Influence of speciation distribution and particle size on heavy metal leaching from MSWI fly ash.

Fly ash from municipal solid waste incineration (MSWI-FA) contains leachable heavy metals. In the present study the correlations between heavy metal content, particle size, speciation distribution with respect to water leaching are investigated, using a combination of solid-state bulk analytical techniques, leaching treatments, sequential extractions and thermodynamic geochemical modelling. Among the analyzed heavy metals, Zn and Pb are the most abundant in any grain size class, followed by Cu, Cr, Cd and Ni, with concentration that tends to increase with a decrease of the grain size. The phase composition is constituted of salt (halite, sylvite, anhydrite and syngenite), which provide the main minerals regardless of the particle size class; calcite, quartz and gehlenite occur in comparatively lower amounts, while 50% wt is composed of amorphous fraction. Heavy metal leaching is strongly correlated to speciation distribution, and in particular to the fraction (F1) associated with salt, carbonate and weak surface sorption. Leaching from speciation due to surface complexation on Al/Fe (hydr)oxide becomes relevant at acidic regime. Particle size and heavy metal content, in turn, moderately correlate with leaching. The F1-speciation as a function of particle size does not exhibit a definite trend shared by all heavy metals under investigation. This suggests that i) differences in speciation distribution, rather than bare heavy metal content or particle size, govern leaching from MSWI-FA; ii) F1 can be regarded as a marker of the potential heavy metal leaching; iii) a comparatively modest efficiency in managing MSWI-FA is expected from grain size separation strategies.

Phlogopite-pargasite coexistence in an oxygen reduced spinel-peridotite ambient.

The occurrence of phlogopite and amphibole in mantle ultramafic rocks is widely accepted as the modal effect of metasomatism in the upper mantle. However, their simultaneous formation during metasomatic events and the related sub-solidus equilibrium with the peridotite has not been extensively studied. In this work, we discuss the geochemical conditions at which the pargasite-phlogopite assemblage becomes stable, through the investigation of two mantle xenoliths from Mount Leura (Victoria State, Australia) that bear phlogopite and the phlogopite + amphibole (pargasite) pair disseminated in a harzburgite matrix. Combining a mineralogical study and thermodynamic modelling, we predict that the P-T locus of the equilibrium reaction pargasite + forsterite = Na-phlogopite + 2 diopside + spinel, over the range 1.3-3.0 GPa/540-1500 K, yields a negative Clapeyron slope of -0.003 GPa K-1 (on average). The intersection of the P-T locus of supposed equilibrium with the new mantle geotherm calculated in this work allowed us to state that the Mount Leura xenoliths achieved equilibrium at 2.3 GPa /1190 K, that represents a plausible depth of ~ 70 km. Metasomatic K-Na-OH rich fluids stabilize hydrous phases. This has been modelled by the following equilibrium equation: 2 (K,Na)-phlogopite + forsterite = 7/2 enstatite + spinel + fluid (components: Na2O,K2O,H2O). Using quantum-mechanics, semi-empirical potentials, lattice dynamics and observed thermo-elastic data, we concluded that K-Na-OH rich fluids are not effective metasomatic agents to convey alkali species across the upper mantle, as the fluids are highly reactive with the ultramafic system and favour the rapid formation of phlogopite and amphibole. In addition, oxygen fugacity estimates of the Mount Leura mantle xenoliths [Δ(FMQ) = -1.97 ± 0.35; -1.83 ± 0.36] indicate a more reducing mantle environment than what is expected from the occurrence of phlogopite and amphibole in spinel-bearing peridotites. This is accounted for by our model of full molecular dissociation of the fluid and incorporation of the O-H-K-Na species into (OH)-K-Na-bearing mineral phases (phlogopite and amphibole), that leads to a peridotite metasomatized ambient characterized by reduced oxygen fugacity.