Re-partitioning of Cu and Zn isotopes by modified protein expression

Cu and Zn have naturally occurring non radioactive isotopes, and their isotopic systematics in a biological context are poorly understood. In this study we used double focussing mass spectroscopy to determine the ratios for these isotopes for the first time in mouse brain. The Cu and Zn isotope ratios for four strains of wild-type mice showed no significant difference (δ65Cu -0.12 to -0.78 permil; δ66Zn -0.23 to -0.48 permil). We also looked at how altering the expression of a single copper binding protein, the prion protein (PrP), alters the isotope ratios. Both knockout and overexpression of PrP had no significant effect on the ratio of Cu isotopes. Mice brains expressing mutant PrP lacking the known metal binding domain have δ65Cu isotope values of on average 0.57 permil higher than wild-type mouse brains. This implies that loss of the copper binding domain of PrP increases the level of 65Cu in the brain. δ66Zn isotope values of the transgenic mouse brains are enriched for 66Zn to the wild-type mouse brains. Here we show for the first time that the expression of a single protein can alter the partitioning of metal isotopes in mouse brains. The results imply that the expression of the prion protein can alter cellular Cu isotope content

Osmium isotope systematics of the Proterozoic and Phanerozoic ophiolitic chromitites : in situ ion probe analysis of primary Os-rich PGM

Author Posting. © Elsevier B.V., 2006. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Earth and Planetary Science Letters 245 (2006): 777-791, doi:10.1016/j.epsl.2006.03.021.In-situ 187Os/188Os ratios are determined on Os-rich platinum-group minerals in podiform chromitites both in the Proterozoic ophiolite, Eastern Desert, Egypt, and in the Phanerozoic Oman ophiolite. Because they have very low Re/Os, these primary minerals reflect the initial 187Os/188Os ratios of their parental magmas. The platinum-group minerals (PGM) in the central Eastern Desert chromitites exhibit sub-chondritic to chondritic 187Os/188Os ratios, 0.1226 on average, which is lower than the primitive upper mantle evolution trend of a comparable age. Those of the southern Eastern Desert chromitites have more radiogenic Os, with supra-chondritic 187Os/188Os ratio of about 0.1293 on average, which could be due to crustal contamination. The three chromitite types in the northern part of the Oman ophiolite are almost indistinguishable in terms of their 187Os/188Os ratios; they have overlapping values ranging from sub-chondritic to supra-chondritic ratios. The PGE-rich, mantle chromitite samples have a wide range of 187Os/188Os ratio from 0.1230 up to 0.1376, with an average of 0.1299. The values of the PGE-poor mantle chromitites overlap in their 187Os/188Os ratios with PGE-rich chromites, but are less variable and have a significantly higher average ratio. The Moho transition zone (MTZ) chromitites are highly variable in the 187Os/188Os ratio, ranging from 0.1208 up to 0.1459. The wide range of 187Os/188Os ratios, from 0.1192 to 0.1459, in platinum-group minerals in Egyptian and Oman ophiolites can be attributed to the diversity of origin of their podiform chromitites. The Os-isotope data combined with spinel chemistry indicate that the way involved in podiform chromitite formation was not substantially different between the Proterozoic ophiolite of Egypt and the Phanerozoic ophiolite in northern Oman. The Os-isotope compositions of the mantle chromitites in the Proterozoic ophiolite of Egypt clearly suggest crustal contamination. The heterogeneity of 187Os/188Os ratios combined with the spinel chemistry and high PGE contents of the PGE-rich chromitite in the Oman ophiolite may give reliable evidence for high degree partial melting at a supra-subduction zone setting. Crustal contamination from the subducted slab, and assimilation of previously altered, lower crustal gabbro, may have contributed to the high Cr# spinel and radiogenic Os characteristics in chromitite formed in the mantle section and along the Moho transition zone, respectively.Kelemen and Hanghøj were supported in this project by US National Science Foundation grants OCE-9819666 and OCE-0118572

Platinum-group elements, S, Se and Cu in highly depleted abyssal peridotites from the Mid-Atlantic Ocean Ridge (ODP Hole 1274A): Influence of hydrothermal and magmatic processes

Highly depleted harzburgites and dunites were recovered from ODP Hole 1274A, near the intersection between the Mid-Atlantic Ocean Ridge and the 15°20′N Fracture Zone. In addition to high degrees of partial melting, these peridotites underwent multiple episodes of melt-rock reaction and intense serpentinization and seawater alteration close to the seafloor. Low concentrations of Se, Cu and platinum-group elements (PGE) in harzburgites drilled at around 35-85 m below seafloor are consistent with the consumption of mantle sulfides after high degrees (>15-20 %) of partial melting and redistribution of chalcophile and siderophile elements into PGE-rich residual microphases. Higher concentrations of Cu, Se, Ru, Rh and Pd in harzburgites from the uppermost and lowest cores testify to late reaction with a sulfide melt. Dunites were formed by percolation of silica- and sulfur-undersaturated melts into low-Se harzburgites. Platinum-group and chalcophile elements were not mobilized during dunite formation and mostly preserve the signature of precursor harzburgites, except for higher Ru and lower Pt contents caused by precipitation and removal of platinum-group minerals. During serpentinization at low temperature (<250 °C) and reducing conditions, mantle sulfides experienced desulfurization to S-poor sulfides (mainly heazlewoodite) and awaruite. Contrary to Se and Cu, sulfur does not record the magmatic evolution of peridotites but was mostly added in hydrothermal sulfides and sulfate from seawater. Platinum-group elements were unaffected by post-magmatic low-temperature processes, except Pt and Pd that may have been slightly remobilized during oxidative seawater alteration