Colloidal Control on the Distribution of Rare Earth Elements in Shallow Groundwaters

A 7-year monitoring period of rare earth element (REE) concentrations and REE pattern shapes was carried out in well water samples from a 450 m long transect setup in the Kervidy/Coët-Dan experimental catchment, France. The new dataset confirms systematic, topography-related REE signatures and REE concentrations variability but challenges the validity of a groundwater mixing hypothesis. Most likely, this is due to REE preferential adsorption upon mixing. However, the coupled mixing–adsorption mechanism still fails to explain the strong spatial variation in negative Ce anomaly amplitude. A third mechanism—namely, the input into the aquifer of REE-rich, Ce anomaly free, organic colloids—is required to account for this variation. Ultrafiltration results and speciation calculations made using Model VI agree with this interpretation. Indeed, the data reveal that Ce anomaly amplitude downslope decrease corresponds to REE speciation change, downhill groundwaters REE being mainly bound to organic colloids. Water table depth monitoring shows that the colloid source is located in the uppermost, organic-rich soil horizons, and that the colloid input occurs mainly when water table rises in response to rainfall events. It appears that the colloids amount that reaches groundwater increases downhill as the distance between soil organic-rich horizons and water table decreases. Topography is, therefore, the ultimate key factor that controls Ce anomaly spatial variability in these shallow groundwaters. Finally, the <0.2 μm REE fraction ultimately comes from two solid sources in these groundwaters: one located in the deep basement schist; another located in the upper, organic-rich soil horizon.     

An improved description of the interactions between rare earth elements and humic acids by modeling: PHREEQC-Model VI coupling

The Humic Ion Binding Model VI (Model VI) - previously used to model the equilibrium binding of rare earth elements (REE) by humic acid (HA) - was modified to account for differences in the REE constant patterns of the HA carboxylic and phenolic groups, and introduced into PHREEQC to calculate the REE speciation on the HA binding sites. The modifications were shown to greatly improve the modeling. They allow for the first time to both satisfactorily and simultaneously model a large set of multi-REE experimental data with the same set of equations and parameters. The use of PHREEQC shows that the light rare earth elements (LREE) and heavy rare earth elements (HREE) do not bind to HA by the same functional groups. The LREE are preferentially bound to carboxylic groups, whereas the HREE are preferentially bound to carboxy-phenolic and phenolic groups. This binding differentiation might lead to a fractionation of REE-HA patterns when competition between REE and other metals occur during complexation. A survey of the available data shows that competition with Al³⁺ could lead to the development of HREE-depleted HA patterns. This new model should improve the hydrochemical modeling of the REE since PHREEQC takes into account chemical reactions such as mineral dissolution/precipitation equilibrium and redox reactions, but also models kinetically controlled reactions and one-dimensional transport.     

Finding outdoor boundaries for 3D space‐based navigation

Outdoor navigation is widely used in daily life, but faces various issues related to the fidelity of outdoor navigation networks. For instance, agents (pedestrians) are often guided via unrealistic detours around places without clear paths (e.g., squares) or if there are vertical constraints such as overpasses/bridges. This is partly explained by the fact that the main sources of navigation networks in current outdoor navigation are two‐dimensional road/street networks. Utilizing a three‐dimensional space‐based navigation model, compatible with some indoor approaches, is a popular way to address the above‐mentioned issues. A 3D space‐based navigation model is generated by treating 3D spaces as nodes and the shared faces as edges. Inputs of this model are enclosed 3D spaces (volumes). However, outdoor spaces are generally open and unbounded. This article puts forward an approach to enclose outdoor spaces and mimic the indoor environments to derive a network based on connectivity and accessibility of spaces. The approach uses 2.5D maps and consists of three major steps: object footprint determination, footprint classification and space creation. Two use cases demonstrate the proposed approach. Enclosing outdoor spaces opens a new research direction toward providing seamless indoor/outdoor navigation for a range of agents.     

Hydrogeochemistry of the Saloum (Senegal) superficial coastal aquifer

Seawater has entered and concentrated in the Saloum hydrologic system up to 100 km upstream, contaminating both the surface water and the superficial 'Continental terminal' (CT) groundwater resources, and large proportions of cultivated lands. In the areas affected by saltwater contamination, chloride concentrations as high as 3,195 mg/l have been measured in the groundwater samples collected from wells located in the vicinity of the Saloum River, making the water inadequate for drinking water purposes. This paper presents the results of a study designed to characterise the current extent of the saline groundwater and the mechanism of saline surface water body/fresh groundwater mixing in relation to the groundwater flow trends. It also describes the groundwater chemical and isotopic composition and geochemical processes controlling the chemical patterns. Four major water types occur in the study area, namely Na-rich saline groundwater, Ca-Na-rich saline groundwater, Na-dominant fresh groundwater and Ca-dominant fresh groundwater. A hydrogeochemical zonation of the aquifer, based on the presence of different water families and on the groundwater flow, led to the identification of the main processes controlling the groundwater chemistry. Cation exchange reactions on the kaolinite clay mineral, calcite dissolution in the eastern zone where calcite minerals have been identified, reverse cation exchange reactions in the saline-contaminated band along the Saloum River and, to a lesser extent, a gypsum dissolution are the predominant processes. Results of i¹⁸O and iD analysis in 15 groundwater samples compared with the local meteoric line indicate that the groundwater has been affected by evaporation, and the groundwater is isotopically lighter as the depth of water table increases. In this study, i¹⁸O data were used in conjunction with chloride data to identify the source of high chloride. Results show a departure of the contaminated water samples from the seawater mixing line, which indicates that other processes rather than mixing between modern seawater and native groundwater alone increase the chloride concentrations.     

