Leaching the Unleachable Mineral: Rare Earth Dissolution from Monazite Ore in Condensed Phosphoric Acid

Monazite is a poorly soluble mineral of rare earth phosphate. It is an ore of the rare earths which is difficult to break down; in industry either concentrated sulphuric acid or caustic soda is used to attack finely ground monazite at between 140 °C and 400 °C. In these processes, the rare earths are converted into different solid compounds, undergoing an incomplete conversion. Here we show a new process for a direct and much faster breakdown of monazite by simple dissolution under milder conditions. Condensed phosphoric acid was used to dissolve rare earths (up to 96 g/L) from unground monazite sand from four sources. Greater than 99% of light rare earths dissolved within 30 min at 260 °C. The cooled solution can be diluted to an extent with water to reduce viscosity for analysis or further processing. This method of dissolution avoids the use of strong acids/bases and reduces the risk of dusk exposure from fine grinding of particles.

Probing electronic structure in berkelium and californium via an electron microscopy nanosampling approach

Due to their rarity and radioactive nature, comparatively little is known about the actinides, particularly those with atomic numbers higher than that of plutonium, and their compounds. In this work, we describe how transmission electron microscopy can provide comprehensive, safe, and cost-effective characterization using only single nanogram amounts of highly-radioactive, solid compounds. Chlorides of the rare elements berkelium and californium are dropcast and then converted in situ to oxides using the electron beam. The f-band occupancies are probed using electron energy loss spectroscopy and an unexpectedly weak spin-orbit-coupling is identified for berkelium. In contrast, californium follows a jj coupling scheme. These results have important implications for the chemistries of these elements and solidify the status of californium as a transitional element in the actinide series.

Silicon Cycling in Soils Revisited

Silicon (Si) speciation and availability in soils is highly important for ecosystem functioning, because Si is a beneficial element for plant growth. Si chemistry is highly complex compared to other elements in soils, because Si reaction rates are relatively slow and dependent on Si species. Consequently, we review the occurrence of different Si species in soil solution and their changes by polymerization, depolymerization, and condensation in relation to important soil processes. We show that an argumentation based on thermodynamic endmembers of Si dependent processes, as currently done, is often difficult, because some reactions such as mineral crystallization require months to years (sometimes even centuries or millennia). Furthermore, we give an overview of Si reactions in soil solution and the predominance of certain solid compounds, which is a neglected but important parameter controlling the availability, reactivity, and function of Si in soils. We further discuss the drivers of soil Si cycling and how humans interfere with these processes. The soil Si cycle is of major importance for ecosystem functioning; therefore, a deeper understanding of drivers of Si cycling (e.g., predominant speciation), human disturbances and the implication for important soil properties (water storage, nutrient availability, and micro aggregate stability) is of fundamental relevance.

Supercritical Fluids as a Tool for Green Energy and Chemicals

Hydrothermal conversion of biomass is a promising technology for the conversion of biomass into biofuels and biobased chemicals. This chapter is focused on the waste biomass conversion for production of biofuels and chemicals by applying sub- and supercritical fluids. One of the biggest disadvantages in biomass conversion by SCF is the extremely high energy requirement for heating the media above the water critical point (374 °C, 221 bar). The idea behind the recent research is to reduce the operating temperature and energy requirements by processing biomass with water at much higher pressures. The importance of knowledge on behavior of multicomponent systems at elevated pressures and temperatures is underlined. Methods, developed by the authors of this chapter for determination of thermodynamic and transport properties for multicomponent systems of different solid compounds and supercritical fluid under extreme conditions, are described. A future perspective of hydrothermal technology as a tool to obtain advanced materials and the possible scope for future research is also discussed.

Birnessite: A New Oxidant for Green Rust Formation

Iron and manganese are ubiquitous in the natural environment. FeII-FeIII layered double hydroxide, commonly called green rust (GR), and MnIII-MnIV birnessite (Bir) are also well known to be reactive solid compounds. Therefore, studying the chemical interactions between Fe and Mn species could contribute to understanding the interactions between their respective biogeochemical cycles. Moreover, ferromanganese solid compounds are potentially interesting materials for water treatment. Here, a {Fe(OH)2, FeIIaq} mixture was oxidized by Bir in sulphated aqueous media in the presence or absence of dissolved O2. In oxic conditions for an initial FeII/OH− ratio of 0.6, a single GR phase was obtained in a first step; the oxidation kinetics being faster than without Bir. In a second step, GR was oxidised into various final products, mainly in a spinel structure. A partial substitution of Fe by Mn species was suspected in both GR and the spinel. In anoxic condition, GR was also observed but other by-products were concomitantly formed. All the oxidation products were characterized by XRD, XPS, and Mössbauer spectroscopy. Hence, oxidation of FeII species by Bir can be considered as a new chemical pathway for producing ferromanganese spinels. Furthermore, these results suggest that Bir may participate in the formation of GR minerals.