Behaviour of REE and mass balance calculations in a lateritic profile over chlorite schists in South Cameroon

An in situ weathering profile overlying chlorite schists in the Mbalmayo-Bengbis formations (South Cameroon) was chosen for the study of the behaviour of REE and the evaluation of geochemical mass balance. After physical and mineralogical studies, the chlorite schists and the undisturbed weathered materials were chemically analyzed for major elements (X-ray fluorescence and titrimetry) and REE (ICP-MS). The behaviour of the REE in the Mbalmayo weathering system was established in comparison with the REE of the reference parent rock. Mass balance calculations were applied to both major elements and REE. The mineralogy of the materials was determined with the aid of a Philips 1720, diffractometer. The chlorite schists of the Mbalmayo sector show low REE contents (Σ=153.44 ppm). These rocks are relatively rich in LREE (about 125 times the chondritic value) and relatively poor in HREE (about 20 times the chondritic value). The REE diagram normalized to chondrites shows a slightly split graph ((La/Yb)_N=6.18) with marked enrichment in LREE (LREE/HREE=9.50) in relation to HREE. Moreover, these spectra do not present any Ce anomaly, but a slightly positive Eu anomaly. The imperfectly evolved profile, whose materials are genetically linked, shows an atypical behaviour of REE. In effect, the LREE are more mobile than the HREE during weathering ((La/Yb)NASC<1) with weak Ce anomalies. This has been rarely reported in lateritic profiles characterized by higher HREE mobility than LREE during weathering processes with high Ce anomalies. This is either due to the difference in the stability of REE-bearing minerals, or to the weak acidic to basic pH conditions (6.70<pH<7.80), or even due to the average evolution of the weathering materials. The pathway of the REE along the profile is as follows: (1) leaching in the saprolites and summit of the profile, except for Ce, which precipitates very weakly in the nodular materials and the coarse saprolite materials, (2) at the base of the profile, solutions come in contact with chlorite schist formations, at this level, the pH increases (pH=7.79), HREE and a part of LREE partially void of Ce precipitate and (3) the other part of LREE precipitates further up in the profile. The geochemical mass balance calculations reveal that these elements are leached in the same phases as the relatively high Si, Al, K and Fe²⁺ contents.     

Analysis of groundwater quality using water quality index and conventional graphical methods: the Volta region,Ghana

Conventional graphical and statistical methods were used with water quality indices to characterize the hydrochemistry of groundwater from the northern part of the Volta region of Ghana. The objective was to determine the processes that affect the hydrochemistry and the variation of these processes in space among the three main geological terrains: the Buem formation, Voltaian System and the Togo series that underlie the area, and to determine the suitability of groundwater from the area for drinking purposes. The Q-mode cluster analysis reveals three main water groups. The groups established from the Q-mode HCA appear to indicate different degrees of weathering which could further indicate varying levels of fracturing aquifer hydraulic properties. R-mode HCA and factor analysis (using varimax rotation and Kaiser Criterion) were then applied to determine the significant sources of variation in the hydrochemistry. This study finds that groundwater hydrochemistry in the area is controlled by the weathering of silicate and carbonate minerals, as well as the chemistry of infiltrating precipitation. Mineral activity diagrams for the CaO–Na₂O–Al₂O₃–SiO₂–H₂O and CaO–MgO–Al₂O₃–SiO₂–H₂O systems plotted for the area indicate stability in the smectite field and attribute hydrochemistry to the weathering of silicate minerals. Silicate mineral weathering and the effects of precipitation appear to be pervasive among all the three main geological terrains, whereas carbonate weathering is localized among the Voltaian aquifers. Cation exchange does not appear to play a significant role in the hydrochemistry but mild Water quality indices (WQI) were calculated for the samples using the concentrations of Na⁺, Ca²⁺, Mg²⁺, Cl⁻, NO₃ ⁻, F⁻, and EC at the various sample locations. The WQI values indicate that groundwater from the study area is of excellent quality for drinking purposes. WQI values from groundwater samples are averagely higher than samples taken from surface water sources in the area. This implies that geology has had an impact on the WQI of groundwater in the area.     

