Sulfur and selenium systematics of the subcontinental lithospheric mantle: Inferences from the Massif Central xenolith suite (France)

Selenium has been analyzed in addition to S in 58 spinel peridotite xenoliths collected in Cenozoic alkali basalts from the Massif Central (France). The S concentration range now available for this suite, calculated from 123 samples, is the largest ever reported for alkali basalt-hosted xenoliths (<3-592 ppm). Likewise, the Se concentrations range between 0.2 and 67 ppb. No partial melting signature can be identified from the S and Se systematic. Half of the analyzed xenoliths have lost S during supergene weathering. By contrast, neither surficial alteration, nor loss of chalcophile elements during eruption can explain the regional-scale variations of S and Se concentrations. A first group of lherzolite xenoliths sampled in Southern Massif Central, from volcanic centers older and spatially unrelated to the Massif Central plume that triggered the Cenozoic volcanism, contains between 20 and 250 ppm S (with occasional S concentrations up to 592 ppm) and 12-67 ppb Se. It is clear that the highest S values, originally interpreted as representing S abundances in the primitive mantle, were in fact enriched by metasomatism. Highly variable S and Se contents (<5-360 ppm; 9-52 ppb) have also been observed in peridotite xenoliths collected in the Northern Massif Central, from volcanic centers mostly older than the plume. Like Group I xenoliths, these Group II xenoliths were strongly metasomatized by volatile-rich carbonated/silicated melts which precipitated Cu-rich sulfides. A third group of xenoliths from Plio-Quaternary basalts spatially related to the Massif Central Plume are uniformly poor in S (10-60 ppm) and Se (9-29 ppb). In this Group III, poikiloblastic textured xenoliths have lost most of their S and Se budget by peridotite-melt interactions at high melt/rock ratios. Taken as a whole, the Massif Central xenolith suite provides further evidence for strong heterogeneities in the S and Se budget of the sub-continental lithospheric mantle. However, the few LREE-depleted fertile lherzolites that escaped strong metasomatic alterations suggest a S- and Se-depleted primitive mantle reservoir compared to currently accepted primitive mantle estimates.     

Boninites as windows into trace element mobility in subduction zones

Boninites are subduction-related rocks originating from re-melting of highly depleted mantle sources left after extraction of tholeiitic melts. Due to their depleted nature, the incompatible trace element inventory of boninites is virtually entirely inherited from slab components without a significant contribution from the refractory mantle wedge. Thus, boninites constitute an excellent window into processes controlling trace element mobilization at the slab-mantle wedge interface. In order to constrain the behaviour of trace elements in subduction zones with a special emphasis on high field strength elements, we analyzed low-Ca boninites and associated tholeiitic basalts from Cape Vogel, Papua New Guinea (PNG) and compare them with compositions of high-Ca boninites and associated tholeiitic basalts from Cyprus. High-precision HFSE (Nb, Ta, Zr, Hf, W) concentration data of the boninites and associated tholeiitic basalts were obtained by isotope dilution. Major, trace element, and Sr-Nd-Hf-Pb isotope compositions clearly document a significant contribution of slab-derived melts involved in the petrogenesis of the PNG boninites, whereas only fluid-like subduction components were involved in the petrogenesis of the PNG basalts and the Cyprus suite. Low-Ca boninites from PNG are derived from a more refractory mantle source (∼21% depletion) than the high-Ca boninites from Cyprus (∼11% depletion) and their respective tholeiitic precursors (<10% depletion). In agreement with the more depleted nature of their mantle source, boninites exhibit a significantly stronger overprint by slab components. High-precision HFSE data indicate that, in comparison to LILE, a somewhat lower but measurable mobilization of all investigated HFSE in both slab-derived fluids and melts is evident. Modelling calculations demonstrate that the subduction components dominate the LILE budget and also largely control LREE and HFSE abundances in the boninite sources. Notably, the increasing influence of slab-derived fluids results in a decrease of the negative Nb-Ta anomaly, most likely reflecting a similar mobility of Nb-Ta and LREE at higher pressures near the critical point of fluid-melt miscibility. Ratios of Zr/Hf and Nb/Ta in the melt-like slab components dominating in the sources of the PNG boninites were probably fractionated in equilibrium with garnet-amphibolitic mafic oceanic crust. HFSE ratios in the Cyprus boninites are best explained by dehydration of subducted pelagic sediments in the absence of Ti-rich phases such as rutile. Our results also confirm previous assertions that the mobility of HFSE decreases in the order Sb > W-Mo > Nb-Ta > Zr-Hf. Furthermore, Mo-W systematics may provide a potential novel tracer for the amount, composition and redox state of subducted pelagic sediments that contribute to the geochemical budget of intra-oceanic arc systems.     

