Colloidal transport and flocculation are the cause of the hyperenrichment of gold in nature

Aqueous complexation has long been considered the only viable means of transporting gold to depositional sites in hydrothermal ore-forming systems. A major weakness of this hypothesis is that it cannot readily explain the formation of ultrahigh-grade gold veins. This is a consequence of the relatively low gold concentrations typical of ore fluids (tens of parts per billion [ppb]) and the fact that these “bonanza” veins can contain weight-percent levels of gold in some epithermal and orogenic deposits. Here, we present direct evidence for a hypothesis that could explain these veins, namely, the transport of the gold as colloidal particles and their flocculation in nanoscale calcite veinlets. These gold-bearing nanoveinlets bear a remarkable resemblance to centimeter-scale ore veins in many hydrothermal gold deposits and give unique insight into the scale invariability of colloidal flocculation in forming hyperenriched gold deposits. Using this evidence, we propose a model for the development of bonanza gold veins in high-grade deposits. We argue that gold transport in these systems is largely mechanical and is the result of exceptionally high degrees of supersaturation that preclude precipitation of gold crystals and instead lead to the formation of colloidal particles, which flocculate and form much larger masses. These flocculated masses aggregate locally, where they are seismically pumped into fractures to locally form veins composed largely of gold. This model explains how bonanza veins may form from fluids containing ppb concentrations of gold and does not require prior encapsulation of colloidal gold particles in silica gel, as proposed by previous studies.

Global(VI)integrating coupled THCinto PA model

The bentonite buffer long-term integrity is of significant interest in the performance assessment (PA) of nuclear waste disposal. This study aims at understanding how the initial geochemical parameters affect long-term chemical properties within the buffer, which will subsequently affect the transport. Using coupled thermal-hydrological-chemical (THC) models for migration of U(VI) in a generic repository, we performed a global sensitivity analysis (GSA) to identify the influence of each parameter on the temporal evolution of a spatially averaged distribution coefficient for the entire buffer. Such an analysis can be used in a repository-scale PA. In this work, we used the TOUGHREACT software to model coupled THC processes in a generic clay repository with bentonite buffer. In this model, U(VI) is released from a canister via schoepite dissolution, which is assumed to occur 1000 years after closure. U(VI) migrates through the bentonite buffer affected by two-site protolysis non-electrostatic surface complexation and cation exchange. GSA results showed that adsorption density on smectite, pH, volume fractions of smectite, calcite, Ca2+ aqueous concentration all play a significant role in U(VI) transport, since roughly 80% of adsorbed U(VI) is absorbed by smectite, and Ca2+ affects the aqueous complexation with U(VI). This work demonstrates the complex process models potential usefulness that can be transferred to the PA model. It also provides information needed to proceed with the development of a reduced-order model, which has the potential to optimize repository designs, site characterization, performance confirmation.

Bis-(1,2,4-triazin-3-yl) ligand structure driven selectivity reversal between Am3+ and Cm3+: Solvent extraction and DFT studies

Selectivity between Am3+ and Cm3+ was investigated after their aqueous complexation with three structurally tailored hydrophilic bis-(1,2,4-triazin-3-yl) ligands followed by their extraction with N,N,N’N’-tetraoctyl diglycolamide (TODGA) dissolved in ionic liquid...

Advancing understanding of actinide(iii) (Ac, Am, Cm) aqueous complexation chemistry

Actinide complexation from aqueous acetic acid/acetate buffered solutions is described. The number of water ligands was directly correlated with the acetate concentration and characterized by X-ray absorption and optical spectroscopy.

Luminescence spectroscopic investigations of europium complexes formed in the kaolinite-humic acid/citric acid systems

In the present study, the nature of Eu(III) complexes (Eu(III) was used as a surrogate for Am(III)) formed in kaolinite–humic acid (HA)/citric acid (CA) system was investigated by luminescence spectroscopy. In addition to the ternary system (kaolinite + Eu + L(CA/HA)), the binary system (Eu-L) was also looked at for a better understanding of the complexes formed at the kaolinite surface. The lifetime and emission spectra of Eu-L complexes on the kaolinite surface differ considerably as compared to the same in the aqueous phase. The Eu-HA aqueous complexation shows differences in the excitation spectra with similar decay lifetimes with increasing aqueous HA concentrations. The ligand-to-metal charger transfer (LMCT) in the Eu-HA excitation spectra suggests the complexation of Eu(III) with HA at pH ∼ 4. Although the mode of Eu(III) binding to the kaolinite surface in the presence of CA/HA was the same i.e. metal-bridged ternary complex formation, the local surroundings around the sorbed Eu(III) differ in the two cases. The loading of HA in the Eu-HA-kaolinite system does not have a large effect on the local structure around the sorbed Eu(III) ion, but enhances the percentage of Eu(III) uptake onto the kaolinite surface. The number of H2O molecules in the primary hydration sphere of sorbed Eu(III) differs in the Eu-HA-kaolinite and Eu-CA-kaolinite systems. In addition, Eu(III) assisted precipitation of HA was also seen using a radiometric method.

The interaction of morin and morin-5’-sulfonic acid with lead(II): Study of the 1:1 complex formation process in aqueous solution

This article focuses on the aqueous complexation between two flavonoids (morin and morinsulfonate) and Pb2+ at constant ionic strength I=0.5 M (NaClO4). The determination of stability constants of ML complexes were performed at wide pH range. Two obtained constants are 14.8 ± 0.1 and 15.2 ± 0.1 logarithmic units for morin and morin-5’-sulfonic acid, respectively. For estimating the thermodynamic stability of the complexes studied, the Def2-SV(P)/DFT/PBE0/SMD method has been used. Different computational models were tested to describe the data obtained. The theoretical values of logK reproduce the experimental parameters within reasonable errors.

Spectrophotometric and quantum-chemical study of acid-base and complexing properties of (±)-taxifolin in aqueous solution

This study reports the acid-base properties of taxifolin (Tf) in HCl media and aqueous complexation with Ni(II). The equilibrium processes was investigated using a spectrophotometric technique and

Voltammetry of the aqueous complexation–dissociation coupled to transfer (ACDT) mechanism with charged ligands

The voltammetry of the ACDT mechanism shows different responses depending on whether the ligand species is neutral or charged. Analytical solutions are deduced to calculate the current–potential signal and gain insight into the physicochemical processes behind it.