Enhanced Nesquehonite Formation and Stability in the Presence of Dissolved Silica.

One possible carbon dioxide sequestration strategy is via the carbonation of dissolved Mg2+ obtained through olivine ((Mg,Fe)2SiO4) dissolution. However, silica is also produced during the breakdown of olivine. This component may have a detrimental effect on the yield of Mg-carbonate as Mg2+ incorporation into complex Mg silicate phases would limit CO2 uptake by this system. Yet this potential competition is currently not considered. Here, we use crystal growth experiments at temperatures applicable for potential coastal applications to test the effect of silica on the formation of the hydrated Mg-carbonate phase nesquehonite (MgCO3·3H2O). Solution chemistry analysis coupled with phase identification demonstrates that the presence of silica in the solution can actually assist the formation of nesquehonite and increase its yield by as much as 60 times. Our findings suggest that the presence of silica changes interfacial stabilities, lowering the energetic barrier for nesquehonite nucleation. In addition, in situ attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) transformation experiments demonstrated that nesquehonite precipitating in a solution containing a high concentration of dissolved silica exhibits enhanced stability against its transformation into hydromagnesite. These findings will help to better constrain what we expect for applications of olivine during carbon remediation strategies as well as assist yields for industrial applications that use Mg-based cement as building materials to facilitate a CO2-neutral or negative footprint.

Fate and Transport of Pharmaceuticals in Iron and Manganese Binary Oxide Coated Sand Columns.

Predicting the fate and transport of pharmaceuticals in terrestrial environments requires knowledge of their interactions with complex mineral assemblages. To advance knowledge along this front, we examined the reactivity of pipemidic acid (PIP), a typical quinolone antibiotic, with quartz particles coated with a mixture of manganese oxide (MnO2) and goethite (α-FeOOH) under static and dynamic flow conditions. Batch and dynamic column experiments showed that PIP binding to MnO2 proceeded through a heterogeneous redox reaction, while binding to goethite was not redox-reactive. Mixed columns of aggregated goethite-manganese particles however enhanced redox reactivity because (i) goethite facilitated the transport of dissolved Mn(II) ion and increased the retention of PIP oxidation products, and (ii) MnO2 was protected from passivation. This mobility behavior was predicted using transport models accounting for adsorption and transformation kinetics of PIP on both goethite and MnO2. This work sheds new light on reactivity changes of mixtures of Fe and Mn oxides under flow-through conditions and will have important implications in predicting the fate and transport of redox-active organic compounds as well as development of new geomedia filters for environmental remediation.

Water Flow and Dissolved MnII Alter Transformation of Pipemidic Acid by Manganese Oxide.

Manganese oxides have been proposed as promising geomedia to remove trace organic contaminants in both natural soils and artificial infiltration systems. Although MnOx-based redox processes have been largely investigated, little is known on the effects of water flow and dissolved MnII on manganese-mediated redox reactions in saturated porous media. Here, we have demonstrated that the reactive transport of a widely used quinolone antibiotic, pipemidic acid (PIP), in MnO2-coated sand (MCS) columns is altered by the presence of dissolved MnII, generated in situ as reduced ions or present in inflow solution. Decreasing the flow rate or flow interruption facilitated oxidation reactions and generated redox byproducts (MnII and PIPox). However, preloading of MCS columns with dissolved MnII led to suppressed reactivity with PIP. When PIP and MnII are simultaneously injected, competition between PIP and MnII for binding at the edge sites takes place during the initial kinetic phase of reaction, while at a later breakthrough time MnII will occupy both edge and vacancy sites due to the continuous supply of MnII. We also developed a reactive transport model that accounts for adsorption kinetics to predict changes in transport behavior of antibiotics in the presence of different doses of dissolved MnII. This work has strong implications for an accurate assessment of the reactivity of manganese oxides used as engineered geomedia for quinolone remediation and in developing transport models of antibiotics in natural systems.

Magnesium Stable Isotope Fractionation on a Cellular Level Explored by Cyanobacteria and Black Fungi with Implications for Higher Plants.

