Mantle Pb paradoxes: the sulfide solution

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. in Earth Planet Sci Lett 79:33–45, 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.     

The influence of water on melting of mantle peridotite

This experimental study examines the effects of variable concentrations of dissolved H₂O on the compositions of silicate melts and their coexisting mineral assemblage of olivine + orthopyroxene ± clinopyroxene ± spinel ± garnet. Experiments were performed at pressures of 1.2 to 2.0 GPa and temperatures of 1100 to 1345 °C, with up to ∼12 wt% H₂O dissolved in the liquid. The effects of increasing the concentration of dissolved H₂O on the major element compositions of melts in equilibrium with a spinel lherzolite mineral assemblage are to decrease the concentrations of SiO₂, FeO, MgO, and CaO. The concentration of Al₂O₃ is unaffected. The lower SiO₂ contents of the hydrous melts result from an increase in the activity coefficient for SiO₂ with increasing dissolved H₂O. The lower concentrations of FeO and MgO result from the lower temperatures at which H₂O-bearing melts coexist with mantle minerals as compared to anhydrous melts. These compositional changes produce an elevated SiO₂/(MgO + FeO) ratio in hydrous peridotite partial melts, making them relatively SiO₂ rich when compared to anhydrous melts on a volatile-free basis. Hydrous peridotite melting reactions are affected primarily by the lowered mantle solidus. Temperature-induced compositional variations in coexisting pyroxenes lower the proportion of clinopyroxene entering the melt relative to orthopyroxene. Isobaric batch melting calculations indicate that fluid-undersaturated peridotite melting is characterized by significantly lower melt productivity than anhydrous peridotite melting, and that the peridotite melting process in subduction zones is strongly influenced by the composition of the H₂O-rich component introduced into the mantle wedge from the subducted slab. Received: 7 April 1997 / Accepted: 9 January 1998     

H<Subscript>2</Subscript>O solubility in basalt at upper mantle conditions

This study presents a new experimental approach for determining H₂O solubility in basaltic melt at upper mantle conditions. Traditional solubility experiments are limited to pressures of ~600 MPa or less because it is difficult to reliably quench silicate melts containing greater than ~10 wt% dissolved H₂O. To overcome this limitation, our approach relies on the use of secondary ion mass spectrometry to measure the concentration of H dissolved in olivine and on using the measured H in olivine as a proxy for the concentration of H₂O in the co-existing basaltic melt. The solubility of H₂O in the melt is determined by performing a series of experiments at a single pressure and temperature with increasing amounts of liquid H₂O added to each charge. The point at which the concentration of H in the olivine first becomes independent of the amount of initial H₂O content of the charge (added + adsorbed H₂O) indicates its solubility in the melt. Experiments were conducted by packing basalt powder into a capsule fabricated from San Carlos olivine, which was then pressure-sealed inside a Ni outer capsule. Our experimental results indicate that at 1000 MPa and 1200 °C, the solubility of H₂O in basaltic melt is 20.6 ± 0.9 wt% (2 × standard deviation). This concentration is considerably higher than predicted by most solubility models but defines a linear relationship between H₂O fugacity and the square of molar H₂O solubility when combined with solubility data from lower pressure experiments. Further, our solubility determination agrees with melting point depression determined experimentally by Grove et al. (2006) for the H₂O-saturated peridotite solidus at 1000 MPa. Melting point depression calculations were used to estimate H₂O solubility in basalt along the experimentally determined H₂O-saturated peridotite solidus. The results suggest that a linear relationship between H₂O fugacity and the square of molar solubility exists up to ~1300 MPa, where there is an inflection point and solubility begins to increase less strongly with increasing H₂O fugacity.     

Partitioning of U and Th during garnet pyroxenite partial melting: Constraints on the source of alkaline ocean island basalts

Uranium series disequilibria in ocean island basalts (OIB) provide evidence for the presence of garnet in their source region. It has been suggested that enriched OIB signatures derive from mantle lithologies other than peridotite, such as eclogite or pyroxenite, and, in particular, that silica-poor garnet pyroxenite is the source lithology for alkali basalts. To test the ability of such a source to produce the U–Th disequilibria observed in alkali OIB, we determined experimentally clinopyroxene-melt and garnet-melt partition coefficients for a suite of trace elements, including U and Th, at 2.5 GPa and 1420–1450 °C. The starting composition for the experiments was a 21% partial melt of a silica-poor garnet pyroxenite. Experimentally determined clinopyroxene-melt partition coefficients range from 0.0083 ± 0.0006 to 0.020 ± 0.002 for Th and from 0.0094 ± 0.0006 to 0.024 ±0.002 for U, and garnet-melt partition coefficients are 0.0032 ± 0.0004 for Th and 0.013 ± 0.002 for U. Comparison of our experimental results with partition coefficients from previous experimental studies shows that the relative compatibilities of U and Th in both garnet and clinopyroxene are different for different mineral compositions, leading to varying degrees of U/Th fractionation with changing lithology. For a given melting rate and extent of partial melting, mafic lithologies tend to produce larger ²³⁰Th excesses than peridotite. However, this effect is minimized by the greater overall extents of melting experienced by eclogites and pyroxenites relative to peridotite. Results from chromatographic, batch, and fractional melting calculations with binary mixing between partial melts of pyroxenite and peridotite, carried out using our new partitioning data for the pyroxenite component and taking into account variable productivities and different solidus depths for the two lithologies, suggest that OIB are not the product of progressive melting of a source containing a fixed quantity of garnet pyroxenite. Melting a peridotite with enriched signatures, and mixing those melts with melts of a depleted, “normal” peridotite, is an alternative explanation for the trends seen in Hawaiian, Azores and Samoan lavas.     

