files obtained from the MGS Navigation Team. A simple troposphere correction was applied to the data. In addition to residuals, the USO frequencies emitted by the spacecraft were estimated. For several passes, the USO frequencies were determined from X-band data and from Ka-band data (referred to X-band by dividing by 3.8) and were found to be in good agreement. In addition, X-band USO frequency estimates from MGS Radio Science data acquired from operational DSN stations were available for comparison and were found to agree within the I Hz level. The remaining sub-Hertz differences were attributed to the different models and software algorithms used by MGS Radio Science and KaBLE-11. A summary of the results of a linear fit of the USO frequency versus time (day of year) is presented in Table I for an initial segment of passes.

Van’t Hoff global analyses of variable temperature isothermal titration calorimetry data

PubMed Central

Freiburger, Lee A.; Auclair, Karine; Mittermaier, Anthony K.

2016-01-01

Isothermal titration calorimetry (ITC) can provide detailed information on the thermodynamics of biomolecular interactions in the form of equilibrium constants, KA, and enthalpy changes, ΔHA. A powerful application of this technique involves analyzing the temperature dependences of ITC-derived KA and ΔHA values to gain insight into thermodynamic linkage between binding and additional equilibria, such as protein folding. We recently developed a general method for global analysis of variable temperature ITC data that significantly improves the accuracy of extracted thermodynamic parameters and requires no prior knowledge of the coupled equilibria. Here we report detailed validation of this method using Monte Carlo simulations and an application to study coupled folding and binding in an aminoglycoside acetyltransferase enzyme. PMID:28018008

Spectrofluorimetric and Potentiometric Determination of Acidity Constants of 4-(4'-Acetyloxy-3'-Methoxybenzylidene)-5-Oxazolone Derivatives.

PubMed

Taskiran, Derya Topkaya; Urut, Gulsiye Ozturk; Ayata, Sevda; Alp, Serap

2017-03-01

4-(4'-acetyloxy-3'-methoxybenzylidene)-5-oxazolone fluorescent molecules bearing four different aryl groups attached to the 2-position of 5-oxazolone ring have been investigated by spectrophotometric and potentiometric techniques in solution media. The acidity constants (pKa) of the fluorescent molecules were precisely determined in acetone, acetonitrile, dimethylformamide and in 1:1 mixture of toluene-isopropanol. The studied derivatives were titrated with tetrabutylammonium hydroxide and non-aqueous perchloric acid by scanning the basic and acidic region of the pH scale. A computerizable derivative method was used in order to descript precisely the end point and pKa values. The molecules investigated performed well-shaped and stoichiometric potentiometric titration curves.

Inverse synthetic aperture radar imagery of a man with a rocket propelled grenade launcher

NASA Astrophysics Data System (ADS)

Tran, Chi N.; Innocenti, Roberto; Kirose, Getachew; Ranney, Kenneth I.; Smith, Gregory

2004-08-01

As the Army moves toward more lightly armored Future Combat System (FCS) vehicles, enemy personnel will present an increasing threat to U.S. soldiers. In particular, they face a very real threat from adversaries using shoulder-launched, rocket propelled grenade (RPG). The Army Research Laboratory has utilized its Aberdeen Proving Ground (APG) turntable facility to collect very high resolution, fully polarimetric Ka band radar data at low depression angles of a man holding an RPG. In this paper, we examine the resulting low resolution and high resolution range profiles; and based on the observed radar cross section (RCS) value, we attempt to determine the utility of Ka band radar for detecting enemy personnel carrying RPG launchers.

Demonstration of Tokamak Ohmic Flux Saving by Transient Coaxial Helicity Injection in the National Spherical Torus Experiment

NASA Astrophysics Data System (ADS)

Raman, R.; Mueller, D.; Nelson, B. A.; Jarboe, T. R.; Gerhardt, S.; Kugel, H. W.; Leblanc, B.; Maingi, R.; Menard, J.; Ono, M.; Paul, S.; Roquemore, L.; Sabbagh, S.; Soukhanovskii, V.

2010-03-01

Transient coaxial helicity injection (CHI) started discharges in the National Spherical Torus Experiment (NSTX) have attained peak currents up to 300 kA and when coupled to induction, it has produced up to 200 kA additional current over inductive-only operation. CHI in NSTX has shown to be energetically quite efficient, producing a plasma current of about 10 A/J of capacitor bank energy. In addition, for the first time, the CHI-produced toroidal current that couples to induction continues to increase with the energy supplied by the CHI power supply at otherwise similar values of the injector flux, indicating the potential for substantial current generation capability by CHI in NSTX and in future toroidal devices.

Impact of Stereospecific Intramolecular Hydrogen Bonding on Cell Permeability and Physicochemical Properties

PubMed Central

2014-01-01

Profiling of eight stereoisomeric T. cruzi growth inhibitors revealed vastly different in vitro properties such as solubility, lipophilicity, pKa, and cell permeability for two sets of four stereoisomers. Using computational chemistry and NMR spectroscopy, we identified the formation of an intramolecular NH→NR3 hydrogen bond in the set of stereoisomers displaying lower solubility, higher lipophilicity, and higher cell permeability. The intramolecular hydrogen bond resulted in a significant pKa difference that accounts for the other structure–property relationships. Application of this knowledge could be of particular value to maintain the delicate balance of size, solubility, and lipophilicity required for cell penetration and oral administration for chemical probes or therapeutics with properties at, or beyond, Lipinski’s rule of 5. PMID:24524242

Cloud-to-ground lightning flash characteristics from June 1984 through May 1985

NASA Technical Reports Server (NTRS)

Orville, Richard E.; Weisman, Robert A.; Pyle, Richard B.; Henderson, Ronald W.; Orville, Richard E., Jr.

1987-01-01

A magnetic direction-finding network for the detection of lightning cloud-to-ground strikes has been installed along the east coast of the United States. Time, location, flash polarity, stroke count, and peak signal amplitude are recorded in real time. The data were recorded from Maine to North Carolina and as far west as Ohio; analyses were restricted to flashes within 300 km of a direction finder. Measurements of peak signal strength have been obtained from 720,284 first return strokes lowering negative charge. The resulting distribution indicates that few negative strokes have peak currents exceeding 100 kA. Measurements have also been obtained of peak signal strength from 17,694 first return strokes lowering positive charge. These strokes have a median peak current of 45 kA, with some peak currents reaching 300-400 kA. The median peak signal strength and the peak current, double from summer to winter for both negative and positive first return strokes. The polarity of ground flashes is observed to be less than 5 percent positive throughout the summer and early fall, then increases to over 50 percent during the winter, and returns to less than 10 percent in early spring. The percent of positive flashes with one stroke is observed to be approximately 90 percent throughout the year. The percent of negative flashes with one stroke is observed to increase from 40 percent in the summer to approximately 80 percent in January, returning to less than 50 percent in the spring.

