Ion exchange | EPFL Graph Search

Ion exchange is a reversible interchange of one kind of ion present in an insoluble solid with another of like charge present in a solution surrounding the solid with the reaction being used especially for softening or making water demineralised, the purification of chemicals and separation of substances. Ion exchange usually describes a process of purification of aqueous solutions using solid polymeric ion-exchange resin. More precisely, the term encompasses a large variety of processes where ions are exchanged between two electrolytes. Aside from its use to purify drinking water, the technique is widely applied for purification and separation of a variety of industrially and medicinally important chemicals. Although the term usually refers to applications of synthetic (human-made) resins, it can include many other materials such as soil. Typical ion exchangers are ion-exchange resins (functionalized porous or gel polymer), zeolites, montmorillonite, clay, and soil humus. Ion exc

Typology of recent groundwaters from different aquifer environments based on geogenic tracer elements

A key problem in environmental science and in engineering geology is the often incomplete understanding of the origin of dissolved components in groundwater. The dissolved contents of trace elements in groundwater are of special importance for groundwater quality control. The AQUITYP project aims to establish a detailed typology of recent groundwaters based on their geogenic trace element compositions, and to derive a so-called "geo-reference" for groundwaters from five principal aquifer lithologies in the Alpine belt. This geo-reference provides a database for investigations related to groundwater contamination, groundwater resources management and engineering geology. Groundwaters from crystalline, carbonate, and evaporite rocks, as well as molasse and flysch sediments in Switzerland and in neighbouring countries were sampled and documented by previous researchers (Dubois, 1993; Dematteis, 1995; Mandia, 1993; Hesske, 1995; Basabe, 1993). Based on a statistical analysis of the data and examination of the relationship between aquifer lithology and chemical groundwater composition these researchers identified a number of characteristic tracer elements (geogenic tracers). The present study includes (1) a synthesis of the hydrogeology and the hydrochemistry of recent groundwaters in these five aquifer types based on groundwater data acquired within the AQUITYP project, and (2) a hydro-geochemical investigation of the origin and chemical behaviour of the geogenic tracer chromium, based on a comprehensive field and laboratory study. To enable a comparison of the chemical groundwater data gathered and analysed over a time span of 20 years, a rigorous quality control of the entire database was made. An assessment was made of the sampling techniques, the sample treatment and the analytical methods applied in the AQUITYP project since 1981. Different tests were carried out to evaluate the quality and comparability of the data, including geochemical model calculations, comparison of different analytical techniques, and tests to estimate the influence of the filtration procedure. In order to make this large number of quality controlled data accessible also for future investigations, a groundwater data storage system was developed (AQUITYP-DataBase). 1.) Typology of recent groundwaters In the synthesis of groundwater hydrochemistry, the emphasis was laid on the hydro-geochemical evolution leading to the characteristic groundwater composition in each of the five aquifer types. Chemical characteristics and differences between the groundwaters from the different aquifer types were identified and natural concentration ranges for each aquifer type derived. The proposed geogenic tracers were evaluated and the potential sources of these tracers identified. The dominant processes leading to the typical mineralisation of recent groundwaters were investigated using geochemical modelling strategies. Finally, the concentrations of chemical elements in the groundwaters from the different aquifer types were compared to the Swiss drinking water standards in order to assess the quality of the investigated groundwaters. It has been found that each rock type contributes in a characteristic way to the major and trace element composition of the corresponding groundwater: The groundwaters derived from the crystalline Mont-Blanc and Aiguilles-Rouges massifs are characterised by a low total mineralisation (TDS 22 to 158 mg/L) dominated by Ca2+, Na+, Mg2+, alkalinity, SO42-, and F- (Ca-Na-HCO3,-SO4, waters). Elevated amounts of Mo, U, W, and As occur. These groundwaters derive their mineralisation mainly from the interaction with hydrothermal minerals present along fractures. Fractures act as major groundwater flow paths. Minerals relevant for groundwater mineralisation include carbonates (Ca2+, Mg2+, HCO3-), clay minerals (Ca-Na ion exchange), fluorite (F-, Ca2+), Fe-, As-, and Mo-sulphides (SO42-, As, Mo), and U- and W-minerals (U, W). In these crystalline groundwaters the natural concentrations of F- (23% of the investigated springs) and As (7%) exceed the Swiss limits for drinking water. In addition, the WHO guideline values for U are exceeded in 65% of the cases and for Mo in 15% of the cases. The carbonate karst groundwaters obtain their low to intermediate mineralisation (TDS 161 to 547 mg/L) from the dissolution of calcite (Ca-HCO3, waters), as well as in certain regions dolomite (Ca-Mg-HCO3, waters) and gypsum (Ca-Mg-HCO3,-SO4, waters). Together with their very short residence times, the carbonate karst groundwaters generally contain very low trace element contents. Nevertheless, geogenic trace elements occur in specific regions in relation