Deriving Optimal Exploration Target Zones on Mineral Prospectivity Maps

This paper describes a quantitative methodology for deriving optimal exploration target zones based on a probabilistic mineral prospectivity map. The methodology is demonstrated in the Rodalquilar mineral district in Spain. A subset of known occurrences of mineral deposits of the type sought was considered discovered and then used as training data, and a map of distances to faults/fractures and three band ratio images of hyperspectral data were used as layers of spatial evidence in weights-of-evidence (WofE) modeling of mineral prospectivity in the study area. A derived posterior probability map of mineral deposit occurrence showing non-violation of the conditional independence assumption and having the highest prediction rate was then put into an objective function in simulated annealing in order to derive a set of optimal exploration focal points. Each optimal exploration focal point represents a pixel or location within a circular neighborhood of pixels with high posterior probability of mineral deposit occurrence. Buffering of each optimal exploration focal point, based on proximity analysis, resulted in optimal exploration target zones. Many of these target zones coincided spatially with at least one occurrence of mineral deposit of the type sought in the subset of cross-validation (i.e., presumed undiscovered) mineral deposits of the type sought. The results of the study showed the usefulness of the proposed methodology for objective delineation of optimal exploration target zones based on a probabilistic mineral prospectivity map.     

An evaluation of the genesis and suitability of groundwater for irrigation in the Volta Region,Ghana

Stable isotope data and concentrations of the major cations and anions of groundwater from the northern part of the Volta Region, Ghana, were used to determine the source of recharge and the suitability of groundwater in the area for irrigation. This study finds that the delta deuterium (δD) and delta Oxygen-18 (δ¹⁸O) data from the area fall along the global meteoric water line (GMWL). An equation of regression derived for the relationship between δD and δ¹⁸O bears very close semblance to the equation which describes the GMWL. On the basis of this, groundwater in the study area is probably meteoric and fresh. The apparently low salinities and sodicities of the groundwater seem to support this interpretation. The suitability of groundwater for domestic and irrigation purposes is related to its source, which determines its constitution. A plot of the sodium adsorption ratio (SAR) and electrical conductivity (EC) data on a semilog axis, suggests that groundwater serves good irrigation quality in the area. Sixty percent (60%), 20% and 20% of the 67 data points used in this study fall within the medium salinity–low sodicity (C2–S1), low salinity–low sodicity (C1–S1) and high salinity–low sodicity (C3–S1) fields, which ascribe good irrigation quality to groundwater from this area. Salinities range from 28.1 to 1,956 μS/cm, whilst SAR values fall within the range 0–3. Extremely low sodicity waters of this kind, with salinities lower than 600 μS/cm, have the tendency to affect the dispersive properties of irrigation soils when used for irrigation. About 50% of the groundwater in the study area fall within this category and need prior treatment before usage.     

Grain boundary and volume diffusion experiments in yttrium aluminium garnet bicrystals at 1,723 K: a miniaturized study

Yb-Y inter-diffusion along a single grain boundary of a synthetic yttrium aluminium garnet (YAG) bicrystal has been studied using analytical transmission electron microscopy (ATEM). To investigate the diffusion, a thin-film containing Yb as the diffusant was deposited perpendicular to the bicrystal grain boundary by pulsed laser deposition (PLD). Structural properties and their change with time in both the diffusant source and the grain boundary are reported. The diffusion profiles are incorporated in a numerical diffusion model, which is applied to determine the grain boundary diffusion coefficient, D _gb , at 1.723 K it is equal to 3 × 10⁻¹⁵ m²/s. We find that grain boundary diffusion is 4.85 orders of magnitude faster than volume diffusion, which was determined from the same diffusion experiment. This result is discussed in the context of special versus general grain boundaries. Finally, we successfully tested the capability of synchrotron-based nano-X-ray fluorescence analysis to map micro-chemical patterns in two dimensions with sub-micrometre resolution.     