Semantic enrichment of octree structured point clouds for multi‐story 3D pathfinding

3D indoor navigation in multi‐story buildings and under changing environments is still difficult to perform. 3D models of buildings are commonly not available or outdated. 3D point clouds turned out to be a very practical way to capture 3D interior spaces and provide a notion of an empty space. Therefore, pathfinding in point clouds is rapidly emerging. However, processing of raw point clouds can be very expensive, as these are semantically poor and unstructured data. In this article we present an innovative octree‐based approach for processing of 3D indoor point clouds for the purpose of multi‐story pathfinding. We semantically identify the construction elements, which are of importance for the indoor navigation of humans (i.e., floors, walls, stairs, and obstacles), and use these to delineate the available navigable space. To illustrate the usability of this approach, we applied it to real‐world data sets and computed paths considering user constraints. The structuring of the point cloud into an octree approximation improves the point cloud processing and provides a structure for the empty space of the point cloud. It is also helpful to compute paths sufficiently accurate in their consideration of the spatial complexity. The entire process is automatic and able to deal with a large number of multi‐story indoor environments.     

Évolution des indices des extrêmes climatiques en République du Tchad de 1960 à 2008

[Translated by the editorial staff] An analysis of climate trends and return levels for the period 1960–2008, using the ETCCDI-CLIVAR/JCOMM project approach, has been conducted for Chad, where droughts and flooding are recurrent. Using the RClimDex software, we show that almost all rainfall trends are decreasing, as in Central and Northern Africa. Rare extreme rain events (R99p) decrease significantly: 0.85?mm per decade. However, we note a slightly upward trend of 0.5 day per decade, in the number of consecutive dry days (CDD). Temperature indices are all positive except for the frequencies of very hot days (TX90p) and very cold nights (TN10p), which decrease significantly: ?0.39% day per year per decade, as in Central Africa and globally. Sequences of hot or cold days decrease as well, but by about 1% per year per decade. Return periods identified with the generalized extreme value (GEV) distributions show that they are well defined from 1 to 10 years. Extremely rare events from 10 to 50 years are associated with a mean return level of 660?mm of annual precipitation.     

Competitive binding of REE to humic acid and manganese oxide: Impact of reaction kinetics on development of cerium anomaly and REE adsorption

The competitive binding of rare earth elements (REE) to purified humic acid (HA) and MnO₂ was studied experimentally using various HA/MnO₂ ratios over a range of pH (3 to 8). MnO₂, humic acid and REE solutions were simultaneously mixed to investigate the kinetics of the competitive reactions. Aqueous REE–HA complex is the dominant species whatever the experiment time, pH and HA/MnO₂ ratio. The value of the distribution coefficients between MnO₂ and solution (log K_d^Ree/Mno₂) increases with the HA/MnO₂ ratio, indicating that part of the REE–HA complexes are adsorbed onto MnO₂. The development of a Ce anomaly appears strongly limited in comparison with inorganic experimental conditions. Throughout the experimental run time, for HA/MnO₂ ratios of less than 0.4, MnO₂ acts as a competitor leading to a partial dissociation of the REE–HA complex. The majority of the dissociated REE is readsorbed onto the MnO₂ surface. The readsorption of REE is expressed by an increased Ce anomaly on the log K_d^Ree/Mno₂ pattern as well as a change in shape of the coefficient distribution of REE between soluble HA and solution pattern (log K_d^Ree/HA decrease for the heavy rare earth elements — HREE). Thus, REE are not only bound to MnO₂ as a REE–HA complex, but also as REE(III). Moreover, the competition between HA and MnO₂ for REE binding is shown to be higher at low pH (< 6) and low DOC/Mn ratio. This study partially confirms previous work that demonstrated the control of REE adsorption by organic matter, while shedding more light on the impact of pH as well as complexation reaction competition on long-term REE partitioning between solid surface and organic solutions. The latter point is important as regards to REE speciation under conditions typical of rock and/or mineral alteration.     

