Geologic factors controlling groundwater chemistry in the coastal aquifer system of Douala/Cameroon: implication for groundwater system functioning

Douala city, located in the littoral province of Cameroon, receives abundant rainfall quantities due to its geographical position in the Gulf of Guinea and bears considerable surface water and groundwater resources. Due to socioeconomic development and rapid demographic growth in the city and its consequences of unplanned urbanization and improper sanitation system, these water resources are poorly protected and managed. Streams in the Wouri watershed receive large amounts of wastewater discharge, and hundreds of boreholes have been drilled into the aquifer system without any management plan. A detailed hydrodynamic and hydrogeochemistry study in Douala town and its environs was conducted to get a better insight into the groundwater system functioning in order to provide information for the sustainable management and protection of the groundwater resource. Two field campaigns were carried out with 187 samples collected and analyzed for major ions, stable isotopes (¹⁸O, ²H), and tritium ³H. The results of the sampling have shown that the weathering of silicate minerals is the dominant geochemical process affecting groundwater chemistry in this system. However, acid rainfall in the humid climate has also caused carbonate mineral dissolution, amorphous silica deposition, and ion exchange reactions to occur in aquifers in the region. The various water types identified were categorized into four major clusters C1 to C4, based on the major ion composition and the local hydrogeological conditions. Environmental isotope data reveal that modern-to-submodern waters occur in the phreatic Quaternary/Mio-Pliocene and Oligocene/Upper Eocene aquifers, respectively. These results corroborate with the conceptual model built where modern groundwater types indicated silicate mineral weathering and calcite dissolution (C1 and C2), whereas submodern groundwater mostly showed silica deposition, ion exchange, and, to a lesser extent, carbonate mineral dissolution (C3 and C4). This improved understanding of the aquifer system functioning is essential to provide a reasonable basis for effective control measures and sustainable water management.     

Thermodynamic properties of chlorite and berthierine derived from calorimetric measurements

In the context of the deep waste disposal, we have investigated the respective stabilities of two iron-bearing clay minerals: berthierine ISGS from Illinois [USA; (Al_0.975FeIII_0.182FeII_1.422Mg_0.157Li_0.035Mn_0.002)(Si_1.332Al_0.668)O₅(OH)₄] and chlorite CCa-2 from Flagstaff Hill, California [USA; (Si_2.633Al_1.367)(Al_1.116FeIII_0.215Mg_2.952FeII_1.712Mn_0.012Ca_0.011)O₁₀(OH)₈]. For berthierine, the complete thermodynamic dataset was determined at 1 bar and from 2 to 310 K, using calorimetric methods. The standard enthalpies of formation were obtained by solution-reaction calorimetry at 298.15 K, and the heat capacities were measured by heat-pulse calorimetry. For chlorite, the standard enthalpy of formation is measured by solution-reaction calorimetry at 298.15 K. This is completing the entropy and heat capacity obtained previously by Gailhanou et al. (Geochim Cosmochim Acta 73:4738–4749, 2009) between 2 and 520 K, by using low-temperature adiabatic calorimetry and differential scanning calorimetry. For both minerals, the standard entropies and the Gibbs free energies of formation at 298.15 K were then calculated. An assessment of the measured properties could be carried out with respect to literature data. Eventually, the thermodynamic dataset allowed realizing theoretical calculations concerning the berthierine to chlorite transition. The latter showed that, from a thermodynamic viewpoint, the main factor controlling this transition is probably the composition of the berthierine and chlorite minerals and the nature of the secondary minerals rather than temperature.     

Oxidation modes and thermodynamics of Fe oxyhydroxycarbonate green rust: Dissolution-precipitation versus in situ deprotonation

Fe^II-III hydroxycarbonate green rust GR(CO₃²⁻), Fe^II₄ Fe^III₂ (OH)₁₂ CO₃·3H₂O, is oxidized in aqueous solutions with varying reaction kinetics. Rapid oxidation with either H₂O₂ or dissolved oxygen under neutral and alkaline conditions leads to the formation of ferric oxyhydroxycarbonate GR(CO₃²⁻)∗, Fe^III₆ O₁₂ H₈ CO₃·3H₂O, via a solid-state reaction. By decreasing the flow of oxygen bubbled in the solution, goethite α-FeOOH forms by dissolution-precipitation mechanism whereas a mixture of non-stoichiometric magnetite Fe_(3−x)O₄ and goethite is observed for lower oxidation rates. The intermediate Fe^II-III oxyhydroxycarbonate of formula Fe^II_6(1−x) Fe^III_6x O₁₂ H_2(7−3x) CO₃·3H₂O, i.e. GR(x)∗ for which x ? [1/3, 1], is the synthetic compound that is homologous to the fougerite mineral present in hydromorphic gleysol; in situ oxidation accounts for the variation of ferric molar fraction x = [Fe^III]/{[Fe^II]+[Fe^III]} observed in the field as a function of depth and season but limited to the range [1/3, 2/3]. The domain of stability for partially oxidized green rust is observed in the E_h-pH Pourbaix diagrams if thermodynamic properties of GR(x)∗ is compared with those of lepidocrocite, γ-FeOOH, and goethite, α-FeOOH. Electrochemical equilibrium between GR(x)∗ and Fe^II in solution corresponds to E_h-pH conditions close to those measured in the field. Therefore, the reductive dissolution of GR(x)∗ can explain the relatively large concentration of Fe^II measured in aqueous medium of hydromorphic soils containing fougerite.     

The LAGEOS satellites orbital residuals determination and the Lense-Thirring effect measurement

The method applied since 1996 for the analysis of the orbital residuals of the LAGEOS satellites in order to measure the Lense-Thirring effect has been the subject of the present work. This method, based on the difference between the orbital elements of consecutive arcs, is explained and analysed also from the analytical point of view. It is proved that this “difference method” works well for the determination of the secular effects, as in the case of the relativistic precession induced by the Earth's angular momentum, but also very useful for the determination and study of the long-term periodic effects. Indeed, the only limitation in the determination of the periodic effects is the possibility of the reduction of their amplitude by a factor which depends from the periodicity of the given perturbation and from the orbital arc length chosen for the satellite during the data analysis. In the case of the Yarkovsky-Schach effect, the main non-gravitational perturbation seen in the LAGEOS satellites orbital residuals, in particular in its perigee rate and eccentricity vector excitation residuals, we show that the “difference method” is quite good also for the determination of the long-period perturbations induced by this subtle non-conservative force.