Palynological dating (Arenig) of the sedimentary sequence overlying the Ishkarwaz Granite (upper Yarkhun valley, Chitral, Pakistan)

A sedimentary sequence overlying a granite pluton near Ishkarwaz (upper Yarkhun valley, Chitral, Pakistan; Karakorum Microplate) contains abundant, but poorly preserved, acritarchs probably referable to the late early Arenig-early late Arenig interval. The palynological assemblages of Karakorum show a marked similarity to the cold water Peri-Gondwana assemblages; i.e. to those of Li Jun's Arbusculidium-Coryphidium-Striatotheca 'Mediterranean' Bioprovince. Biogeographical and geological comparisons suggest that, before the accretion of Cimmerian microplates to the Eurasian continent, the Karakorum Microplate was located along the northern margin of Gondwana in a latitude intermediate between the Mediterranean region and South China (Yangtze Platform).     

Aftershock collapse fragility curves for non‐ductile RC buildings: a scenario‐based assessment

Recent studies have addressed the computation of fragility curves for mainshock (MS)‐damaged buildings. However, aftershock (AS) fragilities are generally conditioned on a range of potential post‐MS damage states that are simulated via static or dynamic analyses performed on an intact building. Moreover, there are very few cases where the behavior of non‐ductile reinforced concrete buildings is analyzed. This paper presents an evaluation of AS collapse fragility conditioned on various return periods of MSs, allowing for the rapid assessment of post‐earthquake safety variations based solely on the intensity of the damaging earthquake event. A refined multi‐degree‐of‐freedom model of a seven‐storey non‐ductile building, which includes brittle failure simulations and the evaluation of a system level collapse, is adopted. Aftershock fragilities are obtained by performing an incremental dynamic analysis for a number of MS–AS ground motion sequences and a variety of MS intensities. The AS fragilities show that the probability of collapse significantly increases for higher return periods for the MS. However, this result is mainly ascribable to collapses occurred during MSs. When collapse cases that occur during a MS are not considered in the assessment of AS collapse probability, a smaller shift in the fragility curves is observed as the MS intensity increases. This result is justified considering the type of model and collapse modes introduced, which strongly depend on the brittle behavior of columns failing in shear or due to axial loads. The analysis of damage that is due to MSs when varying the return period confirms this observation. Copyright © 2017 John Wiley & Sons, Ltd.     

A hydrological onset and withdrawal index for the West African monsoon

We have developed a hydrological prognostic index, HOWI (hydrological onset and withdrawal index), for the onset and the withdrawal of the West African monsoon (WAM), based on the vertically integrated moisture transport (VIMT). The regions of West Africa with the same climatological onset (withdrawal) date are characterized by a large change of the VIMT around the onset (withdrawal) date. By analyzing the variability of the VIMT, we determine the extension and the geographical position of these regions, which we take sufficiently large to filter out the fast weather variability. It turns out that the regions with the same climatological onset date do not usually coincide with the regions with the same climatological withdrawal date, the areas with the maximum variability of the VIMT during the onset phase are usually a fraction of the area where the variability of the VIMT is large during the withdrawal phase. This is because the onset has active phases and pauses in time and it is fragmented in space, while the withdrawal is rather rapid and almost uniformly distributed through the entire monsoonal region. When the monsoon moves inland, the rainfall slightly trails behind the arrival of the moisture, and, when the monsoon moves back towards the gulf of Guinea, the moisture slightly precedes the retreating rainfall. In a specific region, we say that the onset (withdrawal) of the monsoon occurs when the moisture reaches (declines to) half of its climatological value. The level of the moisture relatively to its climatological value is evaluated through the HOWI, i.e., at the onset (withdrawal) the HOWI is zero with a positive (negative) tendency. We find that the dates of the onset of the monsoon determined using the HOWI, computed in the region where the VIMT has its maximum variability during the onset phase of WAM, well agree with the dates of the sudden transition of the ITCZ (Intertropical Convergence Zone) from 5 to 10°N. The uncertainty on the onset date is of the order of 2 pentads, which is comparable to the uncertainty on the date of the sudden transition of the ITCZ. We, then, use the HOWI to determine the onset and the withdrawal dates of the monsoon for the period 1979–2004, finding that an early (late) onset usually preludes to a longer (shorter) monsoonal season with more (less) cumulated rain. Finally, we compare the onset dates in the Sahelian region, for the period 1979–2004, with those determined using methods based on rainfall.     

The Variscan orogeny in Chios (Greece): Carboniferous accretion along a Palaeotethyan active margin

ABSTRACT New stratigraphic and structural data on the turbiditic succession of Chios (Volissos turbidites) suggest that this clastic wedge formed during the Early Carboniferous. These turbidites, fed long-distance by erosion of the Variscan orogen, were most likely deposited in a Palaeotethyan remnant-ocean basin. They were severely deformed and structurally thickened at anchi-metamorphic conditions before the close of the Palaeozoic. Both contractional and layer-parallel extensional structures, high strain rates, and broken-in-matrix fabrics along thick shear zones may suggest deformation at the toe of an accretionary wedge. Stratigraphic, petrographic and structural data indicate that Chios represents the westernmost part of Palaeotethys which escaped the Carboniferous collision between Gondwana and Laurasia, but received great volumes of terrigenous sediments from the Variscan belt, favouring the growth of a large accretionary prism.