Disorder and the extent of polymerization in calcium silicate and aluminosilicate glasses: O-17 NMR results and quantum chemical molecular orbital calculations

Estimation of the framework connectivity and the atomic structure of depolymerized silicate melts and glasses (NBO/T > 0) remains a difficult question in high-temperature geochemistry relevant to magmatic processes and glass science. Here, we explore the extent of disorder and the nature of polymerization in binary Ca-silicate and ternary Ca-aluminosilicate glasses with varying NBO/T (from 0 to 2.67) using O-17 NMR at two different magnetic fields of 9.4 and 14.1 T in conjunction with quantum chemical calculations. Non-random distributions among framework cations (Si and Al) are demonstrated in the variation of relative populations of oxygen sites with NBO/T. The proportion of non-bridging oxygen (NBO, Ca-O-Si) in the binary and ternary aluminosilicate glasses increases with NBO/T. While the trend is consistent with predictions from composition, the detailed fractions apparently deviate from the predicted values, suggesting further complications in the nature of polymerization. The proportion of each bridging oxygen in the glasses also varies with NBO/T. The fractions of Al-O-Si and Al-O-Al increase with increasing polymerization as CaO is replaced with Al₂O₃, while that of Si-O-Si seems to decrease, implying that activity of silica may decrease from calcium silicate to polymerized aluminosilicates (X_SiO2=constant). Quantum chemical molecular orbital calculations based on density functional theory show that a silicate chain with Al-NBO (Ca-O-Al) has an energy penalty (calculated cluster energy difference) of about 108 kJ/mol compared with the cluster with Ca-O-Si, consistent with preferential depolymerization of Si-networks, reported in an earlier O-17 NMR study [Allwardt, J., Lee, S.K., Stebbins, J.F., 2003. Bonding preferences of non-bridging oxygens in calcium aluminosilicate glass: Evidence from O-17 MAS and 3QMAS NMR on calcium aluminate glass. Am. Mineral.88, 949-954]. These prominent types of non-randomness in the distributions suggest significant chemical order in silicate glasses that leads to a decrease in silica activity coefficient and will be useful in modeling transport properties of melts.     

Global parameter estimation of the Cochlodinium polykrikoides model using bioassay data

Cochlodinium polykrikoides is a notoriously harmful algal species that inflicts severe damage on the aquacultures of the coastal seas of Korea and Japan. Information on their expected movement tracks and boundaries of influence is very useful and important for the effective establishment of a reduction plan. In general, the information is supported by a red-tide(a.k.a algal bloom) model. The performance of the model is highly dependent on the accuracy of parameters, which are the coefficients of functions approximating the biological growth and loss patterns of the C. polykrikoides. These parameters have been estimated using the bioassay data composed of growth-limiting factor and net growth rate value pairs. In the case of the C. polykrikoides, the parameters are different from each other in accordance with the used data because the bioassay data are sufficient compared to the other algal species. The parameters estimated by one specific dataset can be viewed as locally-optimized because they are adjusted only by that dataset. In cases where the other one data set is used, the estimation error might be considerable. In this study, the parameters are estimated by all available data sets without the use of only one specific data set and thus can be considered globally optimized. The cost function for the optimization is defined as the integrated mean squared estimation error, i.e., the difference between the values of the experimental and estimated rates. Based on quantitative error analysis, the root-mean squared errors of the global parameters show smaller values, approximately 25%–50%, than the values of the local parameters. In addition, bias is removed completely in the case of the globally estimated parameters. The parameter sets can be used as the reference default values of a red-tide model because they are optimal and representative. However, additional tuning of the parameters using the in-situ monitoring data is highly required.As opposed to the bioassay data, it is necessary because the bioassay data have limitations in terms of the in-situ coastal conditions.     

Kinetics of high-pressure phase transformations: Implications to the evolution of the olivine → spinel transition in the downgoing lithosphere and its consequences on the dynamics of the mantle

The rate of a high-pressure phase transition increases exponentially with temperature (T) and overpressure or pressure beyond equilibrium (ΔP). It is also greatly promoted by introducing shear stress, diminishing grain size, and adding water or other catalysts to the reactants. For an isothermal and isobaric transition with no compositional change, if steady state of nucleation on grain surfaces is attained, the rate equation can be expressed: (1) before site saturation by: X = 1 − exp(−Kt⁴), where

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and (2) after site saturation by: X = 1 − exp(−K′T), where

