Sulfur electronic environments in α-NiS and β-NiS: examination of the relationship between coordination number and core electron binding energies

X-ray photoelectron spectra have been obtained under the same experimental conditions for synthetic α-NiS and natural β-NiS in order to establish any difference in S electronic environment, and to test the proposition that S core electron binding energies increase measurably with coordination number when the same metal is in different sulfide structures or lattice sites. The Ni and S electronic environments in the two NiS structures have been further probed by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and the NEXAFS spectra interpreted by reference to spectra simulated by ab initio calculations. The photoelectron and NEXAFS spectra for freshly prepared surfaces of α-NiS and β-NiS were found to be similar, with only subtle differences in electronic environment evident in the experimental and simulated NEXAFS spectra. The measured and calculated core electron binding energies did not support the previously postulated relationship between S coordination number and electron binding energies.     

Pentlandite sulfur core electron binding energies

A number of freshly abraded surfaces of pentlandite have been characterised by X-ray photoelectron spectroscopy to establish whether the initial intensity of the S 2p component near 161.4 eV, previously assigned to the 25% of S atoms in fourfold coordination by metal atoms in pentlandite, was always at least 25% of the total S 2p intensity. It was found that the intensity of this S 2p component could be lower than 20% for surfaces that were not significantly oxidised. To assess whether the proposed 0.75–0.8 eV 2p binding energy difference for the two sulfur environments in pentlandite was justified, ab initio calculations of the difference in core electron binding energies and of the densities of unfilled states have been carried out. The corresponding simulated S K near-edge X-ray absorption fine structure (NEXAFS) spectra have been compared with experimental spectra. The calculated S 2p and S 1s binding energy differences were 0.45 and 0.5 eV at most, in agreement with the experimental NEXAFS spectra. It was concluded that the S 2p component near 161.4 eV arises entirely from violarite present at the pentlandite surface rather than from 4-coordinate S in pentlandite itself. Ab initio calculations of the difference in S 2p binding energies for the 2- and 3-coordinate S in stibnite have also been carried out and found to be quite small, in agreement with previously reported experimental values. Nevertheless, for both pentlandite and stibnite, calculations have confirmed that an increase in coordination number is associated with an increase in sulfur core electron binding energies, even although that increase is barely measurable for the latter sulfide.     

Generation mechanisms of convectively induced internal gravity waves in a three-dimensional framework

The generation mechanisms of convective gravity waves in the stratosphere are investigated in a three-dimensional framework by conducting numerical simulations of four ideal storms under different environmental conditions: one un-sheared and three constant low-level sheared basic-state winds with the depth of the shear layer of 6 km and the surface wind speeds (U_s) of 8, 18, and 28 m s^?1, using the Advanced Regional Prediction System (ARPS) model. The storms simulated under the un-sheared (U_s = 0 m s^?1), weakly sheared (U_s = 8 and 18ms^?1), and strongly sheared (U_s = 28ms^?1) basicstate winds are classified into single-cell, multicell, and supercell storms, respectively. For each storm, the wave perturbations in a control simulation, including nonlinearity and microphysical processes, are compared with those in quasi-linear dry simulations forced by diabatic forcing and nonlinear forcing that are obtained from the control simulation. The gravity waves generated by the two forcing terms in the quasi-linear dry simulations are out of phase with each other for all of the storms. The gravity waves in the control simulation are represented by a linear sum of the wave perturbations generated by the nonlinear forcing and diabatic forcing. This result is consistent with the results of previous studies in a two-dimensional framework. This implies that both forcing mechanisms are important for generating the convective gravity waves in the three-dimensional framework as well. The characteristics of the three-dimensional gravity waves in the stratosphere were determined by the spectral combination of the forcing terms and the wave-filtering and resonance factor that is determined from the basic-state wind and stability as well as the vertical structure of the forcing.     

Distribution of small plastic debris in cross-section and high strandline on Heungnam beach, South Korea

The spatial distribution of small plastic debris on Heungnam beach in February 2011 was investigated. The abundances of small plastic debris over 2 mm in size along the high strandline and cross-sectional line of the beach were determined. The mean abundances of small plastics were 976 ± 405 particles/m² at the high strandline in the upper tidal zone along the shoreline and 473 ± 866 particles/m² at the cross-section perpendicular to the shoreline. Specifically, styrofoam (expanded polystyrene) spherules accounted for 90.7% of the total plastic abundance in the high strandline and 96.3% in the cross-section. The spatial distribution patterns of small plastic debris differed between the high strandline and cross-sectional line. The cross-sectional distribution of small plastic abundance differed among plastic types, indicating that representative sampling of small plastic debris on a beach is necessary.     