Residual platinum-group minerals from highly depleted harzburgites of the Lherz massif (France) and their role in HSE fractionation of the mantle

In order to constrain the highly siderophile elements (HSE: Re and platinum group elements (PGE: Os, Ir, Ru, Pt and Pd)) host mineral(s) in refractory, base metal sulfide-free mantle residues, four very depleted spinel-harzburgites from the Lherz massif (France) have been analyzed for HSE in whole-rock and in major mineral separates (olivine, orthopyroxene, clinopyroxene and spinel) by isotope dilution. In addition, HSE host minerals have been separated and analyzed with a scanning electron microscope. Olivine and spinel show the highest HSE concentration especially for Os, Ir, Ru and Pt (up to 10 ppb) among the modally-major minerals, while the pyroxenes are 1-2 orders of magnitude poorer in HSE. The major minerals account for less than 30% of the whole-rock platinum group element budget. On the other hand, rare, micron to submicron platinum group minerals (PGM), such as Ru-Os ± Ir sulfides and Pt-Ir ± Os alloys, likely located in the intergranular spaces of the refractory depleted harzburgite, account for 50-100% of the HSE budget. The PGM grains are interpreted to be residual, having formed in response to the complete consumption of the base-metal sulfides by the high degree of partial melting (i.e. 23-24%) experienced by these samples. As they sequester the compatible platinum group elements (Os, Ir, Ru and Pt) in the mantle residue, these PGM provide key constraints for the modelling of PGE contents in terrestrial basalts (e.g. the solid/liquid partition coefficients needed to account for the compatible behavior of these elements in the mantle residue) and for understanding the long-lived Os isotope heterogeneities of the upper mantle, especially the old Re-Os ages found in young oceanic mantle. In fact, because of their Os-rich compositions and high melting temperatures, these microphases are likely to preserve their initial Os isotopic compositions unmodified over multiple events of mantle melting and mixing, and therefore generate, through recycling, heterogeneous Os isotopic signatures at different scales in the convecting mantle.     

Occurrence of soft sediment deformation at Dive Agar beach, west coast of India: possible record of the Indian Ocean tsunami (2004)

We describe here a sequence of soft sediment deformation (SSD) structures at Dive Agar beach near Srivardhan in the west coast of India. The ~120-cm-thick sediment package is represented by a basal undeformed sand (layer A) sharply cut by ~30-cm-thick intermixed beach sand and terrigenous sand (layer B1) followed by complex load structures and convolutions (8?C15?cm) within a coarse sandy layer (B2). The layer B2 is scoured by terrigenous sand (layer C1) which is capped with a silty mud layer (C2). The entire sequence (B2?CC1?CC2) is intruded by sand dykes originating from the lower layer B1. This sediment package is further overlain by a heavy mineral reach marine sand (layer D) with liquefactions long axes inclined southward as a result of forceful long-shore drift. The profile ends up with coarse-grained, poorly sorted sand including angular clasts of terrigenous outwash deposits indicating return of distal inundations. Intense deformation (liquefaction) is restricted to the heavy mineral-rich marine and the intermixed sands (layers B2 and D), whereas the terrigenous sand layers show scoured bases with oscillatory and pebbly tops. The presence of complex load structures injecting into the underlying layers, the top-truncated sand dykes, macro-thrust faults, scouring, and inclusion of coral fragments can explain it as a record of tsunami in the west coast. Occurrence of un-decayed consumer plastic material within the deformed layers suggests it as one of the most recent tsunami events (i.e., 2004 IOT), the only reported event after 1945 in the west coast. Alternative marine and terrigenous sands are characteristic of tsunami run-up and backwash deposits, while the dimensions of SSDs may be related to the <2?m magnitude (height) of the 2004 IOT at Dive Agar.     

