Investigations on Adsorption of Inorganic Ions in Aqueous Solution to Some Metal Oxides, Hydroxides and a Carbonate by the X-Ray Spectroscopic Method.

Why does the adsorption and concentration of inorganic chemical species proceed at aqueous-solid interfaces? In this review paper, we discuss the use of X-ray chemical state analysis to elucidate the intrinsic adsorption mechanism. Based on the chemical states of the species adsorbed to solids as determined by X-ray chemical state analysis, possible adsorption mechanisms are discussed. The driving forces of adsorption are represented by the Gibbs free energy change (ΔGchem = ΔGchem,1 + ΔGchem,2) resulting from the formation of covalent bonds between metal ions (M) in metal oxides or hydroxides and adsorbed species (X) (M-O-X bond, ΔGchem,1) and the formation of new phases consisting of M and X (ΔGchem,2). The concept of ΔGchem,2 is proposed based on the experimental results from chemical state analyses. As examples, the following investigations are discussed in this review paper: the formation of mullite precursors by the adsorption of monosilicic acid to Al(OH)3, the spontaneous reduction of Au(III) to Au(0) by adsorption of Au(III) to Al(OH)3, MnO2 and Ni(OH)2 and the mechanism of concentration of Co2+, Tl+, Pb2+, Pt2+, Au+, and Pd2+ in marine ferromanganese crusts.

Subseafloor sulphide deposit formed by pumice replacement mineralisation.

Seafloor massive sulphide (SMS) deposits, modern analogues of volcanogenic massive sulphide (VMS) deposits on land, represent future resources of base and precious metals. Studies of VMS deposits have proposed two emplacement mechanisms for SMS deposits: exhalative deposition on the seafloor and mineral and void space replacement beneath the seafloor. The details of the latter mechanism are poorly characterised in detail, despite its potentially significant role in global metal cycling throughout Earth's history, because in-situ studies require costly drilling campaigns to sample SMS deposits. Here, we interpret petrographic, geochemical and geophysical data from drill holes in a modern SMS deposit and demonstrate that it formed via subseafloor replacement of pumice. Samples from the sulphide body and overlying sediment at the Hakurei Site, Izena Hole, middle Okinawa Trough indicate that sulphides initially formed as aggregates of framboidal pyrite and matured into colloform and euhedral pyrite, which were replaced by chalcopyrite, sphalerite and galena. The initial framboidal pyrite is closely associated with altered material derived from pumice, and alternating layers of pumiceous and hemipelagic sediments functioned as a factory of sulphide mineralisation. We infer that anhydrite-rich layers within the hemipelagic sediment forced hydrothermal fluids to flow laterally, controlling precipitation of a sulphide body extending hundreds of meters.

A new and practical Se(IV) removal method using Fe3+ type cation exchange resin.

An effective method for removing selenium (Se) from water is required from the viewpoint of environmental preservation. To establish this method, a cation exchange resin that adsorbed ferric ions was applied as an adsorbent. In this study, the adsorption behavior of Se to the adsorbent was examined by both batch and column methods. The batch experiment confirmed that selenite ions (Se(IV)) are effectively adsorbed but selenate ions (Se(VI)) are hardly adsorbed. To elucidate the adsorption mechanism, the Fe in the adsorbent and the Fe in the adsorbent after the adsorption of Se(IV) were characterized by Fe K-edge X-ray absorption spectroscopy and 57Fe Mӧssbauer spectroscopy. The analytical result of Se K-edge EXAFS spectra for the Se(IV) adsorbed on the adsorbent suggests that Se(IV) are adsorbed specifically to the adsorbent through the formation of Fe-O-Se bonds. The breakthrough curve obtained by the column experiment showed that Se(IV) in 3 tons of synthetic solution containing 0.1 ppm Se can be efficiently removed using a column in which 12.8 g (10.4 cm3) of the adsorbent was packed.

Interaction of Au(III) and Pt(IV) complex ions with Fe(II) ions as a scavenging and a reducing agent: a basic study on the recovery of Au and Pt by a chemical method.

In order to develop a chemical technique for the recovery of gold (Au) and platinum (Pt) in the metallic state from spent catalysts, e.g., catalysts for environmental protection and automobile and petroleum catalysts, the coprecipitation behaviors of Au(III) and Pt(IV) complex ions with Fe(OH)(2) as a scavenging and reducing agent were investigated. The Au(III) complex ions were found to be stoichiometrically and rapidly reduced to metallic Au due to electron transfer in acidic aqueous solution prior to coprecipitation with Fe(OH)(2). Conversely, Pt(IV) complex ions were reduced only after coprecipitation with Fe(OH)(2) due to electron transfer through a Pt(IV)-O-Fe(II) bond on the solid Fe(OH)(2). Using this chemical technique, Au and Pt can be selectively and effectively recovered in the metallic state.