Theoretical study of the dimerization of calcium carbonate in aqueous solution under natural water conditions

First principles calculations have been used to investigate the condensation reactions of hydrated calcium bicarbonate monomers in a simulated aqueous environment. The reaction pathway for the calcium bicarbonate dimerization process has been computed at the density functional theory-PBE level with the COSMO dielectric continuum model to simulate the hydrated environment. The results indicate that calcium bicarbonate dimers form via an associative mechanism: the first step involves a sevenfold calcium bicarbonate intermediate followed by the loss of one water molecule from the first coordination shell of calcium. Both steps are characterised by a low energy barrier of approximately 2 kcal mol⁻¹, suggesting that the dimerization process is not kinetically hindered in aqueous solution. However, the Gibbs free energies for the condensation reactions to form the calcium bicarbonate dimers and the species Ca(HCO₃)₂(H₂O)₄, Ca(HCO₃)₃(H₂O)₃⁻ and Ca₂(HCO₃)(H₂O)₁₀³⁺, computed using the PBE and mPW1B95 density functional theory levels for the gas-phase component and the UAHF-CPCM solvation model for the hydration contribution, are all positive, which indicates that the formation of these early calcium bicarbonate clusters is thermodynamically unfavourable in aqueous solutions. Our calculations therefore suggest that the oligomerization of calcium carbonate is not spontaneous in water, at the conditions considered in our simulations, i.e. T = 298 K and neutral pH, which indicates that the nucleation of calcium carbonate cannot occur through a homogeneous process when calcium-bicarbonate ion pairs are the major source of CaCO₃ in the aqueous environment.     

Mineral magnetic record of paleoclimate variation in loess and paleosol from the Buenos Aires formation (Buenos Aires, Argentina)

Environmental magnetic techniques were applied to a loess–paleosol sequence of the Chacopampean plain (Buenos Aires, Argentina). Mineral magnetic carriers and their grain size were identified in order to detect magnetic mineral fluctuations associated with climatic changes. Multidomain magnetite of detrital origin dominates the record. In paleosols, a high coercivity fraction was identified. Horizons with no visual evidence of pedogenesis, but showing magnetic behavior analogous to that of paleosols were observed and are thought to represent environmental conditions similar to those prevailing during paleosol formation.The results suggest that the magnetic signal yielded by paleosols in these South American loess deposits is different from that in the Chinese loess. This may be due to differences in parent materials, diagenetic processes and/or differences in paleoclimatic conditions in both regions.     

Soft proton flux on <Emphasis Type="Italic">ATHENA</Emphasis> focal plane and its impact on the magnetic diverter design

The experience gained with the current generation of X-ray telescopes like Chandra and XMM-Newton has shown that low energy “soft” protons can pose a severe threat to the possibility to exploit scientific data, reducing the available exposure times by up to 50% and introducing a poorly reproducible background component. These soft protons are present in orbits outside the radiation belts and enter the mirrors, being concentrated towards the focal plane instruments, losing energy along their path and finally depositing their remaining energy in the detectors. Their contribution to the residual background will be even higher for ATHENA with respect to previous missions, given the much higher collecting area of the mirrors, even if the instruments will likely suffer no significant radiation damage from this particles flux. As a consequence this soft proton flux shall be damped with the use of a magnetic diverter to avoid excess background loading on the WFI or X-IFU instruments. We present here a first complete evaluation of this background component for the two focal plane instruments of the ATHENA mission in absence of a magnetic diverter, and derive the requirements for such device to reduce the soft protons induced background below the level required to enable the mission science. We estimate the soft proton flux expected in L2 for the interplanetary component and for the component generated locally by acceleration processes in the magnetotail. We produce a proton response matrix for each of the two instruments of ATHENA focal plane, exploiting two independent Monte Carlo simulations to estimate the optics concentration efficiency, and Geant4 simulations to evaluate the energy loss inside the radiation filters and deposited in the detector. With this modular approach we derive the expected fluxes and spectra for the soft protons component of the background. Finally, we calculate the specifics of a magnetic diverter able to reduce such flux below the required level for both X-IFU and WFI.     

The Effects of Nutrients on Natural Organic Matter (NOM) Removal in Biological Activated Carbon (BAC) Filtration

Effective biodegradation of organic compounds is one of the major objectives while optimizing biological drinking water treatment processes. Enhancing the biological activated carbon (BAC) filter performance with nutrient addition was studied using chemically pre-treated and ozonated lake water. Three parallel pilot-scale biofilters were operated: one with phosphorus addition, one with a mixture of inorganic nutrients addition, and one as a reference. The addition of nutrients had no statistically significant influence on the natural organic matter (NOM) removal when monitored by total organic carbon (TOC), UV absorbance, and assimilable organic carbon (AOC). However, the addition of nutrients significantly increased the heterotrophic plate count (HPC) bacteria of the filter effluent, while the adenosine triphosphate (ATP) analysis of the attached bacteria did not show any increase in BAC filters. It seemed that in BAC filters the bacterial growth was limited by phosphorus, but the increased bacteria could not attach themselves during the relatively short acclimatization period.     

A practical method for analysis of river waves and for kinematic wave routing in natural channel networks

The behaviour of river waves is described using a simplified dimensionless form of the momentum equation in conjunction with the continuity equation. Three dimensionless parameters were derived based on a quantitative linear analysis. These parameters, which depend on the Froude number of the steady uniform flow and the geometric characteristics of the river, permit quantification of the influence of inertia and pressure in the momentum equation. It was found that dynamic and diffusion waves occur mainly on gentle channel slopes and the transition between them is characterized by the Froude number. On the other hand, the kinematic wave has a wide range of applications. If the channel slope is greater than 1%, the kinematic wave is particularly suitable for describing the hydraulics of flow. Since slopes in natural channel networks are often greater than 1%, an analytical solution of the linearized kinematic wave equation with lateral inflow uniformly distributed along the channel is desirable and was therefore derived. The analytical solution was then implemented in a channel routing module of an existing simple rainfall–runoff model. The results obtained using the analytical solution compared well with those obtained from a non‐linear kinematic wave model. Copyright © 2000 John Wiley & Sons, Ltd.     