Regional mid-Pleistocene glaciation in central Patagonia

NASA Astrophysics Data System (ADS)

Hein, Andrew S.; Cogez, Antoine; Darvill, Christopher M.; Mendelova, Monika; Kaplan, Michael R.; Herman, Frédéric; Dunai, Tibor J.; Norton, Kevin; Xu, Sheng; Christl, Marcus; Rodés, Ángel

2017-05-01

Southern South America contains a glacial geomorphological record that spans the past million years and has the potential to provide palaeoclimate information for several glacial periods in Earth's history. In central Patagonia, two major outlet glaciers of the former Patagonian Ice Sheet carved deep basins ∼50 km wide and extending over 100 km into the Andean plain east of the mountain front. A succession of nested glacial moraines offers the possibility of determining when the ice lobes advanced and whether such advances occurred synchronously. The existing chronology, which was obtained using different methods in each valley, indicates the penultimate moraines differ in age by a full glacial cycle. Here, we test this hypothesis further using a uniform methodology that combines cosmogenic nuclide ages from moraine boulders, moraine cobbles and outwash cobbles. 10Be concentrations in eighteen outwash cobbles from the Moreno outwash terrace in the Lago Buenos Aires valley yield surface exposure ages of 169-269 ka. We find 10Be inheritance is low and therefore use the oldest surface cobbles to date the deposit at 260-270 ka, which is indistinguishable from the age obtained in the neighbouring Lago Pueyrredón valley. This suggests a regionally significant glaciation during Marine Isotope Stage 8, and broad interhemispheric synchrony of glacial maxima during the mid to late Pleistocene. Finally, we find the dated outwash terrace is 70-100 ka older than the associated moraines. On the basis of geomorphological observations, we suggest this difference can be explained by exhumation of moraine boulders.

Reappraisal of Los Humeros Volcanic Complex by New U/Th Zircon and 40Ar/39Ar Dating: Implications for Greater Geothermal Potential

NASA Astrophysics Data System (ADS)

Carrasco-Núñez, G.; Bernal, J. P.; Dávila, P.; Jicha, B.; Giordano, G.; Hernández, J.

2018-01-01

Longevity and size of magmatic systems are fundamental factors for assessing the potential of a geothermal field. At Los Humeros volcanic complex (LHVC), the first caldera-forming event was reported at 460 ± 40 ka. New zircon U/Th and plagioclase 40Ar/39Ar dates of pre-, syn- and postcaldera volcanics allow a reappraisal of the evolution of the geothermally active LHVC. The age of the voluminous Xaltipan ignimbrite (115 km3 dense rock equivalent [DRE]) associated with the formation of the Los Humeros caldera is now constrained by two geochronometers (zircon U/Th and plagioclase 40Ar/39Ar dating) to 164 ± 4.2 ka, which postdates a long episode of precaldera volcanism (rhyolitic domes), the oldest age of which is 693.0 ± 1.9 ka (40Ar/39Ar). The inferred short residence time (around 5 ka) for the paroxysmal Xaltipan ignimbrite is indicative of rapid assembly of a large magma body and rejuvenation of the system due to recurrent recharge magmas, as it has been occurred in some other large magmatic systems. Younger ages than previously believed have been obtained also for the other voluminous explosive phases of the Faby fall tuff at ˜70 ka and the second caldera-forming Zaragoza ignimbrite with 15 km3 DRE, which erupted immediately after. Thus, the time interval that separates the two caldera-forming episodes at Los Humeros is only 94 kyr, which is a much shorter interval than suggested by previous K-Ar dates (410 kyr). This temporal proximity allows us to propose a caldera stage encompassing the Xaltipan and the Zaragoza ignimbrites, followed by emplacement at 44.8 ± 1.7 ka of rhyolitic magmas interpreted to represent a postcaldera, resurgent stage. Rhyolitic eruptions have also occurred during the Holocene (<7.3 ± 0.1 ka) along with olivine-rich basalts that suggest recharge of the system. The estimated large volume magmatic reservoir for Los Humeros (>˜1,200 km3) and these new ages indicating much younger caldera-forming volcanism than previously believed are fundamental factors in the application of classical conductive models of heat resource, enhancing the heat production capacity and favor a higher geothermal potential.

Conformational responses to changes in the state of ionization of titrable groups in proteins

NASA Astrophysics Data System (ADS)

Richman, Daniel Eric

Electrostatic energy links the structural properties of proteins with some of their important biological functions, including catalysis, energy transduction, and binding and recognition. Accurate calculation of electrostatic energy is essential for predicting and for analyzing function from structure. All proteins have many ionizable residues at the protein-water interface. These groups tend to have ionization equilibria (pK a values) shifted slightly relative to their values in water. In contrast, groups buried in the hydrophobic interior usually have highly anomalous p Ka values. These shifts are what structure-based calculations have to reproduce to allow examination of contributions from electrostatics to stability, solubility and interactions of proteins. Electrostatic energies are challenging to calculate accurately because proteins are heterogeneous dielectric materials. Any individual ionizable group can experience very different local environments with different dielectric properties. The studies in this thesis examine the hypothesis that proteins reorganize concomitant with changes in their state of ionization. It appears that the pKa value measured experimentally reflects the average of pKa values experienced in the different electrostatic environments corresponding to different conformational microstates. Current computational models fail to sample conformational reorganization of the backbone correctly. Staphyloccocal nuclease (SNase) was used as a model protein in nuclear magnetic resonance (NMR) spectroscopy studies to characterize the conformational rearrangements of the protein coupled to changes in the ionization state of titrable groups. One set of experiments tests the hypothesis that proton binding to surface Asp and Glu side chains drives local unfolding by stabilizing less-native, more water-solvated conformations in which the side chains have normalized pKa values. Increased backbone flexibility in the ps-ns timescale, hydrogen bond (H-bond) breaking on at least the mus timescale, and segmental unfolding were detected near titrating groups as pH decreased into the acidic range. The study identified local structural features and stabilities that modulate the magnitude of electrostatic effects. The data demonstrate that computational approaches to pK a calculations for surface groups must account for local fluctuations spanning a wide range of timescales. A comparative NMR spectroscopy study with the L25K and L125K variants of SNase, each with a Lys residue buried in the hydrophobic interior of the protein, determined locations, timescales, and amplitudes of backbone conformational reorganization coupled with ionization of the buried Lys residues. The L25K protein exhibited an ensemble of local fluctuations of the beta barrel in the hundreds of mus timescale and an ensemble of subglobally unfolded beta-barrel states in the hundreds of ms timescale with strong pH dependence. The L125K protein exhibited fluctuations of the helix around site 125 in the mus timescale, with negligible pH dependence. These data illustrate the diverse timescales and local structural properties of conformational reorganization coupled to ionization of buried groups, and the challenge to structure-based electrostatics calculations, which must capture these long-timescale processes.