with fossil organic matter (I, V) and accessory minerals such as barite in deep sea limestones (Ba), evaporite minerals (gypsum, celestite: Sr, Li), clay- and Fe-minerals (V), and Mo-sulphides and U-minerals in dolomitic limestones (Mo, U). In 18% of the carbonate karst springs atmospheric derived Pb exceeds the Swiss drinking water quality target value. The groundwaters from Triassic evaporites in the Swiss Rhone basin are characterised by a high total mineralisation (TDS 760 to 2788 mg/L) expressed by elevated amounts of Ca2+, Mg2+, Sr2+, SO42-, and alkalinity (Ca-Mg-SO4-HCO3 waters). Elevated amounts of the trace elements Mn, Ni, Cu, Li, Rb, Y, and Cd occur. The hydrochemical evolution of these groundwaters is governed by incipient dedolomitisation, involving dissolution of gypsum, celestite and dolomite and simultaneous precipitation of calcite. The Na+ and K+ contents probably controlled by ion-exchange reactions on clay minerals. Characteristic trace elements originate mainly from the dissolution of dolomite (Mn, Ni) and small amounts of apatite (Y, Cd), and from the oxidation of sulphide minerals (Cu, Ni, Cd). The elevated concentrations of the highly soluble Li and Rb may be related to brine inclusions in evaporite minerals and eventually to clay minerals. These evaporite groundwaters contain SO42- concentrations exceeding the Swiss quality target for drinking water in all springs, and the concentrations of U and Ni exceed the WHO guideline values in respectively 58% and 2% of the cases. In addition, Mn, Cd, and As concentrations exceed the Swiss quality targets in respectively 11%, 10%, and 7% of the investigated springs. Recent groundwaters circulating in the porous and fissured molasse sandstones and conglomerates acquire their intermediate mineralisation (TDS 48 to 714 mg/L) primarily by dissolution of calcite and minor dolomite (Ca-Mg-HCO3 waters). The particular mineralogy of certain Molasse formations is reflected in specific trace element compositions of corresponding groundwaters: ophiolite detritus in OMM sandstones in western Switzerland (Cr), barite fracture mineralisations in subalpine and folded Molasse units (Ba), granitic detritus containing sulphides (Mo), U-minerals (U) and abundant mica (Li) in the "Glimmersand" (OSM, Ca-Mg-HCO3-SO4 waters), and evaporite minerals (Li, Sr), sulphides (Mo), and U-minerals (U) in the "Gypsum-bearing Molasse" (USM, highly mineralised Ca-Mg-SO4-HCO3 waters, TDS 984 to 1346 mg/L) . In these molasse groundwaters the Swiss quality target values for drinking water of Cr and Pb are exceeded in 36% and 6% of the springs, respectively. The U concentrations of 14% of the molasse groundwaters ("Gypsum-bearing Molasse" and "Glimmersand"), exceed the WHO guideline value. The groundwaters from the "Gypsum-bearing Molasse" display similar quality problems as the evaporite groundwaters. Groundwaters derived from the shallow flysch aquifers in the Niesen and Gurnigel nappes are poorly evolved Ca-(Mg)-HCO3 waters. Their low to intermediate total mineralisation (TDS 160 to 459 mg/L) is acquired primarily by dissolution of calcite and to a lesser degree dolomite. The low trace element content is dominated by Ba originating from barite fracture mineralisations. The poor chemical evolution of recent flysch groundwaters results from (1) their short residence time in the fractured flysch rocks, and (2) the absence of readily dissolving minerals except carbonates and barite. In 32% of the flysch springs Pb derived from atmospheric sources exceeds the Swiss quality target value. 2.) Case study on the chemical weathering of molasse sandstone: Sources and chemical behaviour of Cr For the characterisation of the potentially toxic tracer element Cr a comprehensive field study was carried out on a selected catchment (Lutry spring catchment near Lausanne) situated in a molasse sandstone (OMM, Burdigalian). The investigation of the processes controlling the dissolved Cr content in these groundwaters was based on the groundwater chemical data, as well as on mineralogical, geochemical, and hydrological data. Relic Cr-bearing spinel and pyroxene in the sandstone were identified to be the primary sources of Cr. An electron microscope study showed that in the Burdigalian sandstone and overlying soil these minerals are strongly weathered. The slow weathering of these minerals is the major Cr releasing process. Under the oxidising conditions reigning in the investigated groundwaters, Cr prevails in solution in its highly soluble and toxic hexavalent state (CrO42-). In this case, retention by secondary Cr-hydroxide phases does not occur, as can be shown by geochemical model calculations. Laboratory leaching experiments were carried out with Burdigalian molasse sandstone from the field site, in order to support the field study findings and to quantify the processes responsible for the Cr mineralisation observed in the Lutry groundwater. Two experiments with mountain-wet oxidised and reduced sandstone were carried out over a time span of 2 months each, to obtain information about the influence of the oxidation state of the substratum on the mobilisation of Cr. The experiments clearly showed that the Cr-releasing processes are fast enough to explain the Cr contents found in the groundwater, and that the release of Cr into the groundwater depends on the weathering state of the sandstone. In the oxidised, Fe-hydroxide-coated sandstone, Cr is faster released into solution than in the less altered reduced sandstone. This indicates that the Cr contained in the reduced sandstone is in a more stable state, i.e. mainly incorporated in detrital minerals, while in the oxidised sandstone, the Cr is partly in an unstable state, i.e. adsorbed on the surface of secondary Fe-hydroxides, from where it is more easily leached.

