The Ca-Eskola component in eclogitic clinopyroxene as a function of pressure, temperature and bulk composition: an experimental study to 15 GPa with possible implications for the formation of oriented SiO2-inclusions in omphacite

Experiments have been conducted in the P-T range 2.5–15 GPa and 850–1,500°C using bulk compositions in the systems SiO₂–TiO₂–Al₂O₃–Fe₂O₃–FeO–MnO–MgO–CaO–Na₂O–K₂O–P₂O₅ and SiO₂–TiO₂–Al₂O₃–MgO–CaO–Na₂O to investigate the Ca-Eskola (CaEs Ca_0.5□_0.5AlSi₂O₆) content of clinopyroxene in eclogitic assemblages containing garnet + clinopyroxene + SiO₂ ± TiO₂ ± kyanite as a function of P, T, and bulk composition. The results show that CaEs_ss in clinopyroxene increases with increasing T and is strongly bulk composition dependent whereby high CaEs-contents are favoured by bulk compositions with high normative anorthite and low diopside contents. In this study, a maximum of 18 mol% CaEs_ss was found at 6 GPa and 1,350°C in a kyanite-eclogite assemblage garnet + clinopyroxene + kyanite + rutile + coesite. By comparison, no significant increase in CaEs_ss with increasing P could be observed. If the formation of oriented SiO₂-rods frequently observed in eclogititc clinopyroxenes is due to the retrogressive breakdown of a CaEs-component then these textures are a cooling rather than a decompression phenomenon and are most likely to be found in kyanite-bearing eclogites cooled from temperatures ≥750°C. The presence of clinopyroxene with approx. 4 mol% CaEs_ss in an experiment conducted at 2.5 GPa/850°C confirms earlier suggestions based on field data that vacancy-rich clinopyroxenes are not necessarily restricted to ultrahigh pressure metamorphic conditions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Zircon coronas around Fe–Ti oxides: a physical reference frame for metamorphic and metasomatic reactions

Ilmenite in coronitic gabbros from the Bamble and Kongsberg sectors, southern Norway, is surrounded by zircons ranging in diameters from a fraction of a micrometer to 10 μm across. The zircons are inert during subsequent metamorphism (amphibolite- to pumpellyite–prehnite facies) and metasomatism (scapolitization and albitization) and can be found as trails in silicates (phlogopite, talc, chlorite, amphibole, albite, and tourmaline) in the altered rocks. The trails link up to form polygons outlining the former oxide grain boundary. This 3-dimensional framework of zircons is used to (a) recognize metasomatic origin of rocks, (b) quantify the mobility of elements during mineral replacement, (c) establish the growth direction of reaction fronts and to identify the reaction mechanism as dissolution–reprecipitation. Zircon coronas on Fe–Ti oxides have been described from a number of terrains and appear to be common in mafic rocks (gabbros and granulites) providing a tool for a better understanding of metasomatic and metamorphic reactions.     

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.     

Application of precise 142Nd/144Nd analysis of small samples to inclusions in diamonds (Finsch,South Africa) and Hadean Zircons (Jack Hills,Western Australia)

¹⁴⁶Sm–¹⁴²Nd and ¹⁴⁷Sm–¹⁴³Nd systematics were investigated in garnet inclusions in diamonds from Finsch (S. Africa) and Hadean zircons from Jack Hills (W. Australia) to assess the potential of these systems as recorders of early Earth evolution. The study of Finsch inclusions was conducted on a composite sample of 50 peridotitic pyropes with a Nd model age of 3.3 Ga. Analysis of the Jack Hills zircons was performed on 790 grains with ion microprobe ²⁰⁷Pb/²⁰⁶Pb spot ages from 3.95 to 4.19 Ga. Finsch pyropes yield 100 × ?¹⁴²Nd = ? 6 ± 12 ppm, ?¹⁴³Nd = ? 32.5, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.1150. These results do not confirm previous claims for a 30 ppm ¹⁴²Nd excess in South African cratonic mantle. The lack of a ¹⁴²Nd anomaly in these inclusions suggests that isotopic heterogeneities created by early mantle differentiation were remixed at a very fine scale prior to isolation of the South African lithosphere. Alternatively, this result may indicate that only a fraction of the mantle experienced depletion during the first 400 Myr of its history. Analysis of the Jack Hills zircon composite yielded 100 × ?¹⁴²Nd = 8 ± 10 ppm, ?¹⁴³Nd = 45 ± 1, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.5891. Back-calculation of this present-day ?¹⁴³Nd yields an unrealistic estimate for the initial ?¹⁴³Nd of ? 160 ?-units, clearly indicating post-crystallization disturbance of the ¹⁴⁷Sm–¹⁴³Nd system. Examination of ^146,147Sm–^142,143Nd data reveals that the Nd budget of the Jack Hills sample is dominated by non-radiogenic Nd, possibly contained in recrystallized zircon rims or secondary subsurface minerals. This secondary material is characterized by highly discordant U–Pb ages. Although the mass fraction of altered zircon is unlikely to exceed 5–10% of total sample, its high LREE content precludes a reliable evaluation of ¹⁴⁶Sm–¹⁴²Nd systematics in Jack Hills zircons.     