A 16 kyr seawater neodymium isotope record from the central Bay of Bengal

NASA Astrophysics Data System (ADS)

Naik, S.; Basak, C.; Pothuri, D.; Goldstein, S. L.

2016-12-01

Present-day thermohaline circulation (THC) can be described as a loop where deep waters sink in the North Atlantic and Circum-Antarctic, transporting salt, nutrients, and other chemical species through the global ocean, eventually returning via surface flow to the North Atlantic. The Indian Ocean is an important component of the THC, receiving deep waters via Circumpolar Deep Water and hosting the shallow return flow of the global THC. Here we use Nd isotope ratios as a water mass proxy to trace past THC changes in the central Bay of Bengal (BoB). The downcore Nd isotope record has been generated using planktonic foraminifera from core SK157/20 (12°09'N; 88°42'E, 3171m), spanning the last 16ka. The record begins with ƐNd -8 and shows decreasing values to ƐNd -9 through the deglacial until 8ka. At that time there is a prominent shift to ƐNd -10.3, where it remains for the rest of the Holocene. Comparison with equatorial Indian Ocean core SK129-CR02 (Piotrowski et al., 2009) and distal BoB core ODP 758 (Gourlan et al., 2010; Wilson et al., 2015) shows that ƐNd values of these cores are similar until 8 ka, after which SK157/20 diverges. We interpret the deglacial to early Holocene ( 16-8 ka) part of the SK157/20 ƐNd record to represent the influence of changing THC in the BoB. Singh et al. (2012) suggest that Ganga-Brahmaputra (GB) water is one of the dominant sources of dissolved Nd to the surface and deep waters of BoB, with ƐNd -16. Following the early Holocene, the ƐNd shift in SK157/20 to lower values suggests that GB influences overprinted the THC signal at the site. This timing of the ƐNd change agrees with a high-resolution salinity record from the BoB (Kudrass et al 2001), which shows lowest salinities associated with intense monsoon conditions during the mid-Holocene. Monsoon intensification enhances river discharge and its particle load (Ramaswamy and Nair, 1994), which can release Nd to the water column (Singh et al., 2012).

The ice age cycle and the deglaciations: an application of nonlinear regression modelling

NASA Astrophysics Data System (ADS)

Dalgleish, A. N.; Boulton, G. S.; Renshaw, E.

2000-03-01

We have applied the nonlinear regression technique known as additivity and variance stabilisation (AVAS) to time series which reflect Earth's climate over the last 600 ka. AVAS estimates a smooth, nonlinear transform for each variable, under the assumption of an additive model. The Earth's orbital parameters and insolation variations have been used as regression variables. Analysis of the contribution of each variable shows that the deglaciations are characterised by periods of increasing obliquity and perihelion approaching the vernal equinox, but not by any systematic change in eccentricity. The magnitude of insolation changes also plays no role. By approximating the transforms we can obtain a future prediction, with a glacial maximum at 60 ka AP, and a subsequent obliquity and precession forced deglaciation.

Simple quantification of surface carboxylic acids on chemically oxidized multi-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Gong, Hyejin; Kim, Seong-Taek; Lee, Jong Doo; Yim, Sanggyu

2013-02-01

The surface of multi-walled carbon nanotube (MWCNT) was chemically oxidized using nitric acid and sulfuric-nitric acid mixtures. Thermogravimetric analysis, transmission electron microscopy and infrared spectroscopy revealed that the use of acid mixtures led to higher degree of oxidation. More quantitative identification of surface carboxylic acids was carried out using X-ray photoelectron spectroscopy (XPS) and acid-base titration. However, these techniques are costly and require very long analysis times to promptly respond to the extent of the reaction. We propose a much simpler method using pH measurements and pre-determined pKa value in order to estimate the concentration of carboxylic acids on the oxidized MWCNT surfaces. The results from this technique were consistent with those obtained from XPS and titration, and it is expected that this simple quantification method can provide a cheap and fast way to monitor and control the oxidation reaction of MWCNT.

Different structural requirements for functional ion pore transplantation suggest different gating mechanisms of NMDA and kainate receptors.

PubMed

Villmann, Carmen; Hoffmann, Jutta; Werner, Markus; Kott, Sabine; Strutz-Seebohm, Nathalie; Nilsson, Tanja; Hollmann, Michael

2008-10-01

Although considerable progress has been made in characterizing the physiological function of the high-affinity kainate (KA) receptor subunits KA1 and KA2, no homomeric ion channel function has been shown. An ion channel transplantation approach was employed in this study to directly test if homomerically expressed KA1 and KA2 pore domains are capable of conducting currents. Transplantation of the ion pore of KA1 or KA2 into GluR6 generated perfectly functional ion channels that allowed characterization of those electrophysiological and pharmacological properties that are determined exclusively by the ion pore of KA1 or KA2. This demonstrates for the first time that KA1 and KA2 ion pore domains are intrinsically capable of conducting ions even in homomeric pore assemblies. NMDA receptors, similar to KA1- or KA2-containing receptors, function only as heteromeric complexes. They are composed of NR1 and NR2 subunits, which both are non-functional when expressed homomerically. In contrast to NR1, the homomeric NR2B ion pore failed to translate ligand binding into pore opening when transplanted into GluR6. Similarly, heteromeric coexpression of the ion channel domains of both NR1 and NR2 inserted into GluR6 failed to produce functional channels. Therefore, we conclude that the mechanism underlying the ion channel opening in the obligatorily heterotetrameric NMDA receptors differs significantly from that in the facultatively heterotetrameric alpha-amino-3-hydroxy-5-methyl-4-isoxazole propionate and KA receptors.