In a controlled growth experiment we found that the cyanobacterium Nostoc punctiforme has a bulk cell 26Mg/24Mg ratio (expressed as δ26Mg) that is -0.27‰ lower than the growth solution at a pH of ca. 5.9. This contrasts with a recently published δ26Mg value that was 0.65‰ higher than growth solution for the black fungus Knufia petricola at similar laboratory conditions, interpreted to reflect loss of 24Mg during cell growth. By a mass balance model constrained by δ26Mg in chlorophyll extract we inferred the δ26 Mg value of the main Mg compartments in a cyanobacteria cell: free cytosolic Mg (-2.64‰), chlorophyll (1.85‰), and the nonchlorophyll-bonded Mg compartments like ATP and ribosomes (-0.64‰). The lower δ26Mg found in Nostoc punctiforme would thus result from the absence of significant Mg efflux during cell growth in combination with either (a) discrimination against 26Mg during uptake by desolvation of Mg or transport across protein channels or (b) discrimination against 24Mg in the membrane transporter during efflux. The model predicts the preferential incorporation of 26Mg in cells and plant organs low in Mg and the absence of isotope fractionation in those high in Mg, corroborated by a compilation of Mg isotope ratios from fungi, bacteria, and higher plants.

Mg Isotope Fractionation during Uptake by a Rock-Inhabiting, Model Microcolonial Fungus Knufia petricola at Acidic and Neutral pH.

The model rock-inhabiting microcolonial fungus Knufia petricola fractionates stable Mg isotopes in a time- and pH-dependent manner. During growth, the increase of 26Mg/24Mg in the fungal cells relative to the growth media amounted to 0.65 ± 0.14‰ at pH 6 and 1.11 ± 0.35‰ at pH 3. We suggest a constant equilibrium fractionation factor during incorporation of Mg into ribosomes and ATP as a cause of enrichment of 26Mg in the cells. We suggest too that the proton gradient across the cell wall and cytoplasmic membrane controls Mg2+ transport into the fungal cell. As the strength of this gradient is a function of extracellular solution pH, the pH-dependence on Mg isotope fractionation is thus due to differences in fungal cell mass fluxes. Through a mass balance model we show that Mg uptake into the fungal cell is not associated with a unique Mg isotope fractionation factor. This Mg isotope fractionation dependence on pH might also be observed in any organism with cells that follow similar Mg uptake and metabolic pathways and serves to reveal Mg cycling in ecosystems.

Accumulation of Sb, Pb, Cu, Zn and Cd by various plants species on two different relocated military shooting range soils.

Annually, more than 400 t Pb and 10 t Sb enter Swiss soils at some 2000 military shooting ranges. After the decommission of military shooting ranges, heavily contaminated soils (>2000 mg kg(-1) Pb) are landfilled or processed by soil washing, whereas for soils with less contamination, alternate strategies are sought. Although the use of military shooting ranges for grazing in Switzerland is common practice, no assessment has been done about the uptake of Sb in plants and its subsequent potential intake by grazing animals. We determined the uptake of Sb, Pb, Cu, Zn and Cd in the aboveground biomass of nine plant species growing on a calcareous (Chur) and a weakly acidic (Losone) military shooting range soil in order to assess if grazing would be safe to employ on decommissioned military shooting ranges. The two soils did not differ in their total concentrations of Cu, Zn, Sb and Cd, they differed however in the total concentration of Pb. Additionally, their physical and chemical properties were significantly different. The accumulation of Zn, Cu, Cd and Pb in the shoots of all nine plant species remained below the Swiss tolerance values for fodder plants (150 mg kg(-1) Zn, 15-35 mg kg(-1) Cu, 40 mg kg(-1) Pb, and 1 mg kg(-1) Cd DW), with the only exception of Pb in Chenopodium album shoots which reached a concentration of 62 mg kg(-1) DW. Antimony concentrations were 1.5-2.6-fold higher in plants growing on the calcareous soil than on the weakly acidic soil. Considering Cu, Zn, Pb, Sb and Cd, all plants, with the exception C. album, would be suitable for grazing on similar shooting range soils.