EPFL2001

Adsorptive Removal of Pb(II) and As(V) from Aqueous Solution by PVDF/HMO Ultrafiltration Mixed Matrix Membrane

Younes Lucas Seghrouchni

Lead and arsenic are among the designated chemicals of major concern by the World Health Organization, they affect millions of people worldwide with both acute and chronic effects on human health. In the current study, mixed matrix membranes (MMMs) were fabricated using polyvinylidene fluoride (PVDF) for the matrix and hydrous manganese dioxide nanoparticles to remove lead, Pb(II), and arsenic, As(V), form water. The objectives of the study were to fabricate membrane with HMO:PVDF ratios from 0 to 1 and to characterize their adsorption properties on the two metals and their filtration performances. The HMO nanoparticles were synthesized using manganese sulfate monohydrate and potassium permanganate. The membranes were fabricated using phase inversion, a dope solution was prepared with HMO:PVDF ratios between 0 and 1, NMP as a solvent at an NMP:PVDF ratio of 5.57 and PVP at a PVP:PVDF ratio of 0.1 to increase the permeance of the membranes. The dope solution was casted and then soaked in a water coagulation bath for phase inversion. The structure of the nanoparticles was observed using TEM, and the structure of the membranes was described using SEM. The adsorption tests assessed the adsorption capacity, the adsorption kinetic and the effect of the pH on the adsorption capacity for the two metals. The concentration in the samples was measured with ICP-OES. A FTIR analysis was performed as a proof of adsorption. The tests that were run to assess the filtration performance of the membranes were the following ones: pure water permeance test, hydrophilicity test, surface analysis using XPS, pore size with AFM and finally filtration capacity on lead and arsenic. The HMO particles that were produced had sizes in the nanometer range and were elongated, which provided them a large surface-to-volume ratio. The membranes had asymmetric structures and the membrane with large HMO ratios had the surface of their pores covered uniformly with HMO particles. The adsorption capacities of pure HMO particles were 36 [mg/g] for arsenic and 283 [mg/g] for lead. The adsorption capacity of the membranes with an HMO:PVDF ratio of 1 was 11 [mg/g] for arsenic and 146 [mg/g] for lead. The Freundlich isotherm was used to describe the adsorption capacity of the membranes for both lead and arsenic. The adsorption kinetic was described by a pseudo-second order kinetic model for arsenic and the results were not significant enough the assess the adsorption kinetic model for lead. The equilibrium was almost reached in 30 minutes for the adsorption of the two metals on pure HMO. The adsorption capacity was enhanced with increasing pH for lead adsorption and it was the opposite for arsenic adsorption. The sensitivity to the pH was higher for lead compared to arsenic and this sensitivity to the pH could be used to regenerate the membrane in case of lead adsorption. The average permeance of the membranes was around 1500 [L/m2h bar], the pore sizes were in the ultrafiltration range, between 41 [nm] and 70 [nm] and the membranes were in the hydrophilic range, with an average contact angle of 69 [°]. The HMO ratio in the membranes had a limited impact on these three parameters. The filtration capacity on arsenic was too low to remove arsenic at ppb concentrations and the results of this test on lead were not significant enough to be interpreted.