Lacustrine Records of Holocene Mountain Glacier Fluctuations from Western Greenland

NASA Astrophysics Data System (ADS)

Schweinsberg, A.; Briner, J. P.; Bennike, O.

2014-12-01

Recent studies have focused on documenting fluctuations of the Greenland Ice Sheet margin throughout the Holocene but few data exist that constrain past changes of local glaciers independent of the ice sheet. Our research combines proglacial lake sediment analysis with cosmogenic 10Be dating of Holocene moraines and radiocarbon dating of ice-cap-killed vegetation with an overall objective to use this multi-proxy approach to generate a detailed record of the coupled climate-glacier system through the Holocene. Here, we present lacustrine records of mountain glacier variability from continuous pro-glacial lake sediment sequences recovered from two glaciated catchments in northeastern Nuussuaq, western Greenland. We use radiocarbon-dated sediments from Sikuiui and Pauiaivik lakes to reconstruct the timing of advance and retreat of local glaciers. Sediments were characterized with magnetic susceptibility (MS), gamma density, Itrax XRF and visible reflectance spectroscopy at 0.2 cm intervals and sediment organic matter at 0.5 cm intervals. Basal radiocarbon ages provide minimum-age constraints on deglaciation from Sikuiui and Pauiaivik lakes of ~9.6 and 8.7 ka, respectively. Organic-rich gyttja from deglaciation until ~5.0 ka in Pauiaivik Lake suggests minimal glacial extent there while slightly elevated MS values from ~9.0 - 7.0 ka in Sikuiui Lake may reflect early Holocene glacial advances. Minerogenic sediment input gradually increases starting at ~5.0 ka in Pauiaivik Lake, which we interpret as the onset of Neoglaciation in the catchment. Furthermore, a distinct episode of enhanced glacial activity from ~4.0 - 2.2 ka in Sikuiui Lake may be correlative to a period of persistent snowline lowering evidenced by radiocarbon dates of ice-killed vegetation from nearby ice cap margins. Results from these lacustrine records and our ice-killed vegetation dataset suggest a middle Holocene onset of Neoglaciation ~5.0 - 4.0 ka in this region. We are supplementing these records with cosmogenic 10Be exposure dating to further constrain the timing of deglaciation. In addition, these sedimentary archives will continue to be compared to radiocarbon dates of ice-killed vegetation along adjacent ice cap margins to determine if times of persistent snowline lowering are correlative to periods of glacier advance.

Terrace sequence along the Yushanguxi River in the southern piedmont of Tian Shan and its relationship to climate and tectonics in northwestern China

NASA Astrophysics Data System (ADS)

Wu, Chuanyong; Zheng, Wenjun; Zhang, Zhuqi; Jia, Qichao; Yu, Jingxing; Zhang, Huiping; Han, Guihong; Yao, Yuan

2018-07-01

Controversies persist regarding the formation of terraces under the control of tectonic factors or climatic changes. This work focuses on the Yushanguxi River in the southern piedmont of Tian Shan, which is an intense tectonic uplift area where the terraces are very developed and the river has deeply downcut. Nine main terraces are distinguished (labelled T1 to Th, from youngest to oldest) based on the interpretation of a high-resolution remote sensing image, field investigations and detailed surveying with differential GPS. The results of the determination of 10Be exposure and 14C show abandoned ages of 2.1 ka for T1, 4.1 ka for T2, 4.2 ka for T3, 8.2 ka for T4, 18.1 ka for T5, 18.8 ka for T6, 102.1 ka for T7, 100.6 ka for T81, 113.9 ka for T82, 144.6 ka for Th1, 210.7 ka for Th2, and 284.3 ka for Th3. Since 18 ka, the incision rate began to increase from 0.6 mm a-1 to 12 mm a-1, which is obviously higher than the fault slip rate of 0.7 mm a-1. We suggest that the rapid downcutting along the Yushanguxi River during the Holocene has mainly been caused by frequent climate fluctuations.

Levetiracetam protects against kainic acid-induced toxicity.

PubMed

Marini, Herbert; Costa, Cinzia; Passaniti, Maria; Esposito, Maria; Campo, Giuseppe M; Ientile, Riccardo; Adamo, Elena Bianca; Marini, Rolando; Calabresi, Paolo; Altavilla, Domenica; Minutoli, Letteria; Pisani, Francesco; Squadrito, Francesco

2004-01-23

We investigated the Levetiracetam (LVT) ability to protect the brain against kainic acid (KA) induced neurotoxicity. Brain injury was induced by intraperitoneal administration of KA (10 mg/kg). Sham brain injury rats were used as controls. Animals were randomized to receive either LVT (50 mg/kg) or its vehicle (1 ml/kg) 30 min. before KA administration. Animals were sacrificed 6 hours after KA injection to measure brain malonildialdehyde (MDA), glutathione levels (GSH) and the mRNA for interleukin-1beta (IL-1beta) in the cortex and in the diencephalon. Behavioral changes were also monitored. Intraperitoneal administration of LVT decreased significantly MDA in the cortex (KA + vehicle = 0.25 +/- 0.03 nmol/mg protein; KA + LVT = 0.13 +/- 0.01 nmol/mg protein; P < 0.005), and in the diencephalons (KA + vehicle = 1,01 +/- 0.2 nmol/mg protein; KA + LVT = 0,33 +/- 0,08 nmol/mg protein; P < 0.005), prevented the brain loss of GSH in both cortex (KA + vehicle = 5 +/- 1 micromol/g protein; KA + LVT = 15 +/- 2 micromol/g protein; P < 0.005) and diencephalons (KA + vehicle = 9 +/- 0.8 micromol/g protein; KA + LVT = 13 +/- 0.3 micromol/g protein; P < 0.05), reduced brain IL-1beta mRNA and markedly controlled seizures. Histological analysis showed a reduction of cell damage in LVT treated samples. The present data indicate that LVT displays neuro-protective effects against KA induced brain toxicity and suggest that these effects are mediated, at least in part, by inhibition of lipid peroxidation.