Influence of morphodynamic variability over seasonal beach sediments and its probable effect on coastal development

Seasonal variations and effect of oceanographic processes such as erosion and/or accretion along beaches are important to understand their impact on coastal morphological variations. Detailed investigations were taken up to analyse the volumetric and morphologic variations of the beaches between Pirwadi (latitude 16° 12′ N, longitude 73° 26.55′ E) and Sarjekot (latitude 16° 05′ N, longitude 73° 27.80′ E) of South Maharashtra, Central West Coast of India. This stretch is known for its rich deposits of ilmenite, magnetite and chromite. This study is based on the results of seasonal topographic profiles carried out between October 2004 and December 2005. The volume variations of the sediments, i.e. an account of accretion and/or erosion, were estimated considering the October 2004 profile as the base reference, over which the values of other seasons are compared. The results of beach profiling from Pirwadi to Talashil indicate the seasonal variations in the beach configuration and the gradient.In the studied areas the vulnerable areas are Tondavali, Talashil and Pirwadi in a decreasing order of erosion while Bagwadi shows lesser erosion. Several reasons can be attributed for these erosional trends. Among which the prominent are rip currents, wave dynamics, variable coastal configuration, beach gradient and temporary monsoonal seaward flowing streams. In contrast, significant deposition occurs throughout the year at Hirlewadi due to sediment transported by due south by littoral currents. Therefore, considering the sensitivity of the fragile coastal system, future developmental activities (mining, tourism, etc.) need to be planned in tandem with the required protective measures such as construction of reinforced concrete curved wall and geotextiles.     

Target rocks,impact glasses,and melt rocks from the Lonar crater,India: Highly siderophile element systematics and Sr‐Nd‐Os isotopic signatures

The Lonar crater is a ~0.57‐Myr‐old impact structure located in the Deccan Traps of the Indian peninsula. It probably represents the best‐preserved impact structure hosted in continental flood basalts, providing unique opportunities to study processes of impact cratering in basaltic targets. Here we present highly siderophile element (HSE) abundances and Sr‐Nd and Os isotope data for target basalts and impactites (impact glasses and impact melt rocks) from the Lonar area. These tools may enable us to better constrain the interplay of a variety of impact‐related processes such as mixing, volatilization, and contamination. Strontium and Nd isotopic compositions of impactites confirm and extend earlier suggestions about the incorporation of ancient basement rocks in Lonar impactites. In the Re‐Os isochron plot, target basalts exhibit considerable scatter around a 65.6 Myr Re‐Os reference isochron, most likely reflecting weathering and/or magma replenishment processes. Most impactites plot at distinctly lower ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios compared to the target rocks and exhibit up to two orders of magnitude higher abundances of Ir, Os, and Ru. Moreover, the impactites show near‐chondritic interelement ratios of HSE. We interpret our results in terms of an addition of up to 0.03% of a chondritc component to most impact glasses and impact melt rocks. The magnitude of the admixture is significantly lower than the earlier reported 12–20 wt% of extraterrestrial component for Lonar impact spherules, reflecting the typical difference in the distribution of projectile component between impact glass spherules and bulk impactites.     