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, where X is volume fraction of completion of transformation, t is time, and the C's are characteristic constants. C₁ and C₉ are functions of grain size, C₃ and C₆ are functions of shear stress. All the C's are almost independent of temperature and pressure. Thus, if X as a function of T, ΔP, and t over a narrow P-T range can be experimentally determined, the C's can be calculated and the effect of grain size and shear stress on the rate of transformation can be evaluated. The isothermal and isobaric rate equations for a given composition, shear stress, and grain size are then experimentally determinable. The non-isothermal and non-isobaric rate equation can be calculated from the isothermal and isobaric ones if the rate of penetration into the metastability field is known. The important feature of the kinetics of high-pressure phase transitions predicted by these rate equations is that for a given rate of penetration into the metastability field, there can be defined a characteristic temperature, T_ch, below which the rate of the transition is virtually zero no matter how metastable the material is. For the olivine → spinel transition in the mantle, this characteristic temperature may be as high as 700° C. Thus, in a fast moving downgoing slab, the temperature at its cold center may remain below T_ch even down to depths in excess of 600 km, thereby greatly depressing the olivine—spinel phase boundary.At an early stage in the development of a downgoing slab, the plunging speed is slow. This allows the interior of the slab to heat up and the olivine → spinel transition to proceed rapidly and near equilibrium. As a result, the olivine—spinel phase boundary in the slab will be distorted upwards. The rising of the denser spinel phase then provides an additional driving force which accelerates the plate. Since the upper portion of the slab is pulled from below and the lower portion pushed from above, earthquakes of down-dip extension will occur in the upper mantle while those of down-dip compression will originate in the transition zone. Because the transformation occurs close to equilibrium, there will be an aseismic region separating the two seismic zones. When the plate velocity exceeds a certain limit, the temperature in the cold interior becomes low enough to depress the olivine → spinel transition. The phase boundary is then distorted downwards. The buoyant force thereby created will reduce the driving force, and the plunging speed of the plate will approach a steady state. In addition, the buoyant force will compress the slab from below and result in earthquakes of down-dip compression throughout the length of the slab. Now the olivine → spinel transition is so far from equilibrium that the reaction becomes implosive. A rise in frequency of deep earthquakes towards the implosion region in the lower transition zone is thus predicted. Therefore, as well as stabilizing the plate velocity, the olivine → spinel transition may also control earthquake distributions throughout the downgoing slab.     

Biomarker responses in pelagic and benthic fish over 1 year following the Hebei Spirit oil spill (Taean, Korea)

After the Hebei Spirit oil spill incident (7th December, 2007) in the west coast of Korea, contamination of biliary PAH metabolite and hepatic biomarkers in a pelagic and a benthic fish was monitored for 1 year. Concentrations of 16 PAHs and alkylated PAHs in fish muscle were highest (22.0 ng/g d.w. for 16 PAHs and 284 ng/g d.w. for alkylated PAHs) at 5 days after the spill and then decreased rapidly to background levels at 11 months after the spill. Fish from the oiled site had elevated biliary PAH metabolite concentrations immediately after the spill; these declined steadily in both species, but were still above reference site concentrations 2 months after the spill. Oiled-site fish showed hepatic CYP 1A induction whose trend closely followed those of biliary PAH metabolite concentrations, implying continuous exposure to PAHs. Brain acetylcholinesterase activity was not related to oil exposure.     

Evaluation of building period formulas for seismic design

Building period formulas in seismic design code are evaluated with over 800 apparent building periods from 191 building stations and 67 earthquake events. The evaluation is carried out with the formulas in ASCE 7‐05 for steel and RC moment‐resisting frames, shear wall buildings, braced frames, and other structural types. Qualitative comparison of measured periods and periods calculated from the code formulas shows that the formula for steel moment‐resisting frames generally predicts well the lower bound of the measured periods for all building heights. But the differences between the periods from code formula and measured periods of low‐ to‐medium rise buildings are relatively high. In addition, the periods of essential buildings designed with the importance factor are about 40% shorter than the periods of non‐essential buildings. The code formula for RC moment‐resisting frames describes well the lower bound of measured periods. The formula for braced frames accurately predicts the lower bound periods of low‐to‐medium rise buildings. The formula for shear wall buildings overestimates periods for all building heights. For buildings that are classified as other structural types, the measured building periods can be much shorter than the periods calculated with the code formula. Based on these observations, it is suggested to use C_r factor of 0.015 for shear walls and other structural types. Copyright © 2010 John Wiley & Sons, Ltd.     