Carbonate assimilation in magmas: A reappraisal based on experimental petrology

The main effect of magma–carbonate interaction on magma differentiation is the formation of a silica-undersaturated, alkali-rich residual melt. Such a desilication process was explained as the progressive dissolution of CaCO₃ in melt by consumption of SiO₂ and MgO to form diopside sensu stricto. Magma chambers emplaced in carbonate substrata, however, are generally associated with magmatic skarns containing clinopyroxene with a high Ca-Tschermak activity in their paragenesis. Data are presented from magma–carbonate interaction experiments, demonstrating that carbonate assimilation is a complex process involving more components than so far assumed. Experimental results show that, during carbonate assimilation, a diopside–hedenbergite–Ca-Tschermak clinopyroxene solid solution is formed and that Ca-Tschermak/diopside and hedenbergite/diopside ratios increase as a function of the progressive carbonate assimilation. Accordingly, carbonate assimilation reaction should be written as follows, taking into account all the involved magmatic components:CaCO₃^solid + SiO₂^melt + MgO^melt + FeO^melt + Al₂O₃^melt → (Di–Hd–CaTs)_ss^solid + CO₂^fluidThe texture of experimental products demonstrates that carbonate assimilation produces three-phases (solid, melt, and fluid) whose main products are: i) diopside–hedenbergite–Ca-Tschermak clinopyroxene solid solution; ii) silica-undersaturated CaO-rich melt; and iii) C–O–H fluid phase. The silica undersaturation of the melt and, more importantly, the occurrence of a CO₂-rich fluid phase, must be taken into account as they significantly affect partition coefficients and the redox state of carbonated systems, respectively.     

Improving the representation of soil moisture by using a semi‐analytical infiltration model

Soil moisture is widely recognized as a fundamental variable governing the mass and energy fluxes between the land surface and the atmosphere. In this study, the soil moisture modelling at sub‐daily timescale is addressed by using an accurate representation of the infiltration component. For that, the semi‐analytical infiltration model proposed by Corradini et al. (1997) has been incorporated into a soil water balance model to simulate the evolution in time of surface and profile soil moisture. The performances of this new soil moisture model [soil water balance module‐semi‐analytical (SWBM‐SA)] are compared with those of a precedent version [SWBM‐Green–Ampt (GA)] where the GA approach was employed. Their capability to reproduce in situ soil moisture observations at three sites in Italy, Spain and France is analysed. Hourly observations of quality‐checked rainfall, temperature and soil moisture data for a 2‐year period are used for testing the modelling approaches. Specifically, different configurations for the calibration and validation of the models are adopted by varying a single parameter, that is, the saturated hydraulic conductivity. Results indicate that both SWBMs are able to reproduce satisfactorily the hourly soil moisture temporal pattern for the three sites with root mean square errors lower than 0.024 m³/m³ both in the calibration and validation periods. For all sites, the SWBM‐SA model outperforms the SWBM‐GA with an average reduction of the root mean square error of ~20%. Specifically, the higher improvement is observed for the French site for which in situ observations are measured at 30 cm depth, and this is attributed to the capability of the SA infiltration model to simulate the time evolution of the whole soil moisture profile. The reasonable models performance coupled with the need to calibrate only a single parameter makes them useful tools for soil moisture simulation in different regions worldwide, also in scarcely gauged areas. Copyright © 2013 John Wiley & Sons, Ltd.     

Displacement of a landslide retaining wall and application of an enhanced failure forecasting approach

The 10-mile Slide is contained within an ancient earthflow located in British Columbia, Canada. The landslide has been moving slowly for over 40 years, requiring regular maintenance work along where a highway and a railway track cross the sliding mass. Since 2013, the landslide has shown signs of retrogression. Monitoring prisms were installed on a retaining wall immediately downslope from the railway alignment to monitor the evolution of the retrogression. As of September 2016, cumulative displacements in the horizontal direction approached 4.5 m in the central section of the railway retaining wall. After an initial phase of acceleration, horizontal velocities showed a steadier trend between 3 and 9 mm/day, which was then followed by a second acceleration phase. This paper presents an analysis of the characteristics of the surface displacement vectors measured at the monitoring prisms. Critical insight on the behavior and kinematics of the 10-mile Slide retrogression was gained. An advanced analysis of the trends of inverse velocity plots was also performed to assess the potential for a slope collapse at the 10-mile Slide and to obtain further knowledge on the nature of the sliding surface.     

A study on hydrological series of the Niger River

Abstract

The Hubert segmentation procedure has been applied to historical series of annual average discharges of the Niger River at Koulikoro (Mali), Niamey (Niger) and Lokoja (Nigeria) stations. The breaks, especially those identified at Koulikoro and Niamey, match well with those identified in the Senegal River series at Bakel using the same procedure. Lokoja departs from this regional pattern, as it shows in the late 1980s a return to wetter conditions much earlier than the other three stations. The magnitudes of the variation of the inter-annual means between the alternating wet and dry periods are significant and similar. These results seem to suggest that phenomena causing non-stationarity in hydrological series can have a sub-continental impact or, in contrast, may be more limited in their spatial coverage.

Editor Z.W. Kundzewicz; Associate editor H. Aksoy

Citation Abrate, T., Hubert, P., and Sighomnou, D., 2013. A study on hydrological series of the Niger River. Hydrological Sciences Journal, 58 (2), 271–279.