Zinc surface complexes on birnessite: A density functional theory study

Biogeochemical cycling of zinc is strongly influenced by sorption on birnessite minerals (layer-type MnO₂), which are found in diverse terrestrial and aquatic environments. Zinc has been observed to form both tetrahedral (Zn^IV) and octahedral (Zn^VI) triple-corner-sharing surface complexes (TCS) at Mn(IV) vacancy sites in hexagonal birnessite. The octahedral complex is expected to be similar to that of Zn in the Mn oxide mineral, chalcophanite (ZnMn₃O₇·3H₂O), but the reason for the occurrence of the four-coordinate Zn surface species remains unclear. We address this issue computationally using spin-polarized density functional theory (DFT) to examine the Zn^IV-TCS and Zn^VI-TCS species. Structural parameters obtained by DFT geometry optimization were in excellent agreement with available experimental data on Zn-birnessites. Total energy, magnetic moments, and electron overlap populations obtained by DFT for isolated Zn^IV-TCS revealed that this species is stable in birnessite without a need for Mn(III) substitution in the octahedral sheet and that it is more effective in reducing undersaturation of surface O at a Mn vacancy than is Zn^VI-TCS. Comparison between geometry-optimized ZnMn₃O₇·3H₂O (chalcophanite) and the hypothetical monohydrate mineral, ZnMn₃O₇·H₂O, which contains only tetrahedral Zn, showed that the hydration state of Zn significantly affects birnessite structural stability. Finally, our study also revealed that, relative to their positions in an ideal vacancy-free MnO₂, Mn nearest to Zn in a TCS surface complex move toward the vacancy by 0.08-0.11 Å, while surface O bordering the vacancy move away from it by 0.16-0.21 Å, in agreement with recent X-ray absorption spectroscopic analyses.     

The 2006/2007 photometric activity of three chromospherically active stars: V2075 Cyg,FG UMa and BM CVn

We present new multiband CCD photometric observations of three chromospherically active stars with long periods (V2075 Cyg, FG UMa and BM CVn). The observations were made at the Çanakkale Onsekiz Mart University Observatory in 2006 and 2007. We analyzed BVRI (Bessell) CCD observations of these three RS CVn-type SB1 binaries with the following three steps: (i) Photometric rotation periods were obtained by analyzing their light variations with a differential corrections method and a Fourier transform technique. (ii) Light variations, observed over three or more consecutive orbital cycles, were investigated by using dark (cool) spot models with the program SPOT. (iii) Surface differential rotation coefficients for the primary components of these binaries were derived using our own photometric periods together with orbital periods taken from the literature.     

A study of the durability of some shales,mudrocks and siltstones from Brazil

In spite of the considerable area covered by argillaceous sedimentary rocks (comprising shales, mudrocks and siltstones) in Brazil and the number of engineering works associated with these materials, little is known about their geotechnical, physical, chemical, mineralogical and textural characteristics and the effects of weathering processes on them. This work presents results obtained in a research project aiming primarily at identifying degradation processes responsible for the weathering of some of these rocks in Brazil. The rocks under investigation come from two different parts of the country, each one related to a specific engineering problem and to different geoenvironments. The project involved a comprehensive laboratory testing program for basic characterization (chemical and mineralogical composition, index properties, etc.) and evaluation of durability characteristics of these rocks. The present paper describes the testing program carried out and discusses the results obtained.     

Haeundae Beach in Korea: Seasonal-to-decadal wave statistics and impulsive beach responses to typhoons

Haeundae Beach represents Korean pocket beaches that are currently erosional and dominated by summertime typhoons. The decadal wave characteristics 9 km offshore of Haeundae Beach were analyzed using the WAM model that was validated through the 2007 wave observations. The wave statistics modelled for 1979–2007 indicates that the seasonal mean significant wave height (H _s ) is highest (0.6–0.7 m) in summer due to typhoons, in contrast to the lowest (around 0.5 m) autumn analog. The wave direction is also pronouncedly seasonal with the principal bearings of SSW and NE in the summer and winter seasons, respectively. The WAM results additionally show that the H _s has gradually increased over the region of Haeundae Beach since 1993. Beach profiling during June–November 2014 shows the opposite processes of the typhoon and fair-weather on beach sands. During a typhoon, foreshore sands were eroded and then accumulated as sand bars on the surf zone. In the subsequent fair-weather, the sand bars moved back to the beach resulting in the surf-zone erosion and foreshore accretion. A total of 5 cycles of these beach-wide sand movements yielded a net retreat (up to 20 m) of the shoreline associated with large foreshore erosion. However, the surf zone only slightly accumulated as a result of the sand cycles. This was attributed to the sand escape offshore from the westernmost tip of the beach. The present study may provide an important clue to understanding the erosional processes in Haeundae Beach.     

