55 research outputs found
Behavior and Impact of Zirconium in the Soil–Plant System: Plant Uptake and Phytotoxicity
Because of the large number of sites they pollute, toxic metals that contaminate terrestrial ecosystems are increasingly of environmental and sanitary concern (Uzu et al. 2010, 2011; Shahid et al. 2011a, b, 2012a). Among such metals is zirconium (Zr), which has the atomic number 40 and is a transition metal that resembles titanium in physical and chemical properties (Zaccone et al. 2008). Zr is widely used in many chemical industry processes and in nuclear reactors (Sandoval et al. 2011; Kamal et al. 2011), owing to its useful properties like hardness, corrosion-resistance and permeable to neutrons (Mushtaq 2012). Hence, the recent increased use of Zr by industry, and the occurrence of the Chernobyl and Fukashima catastrophe have enhanced environmental levels in soil and waters (Yirchenko and Agapkina 1993; Mosulishvili et al. 1994 ; Kruglov et al. 1996)
Mantle Pb paradoxes : the sulfide solution
Author Posting. © Springer, 2006. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Contributions to Mineralogy and Petrology 152 (2006): 295-308, doi:10.1007/s00410-006-0108-1.There is growing evidence that the budget of Pb in mantle peridotites is largely
contained in sulfide, and that Pb partitions strongly into sulfide relative to silicate melt. In
addition, there is evidence to suggest that diffusion rates of Pb in sulfide (solid or melt)
are very fast. Given the possibility that sulfide melt ‘wets’ sub-solidus mantle silicates,
and has very low viscosity, the implications for Pb behavior during mantle melting are
profound. There is only sparse experimental data relating to Pb partitioning between
sulfide and silicate, and no data on Pb diffusion rates in sulfides. A full understanding of
Pb behavior in sulfide may hold the key to several long-standing and important Pb
paradoxes and enigmas. The classical Pb isotope paradox arises from the fact that all
known mantle reservoirs lie to the right of the Geochron, with no consensus as to the
identity of the “balancing” reservoir. We propose that long-term segregation of sulfide
(containing Pb) to the core may resolve this paradox. Another Pb paradox arises from the fact that the Ce/Pb ratio of both OIB and MORB
is greater than bulk earth, and constant at a value of 25. The constancy of this “canonical
ratio” implies similar partition coefficients for Ce and Pb during magmatic processes
(Hofmann et al. 1986), whereas most experimental studies show that Pb is more
incompatible in silicates than Ce. Retention of Pb in residual mantle sulfide during
melting has the potential to bring the bulk partitioning of Ce into equality with Pb if the
sulfide melt/silicate melt partition coefficient for Pb has a value of ~ 14. Modeling shows
that the Ce/Pb (or Nd/Pb) of such melts will still accurately reflect that of the source, thus
enforcing the paradox that OIB and MORB mantles have markedly higher Ce/Pb (and
Nd/Pb) than the bulk silicate earth. This implies large deficiencies of Pb in the mantle
sources for these basalts. Sulfide may play other important roles during magmagenesis:
1). advective/diffusive sulfide networks may form potent metasomatic agents (in both
introducing and obliterating Pb isotopic heterogeneities in the mantle); 2). silicate melt
networks may easily exchange Pb with ambient mantle sulfides (by diffusion or
assimilation), thus ‘sampling’ Pb in isotopically heterogeneous mantle domains
differently from the silicate-controlled isotope tracer systems (Sr, Nd, Hf), with an
apparent ‘de-coupling’ of these systems.Our intemperance
should not be blamed on the support we gratefully acknowledge from NSF: EAR-
0125917 to SRH and OCE-0118198 to GAG
Experimental study of uraninite solubility in aqueous HCl solutions at 500°C and 1 kbar
Uraninite solubility in 0.001–2.0 m HCl solutions was experimentally studied at 500°C, 1000 bar, and hydrogen fugacity corresponding to the Ni/NiO buffer. It was shown that the following U(IV) species dominate in the aqueous solution: U(OH)40, U(OH)2Cl20, and UOH Cl30 Using the results of uraninite solubility measurement, the Gibbs free energies of U(IV) species at 500°C and 1000 bar were calculated (kJ/mol): −9865.55 for UO2(aq), −1374.57 for U(OH)2 Cl20, and −1265.49 for UOH Cl30, and the equilibrium constants of uraninite dissolution in water and aqueous HCl solutions were estimated: UO2(cr) = UO2(aq), pK0 = 6.64; UO2(cr) + 2HCl0 = U(OH)2 Cl20, pK2 = 3.56; and UO2(cr) + 3HCl0 = UOHcl30 + H2O, pK3 = 3.05. The value pK1 ≈ 5.0 was obtained as a first approximation for the equilibrium UO2(cr) + H2O + HCl0 = U(OH)3Cl0. The constant of the reaction UO2(cr) + 4HCl0 = UCl40 + 2H2O (pK4 = 7.02) was calculated taking into account the ionization constants of U Cl40 and U(OH)40, obtained by extrapolation from 25 to 500°C at 1000 bar using the BR model. Intense dissolution and redeposition of gold (material of experimental capsules) was observed in our experiments. The analysis and modeling of this phenomenon suggested that the UO2 + x/UO2 redox pair oxidized Au(cr) to Au+(aq), which was then reduced under the influence of stronger reducers
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