Reconstructing Atmospheric CO2 Through The Paleocene-Eocene Thermal Maximum Using Stomatal Index and Stomatal Density Values From Ginkgo adiantoides

NASA Astrophysics Data System (ADS)

Barclay, R. S.; Wing, S. L.

2013-12-01

The Paleocene-Eocene Thermal Maximum (PETM) was a geologically brief interval of intense global warming 56 million years ago. It is arguably the best geological analog for a worst-case scenario of anthropogenic carbon emissions. The PETM is marked by a ~4-6‰ negative carbon isotope excursion (CIE) and extensive marine carbonate dissolution, which together are powerful evidence for a massive addition of carbon to the oceans and atmosphere. In spite of broad agreement that the PETM reflects a large carbon cycle perturbation, atmospheric concentrations of CO2 (pCO2) during the event are not well constrained. The goal of this study is to produce a high resolution reconstruction of pCO2 using stomatal frequency proxies (both stomatal index and stomatal density) before, during, and after the PETM. These proxies rely upon a genetically controlled mechanism whereby plants decrease the proportion of gas-exchange pores (stomata) in response to increased pCO2. Terrestrial sections in the Bighorn Basin, Wyoming, contain macrofossil plants with cuticle immediately bracketing the PETM, as well as dispersed plant cuticle from within the body of the CIE. These fossils allow for the first stomatal-based reconstruction of pCO2 near the Paleocene-Eocene boundary; we also use them to determine the relative timing of pCO2 change in relation to the CIE that defines the PETM. Preliminary results come from macrofossil specimens of Ginkgo adiantoides, collected from an ~200ka interval prior to the onset of the CIE (~230-30ka before), and just after the 'recovery interval' of the CIE. Stomatal index values decreased by 37% within an ~70ka time interval at least 100ka prior to the onset of the CIE. The decrease in stomatal index is interpreted as a significant increase in pCO2, and has a magnitude equivalent to the entire range of stomatal index adjustment observed in modern Ginkgo biloba during the anthropogenic CO2 rise during the last 150 years. The inferred CO2 increase prior to the CIE coincides in part with the 'pre-warming' interval documented from δ18O in mammalian tooth enamel from the Bighorn Basin. Stomatal density values increase ~30ka prior to the CIE, suggesting a decrease in cell size from water stress, a change that closely matches the timing of a trend towards drier paleosols in the same region of the Bighorn Basin. All evidence collected to date suggests a long-term rise in pCO2 and temperature, and drying of soils prior to the prominent CIE. Presumably the source for CO2 released prior to the CIE did not significantly alter the isotopic value of atmospheric CO2. As suggested by previous authors, warming prior to the CIE may have triggered the release of carbon from a source depleted in 13C at the onset of the PETM. Well-preserved dispersed cuticle has been extracted from stratigraphic levels within the CIE, and may permit reconstruction of changes in pCO2 during the PETM.

Electrostatics of cysteine residues in proteins: Parameterization and validation of a simple model

PubMed Central

Salsbury, Freddie R.; Poole, Leslie B.; Fetrow, Jacquelyn S.

2013-01-01

One of the most popular and simple models for the calculation of pKas from a protein structure is the semi-macroscopic electrostatic model MEAD. This model requires empirical parameters for each residue to calculate pKas. Analysis of current, widely used empirical parameters for cysteine residues showed that they did not reproduce expected cysteine pKas; thus, we set out to identify parameters consistent with the CHARMM27 force field that capture both the behavior of typical cysteines in proteins and the behavior of cysteines which have perturbed pKas. The new parameters were validated in three ways: (1) calculation across a large set of typical cysteines in proteins (where the calculations are expected to reproduce expected ensemble behavior); (2) calculation across a set of perturbed cysteines in proteins (where the calculations are expected to reproduce the shifted ensemble behavior); and (3) comparison to experimentally determined pKa values (where the calculation should reproduce the pKa within experimental error). Both the general behavior of cysteines in proteins and the perturbed pKa in some proteins can be predicted reasonably well using the newly determined empirical parameters within the MEAD model for protein electrostatics. This study provides the first general analysis of the electrostatics of cysteines in proteins, with specific attention paid to capturing both the behavior of typical cysteines in a protein and the behavior of cysteines whose pKa should be shifted, and validation of force field parameters for cysteine residues. PMID:22777874

Three-dimensional simulation of rivulet and film flows over an inclined plate: Effects of solvent properties and contact angle

DOE PAGES

Singh, Rajesh K.; Galvin, Janine E.; Sun, Xin

2015-12-10

We numerically investigated the film flow down an inclined plate using the volume of fluid (VOF) method. The flow simulations have been systematically carried out for a wide range of parameters, such as inlet size, inclination angle, contact angle, flow rates and solvent properties (viscosity and surface tension). Based on the simulation results, scaling theory is proposed for both interfacial area and for film thickness in terms of the Kapitza number (Ka).The Kapitza number is advantageous because it depends only on solvent properties. The Kapitza number decreases with increased solvent viscosity and is fixed for a given fluid. Here, tomore » investigate the effects of solvent properties on interfacial area a small inlet cross-section was used. The interfacial area decreases with increased value of Ka. The time to reach pseudo-steady state of rivulet is also observed to increase with decreasing Ka. For a fixed flow rate, the inlet cross-section has marginal effect on the interfacial area; however, the developed width of the rivulet remains unchanged. In addition to inlet size, flow rate and solvent properties, the impact of contact angle on film thickness and interfacial area was also investigated. The contact angle has negligible effect for a fully wetted plate, but it significantly affects the interfacial area of the rivulet. Finally, a scaling theory for interfacial area in terms of the contact angle and Ka is presented.« less

A simple expression for the cold compression curve.

NASA Astrophysics Data System (ADS)

Čelebonović, V.

1996-10-01

The aim of this contribution is to present expressions for the bulk modulus of a material and its pressure derivative obtained by using the semi-classical theory of dense matter proposed by P. Savić and R. Kašanin. Some possibilities for the application of these expressions are briefly discussed.

Chronology of Terra Firme formation in western Amazonia and implications for the diversification of Amazonian biota

NASA Astrophysics Data System (ADS)

Pupim, Fabiano do N.; Sawakushi, André O.; Hartmann, Gelvam A.; Savian, Jairo F.; Kern, Andrea K.; Mineli, Thays D.; Cruz, Francisco W.; Almeida, Renato P.; Grohmann, Carlos H.; Ribas, Camila C.; d'Horta, Fernando M.; Bertassoli, Dailson J.; Marconato, André; Nogueira, Luciana; Lohmann, Lúcia G.