Equatorial electrojet as part of the global circuit: a case-study from the IEEY

Geomagnetic storm-time variations often occur coherently at high latitude and the day-side dip equator where they affect the normal eastward Sq field. This paper presents an analysis of ground magnetic field and ionospheric electrodynamic data related to the geomagnetic storm which occured on 27 May 1993 during the International Equatorial Electrojet Year (IEEY) experiment. This storm-signature analysis on the auroral, mid-latitude and equatorial ground field and ionospheric electrodynamic data leads to the identification of a sensitive response of the equatorial electrojet (EEJ) to large-scale auroral return current: this response consists in a change of the eastward electric field during the pre-sunrise hours (0400–0600 UT) coherently to the high-, mid-, and equatorial-latitude H decrease and the disappearance of the EEJ irregularities between the time-interval 0800–0950 UT. Subsequent to the change in hF during pre-sunrise hours, the observed foF2 increase revealed an enhancement of the equatorial ionization anomaly (EIA) caused by the high-latitude penetrating electric field. The strengthening of these irregularities attested by the Doppler frequency increase tracks the H component at the equator which undergoes a rapid increase around 0800 UT. The H variations observed at the equator are the sum of the following components: S_R, DP, DR, DCF and DT.     

Comparison of marine insolation estimating methods in the adriatic sea

We compare insolation results calculated from two well-known empirical formulas (Seckel and Beaudry’s SB73 formula and the original Smithsonian (SMS) formula) and a radiative transfer model using input data predicted from meteorological weather-forecast models, and review the accuracy of each method. Comparison of annual mean daily irradiance values for clear-sky conditions between the two formulas shows that, relative to the SMS, the SB73 underestimates spring values by 9 W m^-2 in the northern Adriatic Sea, although overall there is a good agreement between the annual results calculated with the two formulas. We also elucidate the effect on SMS of changing the ‘Sun-Earth distance factor (f)’, a parameter which is commonly assumed to be constant in the oceanographic context. Results show that the mean daily solar radiation for clear-sky conditions in the northern Adriatic Sea can be reduced as much as 12 W m^-2 during summer due to a decrease in thef value. Lastly, surface irradiance values calculated from a simple radiative transfer model (GM02) for clear-sky conditions are compared to those from SB73 and SMS. Comparison within situ data in the northern Adriatic Sea shows that the GM02 estimate gives more realistic surface irradiance values than SMS, particularly during summer. Additionally, irradiance values calculated by GM02 using the buoy meteorological fields and ECMWF (The European Centre for Medium Range Weather Forecasts) meteorological data show the suitability of the ECMWF data usage. Through tests of GM02 sensitivity to key regional meteorological factors, we explore the main factors contributing significantly to a reduction in summertime solar irradiance in the Adriatic Sea.     

Robust path-following of underactuated ships: Theory and experiments on a model ship

A method is proposed to design a new global controller that forces an underactuated ship to follow a reference path under disturbances induced by wave, wind and ocean-current. The controller is designed such that the ship moves on the path with an adjustable forward speed and its total velocity is tangential to the path. The ship under consideration is not actuated in the sway axis, and the mass and damping matrices are not assumed to be diagonal. Nonlinear damping terms are also included to cover both low- and high-speed applications. The new result is facilitated by choosing an appropriate origin of the body-fixed frame, designing a suitable filter of sway velocity, several nonlinear coordinate changes, the backstepping technique, and utilizing the ship dynamic structure. Experimental results on a model ship illustrate the effectiveness of the proposed method.     

