25 research outputs found
Mantle Pb paradoxes : the sulfide solution
Author Posting. Š 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 âwetsâ 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 âbalancingâ 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 âcanonical
ratioâ 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 âsamplingâ Pb in isotopically heterogeneous mantle domains
differently from the silicate-controlled isotope tracer systems (Sr, Nd, Hf), with an
apparent âde-couplingâ 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
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°20â˛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
Extreme enrichment of Se, Te, PGE and Au in Cu sulfide microdroplets: evidence from LA-ICP-MS analysis of sulfides in the Skaergaard Intrusion, east Greenland
The Platinova Reef, in the Skaergaard Intrusion, east Greenland, is an example of a magmatic CuâPGEâAu sulfide deposit formed in the latter stages of magmatic differentiation. As is characteristic with such deposits, it contains a low volume of sulfide, displays peak metal offsets and is Cu rich but Ni poor. However, even for such deposits, the Platinova Reef contains extremely low volumes of sulfide and the highest Pd and Au tenor sulfides of any magmatic ore deposit. Here, we present the first LA-ICP-MS analyses of sulfide microdroplets from the Platinova Reef, which show that they have the highest Se concentrations (up to 1200 ppm) and lowest S/Se ratios (190â700) of any known magmatic sulfide deposit and have significant Te enrichment. In addition, where sulfide volume increases, there is a change from high Pd-tenor microdroplets trapped in situ to larger, low tenor sulfides. The transition between these two sulfide regimes is marked by sharp peaks in Au, and then Te concentration, followed by a wider peak in Se, which gradually decreases with height. Mineralogical evidence implies that there is no significant post-magmatic hydrothermal S loss and that the metal profiles are essentially a function of magmatic processes. We propose that to generate these extreme precious and semimetal contents, the sulfides must have formed from an anomalously metal-rich package of magma, possibly formed via the dissolution of a previously PGE-enriched sulfide. Other processes such as kinetic diffusion may have also occurred alongside this to produce the ultra-high tenors. The characteristic metal offset pattern observed is largely controlled by partitioning effects, producing offset peaks in the order Pt+Pd>Au>Te>Se>Cu that are entirely consistent with published D values. This study confirms that extreme enrichment in sulfide droplets can occur in closed-system layered intrusions in situ, but this will characteristically form ore deposits that are so low in sulfide that they do not conform to conventional deposit models for CuâNiâPGE sulfides which require very high R factors, and settling of sulfide liquids
Fluxing of mantle carbon as a physical agent for metallogenic fertilization of the crust
Magmatic systems play a crucial role in enriching the crust with volatiles and elements that
reside primarily within the Earthâs mantle, including economically important metals like nickel,
copper and platinum-group elements. However, transport of these metals within silicate
magmas primarily occurs within dense sulfide liquids, which tend to coalesce, settle and not
be efficiently transported in ascending magmas. Here we show textural observations, backed
up with carbon and oxygen isotope data, which indicate an intimate association between
mantle-derived carbonates and sulfides in some mafic-ultramafic magmatic systems
emplaced at the base of the continental crust. We propose that carbon, as a buoyant
supercritical CO2 fluid, might be a covert agent aiding and promoting the physical transport of
sulfides across the mantle-crust transition. This may be a common but cryptic mechanism
that facilitates cycling of volatiles and metals from the mantle to the lower-to-mid continental
crust, which leaves little footprint behind by the time magmas reach the Earthâs surface.NERC Minerals Security of Supply (SOS)
NE/M010848/1Australian Research Council
CE11E0070Consolidated Nickel MinesUniversity of Leiceste