Nucleosynthetic osmium isotope anomalies in acid leachates of the Murchison meteorite

We present osmium isotopic results obtained by sequential leaching of the Murchison meteorite, which reveal the existence of very large internal anomalies of nucleosynthetic origin (ε¹⁸⁴Os from ? 108 to 460; ε¹⁸⁶Os from ? 14.1 to 12.6; ε¹⁸⁸Os from ? 2.6 to 1.6; ε¹⁹⁰Os from ? 1.7 to 1.1). Despite these large variations, the isotopic composition of the total leachable osmium (weighted average of the leachates) is close to that of bulk chondrites. This is consistent with efficient large-scale mixing of Os isotopic anomalies in the protosolar nebula. The Os isotopic anomalies are correlated, and can be explained by the variable contributions of components derived from the s, r and p-processes of nucleosynthesis. Surprisingly, much of the s-process rich osmium is released by relatively mild leaching, suggesting the existence of an easily leachable s-process rich presolar phase, or alternatively, of a chemically resistant r-process rich phase. Taken together with previous evidence for a highly insoluble s-process rich carrier, such as SiC, these results argue for the presence of several presolar phases with anomalous nucleosynthetic compositions in the Murchison meteorite. The s-process composition of Os released by mild leaching diverges slightly from that released by aggressive digestion techniques, perhaps suggesting that the presolar phases attacked by these differing procedures condensed in different stellar environments. The correlation between ε¹⁹⁰Os and ε¹⁸⁸Os can be used to constrain the s-process ¹⁹⁰Os/¹⁸⁸Os ratio to be 1.275 ± 0.043. Such a ratio can be reproduced in a nuclear reaction network for a MACS value for ¹⁹⁰Os of ~ 200 ± 22 mbarn at 30 keV. More generally, these results can help refine predictions of the s-process in the Os mass region, which can be used in turn to constrain the amount of cosmoradiogenic ¹⁸⁷Os in the solar system and hence the age of the Galaxy.We also present evidence for extensive internal variation of ¹⁸⁴Os abundances in the Murchison meteorite. A steep anti-correlation is observed between ε¹⁸⁴Os and ε¹⁸⁸Os. Since ¹⁸⁴Os is formed uniquely by the p-process, this anti-correlation cannot be explained by variable addition or subtraction of s-process Os to average solar system material. Instead, this suggests that p-process rich presolar grains (e.g., supernova condensates) may be present in meteorites in sufficient quantities to influence the Os isotopic compositions of the leachates. Nevertheless, ¹⁸⁴Os is a low abundance isotope and we cannot exclude the possibility that the measured anomalies for this isotope reflect unappreciated analytical artifacts.     

Platinum-group element micronuggets and refertilization process in Lherz orogenic peridotite (northeastern Pyrenees,France)

Highly siderophile elements (Platinum-group elements, Au and Re) are currently assumed to reside inside base metal sulfides (BMS) in the convecting upper mantle. However, fertile lherzolites sampled by Pyrenean orogenic peridotite massifs are unexpectedly rich in 0.5–3 µm large micronuggets of platinum-group minerals (PGM). Among those, sulfides from the laurite-erlichmanite series (Ru, Os(Ir)S(As)₂), Pt–Ir–Os alloys and Pt–Pd–Te–Bi phases (moncheite–merenskyite) are predominant. Not only the BMS phases but also the PGM micronuggets must be taken into account in calculation of the PGE budget of orogenic fertile lherzolites. Laurite is a good candidate for equilibrating the whole-rock budget of Os, Ir and Ru while accounting for supra-chondritic Ru/Ir_N. Textural relationships between PGMs and BMS highlight heterogeneous mixing between refractory PGMs (laurite/Pt–Ir–Os alloys) inherited from ancient refractory lithospheric mantle and late-magmatic metasomatic sulfides precipitated from tholeiitic melts. “Low-temperature” PGMs, especially Pt–Pd bismuthotellurides should be added to the list of mineral indicators of lithosphere refertilization process. Now disseminated within fertile lherzolites, “lithospheric“ PGMs likely account for local preservation of ancient Os model ages (up to 2 Ga) detected in BMS by in-situ isotopic analyses. These PGMs also question the reliability of orogenic lherzolites for estimating the PGE signature of the Primitive Silicate Earth.     

