Kinetic,equilibrium and thermodynamic studies of thiamethoxam adsorption by multi-walled carbon nanotubes

Because of their high adsorption capacity, carbon nanotubes have caught the attention of the scientific community and a number of experimental results confirmed their ability to adsorb many toxins from water. The aim of this work was to study the kinetics, equilibrium and thermodynamics of thiamethoxam adsorption by multi-walled carbon nanotubes in aqueous solutions. To further elucidate the influence of nanotube structure on the adsorption mechanism, the experiments were performed on both fresh (pristine) and nitric acid-modified multi-walled carbon nanotubes. The results of the kinetic studies were analyzed using three kinetic models, while the adsorption equilibrium was tested against four different adsorption models. Based on the results, and the physico-chemical properties of the adsorbent and adsorbate, it is proposed that the dominant mechanism for thiamethoxam molecules attaching to multi-walled carbon nanotubes is caused by aromatic π–π interactions (electron donor–acceptor interactions). The results of thermodynamic calculations based on the adsorption data indicate the exothermic nature of the process, regardless of the carbon nanotube type used. The decrease in entropy and the consequent negative change in Gibbs free energy, as expected, confirm the spontaneity of thiamethoxam adsorption on both pristine and functionalized multi-walled carbon nanotubes.     

Estimation of the transfer function by autoregressive deconvolution techniques—An application to time series analysis

The transfer function of time-dependent models is classically inferred by the ordinary least squares (OLS) techniques. This OLS technique assumes independence of the residuals with time. However, in practical cases, this hypothesis is often not justified producing inefficient estimation of the transfer function. When the residuals constitute an autoregressive process, we propose to apply the Box-Jenkins' method to model the residuals, and to modify in a simple manner the primary convolution equation. Then, a multivariate regression technique is used to infer the transfer function of the new equation producing time-independent residuals. This three-step autoregressive deconvolution technique is particularly efficient for time series analysis. The reconstitution and the forecasting of real data are improved efficiently. Theoretically, the proposed method can be extended to the convolution equations for which the residuals follow a moving average or an autoregressive-moving average process, but the mathematical formulation is no longer direct and explicit. For this general case, we propose to approximate the moving average or the autoregressive-moving average process by an autoregressive process of sufficient order, and then the transfer function. Two case studies in hydrogeology will be used to illustrate the procedure.     

Geomagnetic multipoles, 1829 to 1960

Summary Using the results of spherical harmonic analyses of the geomagnetic field for some fourteen different epochs, includingGauss' first analysis for epoch 1835, and theErman-Petersen analysis for epoch 1829, the strength and axes of geomagnetic multipoles have been computed. In particular, a dipole from the three first order spherical harmonic coefficients, a quadrupole from five second order coefficients, and an octupole from seven third order coefficients. The axes of the quadrupole and octupole have moved quite rapidly when compared with movements of the dipole axis, and show a general movement westwards. Although the strength of the dipole has generally diminished, the strengths of the quadrupole and octupole have generally increased.On leave National University of La Plata, Argentina     

Euro-Cordex Regional Projection Models: What Kind of Agreement for Europe?

Mathematical Geosciences - EURO-CORDEX is an international initiative which provides regional climate projections based on multiple dynamical and empirical–statistical downscaling models. The...     

Impact of lightning on organic matter-rich soils: influence of soil grain size and organic matter content on underground fires

A detailed study was carried out on a piece of land that had been struck by lightning during the violent rainstorm that raged over the Island of S?o Miguel (Azores Archipelago) in late October 2006. Temperature and gas measurements (CO₂, CO, H₂S and CH₄) were performed in four study trenches, dug in an area of ∼3 m², where an underground fire had been initiated by the impact with a lightning stroke, followed by the emission of a column of gases and smoke. The soil under study was originally a well-pedogenized about 80 cm thick bed, made of volcanic clayey to silty tephra fallouts and contained 5.5–9.7% of organic matter. The underground fire was monitored for one week and revealed a peak release of 404 ppm CO and 3.4% CO₂ originating from a horizon located about 45 cm under the soil surface. Measurements of temperature, performed one week after the impact, indicated a maximum value of 326°C inside the soil, while 516.5°C were measured on the surface of a lava block interred about 20 cm under the surface. Subsequently, a stratigraphic and sedimentologic study proved the role of the grain-size of the soil and of the organic matter content of the different horizons of the impact area, in determining the ratio between anoxic/oxidised combustion conditions and in the progress of the process itself. It was also noticed that combustion was not total all over in the soil bed and that the process had slightly migrated toward SW during the observation period. The combustion process went on for about ten days, in spite of several other violent rainstorms, until it was artificially extinguished through the excavations made to obtain study trenches. This particular circumstance evidenced the potential natural hazard represented by this kind of atmospheric event, especially in a land where the volcanic nature of the soil may easily mislead inexperienced observers and, consequently, delay proper action.     

Finite volume approximation for an immiscible two-phase flow in porous media with discontinuous capillary pressure

We consider an immiscible incompressible two-phase flow in a porous medium composed of two different rocks so that the capillary pressure field is discontinuous at the interface between the rocks. This leads us to apply a concept of multivalued phase pressures and a notion of weak solution for the flow which have been introduced in Cancès and Pierre (SIAM J Math Anal 44(2):966–992, 2012). We discretize the problem by means of a numerical algorithm which reduces to a standard finite volume scheme in each rock and prove the convergence of the approximate solution to a weak solution of the two-phase flow problem. The numerical experiments show in particular that this scheme permits to reproduce the oil-trapping phenomenon.     