2018

Hydrogeochemical Modelling of Variably Saturated Soils

Laurin Wissmeier

This thesis is about the simulation of flow, transport and geochemical reactions in variably saturated soils. Motivated by the problematic disposal and revegetation of residue from aluminium refining, novel modelling tools for general geochemical reactions in variably saturated flow conditions were developed. In addition, a new model for the effect of mineral reactions on unsaturated hydraulic properties was established. The most sophisticated of the presented series of models was applied in a comprehensive simulation of the geochemical evolution of residue from aluminium refining in response to rainfall- and evaporation-induced leaching. Model development commenced with the direct implementation of the one-dimensional moisture-based form of Richards' equation into the geochemical modelling framework PHREEQC for the simulation of biogeochemical reactions in the vadose zone. The implementation gives access to the full suite of reactions in PHREEQC with activity corrected solution speciation, advanced adsorption models and the flexible definition of kinetic mineral reactions. The numerical approach is based on the conceptual treatment of liquid phase flow and solute transport as time- and space-dependent reactions. The accuracy of the applied finite difference scheme profits from the Kirchhoff transformation on the diffusivity term. In case of the van Genuchten hydraulic model, the integration of soil moisture diffusivity led to analytical series solutions that necessitate numerical approximation. The model's novel capabilities for the simulation of unsaturated flow and ion complexation with variable charge surface sites as well as water content modifying mineral reactions, such as dissolution of hydrated minerals were demonstrated in examples. In a second step, the applicability of this simulation tool was extended to soil profiles with heterogeneous hydraulic properties and variably saturated conditions where parts of the domain may be fully saturated. For this, the head-based form of Richards' equation was implemented using a mass balancing, implicit finite difference scheme with Picard iteration. The use of a total variation-diminishing scheme for solute transport yields second order accurate yet oscillation free solutions for the advective transport of sharp concentration fronts. Applications of the scheme were illustrated for (i) infiltration with saturation-dependent cation exchange capacity, (ii) changes in hydraulic properties due to mineral reactions and (iii) transport of mobile organic substances with complexation of heavy metals. Using this extended simulation tool, an advanced model for the effect of mineral reactions on unsaturated hydraulic properties was developed. The selective radius shift model accounts for the fact that mineral reactions in unsaturated conditions only affect the water filled pore size fraction. In addition, the volume change in each pore due to dissolution/precipitation is proportional to the pore volume. Changes in mineral volume according to geochemical speciation are translated to the pore-size distribution considering the actual moisture content. The resulting discontinuous pore-size distribution is related to the water retention curve by the pore-bundle concept. From the updated discontinuous water retention curve, a smooth water retention function is deduced by means of parameter optimization. Applications of the selective radius shift model were presented for kinetic halite dissolution and calcite precipitation as a consequence of cation exchange. In a further development, the simulation of geochemical reactions in variably saturated soils was extended to two and three-dimensional domains by coupling the general finite element solver COMSOL Multiphysics® to IPhreeqc. IPhreeqc is an object-oriented version of PHREEQC that is specifically designed for couplings to flow and solute transport simulators. The resulting model combines COMSOL's capabilities for the computation of variably saturated flow and solute transport in domains of arbitrary complexity with the full suite of geochemical reaction calculations in PHREEQC. Code verification was performed for point source infiltration and degradation of the pesticide Aldicarb via a kinetic reaction chain. An application example of the new software features subsurface irrigation and fertigation, with cation exchange, proton adsorption and pressure- and space dependent root-water uptake. Using the coupled software, the coarse fraction of the leftover from aluminium refining using Bayer's process was investigated as a covering substrate for residue disposal areas and substrate for plant growth. The solid phase mineral assembly in the residue sand was derived from measured acid neutralization curves. Ion adsorption was modelled and parameterized as an exchange process. A column experiment under saturated flow conditions partially validated the model. The parameterized model was used to predict the geochemical evolution of fertigated and gypsum amended residue sand as response to rainfall- and evaporation-induced leaching in the climatic conditions of southwest Western Australia. Scenarios were calculated for a vertical flow lysimeter and a sloping cover layer for a disposal facility with dimensions 3 m × 50 m. Results show poor long-term retention of fertilizers and the stabilization of the pH at around 10 for at least 5 years of leaching. Soil moisture conditions in the cover layer could be ameliorated by appropriate design of the layer thickness, slope and distance between lateral drains.

EPFL2010