Role of tropical atlantic SST variability as a modulator of El Niño teleconnections

The present study suggests that the off-equatorial North Atlantic (NATL) SST warming plays a significant role in modulating El Niño teleconnection and its impact on the North Atlantic and European regions. The El Niño events accompanied by NATL SST warming exhibit south-north dipole pattern over the Western Europe to Atlantic, while the ENSO teleconnection pattern without NATL warming exhibits a Rossby wave-like pattern confined over the North Pacific and western Atlantic. Especially, the El Niño events with NATL warming show positive (negative) geopotential-height anomalies over the North Atlantic (Western Europe) which resemble the negative phase of the NAO. Consistently, it is shown using a simple statistical model that NATL SSTA in addition to the tropical Pacific SSTA leads to better prediction on regional climate variation over the North Atlantic and European regions. This role of NATL SST on ENSO teleconnection is also validated and discussed in a long term simulation of coupled global circulation model (CGCM).     

Occurrence of gorgosterol in diatoms of the genus Delphineis

The presence of the C₃₀ sterol gorgosterol (22,23-methylene-23,24-dimethylcholest-5-en-3ß-ol) and its analogues in some marine and freshwater environments is generally associated with invertebrate animals or dinoflagellates since there have been no reports of them in other microalgal classes. Here we show that two unialgal cultures of different species of the marine diatom Delphineis contain gorgosterol in addition to sterols more commonly found in diatoms. Our findings suggest that some reports of gorgosterol in seawater and marine sediments may well have an origin, at least in part, from diatoms.     

The Local Magnitude Scale in the Korean Peninsula

A formula to determine the local magnitude (M_L) following Richters original definition was empirically derived for the Korean Peninsula. A total of 1,644 digital seismograms from 142 Korean earthquakes that occurred from 1997 to 2000 were corrected for instrument response and convolved with the nominal Wood-Anderson torsion seismograph response to be appropriate for the original definition of M_L. Then, the zero-to-peak amplitude was measured in millimeters on the synthetic Wood-Anderson seismogram. Multiple regression analysis was conducted to determine distance and station correction terms for the measured peak amplitudes. The best-fit solution for M_L yielded the following formula for the Korean Peninsula:where A() and S denote the peak amplitude on the synthetic Wood-Anderson seismogram at distance and the station correction term, respectively. Note that the second term, distance correction, was adjusted with Richters M_L, taking into consideration attenuation differences between the Korean Peninsula and southern California, where Richter originally introduced M_L. On average, the magnitudes determined in this study are nearly the same as those determined by the Korea Institute of Geoscience and Mineral Resources (KIGAM), but are larger than those of the Korea Meteorological Administration (KMA) by as much as 0.36.     

High-resolution numerical simulation of the Pacific Ocean

The present study developed Pacific Ocean models from the Research Institute for Applied Mechanics Ocean Model (RIAMOM) with very high horizontal (1/6° and 1/12°) and vertical (70 levels) resolutions. The hydrographic features of the simulations show good agreement with observed climatological features. Solution differences between the 1/6° and 1/12° models are small for general features of various physical components, but large for eddy fields and the strengths of western boundary currents and their extensions. However, the two high-resolution models show realistic climatological features of Pacific Ocean circulation patterns. Volume transports through major straits in the northwestern Pacific Ocean were also simulated and compared with previous observational results.     

Tidal Influences on Biotic and Abiotic Factors in the Seomjin River Estuary and Gwangyang Bay,Korea

To assess changes in abiotic and biotic factors between flood and ebb tides, we investigated the seasonal phytoplankton dynamics and environmental conditions along a salinity gradient at 14 stations in the Seomjin River estuary (SRE), Korea, and conducted bioassays to investigate the effect of nutrient addition (+N, +P, and +NP) on phytoplankton growth. Saltwater intrusion upstream was greatly dependent on the amount of freshwater discharge resulting from seasonal rainfall. There was a strong negative correlation between salinity and the nitrate+nitrite concentration (p?<?0.001), and between salinity and the silicate concentration (p?<?0.001), but no clear correlation between salinity and the ammonium concentration, or salinity and the phosphate concentration (p?>?0.01). This indicates that the N and Si loading increased as a result of freshwater input. The algal bioassays showed that high phytoplankton growth rates were usually recorded in response to the +NP treatment, but in the saltwater zone, the phytoplankton community also responded rapidly to the +N treatment, and to the +P treatment in the freshwater zone. The range of nutrient limitation depended on freshwater discharge. The seasonal and horizontal distribution of phytoplankton communities changed along the salinity gradient. The significant differences in abiotic factors between flood and ebb tides play important roles in controlling the biotic factors, including the occurrence of aquatic organisms including microalgae.