Hexavalent chromium (Cr6+) is a toxic carcinogenic pollutant that might be released by the mining and processing of ultramafic rocks and nickel laterites and which requires permanent removal from the contaminated biosphere. Ultramafic material can also serve as a feedstock for the sequestration of CO2 resulting from the growth of new minerals, raising the intriguing proposition of integrated sequestration of both pollutants, CO2 and chromium, into magnesium carbonates. Such a synergistic process downstream of ore recovery and mineral processing could be an elegant proposition for more sustainable utilisation and management of the Earth's resources. We have therefore carried out an experimental and microanalytical study to investigate potentially suitable carbonate minerals. Uptake of chromium in carbonate phases was determined, followed by identification of the crystalline phases and characterisation of the local structural environment around the incorporated chromium centres. The results suggest that neither nesquehonite nor hydromagnesite have the structural capacity to incorporate Cr6+ or Cr3+ significantly at room temperature. We therefore propose that further research into this technology should focus on laboratory assessments of other phases, such as layered double hyroxides, that have a natural structural capacity to uptake both chromium and CO2.

The process of transforming hydromagnesite to magnesite is analysed in the context of the theory of solvent-mediated transformations. A series of experiments at 120, 150 and 180ºC with different heating times was designed to determine, by powder X-ray diffraction, the amount of magnesite generated as a function of time. The aqueous-phase composition was monitored by inductively coupled plasma-mass spectrometry and carbonate alkalimetry. From the analytical data, the evolution of saturation indexes with respect to both phases was determined using the geochemical code PHREEQC. Finally, two different methods were applied to obtain the activation energy of the process and a TTT (Temperature- Transformation-Time) graph was constructed to define suitable conditions in which to obtain magnesite.

Screes on high serpentinite sea cliffs in Shetland have been internally cemented by deposits of brucite, hydromagnesite and aragonite since the last glaciation. These minerals have been deposited from solutions originating as rain (often contaminated with salt spray), which fell on the serpentinite screes and dissolved Mg and minor amounts of Ca from the more finely divided and powdery scree components. As the solutions filtered down through the screes they deposited cements in the form of spherulitic layers of brucite and hydromagnesite with minor amounts of aragonite. At sea level the Mg-rich solutions mingled with sea water impregnating the scree and there cementation within the scree took place by the crystallization of plush-type layers of aragonite on the serpentinite fragments.

Natural hydromagnesite (Mg5(CO3)4(OH)2·4H2O) dissolution and precipitation experiments were performed in closed-system reactors as a function of temperature from 22.5 to 75ºC and at 8.6 < pH < 10.7. The equilibrium constants for the reaction Mg5(CO3)4(OH)2·4H2O + 6H+ = 5Mg2+ + 4HCO3– + 6H2O were determined by bracketing the final fluid compositions obtained from the dissolution and precipitation experiments. The resulting constants were found to be 1033.7±0.9, 1030.5±0.5 and 1026.5±0.5 at 22.5, 50 and 75ºC, respectively. Whereas dissolution rates were too fast to be determined from the experiments, precipitation rates were slower and quantified. The resulting BET surface areanormalized hydromagnesite precipitation rates increase by a factor of ~2 with pH decreasing from 10.7 to 8.6. Measured rates are approximately two orders of magnitude faster than corresponding forsterite dissolution rates, suggesting that the overall rates of the low-temperature carbonation of olivine are controlled by the relatively sluggish dissolution of the magnesium silicate mineral.

Around the world large quantities of sludge wastes derived from nuclear energy production are currently kept in storage facilities. In the UK, the British government has marked sludge removal as a top priority as these facilities are nearing the end of their operational lifetimes. Therefore chemical understanding of uranium uptake in Mg-rich sludge is critical for successful remediation strategies. Previous studies have explored uranium uptake by the calcium carbonate minerals, calcite and aragonite, under conditions applicable to both natural and anthropogenically perturbed systems. However, studies of the uptake by Mg-rich minerals such as brucite [Mg(OH)2], nesquehonite [MgCO3·3H2O] and hydromagnesite [Mg5(CO3)4 (OH)2·4H2O], have not been previously conducted. Such experiments will improve our understanding of the mobility of uranium and other actinides in natural lithologies as well as provide key information applicable to nuclear waste repository strategies involving Mg-rich phases. Experiments with mineral powders were used to determine the partition coefficients (Kd) and coordination of UO22+ during adsorption and co-precipitation with brucite, nesquehonite and hydromagnesite. The Kd values for the selected Mg-rich minerals were comparable or greater than those published for calcium carbonates. Extended X-ray absorption fine structure analysis results showed that the structure of the uranyl-triscarbonato [UO2(CO3)3] species was maintained after surface attachment and that uptake of uranyl ions took place mainly via mineral surface reactions.

A regional chemical boundary termed the ‘salt line’, in the Vestfold Hills of East Antarctica, has been investigated using X-ray diffraction and electron probe analyses of surficial salts, and conductivity of surficial sediments. West of the salt line, halite and thenardite are abundant. These salts are derived from dispersal of marine aerosols, saturation of sediment by seawater during postglacial marine transgression, and glacial dispersal of salt-saturated fjord bottom sediments. East of the salt line, subglacial calcium carbonates and salts formed by chemical weathering of their substrates occur. Chemically and morphologically diverse minerals form the weathering products. They include two minerals not found previously in Antarctica, dypingite and hydromagnesite, and the first confirmed occurrence of brushite.