Meteoritic highly siderophile element and Re‐Os isotope signatures of Archean spherule layers from the CT3 drill core,Barberton Greenstone Belt,South Africa

Archean spherule layers represent the only currently known remnants of the early impact record on Earth. Based on the lunar cratering record, the small number of spherule layers identified so far contrasts to the high impact flux that can be expected for the Earth at that time. The recent discovery of several Paleoarchean spherule layers in the BARB5 and CT3 drill cores from the Barberton area, South Africa, drastically increases the number of known Archean impact spherule layers and may provide a unique opportunity to improve our knowledge of the impact record on the early Earth. This study is focused on the spherule layers in the CT3 drill core from the northeastern Barberton Greenstone Belt. We present highly siderophile element (HSE: Re, Os, Ir, Pt, Ru, and Pd) concentrations and Re‐Os isotope signatures for spherule layer samples and their host rocks in order to unravel the potential presence of extraterrestrial fingerprints within them. Most spherule layer samples exhibit extreme enrichments in HSE concentrations of up to superchondritic abundances in conjunction with, in some cases, subchondritic present‐day ¹⁸⁷Os/¹⁸⁸Os isotope ratios. This indicates a significant meteoritic contribution to the spherule layers. In contrast to some of the data reported earlier for other Archean spherule layers from the Barberton area, the CT3 core is significantly overprinted by secondary events. However, HSE and Re‐Os isotope signatures presented in this study indicate chondritic admixtures of up to (and even above) 100% chondrite component in some of the analyzed spherule layers. There is no significant correlation between HSE abundances and respective spherule contents. Although strongly supporting the impact origin of these layers and the presence of significant meteoritic admixtures, peak HSE concentrations are difficult to explain without postdepositional enrichment processes.     

Sulfide petrology and highly siderophile element geochemistry of abyssal peridotites: a coupled study of samples from the Kane Fracture Zone (45°W 23°20N, MARK area, Atlantic Ocean)

Nineteen samples from the Kane Fracture Zone have been studied for sulfide mineralogy and analyzed for S, Se, platinum-group elements (PGE), and Au to assess the effect of refertilization processes on the PGE systematics of abyssal peridotites. The lherzolites show broadly chondritic PGE ratios and sulfide modal abundances (0.01 to 0.03 wt%) consistent with partial melting models, although the few pyroxene-hosted sulfide inclusions and in situ LAM-ICPMS analyses provide evidence for in situ mobilization of a Cu-Ni-rich sulfide partial melt. The most refractory harzburgites (spinel Cr# > 29) are almost devoid of magmatic sulfides and show uniformly low Pd_N/Ir_N (<0.5) for variable Pt_N/Ir_N (0.8 to 1.2). The compatible behavior of Os, Ir, Ru, Rh, and Pt reflects the presence of primary Os-Ru alloys. Some harzburgites displaying petrographic evidence for refertilization by incremental melts en route to the surface are enriched in sulfides (up to 0.1 wt%). Some of these sulfides are concentrated in small veinlets of clinopyroxene and spinel crystallized from these melts. These S-rich harzburgites display superchondritic Pd_N/Ir_N (up to 2.04) positively correlated with sulfide modal contents. It is concluded that refertilization processes resulting in precipitation of metasomatic sulfides may significantly enhance Pd concentrations of abyssal peridotites while marginally affecting Pt (Pt_N/Ir_N ≤ 1.24) and Rh (Rh_N/Ir_N ≤ 1.23) as well. When the effects of such processes are screened out, our database suggests PGE relative abundances in the DMM (Depleted MORB Mantle; MORB: Mid-Ocean Ridge) within the uncertainty range of chondritic meteorites, without evidence of superchondritic Pt/Ir and/or Rh/Ir ratios.