Biosorption of divalent Pb, Cd and Zn on aragonite and calcite mollusk shells

The potential of using mollusk shell powder in aragonite (razor clam shells, RCS) and calcite phase (oyster shells, OS) to remove Pb²⁺, Cd²⁺ and Zn²⁺ from contaminated water was investigated. Both biogenic sorbents displayed very high sorption capacities for the three metals except for Cd on OS. XRD, SEM and XPS results demonstrated that surface precipitation leading to crystal growth took place during sorption. Calcite OS displayed a remarkably higher sorption capacity to Pb than aragonite RCS, while the opposite was observed for Cd. However, both sorbents displayed similar sorption capacities to Zn. These could be due to the different extent of matching in crystal lattice between the metal bearing precipitate and the substrates. The initial pH of the solution, sorbent’s dosage and grain size affected the removal efficiency of the heavy meals significantly, while the organic matter in mollusk shells affected the removal efficiency to a lesser extent.     

Variation in groundwater composition and decalcification depth in a dune slack: effects on basiphilous vegetation

Basiphilous, open, species-rich vegetation types of young dune slacks have declined throughout Europe in recent years, and have largely been replaced by often acidophilous, tall marsh and scrub vegetation. This succession appears to be accelerated by a decrease in the discharge of calcareous groundwater from sandy ridges or small dune hummocks. The present study deals with spatial and temporal variation in the chemical composition of the groundwater in the upper metres of the soil of a degraded dune slack complex on the Dutch barrier island of Schiermonnikoog, with emphasis on (1) groundwater composition, (2) water level and (3) decalcification patterns. The main aim was to assess perspectives for restoring basiphilous vegetation types which had been abundant in this slack from 1954 to 1977. The depth of decalcification was related to former hydrological conditions along a transect of 200 m. Acidifying effects of rainfall were reflected in the chemical composition of the groundwater below small dune hummocks within the slack. Distinct precipitation water lenses, poor in dissolved ions, were formed under the dune hummocks during a wet period. This microtopography did not contribute to the discharge of calcareous groundwater to lowlying parts of the slack. Here, groundwater showed decreasing concentrations of the dissolved ions after a rain shower. Except for the peripheral sections of the slack—where upward seepage of groundwater (exfiltration)still occurs—infiltration conditions are now dominant in the slack. The consequences of the present hydrological conditions for restoration are briefly discussed.     

A calcite permeable reactive barrier for the remediation of Fluoride from spent potliner (SPL) contaminated groundwater

The use of calcite (CaCO3) as a substrate for a permeable reactive barrier (PRB) for removing fluoride from contaminated groundwater is proposed and is illustrated by application to groundwater contaminated by spent potliner leachate (SPL), a waste derived from the aluminium smelting process. The paper focuses on two issues in the implementation of calcite permeable reactive barriers for remediating fluoride contaminated water: the impact of the groundwater chemical matrix and CO2 addition on fluoride removal. Column tests comparing pure NaF solutions, synthetic SPL solutions, and actual SPL leachate indicate that the complex chemical matrix of the SPL leachate can impact fluoride removal significantly. For SPL contaminant mixtures, fluoride removal is initially less than expected from idealized, pure, solutions. However, with time, the effect of other contaminants on fluoride removal diminishes. Column tests also show that pH control is important for optimizing fluoride removal with the mass removed increasing with decreasing pH. Barrier pH can be regulated by CO2 addition with the point of injection being critical for optimising the remediation performance. Experimental and model results show that approximately 99% of 2300 mg/L fluoride can be removed when CO2 is injected directly into the barrier. This can be compared to approximately 30-50% removal when the influent solution is equilibrated with atmospheric CO2 before contact with calcite.     

Neptunium(V) adsorption to calcite

The migration behavior of the actinyl ions U(VI)O₂²⁺, Np(V)O₂⁺ and Pu(V,VI)O₂^(+,2+) in the geosphere is to a large extend controlled by sorption reactions (inner- or outer-sphere adsorption, ion-exchange, coprecipitation/structural incorporation) with minerals. Here NpO₂⁺ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0–9.4) and concentration (0.4 μM–40 μM) conditions. pH is adjusted by variation of CO₂ partial pressure. Adsorption is found to be pH dependent with maximal adsorption at pH 8.3 decreasing with increasing and decreasing pH. pH dependence of adsorption decreases with increasing Np(V) concentration. EXAFS data of neptunyl adsorbed to calcite and neptunyl in the supernatant shows differences in the Np(V)-O-yl distance, 1.85 ± 0.01 Å for the adsorbed and 1.82 ± 0.01 Å for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45 ± 0.02 Å. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46 ± 0.01 Å. An additional feature in the adsorbed species' R-space spectrum can be related to carbonate neighbours, 3 to 6 carbon backscatterers (C-eq) at 3.05 ± 0.03 Å and 3 to 6 oxygen backscatterers (O-eq2) at 3.31 ± 0.02 Å. The differences in the Np(V)-O-yl distance and the C-eq and O-eq2 backscatterers which are only present for the adsorbed species indicate inner-sphere bonding of the adsorbed neptunyl species to the calcite surface. Experiments on adsorption kinetics indicate that after a fast surface adsorption process a continuous slow uptake occurs which may be explained by incorporation via surface dissolution and reprecipitation processes. This is also indicated by the part irreversibility of the adsorption as shown by increased K_D values after desorption compared to adsorption.