Chrome-spinels in serpentinites and talc carbonates of the El Ideid-El Sodmein District, central Eastern Desert, Egypt: their metamorphism and petrogenetic implications

Serpentinites and talc-carbonate rocks of El Ideid-El Sodmein District (ISD), central Eastern Desert, Egypt, contain variably altered chrome-spinels. Back-scattered electron images and electron microprobe analyses of chrome-spinels and associated silicates are made to evaluate their textural and compositional variations with metamorphism. In most cases the chrome-spinel crystals are concentrically zoned with unaltered cores through transitional zone of ferritchromit to Cr-magnetite toward the rims. In talc-carbonate rocks chrome-spinels are extensively altered to Cr-magnetite. Compared to cores, the metamorphic rims are enriched in Cr# (0.83–1.0 vs. 0.58–0.63 for rims and cores, respectively) and impoverished in Mg# (0.05–0.29 vs. 0.57–0.63), due to Mg–Fe and Al(Cr)–Fe³⁺ exchange with the surrounding silicates during regional metamorphism rather than serpentinization process. Textural and compositional features of the chrome-spinels suggest transitional greenschist-amphibolite up to lower amphibolite facies metamorphism (at 500–600 °C), which is isofacial with the country rocks. The common preservation of unaltered chrome-spinel cores in the serpentinites, contrary to talc-carbonate rocks, implies that full equilibration has not been attained due to small metamorphic fluid–rock ratio. Microprobe analyses profile across a concentrically zoned grain confirms the presence of two compositional (miscibility?) gaps; one between chrome-spinel core and ferritchromit zone; and another one between ferritchromit zone and Cr-magnetite outer rim.Chrome-spinel cores do not appear to have re-equilibrated completely with the metamorphic spinel rims and surrounding silicates, indicating relic magmatic composition not affected by metamorphism. Core compositions suggest an ophiolitic origin and derivation by high degrees of melting of reduced, depleted harzburgite to dunite mantle peridotites in an oceanic supra-subduction zone (marginal-basin) tectonic environment.     

Complex replacement patterns in garnets from Bergen Arcs eclogites: A combined EBSD and analytical TEM study

Eclogite-facies rocks within the Bergen Arcs, western Norway, have formed from granulites along shear zones and fluid pathways. Garnets that were inherited from granulite facies protoliths show different types of replacement patterns due to an incomplete eclogitisation process including concentric rim zoning, zoning along vein fillings and inclusion trails, and zoning bands without inclusions. The interfacial part between the granulitic core and the eclogitic rim of garnet as well as the microstructure of other relevant minerals (omphacite, plagioclase) has been analysed using analytical transmission electron microscopy (ATEM). In garnet, the interface is characterised by gradual changes in composition from X_alm=0.31, X_pyr=0.50 to X_alm=0.54, and X_pyr=0.25 within ≈20 μm and exhibits no distinct change in microstructure. Granulitic plagioclase shows exsolution lamellae of the Bøggild intergrowth. In omphacite, anti-phase domains (APDs) which potentially record the temperature of cation ordering after mineral growth have been observed and their size suggest eclogitisation at 600–700 °C. The electron backscatter diffraction (EBSD) analysis revealed that the lattice orientation of the granulitic feldspar is basically unrelated to tectonic axes whereas newly formed eclogitic minerals omphacite and kyanite show a crystallographic relation to the foliation. In garnet, no change in the basic crystallographic orientation between the eclogitic and granulitic garnet composition was confirmed. However, misorientation analysis suggests a cellular microstructure not more than 1° misorientation in the core of the garnets, which is missing in the eclogitic rim indicating textural equilibration of the latter. The heterogeneous replacement patterns are characteristic for dissolution and re-precipitation reactions in an open system limited to fluid availability. The appearance of the compositional profile in garnet is interpreted as a diffusional re-equilibration step after the time-limited, fluid-mediated eclogitisation event that apparently obscured the initially sharp interface within the further retrograde metamorphic history.     

Oxidation of pyrite during extraction of carbonate associated sulfate

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.     