Mobilization and redistribution of major and trace elements in two weathering profiles developed on serpentinites in the Lomié ultramafic complex, South-East Cameroon

The behaviour of major and trace elements have been studied along two serpentinite weathering profiles located in the Kongo-Nkamouna and Mang North sites of the Lomié ultramafic complex.The serpentinites are characterized by high SiO₂ and MgO contents, very low trace, rare earth and platinum-group element contents. Lanthanide and PGE contents are higher in the Nkamouna sample than in Mang North. Normalized REE patterns according to the CI chondrites reveal that: (i) all REE are below chondrites abundances in the Mang North sample; (ii) the (La/Yb)_N ratio value is higher in the Nkamouna sample (23.72) than in the Mang one (1.78), this confirms the slightly more weathered nature of the Nkamouna sample. Normalized PGE patterns according to the same CI chondrites reveal a negative Pt anomaly in the Mang sample. The Nkamouna sample is characterized by a flat normalized PGE pattern.All element contents increase highly from the parent rock to the coarse saprolite.In the weathering profiles, Fe₂O₃ contents decrease from the bottom to the top contrarily to Al₂O₃, SiO₂ and TiO₂. The contents of alkali and alkaline oxides are under detection limit.Concerning trace elements, Cr, Ni, Co, Cu, Zn and Sc decrease considerably from the bottom to the top while Zr, Th, U, Be, Sb, Sn, W, Ta, Sr, Rb, Hf, Y, Li, Ga, Nb and Pb increase towards the clayey surface soil. Chromium, Ni and Co contents are high in the weathered materials in particular in the saprolite zone and in the nodules.REE contents are high in the weathered materials, particularly in Nkamouna. Their concentrations decrease along both profiles. Light REE are more abundant than heavy REE. Normalized REE patterns according to the parent rock reveal positive Ce anomalies in all the weathered materials and negative Eu anomalies only at the bottom of the coarse saprolite (Nkamouna site). Positive Ce anomalies are higher in the nodular horizon of both profiles. An additional calculation method of lanthanide anomalies, using NASC data, confirms positive Ce anomalies ([Ce/Ce^*]_NASC = 1.15 to 60.68) in several weathered materials except in nodules ([Ce/Ce^*]_NASC = 0.76) of the upper nodular horizon (Nkamouna profile). The (La/Yb)_N ratios values are lower in the Nkamouna profile than in Mang site.PGE are more abundant in the weathered materials than in the parent rock. The highest contents are obtained in the coarse saprolite and in the nodules. The elements with high contents along both profiles are Pt (63–70 ppb), Ru (49–52 ppb) and Ir (41 ppb). Normalized PGE patterns show positive Pt anomalies and negative Ru anomalies.The mass balance evaluation, using thorium as immobile element, reveals that:

– major elements have been depleted along the weathering profile, except for Fe, Mn and Ti that have been enriched even only in the coarse saprolite;

– all the trace elements have been depleted along both profiles, except for Cr, Co, Zn, Sc, Cu, Ba, Y, Ga, U and Nb that have been enriched in the coarse saprolite;

– rare earth elements have been abundantly accumulated in the coarse saprolite, before their depletion towards the top of the profiles;

– platinum-group elements have been abundantly accumulated in the coarse saprolite but have been depleted towards the clayey surface soil.

Moreover, from a pedogenetical point of view, this study shows that the weathering profiles are autochtonous, except in the upper part of the soils where some allochtonous materials are revealed by the presence of zircon grains.     

Spatial subdivision of complex indoor environments for 3D indoor navigation

As we realize that we spend most of our time in increasingly complex indoor environments, applications to assist indoor activities (e.g. guidance) have gained a lot of attention in the recent years. The advances in ubiquitous computing made possible the development of several spatial models intending to support context-aware and fine-grained indoor navigation systems. However, the available models often rely on simplified representations (e.g. 2D plans) and ignore the indoor features (e.g. furniture), thereby missing to reflect the complexity of the indoor environment. In this paper, we introduce the Flexible Space Subdivision framework (FSS) that allows to automatically identify the spaces that can be used for indoor navigation purpose. We propose a classification of indoor objects based on their ability to autonomously change location and we define a spatial subdivision of the indoor environment based on the classified objects and their functions. The framework can consider any 3D indoor configuration, the static and dynamic activities it hosts and it enables the possibility to consider all types of locomotion (e.g. walking, flying, etc.). It relies on input 3D models with geometric, semantic and topological information and identifies a set of subspaces with dedicated properties. We assess the framework against criteria defined in previous researches and we provide an example.     

Effect of phosphatation and calcination on the environmental behaviour of sediments

Dredging operations produce considerable quantities of materials, to be managed and this opens an opportunity for valorization in civil engineering. However, the contamination of the dredged sediments has become a major problem to solve. The major contaminants are heavy metals and organic compounds. This study focuses on the use of phosphoric acid (H3PO4) to stabilize heavy metals from sediments and destroy organic matter by calcination at 650 °C with a goal of using sediments in roadworks. Several studies have been conducted in this eld. The stabilized materials obtained have been used in civil engineering. The main purpose of this work is to discuss the environmental behavior of marine sediment treated by phosphatation and calcination. Two types of phosphoric acids were used. The pH dependence leaching test has been used as the basic characterization to evaluate the effect of the type of phosphoric acid on the metals behavior in a valorization scenario. The standard leaching test and the Toxicity Characteristic Leaching Procedure (TCLP) were conducted as compliance tests. In regards of the obtained results, the environmental assessment has also shown a reduction in the availability of targeted heavy metals in alkaline environment whatever the type of acid used for treatment. This opens opportunities for co-valorization.