Probabilistic compressive strength of sound dry granite

Summary The different functions of cumulative probability of fracture that can be used in the Probabilistic Strength of Materials in the case of constant uniaxial compression are described. Sound fine-grained granite was used to study volume influence by fracturing rectangular prisms, and then no noticeable influence was observed. Since this is showing that all the fracture stresses are belonging to a single set they were included in a single group that exhibited two functions of specific risk of fracture. The population with the lesser fracture stress has no critical zone while the other population does have it and a critical zone in the order of 10^–6 m³ is the minimum size exhibiting a complete fracture of the specimen when the same collapses. All the statistical functions were found to be acceptable according to theX ² criterion.     

Mississippian coral assemblages from the Khenifra area,Central Morocco: Biostratigraphy,biofacies, palaeoecology and palaeobiogeography

Analysis of Mississippian coral assemblages from the Khenifra region of Central Morocco together with data from foraminiferal/algal microfossils has established new age dating of 5 localities within the Azrou–Khenifra Basin: Souk El Had and Sidi Lamine, where corals occur mainly in biostromes protected by oolitic shoals, Tabainout, where corals have been recorded in different environments related to microbial mounds, Alhajra Almatkouba, where corals occur in biostromal reworked beds and Tiouinine, where corals occur in a well structured, fringing reef. This study demonstrates the presence of richer more diverse coral assemblages than previously recorded, in a variety of environmental settings. These coral assemblages strengthen correlations with the Adarouch area in the NE part of the Azrou–Khenifra Basin. It is emphasised that in the upper Viséan there are close similarities with rugose coral assemblages in other parts of the Western Palaeotethys including North Africa, SW Spain and NW Europe, and that all belong to the same biogeographic province.     

The last deglaciation in the Picos de Europa National Park (Cantabrian Mountains,northern Spain)

A sedimentological and geochemical study of the Lago Enol sequence (Cantabrian Mountains, northern Spain), together with detailed geomorphological mapping, provides a first record of glacier evolution and climate change over the last 40 ka in the Picos de Europa National Park. The Enol glacier retreated from its maximum extent prior to 40 ka BP as demonstrated by the onset of proglacial lacustrine sedimentation in two glaciated depressions: the Comella hollow to the north (before 40 ka BP) and the Lago Enol (before 38 ka BP). These results support previous evidence that the maximum extent of southern European glaciers occurred earlier than in northern Europe. Alternation of homogeneous and laminated proglacial sediments during the glacier retreat illustrate a dynamic glacial evolution during the Marine Isotope Stage (MIS) 3 (40–26 ka BP). A slight warming is detected at 26 ka ago with the change from proglacial sediments (in a lake located in contact to the glacier) to glaciolacustrine sedimentation (in a non‐contact or distal lake). Finally, the onset of organic‐rich sediments took place at 18 ka ago. This last transition occurred in two phases, similarly to the North Atlantic Last Termination, suggesting a link between North Atlantic Deep Water formation oscillations and palaeohydrological variability in the Cantabrian Mountains. Copyright © 2009 John Wiley & Sons, Ltd.     

Magnitude-Intensity Relationships in the Ibero-Magrebhian Region

In this paper we present magnitude (Ms) – magnitude(mb) and magnitude-intensity relationships which areconsidered the most adequate in the Ibero-Maghrebianregion. This work is based on selected samples ofrecently revised events with magnitude mb assigned bythe Instituto Geográfico Nacional (I.G.N.) and Msassigned by I.S.C and N.E.I.C., and isoseismal mapsfrom 142 events. Using these data, we have obtainedone magnitude (Ms) – magnitude (mb) relationship, twomagnitude (mb and Ms) assignment relationships viaepicentral intensity (I₀), and ten magnitude (mb andMs) assignments relationships via macroseismicinformation: four using Ambraseys' methodology (1985)and six using the isoseismal area of degree III, IV and VI.According to the obtained results it could be concluded that historical magnitude assignment with lesser uncertainties are those obtained via macroseismic information using magnitude-intensity relationships with Ambraseys' methodology (1985). The magnitude-isoseismal area assignment relationships have, in most cases, great differences depending on the degree of the isoseismal area used. Magnitude assignments via epicentral intensity have the highest uncertainties. Geographic regionalization of the relationshipshas been studied but the highest correlations and statistical significance are obtained when we fit all the Ibero-Maghrebian region data.Finally we have used the results obtained in this workto assign magnitude to some important historicalearthquakes in the Ibero-Maghrebian region: the 1755Lisbon earthquake, the 1680 Málaga earthquake, the1829 Torrevieja earthquake and the 1884 Arenas del Reyearthquake. According to our relationships andmethodology we have assigned an Ms value of 9.3 ±0.6 to the 1755 Lisbon earthquake (its mb magnitudecannot be estimated due to the saturation of the mbscale), an mb value of 6.3 ±0.4 and an Ms valueof 6.9 ± 0.6 to the 1829 Torrevieja earthquake, anmb value of 6.2 ± 0.4 and an Ms value of 6.4 ±0.6 to the 1680 Málaga earthquake and an mb valueof 6.1 ± 0.4 and an Ms value of 6.5 ± 0.6 tothe 1884 Arenas del Rey earthquake.