通辽市R_(5d)的气候特征分析

文章利用通辽市境内科尔沁区、开鲁、鲁北、保康、甘旗卡、库伦、大沁他拉七个测站53a(1959—2011年)逐日降水量资料进行通辽市连续5d最大降水量(R5d)的气候特征分析,结果表明,通辽市R5d为减小趋势,在0.05显著性水平以上,倾向率为-4.56mm/10a,各站R5d均为减少趋势,其中库伦、开鲁、科尔沁区的倾向率为-7.0^-5.64mm/10a,减少较为明显;R/S分析结果为,全市及各站均符合赫斯特现象,H指数>0.5,未来将持续减少,其中鲁北、科尔沁区、开鲁的H指数较大,维持减少趋势将较为强劲;M-K突变检测发现,R5d在1965年发生突变,此后UF下降趋势超过了0.001极显著水平。     

Impacts of Shallow Convection Processes on a Simulated Boreal Summer Climatology in a Global Atmospheric Model

This study investigates the impacts of shallow convection schemes on a simulated seasonal climatology in the Global and Regional Integrated Model system (GRIMs). The eddy-diffusivity scheme of Tiedtke (TDK) is evaluated, focusing on the dependency upon deep convection schemes. Drying and warming near the top of the planetary boundary layer (PBL) and opposing effects above are observed. The height of PBL is reduced due to the increase of thermal stability near the PBL top. The weakened PBL turbulence is partly compensated with the increased downward solar radiation due to the reduction of low clouds. These effects are pronounced over the oceans, which leads to the modulation of tropical precipitation. It is found that the original TDK scheme shows similar behavior regardless of the choice of deep convection schemes. A revised TDK scheme that explicitly couples the PBL and shallow convection processes is proposed and evaluated. The proposed scheme generally improves the simulated climatology over the results with the original TDK scheme, along with further improvement in the case of the revised deep convection scheme. Our results indicate that the role of the shallow convection scheme needs to be carefully examined to improve the performance of atmospheric models, with a focus on modulated PBL and deep convection processes.     

Examination of multi-perturbation methods for ensemble prediction of the MJO during boreal summer

The impact of initialization and perturbation methods on the ensemble prediction of the boreal summer intraseasonal oscillation was investigated using 20-year hindcast predictions of a coupled general circulation model. The three perturbation methods used in the present study are the lagged-averaged forecast (LAF) method, the breeding method, and the empirical singular vector (ESV) method. Hindcast experiments were performed with a prediction interval of 10 days for extended boreal summer (May–October) seasons over a 20 year period. The empirical orthogonal function (EOF) eigenvectors of the initial perturbations depend on the individual perturbation method used. The leading EOF eigenvectors of the LAF perturbations exhibit large variances in the extratropics. Bred vectors with a breeding interval of 3 days represent the local unstable mode moving northward and eastward over the Indian and western Pacific region, and the leading EOF modes of the ESV perturbations represent planetary-scale eastward moving perturbations over the tropics. By combining the three perturbation methods, a multi-perturbation (MP) ensemble prediction system for the intraseasonal time scale was constructed, and the effectiveness of the MP prediction system for the Madden and Julian oscillation (MJO) prediction was examined in the present study. The MJO prediction skills of the individual perturbation methods are all similar; however, the MP‐based prediction has a higher level of correlation skill for predicting the real-time multivariate MJO indices compared to those of the other individual perturbation methods. The predictability of the intraseasonal oscillation is sensitive to the MJO amplitude and to the location of the dominant convective anomaly in the initial state. The improvement in the skill of the MP prediction system is more effective during periods of weak MJO activity.     

Analysis of flow behavior in a landfill with cover soil of low hydraulic conductivity

 This paper presents the results of field tests of hydrologic parameters in a landfill and the results of numerical simulation to find the efficiency of the pumping method to reduce leachate levels in the landfill. The field hydraulic conductivity and storativity of waste and buried cover soils in the landfill are measured by pumping and slug tests. The hydrologic condition inside the landfill is first calibrated using the drawdown-time curve obtained from the pumping test, and the flow behavior of leachate during pumping in the landfill, when various layers of waste and buried cover soil exist, is analyzed through three-dimensional numerical simulation of flow. The results of the field investigation show that the buried cover soil of low hydraulic conductivity forms an impermeable layer preventing the downward flow of leachate and upward flow of landfill gas. The hydraulic conductivities of the pumping test and slug tests were quite close on the same order of magnitude. It was also possible to match the drawdown-time data of the field tests with those of the model using input data close to the hydrologic property obtained from the field tests. The numerical flow analysis showed that pumping was possible up to 120 tons/day for a single well without a drain, while the pumping rate could be increased to 300 tons/day for the same well with the drain. From the vertical section of the flow vector with a horizontal drain, the barrier role of buried cover soil is identified, which was proposed by examining the water contents of the disposed cover soil and waste in the field. Received: 15 May 1998 · Accepted: 4 January 1999