2017-04-01

The shift from a large wetland dominated by avulsive channels and flooded forests to the incised transcontinental Amazon River valley (Várzea) bounded by non-flooded forests (Terra Firme) is suggested as one of the main drivers of diversification of the mega diverse Amazonian Biota. Nonetheless, there is no consensus about the timing of this landscape shift, with the current literature suggesting a period that ranges from the Miocene (11 Ma) and the Late Pleistocene (100 ka). This uncertainty may be due to a lack of absolute ages for the sediments forming Terra Firme forest substrates in western Amazonian lowlands. In Brazil, the Içá Formation represents the uppermost fluvial deposits of Terra Firme forests substrates in western Amazonia. Therefore, a reliable chronology for the last depositional stage of the Içá Formation is key for an improved understanding of the formation of the current Terra Firme-Várzea system. Four sediment profiles were sampled along the margins of the Solimões and Içá rivers for Optically Stimulated Luminescence (OSL) dating, geomagnetic excursions, and palynological analysis. OSL dating was performed in twelve samples using a Single Aliquot Regeneration (SAR) protocol in quartz sand grains. The equivalent doses ranged from 47 to 130 Gy (Central Age Model) and the dose rate values ranged from 0.4 to 2.0 Gy/ka. The resulting sediment burial ages range from 48 to 112 ka. Paleomagnetic data were obtained from samples collected at same profiles sampled for OSL dating and results suggest the presence of Post-Blake geomagnetic excursion ( 100 ka). The age of 100 ka for Post-Blake excursion are adopted for the Geomagnetic Instability Time Scale. Pollen assemblage data show a similarity to a more modern flora and the presence of Alnus clearly points towards Pleistocene deposition as it is unknown before in South America. The combined OSL, paleomagnetism and pollen data is a robust geochronological dataset that indicates Late Pleistocene ages for the last stage of built up of the Terra Firme in a broad region of the western Brazilian Amazonian lowlands. Therefore, the present-day unconformity between Terra Firme and Várzea deposits were formed by fluvial incision during the late Pleistocene and Holocene, which seems to be related with precipitation changes in the South American monsoon system. Our geochronological dataset point to important landscape changes during the late Pleistocene, with expansion of non-flooded Terra Firme and retraction of Várzea floodplain forests. This transition probably had important implications for the development of modern phylogeographical and biogeographical patterns in western Amazonia during the Quaternary. Future efforts will focus on dating drill-core sediment records using cosmogenic nuclides to extend the age range. Financial support: FAPESP 2009/53988-8, 2012/50260-6, 2014/23334-4, 2014/09800-2, 2016/09293-9; 2016/02656-9; CNPq 3009223/2014-8, 307647/2015-3; NSF DEB 1241066 and NASA.

Luminescence chronology of the loess record from the Tönchesberg section - a comparison of using quartz and feldspar as dosimeter to extend the age range beyond the Eemian

NASA Astrophysics Data System (ADS)

Dorothe Schmidt, Esther; Frechen, Manfred; Murray, Andrew S.; Tsukamoto, Sumiko

2010-05-01

The loess-paleosol sequences of the Tönchesberg section, located in the East Eifel Volcanic field (Germany) provide an excellent climate archive of the late Middle and the Upper Pleistocene in the Middle Rhine area. Loess deposits from the last Glacial (Würmian) and the penultimate Glacial (Rissian) are up to 12 m and 15 m thick, respectively, and intercalated by palaeosols. Optically stimulated luminescence (OSL), thermally transferred optically stimulated luminescence (TT-OSL) and infrared stimulated luminescence (IRSL) measurements were carried out on 14 samples from the Tönchesberg section to determine the deposition age and to set up a more reliable chronological framework for the penultimate and last interglacial-glacial cycle. The fine-grained quartz OSL and polymineral IRSL ages are in good agreement with each other and also with the geologically estimated age, but the quartz TT-OSL ages are overestimated. The OSL and IRSL ages range from 16.8 ± 1.2 to 189 ± 16 ka indicating that the youngest loess and the weakly developed soils were deposited during marine isotope stage (MIS) 2 and 3 and that the two marker loess were most likely accumulated in the transition MIS 4/5. Loess and reworked loess postdating the Eemian soil yield ages of 110-115 ka indicating that these deposits very likely correlate to MIS 5d. Loess deposits taken below the Eemian soil are attributed to the transition MIS 6/7. A weakly developed soil above the Tönchesberg scoria yield an age of 189 ± 16 ka indicating an interstadial soil formation during MIS 7. This is in good agreement with preliminary 40Ar/39Ar-ages for the Tönchesberg scoria and the intercalated tephra layers. Reliable age estimates up to ~70 ka could be obtained using quartz OSL and up to ~190 ka using the pulsed post-IR IR signal from feldspar. Hence the infrared stimulated luminescence (IRSL) is considered as the best approach to date the loess from the Middle Rhine area > 70 ka.

Atmospheric CO2 and abrupt climate change on submillennial timescales

NASA Astrophysics Data System (ADS)

Ahn, Jinho; Brook, Edward

2010-05-01

How atmospheric CO2 varies and is controlled on various time scales and under various boundary conditions is important for understanding how the carbon cycle and climate change are linked. Ancient air preserved in ice cores provides important information on past variations in atmospheric CO2. In particular, concentration records for intervals of abrupt climate change may improve understanding of mechanisms that govern atmospheric CO2. We present new multi-decadal CO2 records that cover Greenland stadial 9 (between Dansgaard-Oeschger (DO) events 8 and 9) and the abrupt cooling event at 8.2 ka. The CO2 records come from Antarctic ice cores but are well synchronized with Greenland ice core records using new high-resolution CH4 records,precisely defining the timing of CO2 change with respect to abrupt climate events in Greenland. Previous work showed that during stadial 9 (40~38 ka), CO2 rose by about 15~20 ppm over around 2,000 years, and at the same time temperatures in Antarctica increased. Dust proxies indicate a decrease in dust flux over the same period. With more detailed data and better age controls we now find that approximately half of the CO2 increase during stadial 9 occurred abruptly, over the course of decades to a century at ~39.6 ka. The step increase of CO2 is synchronous with a similar step increase of Antarctic isotopic temperature and a small abrupt change in CH4, and lags after the onset of decrease in dust flux by ~400 years. New atmospheric CO2 records at the well-known ~8.2 ka cooling event were obtained from Siple Dome ice core, Antarctica. Our preliminary CO2 data span 900 years and include 19 data points within the 8.2 ka cooling event, which persisted for ~160 years (Thomas et al., Quarternary Sci. Rev., 2007). We find that CO2 increased by 2~4 ppm during that cooling event. Further analyses will improve the resolution and better constrain the CO2 variability during other times in the early Holocene to determine if the variations observed during at 8.2 ka event are significant.