Susceptibility assessment of the precursor stage of a landslide threatening Haivan Railway Station,Vietnam

Haivan Station is an important station on the North-South railway line in central Vietnam. Field investigation has identified a precursor stage of a landslide that would threaten this railway. Therefore, a landslide susceptibility assessment for Haivan Station was urgently needed to protect passenger safety and the national railway. Conducted investigations included air-photo interpretation, drilling, ground water and inclinometer monitoring, laboratory testing, and landslide simulation. This research applied the undrained dynamic loading ring shear apparatus ICL-2 to drill-core samples from the precursor landslide. Samples for ring shear tests were taken from sandy soil layers found at depths of ~21, ~31, and ~50 m in the cores. Each of these was believed to be a possible sliding surface of a landslide, and all were tested to shear failure in the ICL-2 apparatus. The boundary between highly weathered granitic rock and weathered granitic rock was identified at about 50 m depth. The inclinometer monitoring detected slight movement at this depth. Therefore, the present day risk of a landslide forming at 50 m is higher than for one forming at either 21 or 31 m. The landslide dynamic parameters obtained from the ring shear test of the 50-m-deep sample were used in an integrated numerical simulation model LS-RAPID. The simulation result gave the critical pore-pressure ratio for landslide occurrence, and landslide’s likely maximum speed, total volume, and depth of landslide debris that could cover the railway. These estimates serve to raise awareness of the vulnerability of the Vietnam national railway sector to landslide impact.     

Source Parameters for 1999 North Anatolian Fault Zone Aftershocks

We develop a data set of aftershock recordings of the 1999, M = 7.4 Izmit and M = 7.2 Duzce (Turkey) earthquakes to study their source parameters. We combined seismograms from 44 stations maintained by several sources (organizations) to obtain a unified data set of events (2.1 ≤ M_w ≤ 5.5). We calculate source parameters of these small earthquakes by two methods that use different techniques to address the difficulty in obtaining source spectra for small earthquakes subject to interference from site response. One method (program NetMoment (NM), Hutchings, 2004) uses spectra of direct S waves in a simultaneous inversion of local high-frequency network data to estimate seismic moment, source corner frequency (f_c), site attenuation (k) and whole-path Q. This approach takes advantage of the source commonality in all recordings for a particular earthquake by fitting a common Brune source spectrum to the data with a and individual k. The second approach (Mayeda et al., 2003) uses the coda method (CM) to obtain “nonmodel-based” source spectra and moment estimates from selected broadband recording sites. We found that both methods do well for events that allow the comparison with seismic moment estimates derived from waveform modeling. Also, source spectra obtained from the two methods are very closely matched for most of the events they have in common. We use an F test to examine the trade-off between k and f_c picks identified by the direct S-wave method. About half of the events could be constrained to have less than a 50% average uncertainty in f_c and k. We used these source spectra solutions to calculate energy and apparent stress and compare these to estimates from the selected “good quality” source spectra from CM. Both studies have values mutually consistent and show a similar increase in apparent stress with increasing moment. This result has added merit due to the independent approaches to calculate apparent stress. We conclude that both methods are at least partially validated by our study, and they both have usefulness for different circumstances of recording local small earthquakes. CM would work well in studies for which there is a broad magnitude range of events and NM works well for local events recorded by band-limited recorders.     

Source mechanism and stress analysis of 23 October 2011 Van Earthquake (Mw = 7.1) and aftershocks

On 23 October 2011 at 1341 local time, a strong earthquake (Mw?=?7.1) occurred east of Lake Van (KOERI; Kandilli Observatory and Earthquake Research Institute). The focal parameters of the main shock and 29 aftershocks with M?≥?4.0 were obtained from regional broadband seismic data from KOERI network by using Regional Moment Tensor Inversion Code (Dreger 2002). It is confirmed that the main shock had thrust faulting mechanism. The stress tensor analysis was completed using the focal mechanism solutions and the software developed by (Gephart Comp Geosci 16: 953-989, 1990). The maximum principal stress (P compressional) of the main shock is aligned in a N-S (NNW/SSE) direction and the tensional axis (T dilatation) is aligned in an E-W (ENE-WSW) direction. The b value is calculated as 0.96 using the maximum likelihood method (Utsu 1999).