Development and morphometry of sinkholes in coastal plains of Apulia, southern Italy. Preliminary sinkhole susceptibility assessment

Evolution of coastlines in karst areas may be strongly controlled by dissolution processes which favour the development of surface and subsurface landforms. The generation of caves in these environments is commonly favoured by the mixing between fresh and brackish waters. The sinkholes resulting from the upward propagation of the caves may interfere with the anthropogenic environment and cause damage to human elements (property and activities). To highlight the often underestimated importance of karst phenomena in coastal areas, we have analyzed a coastal stretch of Apulia, in southern Italy. The study area, covering an extension of about 6 km², is situated in the Ionian coast, and presents several interesting karst landforms that are generally connected to caves. Tens of sinkholes were mapped through field surveys, multi-year aerial-photographs (dating back to the 1940s) and archival research. We have performed a morphometric analysis of the sinkholes. The analysis describes the main parameters of the sinkholes (area, length, width, and depth), and the control exerted by the main discontinuity systems in the area. The detrimental effects derived from interaction between human environment and these karst landforms is also under consideration. A sinkhole susceptibility map, which may provide useful information for planners, developers and the insurance industry has eventually been produced through application of a decision tree model.     

Oxygen isotopic compositions of Allende Type C CAIs: Evidence for isotopic exchange during nebular melting and asteroidal metamorphism

In situ oxygen isotopic measurements of primary and secondary minerals in Type C CAIs from the Allende CV3 chondrite reveal that the pattern of relative enrichments and depletions of ¹⁶O in the primary minerals within each individual CAI are similar to the patterns observed in Types A and B CAIs from the same meteorite. Spinel is consistently the most ¹⁶O-rich (Δ¹⁷O = −25‰ to −15‰), followed by Al,Ti-dioside (Δ¹⁷O = −20‰ to −5‰) and anorthite (Δ¹⁷O = −15‰ to 0‰). Melilite is the most ¹⁶O-depleted primary mineral (Δ¹⁷O = −5‰ to −3‰). We conclude that the original melting event that formed Type C CAIs occurred in a ¹⁶O-rich (Δ¹⁷O  −20‰) nebular gas and they subsequently experienced oxygen isotopic exchange in a ¹⁶O-poor reservoir. At least three of these (ABC, TS26F1 and 93) experienced remelting at the time and place where chondrules were forming, trapping and partially assimilating ¹⁶O-poor chondrule fragments. The observation that the pyroxene is ¹⁶O-rich relative to the feldspar, even though the feldspar preceded it in the igneous crystallization sequence, disproves the class of CAI isotopic exchange models in which partial melting of a ¹⁶O-rich solid in a ¹⁶O-poor gas is followed by slow crystallization in that gas. For the typical (not associated with chondrule materials) Type C CAIs as well for as the Types A and B CAIs, the exchange that produced internal isotopic heterogeneity within each CAI must have occurred largely in the solid state. The secondary phases grossular, monticellite and forsterite commonly have similar oxygen isotopic compositions to the melilite and anorthite they replace, but in one case (CAI 160) grossular is ¹⁶O-enriched (Δ¹⁷O = −10‰ to −6‰) relative to melilite (Δ¹⁷O = −5‰ to −3‰), meaning that the melilite and anorthite must have exchanged its oxygen subsequent to secondary alteration. This isotopic exchange in melilite and anorthite likely occurred on the CV parent asteroid, possibly during fluid-assisted thermal metamorphism.     