Regulation of blood glucose level by kainic acid in mice: involvement of glucocorticoid system and non-NMDA receptors.

PubMed

Kim, Chea-Ha; Park, Soo-Hyun; Sim, Yun-Beom; Kim, Sung-Su; Jung, Jun-Sub; Sharma, Naveen; Suh, Hong-Won

2017-02-28

Kainic acid (KA) is a well-known excitatory neurotoxic substance. In the present study, effects of KA-injected intraperitoneally (i.p.), intracerebroventricularly (i.c.v.) or intrathecally (i.t.) on the blood glucose level were investigated in ICR mice. We found that KA administered intraperitoneally (i.p.), intracerebroventricularly (i.c.v.) or intrathecally (i.t.) increased the blood glucose and corticosterone levels, suggesting that KA-induced hyperglycemia appeared to be due to increased blood corticosterone level. In support of this finding, adrenalectomy causes a reduction of KA-induced hyperglycemia and neuronal cell death in CA3 regions of the hippocampus. In addition, pretreatment with i.c.v. or i.t. injection of CNQX (6-cyano-7-nitroquinoxaline-2, 3-dione; a non-NMDA receptor blocker) attenuated the i.p. and i.c.v. administered KA-induced hyperglycemia. KA administered i.c.v. caused an elevation of the blood corticosterone level whereas the plasma insulin level was reduced. Moreover, i.c.v. pretreatment with CNQX inhibited the decrease of plasma insulin level induced by KA i.c.v. injection, whereas the KA-induced plasma corticosterone level was further enhanced by CNQX pretreatment. Our results suggest that KA administered systemically or centrally produces hyperglycemia. A glucocorticoid system appears to be involved in KA-induced hyperglycemia. Furthermore, central non-N-methyl-D-aspartate receptors may be responsible for KA-induced hyperglycemia.

Influence of the solution pH in the 6-mercaptopurine self-assembled monolayer (6MP-SAM) on a Au(111) single-crystal electrode.

PubMed

Madueño, Rafael; García-Raya, Daniel; Viudez, Alfonso J; Sevilla, José M; Pineda, Teresa; Blázquez, Manuel

2007-10-23

Self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) have been prepared on a Au(111) single-crystal electrode by immersion of the metal surface in a 100 microM 6MP and 0.01 M HClO4 solution. The 6MP-SAM Au(111) single-crystal electrodes were transferred to the cell and allowed to equilibrate with the different aqueous working solutions before the electrochemical experiments. The influence of the solution pH was studied by cyclic voltammetry, double layer capacitance curves, and electrochemical impedance spectroscopy. The electrochemical behavior of the 6MP-SAM in acetic acid at pH 4 presents important differences in comparison to that obtained in 0.1 M KOH solutions. Cyclic voltammograms for the reductive desorption process in acid medium are broad and show some features that can be explained by a phase transition between a chemisorbed and a physisorbed state of the 6MP molecules. The low solubility of these molecules in acid medium could explain this phenomenon and the readsorption of the complete monolayer when the potential is scanned in the positive direction. The variation of the double-layer capacitance values in the potential range of monolayer stability with the pH suggests that the acid-base chemistry of the 6MP molecules is playing a role. This fact has been studied by following the variations of the electron-transfer rate constant of the highly charged redox probes as are Fe(CN)(6)-3/-4 and Ru(NH3)(6)+3/+2 as a function of solution pH. The apparent surface pKa value for the 6MP-SAM (pKa approximately 8) is explained by the total conversion of the different 6MP tautomers that exist in solution to the thiol species in the adsorbed state.

Correcting for initial Th in speleothems to obtain the age of calcite nucleation after a growth hiatus

NASA Astrophysics Data System (ADS)

Richards, D. A.; Nita, D. C.; Moseley, G. E.; Hoffmann, D. L.; Standish, C. D.; Smart, P. L.; Edwards, R.

2013-12-01

In addition to the many U-Th dated speleothem records (δ18O δ13C, trace elements) of past environmental change based on continuous phases of calcite growth, discontinuous records also provide important constraints for a wide range of past states of the Earth system, including sea levels, permafrost extent, regional aridity and local cave flooding. Chronological information about human activity or faunal evolution can also be obtained where calcite can be seen to overlie cave art or mammalian bones, for example. Among the important considerations when determining the U-Th age of calcite that nucleates on an exposed surface are (1) initial 230Th/232Th, which can be elevated and variable in some settings, and (2) growth rate and sub-sample density, where extrapolation is required. By way of example, we present sea level data based on U-Th ages of vadose speleothems (i.e. formed above the water table and distinct from 'phreatic' examples) from caves of the circum-Caribbean , where calcite growth was interrupted by rising sea levels and then reinitiated after regression. These estimates demand large corrections and derived sea level constraints are compared with alternative data from coral reef terraces, phreatic overgrowths on speleothems or indirect, proxy evidence from oxygen isotopes to constrain rates of ice volume growth. Flowstones from the Bahamas provide useful sea level constraints because they present the longest and most continuous records in such settings (a function of preservation potential in addition to hydrological routing) and also earliest growth post-emergence after sea level fall. We revisit estimates for sea level regression at the end of MIS 5 at ~ 80 ka (Richards et al, 1994; Lundberg and Ford, 1994) and make corrections for non-Bulk Earth initial Th contamination (230Th/232Th activity ratio > 10), based on isochron analysis of alternative stalagmites from the same settings and recent high resolution analysis. We also present new U-Th ages for contiguous layers sub-sampled from the first 2-3 mm of flowstone growth after the MIS 5 hiatus, using a sub-sample milling strategy that matches spatial resolution with maximum achievable precision (ThermoFinnigan Neptune MC-ICPMS methodology; 20-30 mg calcite, U = ~ 300 ng.g-1, 2σ age uncertainty is × 600 a at ~80 ka). Isochron methods are used to estimate the range of initial 230Th/232Th ratio and are compared with elevated values obtained from stalagmites from the same cave (Beck et al, 2001; Hoffmann et al, 2010). A similar strategy is presented for a stalagmite with much faster axial growth data, and the data are combined with additional sea level information from the same region to estimate the rate and uncertainty of sea level regression at the MIS stage 5/4 boundary. Elevated initial 230Th/232Th values have also been observed in a stalagmite from 6 m below present sea level in a cenote from the Yucatan, Mexico, where 5 phases of calcite between 10 and 5.5 ka are separated by serpulid worm tubes formed during periods of submergence. The transition between each phase provides constraints on age and elevation of relative sea level, but the former is hampered by the uncertainty of the high initial 230Th/232Th correction. We consider the possible sources of elevated Th ratios: hydrogenous, colloidal and carbonate or other detrital components.