Paleoproterozoic volcanic rocks in the southern margin of the North China Craton,central China:Implications for the Columbia supercontinent

The volcanic rocks of the Xiong'er Group are situated in the southern margin of the North China Craton(NCC).Research on the Xiong er Group is important to understand the tectonic evolution of the NCC and the Columbia supercontinent during the Paleoproterozoic.In this study,to constrain the age of the Xiong'er volcanic rocks and identify its tectonic environment,we report zircon LA-ICP-MS data with Hf isotope,whole-rock major and trace element compositions and Sr-Nd-Pb-Hf isotopes of the volcanic rocks of the Xiong'er Group.The Xiong'er volcanic rocks mainly consist of basaltic andesite,andesite.dacite and rhyolite,with minor basalt.Our new sets of data combined with those from previous studies indicate that Xiong'er volcanism should have lasted from 1827 Ma to 1746 Ma as the major phase of the volcanism.These volcanics have extremely low MgO.Cr and Ni contents,are enriched in LREEs and LILEs but depleted in HFSEs(Nb,Ta,and Ti),similar to arc-related volcanic rocks.They are characterized by negative zircon ε_(Hf)_(t) values of-17.4 to 8.8,whole-rock initial ~(87)Sr/~(86)Sr values of 0.7023 to 0.7177 andε_(Nd)(t) values of-10.9 to 6.4.and Pb isotopes(~(206)Pb/~(204)Pb =14.366-16.431,~(207)Pb/~(204)Pb =15.106-15.371,~(208)Pb/~(204)Pb= 32.455-37.422).The available elemental and Sr-Nd-Pb-Hf isotope data suggest that the Xiong'er volcanic rocks were sourced from a mantle contaminated by continental crust.The volcanic rocks of the Xiong'er Group might have been generated by high-degree partial melting of a lithospheric mantle that was originally modified by oceanic subduction in the Archean.Thus,we suggest that the subduction-modified lithospheric mantle occurred in an extensional setting during the breakup of the Columbia supercontinent in the Late Paleoproterozoic,rather than in an arc setting.     

Experimental growth of åkermanite reaction rims between wollastonite and monticellite: evidence for volume diffusion control

Growth rates of monomineralic, polycrystalline åkermanite (Ca₂MgSi₂O₇) rims produced by solid-state reactions between monticellite (CaMgSiO₄) and wollastonite (CaSiO₃) single crystals were determined at 0.5 GPa dry argon pressure, 1,000–1,200°C and 5 min to 60 h, using an internally heated pressure vessel. Inert Pt-markers, initially placed at the monticellite–wollastonite interface, indicate symmetrical growth into both directions. This and mass balance considerations demonstrate that rim growth is controlled by transport of MgO. At 1,200°C and run durations between 5 min and 60 h, rim growth follows a parabolic rate law with rim widths ranging from 0.4 to 16.3 μm indicating diffusion-controlled rim growth. The effective bulk diffusion coefficient \( D_{\text{eff,MgO}}^{\text{Ak}} \) is calculated to 10^?15.8±0.1 m² s^?1. Between 1,000°C and 1,200°C, the effective bulk diffusion coefficient follows an Arrhenius law with E _a = 204 ± 18 kJ/mol and D ₀ = 10^?8.6±1.6 m² s^?1. Åkermanite grains display a palisade texture with elongation perpendicular to the reaction interface. At 1,200°C, average grain widths measured normal to elongation, increase with the square root of time and range from 0.4 to 5.4 μm leading to a successive decrease in the grain boundary area fraction, which, however, does not affect \( D_{\text{eff,MgO}}^{\text{Ak}} \) to a detectible extent. This implies that grain boundary diffusion only accounts for a minor fraction of the overall chemical mass transfer, and rim growth is essentially controlled by volume diffusion. This is corroborated by the agreement between our estimates of the effective MgO bulk diffusion coefficient and experimentally determined volume diffusion data for Mg and O in åkermanite from the literature. There is sharp contrast to the MgO–SiO₂ binary system, where grain boundary diffusion controls rim growth.     