Temperature effects on non-bridging oxygen and aluminum coordination number in calcium aluminosilicate glasses and melts

Configurational changes with temperature are important for the thermodynamic and transport properties of most aluminosilicate melts, but in general are not well understood. Here, we present high-resolution ²⁷Al and ¹⁷O NMR data on several calcium aluminosilicate glasses prepared with varying quench rates and thus with fictive temperatures that span ranges up to about 200 K. In all compositions the content of five-coordinated aluminum increases with fictive temperature, in agreement with recent high temperature NMR data on melts. In a glass of CaAl₂Si₂O₈ (“anorthite”) composition, the content of non-bridging oxygens also increases with temperature; however this effect was not observed in a sample with a much higher CaO/Al₂O₃ ratio. We present a consistent notation for reactions among structural species in these systems that clarify why in some cases, high-coordinated network cations may appear on the same side of the reaction, while in others they occur on the opposite sides: the key difference is in accounting for all coordination changes for oxygens. Mixing of non-bridging oxygens and of high-coordinated aluminum make significant contributions to the overall configurational entropy and heat capacity of the melts, as does the mixing of various bridging oxygens and of tetrahedral network cations. Other, less well known, types of increase in disorder with temperature may be important as well.     

The age of the martian meteorite Northwest Africa 1195 and the differentiation history of the shergottites

Samarium-neodymium isotopic analyses of unleached and acid-leached mineral fractions from the recently identified olivine-bearing shergottite Northwest Africa 1195 yield a crystallization age of 347 ± 13 Ma and an value of +40.1 ± 0.9. Maskelynite fractions do not lie on the Sm-Nd isochron and appear to contain a martian surface component with low ¹⁴⁷Sm/¹⁴⁴Nd and ¹⁴³Nd/¹⁴⁴Nd ratios that was added during shock. The Rb-Sr system is disturbed and does not yield an isochron. Terrestrial Sr appears to have affected all of the mineral fractions, although a maximum initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7016 is estimated by passing a 347 Ma reference line through the maskelynite fraction that is least affected by contamination. The high initial value and the low initial ⁸⁷Sr/⁸⁶Sr ratio, combined with the geologically young crystallization age, indicate that Northwest Africa 1195 is derived from a source region characterized by a long-term incompatible-element depletion.The age and initial Sr and Nd isotopic compositions of Northwest Africa 1195 are very similar to those of Queen Alexandra Range 94201, indicating these samples were derived from source regions with similar Sr-Nd isotopic systematics. These similarities suggest that these two meteorites share a close petrogenetic relationship and might have been erupted from a common volcano. The meteorites Yamato 980459, Dar al Gani 476, Sayh al Uhaymir 005/008, and Dhofar 019 also have relatively old ages between 474 and 575 Ma and trace element and/or isotopic systematics that are indicative of derivation from incompatible-element-depleted sources. This suggests that the oldest group of meteorites is more closely related to one another than they are to the younger meteorites that are derived from less incompatible-element-depleted sources. Closed-system fractional crystallization of this suite of meteorites is modeled with the MELTS algorithm using the bulk composition of Yamato 980459 as a parent. These models reproduce many of the major element and mineralogical variations observed in the suite. In addition, the rare earth element systematics of these meteorites are reproduced by fractional crystallization using the proportions of phases and extents of crystallization that are calculated by MELTS. Other shergottites that demonstrate enrichments in incompatible-elements and have evolved Sr and Nd isotopic systematics have some geochemical systematics that are similar to those observed in the depleted group. Most notably, although they exhibit a very limited range of incompatible trace element and isotopic compositions, they have highly variable major element compositions. This is also consistent with evolution from a common mantle source region by variable amounts of fractional crystallization. If this scenario is correct, it suggests that the combined effects of source composition and fractional crystallization are likely to account for the major element, trace element, and isotopic diversity of all shergottites.     

Size scales over which ordinary chondrites and their parent asteroids are homogeneous in oxidation state and oxygen-isotopic composition