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.     

Mineral inclusions in diamonds from the Kelsey Lake Mine, Colorado, USA: Depleted Archean mantle beneath the Proterozoic Yavapai province

Thirty-four silicate and oxide inclusions large enough for in situ WDS electron microprobe analysis were exposed by grinding/polishing of 19 diamonds from the Kelsey Lake Mine in the Colorado-Wyoming State Line Kimberlite district. Eighteen olivines, seven Cr-pyropes, four Mg-chromites, and one orthopyroxene in 15 stones belong to the peridotite (P) suite and three garnets and one omphacite in three stones belong to the eclogite (E) suite. The fact that this suite is dominated by the peridotite population is in stark contrast to the other diamond suites studied in the State Line district (Sloan, George Creek), which are overwhelmingly eclogitic. Kelsey Lake olivine inclusions are magnesian (17 of 18 grains in 9 stones are in the range Fo 92.7-93.1), typical of harzburgitic P-suite stones worldwide, but unlike the more Fe-rich (lherzolitic) Sloan olivine suite. Mg-chromites (wt% MgO = 12.8-13.8; wt% Cr₂O₃ = 61.4-66.6) are in the lower MgO range of diamond inclusion chromites worldwide. Seven harzburgitic Cr-pyropes in five stones have moderately low calcium contents (wt% CaO = 3.3-4.3) but are very Cr-rich (wt% Cr₂O₃ = 9.7-16.7). A few stones have been analyzed by SIMS for carbon isotope composition and nitrogen abundance. One peridotitic stone is apparently homogeneous in carbon isotope composition (δ¹³C_PDB = −6.2‰) but with variable nitrogen abundance (1296-2550 ppm). Carbon isotopes in eclogitic stones range from “normal” for the upper mantle (δ¹³C_PDB = −5.5‰) to somewhat low (δ¹³C_PDB = −10.2‰), with little internal variation in individual stones (maximum difference is 3.6‰). Nitrogen contents (2-779 ppm) are lower than in the peridotitic stone, and are lower in cores than in rims. As, worldwide, harzburgite-suite diamonds have been shown to have formed in Archean time, we suggest that the Kelsey Lake diamond population was derived from a block of Archean lithosphere that, at the time of kimberlite eruption, existed beneath the Proterozoic Yavapai province. The mixed diamond inclusion populations from the State Line kimberlites appear to support models in which volumes of Wyoming Craton Archean mantle survive buried beneath Proterozoic continental crust. Such material may be mixed with eclogitic/lherzolitic regimes emplaced beneath or intermingled with the Archean rocks by Proterozoic subduction.     

Iron isotopes constrain biologic and abiologic processes in banded iron formation genesis

The voluminous 2.5 Ga banded iron formations (BIFs) from the Hamersley Basin (Australia) and Transvaal Craton (South Africa) record an extensive period of Fe redox cycling. The major Fe-bearing minerals in the Hamersley-Transvaal BIFs, magnetite and siderite, did not form in Fe isotope equilibrium, but instead reflect distinct formation pathways. The near-zero average δ⁵⁶Fe values for magnetite record a strong inheritance from Fe³⁺ oxide/hydroxide precursors that formed in the upper water column through complete or near-complete oxidation. Transformation of the Fe³⁺ oxide/hydroxide precursors to magnetite occurred through several diagenetic processes that produced a range of δ⁵⁶Fe values: (1) addition of marine hydrothermal , (2) complete reduction by bacterial dissimilatory iron reduction (DIR), and (3) interaction with excess that had low δ⁵⁶Fe values and was produced by DIR. Most siderite has slightly negative δ⁵⁶Fe values of ∼ −0.5‰ that indicate equilibrium with Late Archean seawater, although some very negative δ⁵⁶Fe values may record DIR. Support for an important role of DIR in siderite formation in BIFs comes from previously published C isotope data on siderite, which may be explained as a mixture of C from bacterial and seawater sources.Several factors likely contributed to the important role that DIR played in BIF formation, including high rates of ferric oxide/hydroxide formation in the upper water column, delivery of organic carbon produced by photosynthesis, and low clastic input. We infer that DIR-driven Fe redox cycling was much more important at this time than in modern marine systems. The low pyrite contents of magnetite- and siderite-facies BIFs suggests that bacterial sulfate reduction was minor, at least in the environments of BIF formation, and the absence of sulfide was important in preserving magnetite and siderite in the BIFs, minerals that are poorly preserved in the modern marine record. The paucity of negative δ⁵⁶Fe values in older (Early Archean) and younger (Early Proterozoic) BIFs suggests that the extensive 2.5 Ga Hamersley-Transvaal BIFs may record a period of maximum expansion of DIR in Earth’s history.