From Predictive Mapping of Mineral Prospectivity to Quantitative Estimation of Number of Undiscovered Prospects

This paper proposes that the spatial pattern of known prospects of the deposit‐type sought is the key to link predictive mapping of mineral prospectivity (PMMP) and quantitative mineral resource assessment (QMRA). This proposition is demonstrated by PMMP for hydrothermal Au‐Cu deposits (HACD) and by estimating the number of undiscovered prospects for HACD in Catanduanes Island (Philippines). The results of analyses of the spatial pattern of known prospects of HACD and their spatial associations with geological features are consistent with existing knowledge of geological controls on hydrothermal Au‐Cu mineralization in the island and elsewhere, and are used to define spatial recognition criteria of regional‐scale prospectivity for HACD. Integration of layers of evidence representing the spatial recognition criteria of prospectivity via application of data‐driven evidential belief functions results in a map of prospective areas occupying 20% of the island with fitting‐ and prediction‐rates of 76% and 70%, respectively. The predictive map of prospective areas and a proxy measure for degrees of exploration based on the spatial pattern of known prospects of HACD were used in one‐level prediction of undiscovered mineral endowment, which yielded estimates of 79 to 112 undiscovered prospects of HACD. Application of radial‐density fractal analysis of the spatial pattern of known prospects of HACD results in an estimate of 113 undiscovered prospects of HACD. Thus, the results of the study support the proposition that PMMP can be a part of QMRA if the spatial pattern of discovered prospects of the deposit‐type sought is considered in both PMMP and QMRA.     

Human choices and environmental constraints: deciphering the variability of large game procurement from Mousterian to Aurignacian times (MIS 5-3) in southwestern France

The evolution in the selection of prey made by past humans, especially the Neandertals and the first anatomically modern humans, has been widely debated. Between Marine Isotope Stages (MIS) 5 and 3, the accuracy of absolute dating is still insufficient to precisely correlate paleoclimatic and archaeological data. It is often difficult, therefore, to estimate to what extent changes in species procurement are correlated with either climate fluctuations or deliberate cultural choices in terms of subsistence behavior. Here, the full development of archeostratigraphy and Bayesian statistical analysis of absolute dates allows the archeological and paleoclimatic chronologies to be compared. The variability in hunted fauna is investigated using multivariate statistical analysis of quantitative faunal lists of 148 assemblages from 39 archeological sequences from MIS 5 through MIS 3. Despite significant intra-technocomplex variability, it is possible to identify major shifts in the human diet during these stages. The integration of archeological data, paleoclimatic proxies and the ecological characteristics of the different species of prey shows that the shifts in large game hunting can be explained by an adaptation of the human groups to climatic fluctuations. However, even if Middle and Early Upper Paleolithic men adapted to changes in their environment and to contrasting landscapes, they ultimately belonged to the ecosystems of the past and were limited by environmental constraints.     

Lake Neor reveals how mountain vegetation responded to 7000 years of hydroclimate variability in northwestern Iran

Palynological and geochemical analyses provide valuable information about modern and past climatic regimes and vegetation. The impact of climate and humans on past vegetation in the semi-arid areas of northwestern Iran has received increased interest in the wake of warming temperatures in the Middle East. Palynological and down-core XRF elemental abundances from a peat core from Lake Neor enabled a reconstruction of vegetational changes of the past 7000 years over the highlands of northwestern Iran. Periods of increased arboreal pollen (AP) types and high (Artemisia + Poaceae)/Chenopodiaceae ratios along with low titanium abundances, high percentages of total organic carbon, more negative δD values, and higher carbon accumulation rates suggest a relatively wet climate. These conditions have persisted during the periods 6700–6200, 5200–4450 and 3200–2200 cal a bp. The overall low AP values, substantial rise of Chenopodiaceae, high Ti abundances and low values of palaeo-redox proxies, are all evidences of a drier climate, as has been reconstructed for the periods 6200–5200 and 4030–3150 cal a bp and the last 2200 years. An important feature of the last centuries is the increase of anthropogenic and pastoral indicator pollen types. Our results may provide basic data to predict future trends in vegetation dynamics under future climate change in western Asia.