Literature data demonstrate that on a global, asteroid-wide scale (plausibly on the order of 100 km), ordinary chondrites (OC) have heterogeneous oxidation states and O-isotopic compositions (represented, respectively, by the mean olivine Fa and bulk Δ¹⁷O compositions of equilibrated samples). Samples analyzed here include: (a) two H5 chondrite Antarctic finds (ALHA79046 and TIL 82415) that have the same cosmic-ray exposure age (7.6 Ma) and were probably within ∼1 km of each other when they were excavated from the H-chondrite parent body, (b) different individual stones from the Holbrook L/LL6 fall that were probably within ∼1 m of each other when their parent meteoroid penetrated the Earth’s atmosphere, and (c) drill cores from a large slab of the Estacado H6 find located within a few tens of centimeters of each other. Our results indicate that OC are heterogeneous in their bulk oxidation state and O-isotopic composition on 100-km-size scales, but homogeneous on meter-, decimeter- and centimeter-size scales. (On kilometer size scales, oxidation state is heterogeneous, but O isotopes appear to be homogeneous.) The asteroid-wide heterogeneity in oxidation state and O-isotopic composition was inherited from the solar nebula. The homogeneity on small size scales was probably caused in part by fluid-assisted metamorphism and mainly by impact-gardening processes (which are most effective at mixing target materials on scales of ?1 m).     

Atomistic simulation of the mechanisms of noble gas incorporation in minerals

Atomistic simulations have been carried out to investigate the mechanisms of noble gas incorporation in minerals using both the traditional two-region approach and the “supercell” method. The traditional two-region approach has been used to calculate defect energies for Ne, Ar, Kr and Xe incorporation in MgO, CaO, diopside and forsterite in the static limit and at one atmosphere pressure. The possibilities of noble gas incorporation via both substitution and interstitial mechanisms are studied. The favored mechanism varies from mineral to mineral and from noble gas to noble gas. In all minerals studied, the variation of the solution energies of noble gas substitution with atomic radius appears approximately parabolic, analogous to those for 1⁺, 2⁺, 3⁺ and 4⁺ trace element incorporation on crystal lattice sites. Noble gas solution energies thus also fall on a curve, similar to those previously observed for cations with different charges, but with much lower curvature.The “supercell” method has been used to investigate the pressure dependence of noble gas incorporation in the same systems. Results indicate a large variation of the solubility of the larger noble gases, Kr and Xe with pressure. In addition, explicit simulation of incorporation at the (0 0 1) surface of MgO shows that the solubility of the heavier noble gases may be considerably enhanced by the presence of interfaces.     

Determination of fluid/melt partition coefficients by LA-ICPMS analysis of co-existing fluid and silicate melt inclusions: Controls on element partitioning

Analyses of co-existing silicate melt and fluid inclusions, entrapped in quartz crystals in volatile saturated magmatic systems, allowed direct quantitative determination of fluid/melt partition coefficients. Investigations of various granitic systems (peralkaline to peraluminous in composition, log fO₂ = NNO−1.7 to NNO+4.5) exsolving fluids with various chlorinities (1-14 mol/kg) allowed us to assess the effect of these variables on the fluid/melt partition coefficients (D). Partition coefficients for Pb, Zn, Ag and Fe show a nearly linear increase with the chlorinity of these fluid (D_Pb ∼ 6 ∗ m_Cl, D_Zn ∼ 8 ∗ m_Cl, D_Ag ∼ 4 ∗ m_Cl, D_Fe ∼ 1.4 ∗ m_Cl, where m_Cl is the molinity of Cl). This suggests that these metals are dissolved primarily as Cl-complexes and neither oxygen fugacity nor the composition of the melt affects significantly their fluid/melt partitioning. By contrast, partition coefficients for Mo, B, As, Sb and Bi are highest in low salinity (1-2 mol/kg Cl) fluids with maximum values of D_Mo ∼ 20, D_B ∼ 15, D_As ∼ 13, D_Sb ∼ 8, D_Bi ∼ 15 indicating dissolution as non-chloride (e.g., hydroxy) complexes. Fluid/melt partition coefficients of copper are highly variable, but highest between vapor like fluids and silicate melt (D_Cu ? 2700), indicating an important role for ligands other than Cl. Partition coefficients for W generally increase with increasing chlorinity, but are exceptionally low in some of the studied brines which may indicate an effect of other parameters. Fluid/melt partition coefficients of Sn show a high variability but likely increase with the chlorinity of the fluid (D_Sn = 0.3-42, D_W = 0.8-60), and decrease with decreasing oxygen fugacity or melt peraluminosity.