Biomolecular Interaction Analysis Using an Optical Surface Plasmon Resonance Biosensor: The Marquardt Algorithm vs Newton Iteration Algorithm

PubMed Central

Hu, Jiandong; Ma, Liuzheng; Wang, Shun; Yang, Jianming; Chang, Keke; Hu, Xinran; Sun, Xiaohui; Chen, Ruipeng; Jiang, Min; Zhu, Juanhua; Zhao, Yuanyuan

2015-01-01

Kinetic analysis of biomolecular interactions are powerfully used to quantify the binding kinetic constants for the determination of a complex formed or dissociated within a given time span. Surface plasmon resonance biosensors provide an essential approach in the analysis of the biomolecular interactions including the interaction process of antigen-antibody and receptors-ligand. The binding affinity of the antibody to the antigen (or the receptor to the ligand) reflects the biological activities of the control antibodies (or receptors) and the corresponding immune signal responses in the pathologic process. Moreover, both the association rate and dissociation rate of the receptor to ligand are the substantial parameters for the study of signal transmission between cells. A number of experimental data may lead to complicated real-time curves that do not fit well to the kinetic model. This paper presented an analysis approach of biomolecular interactions established by utilizing the Marquardt algorithm. This algorithm was intensively considered to implement in the homemade bioanalyzer to perform the nonlinear curve-fitting of the association and disassociation process of the receptor to ligand. Compared with the results from the Newton iteration algorithm, it shows that the Marquardt algorithm does not only reduce the dependence of the initial value to avoid the divergence but also can greatly reduce the iterative regression times. The association and dissociation rate constants, ka, kd and the affinity parameters for the biomolecular interaction, KA, KD, were experimentally obtained 6.969×105 mL·g-1·s-1, 0.00073 s-1, 9.5466×108 mL·g-1 and 1.0475×10-9 g·mL-1, respectively from the injection of the HBsAg solution with the concentration of 16ng·mL-1. The kinetic constants were evaluated distinctly by using the obtained data from the curve-fitting results. PMID:26147997

Effect of pertussis and cholera toxins administered supraspinally on CA3 hippocampal neuronal cell death and the blood glucose level induced by kainic acid in mice.

PubMed

Kim, Chea-Ha; Park, Soo-Hyun; Sim, Yun-Beom; Sharma, Naveen; Kim, Sung-Su; Lim, Su-Min; Jung, Jun-Sub; Suh, Hong-Won

2014-12-01

The effect of cholera toxin (CTX) or pertussis toxin (PTX) administered supraspinally on hippocampal neuronal cell death in CA3 region induced by kainic acid (KA) was examined in mice. After the pretreatment with either PTX or CTX intracerebroventricularly (i.c.v.), mice were administered i.c.v. with KA. The i.c.v. treatment with KA caused a neuronal cell death in CA3 region and PTX, but not CTX, attenuated the KA-induced neuronal cell death. In addition, i.c.v. treatment with KA caused an elevation of the blood glucose level. The i.c.v. PTX pretreatment alone caused a hypoglycemia and inhibited KA-induced hyperglycemic effect. However, i.c.v. pretreatment with CTX did not affect the basal blood glucose level and KA-induced hyperglycemic effect. Moreover, KA administered i.c.v. caused an elevation of corticosterone level and reduction of the blood insulin level. Whereas, i.c.v. pretreatment with PTX further enhanced KA-induced up-regulation of corticosterone level. Furthermore, i.c.v. administration of PTX alone increased the insulin level and KA-induced hypoinsulinemic effect was reversed. In addition, PTX pretreatment reduces the KA-induced seizure activity. Our results suggest that supraspinally administered PTX, exerts neuroprotective effect against KA-induced neuronal cells death in CA3 region and neuroprotective effect of PTX is mediated by the reduction of KA-induced blood glucose level. Copyright © 2014 Elsevier Ireland Ltd and the Japan Neuroscience Society. All rights reserved.

Effects of kainic acid on rat body temperature: unmasking by dizocilpine.

PubMed

Ahlenius, S; Oprica, M; Eriksson, C; Winblad, B; Schultzberg, M

2002-07-01

The effects of intraperitoneal (i.p.) administration of kainic acid (KA) and dizocilpine, alone or in combination, on body temperature of freely moving rats were examined. Injection of saline or dizocilpine (3.0 or 5.0 mg/kg) was followed after an hour by injection of saline or KA (10 mg/kg) and the body temperature was measured at different time points during the first 5 h. KA alone produced an initial short-lasting hypothermia followed by a longer-lasting hyperthermic effect. Administration of dizocilpine alone produced an early increase in core temperature. Pretreatment of KA-injected rats with dizocilpine potentiated the KA-induced hypothermic effect at 30 min and dose-dependently reduced the temperature measured at 1 h after KA-injection without influencing the ensuing hyperthermia.These data suggest that the KA-induced changes in body temperature do not necessarily involve the activation of NMDA-receptors as opposed to KA-induced behavioural changes that are blocked by dizocilpine in a dose-dependent manner. It is unlikely, therefore, that the KA-induced hyperthermia is a result of the KA-induced seizure motor activity. Furthermore, our findings indicate that KA-induced changes in core temperature may be used as a criterion of drug-responsiveness when the behavioural changes are blocked, e.g. with dizocilpine.