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.     

Controls on porphyroblast size along a regional metamorphic field gradient

Garnet-bearing schists from the Waterville Formation of south-central Maine provide an opportunity to examine the factors governing porphyroblast size over a range of metamorphic grade. Three-dimensional sizes and locations for all garnet porphyroblasts were determined for three samples along the metamorphic field gradient spanning lowest garnet through sillimanite grade, using high-resolution X-ray computed tomography. Comparison of crystal size distributions to previous data sets obtained by stereological methods for the same samples reveals significant differences in mode, mean, and shape of the distributions. Quantitative textural analysis shows that the garnets in each rock crystallized in a diffusion-controlled nucleation and growth regime. In contrast to the typical observation of a correlation between porphyroblast size and position along a metamorphic field gradient, porphyroblast size of the lowest-grade specimen is intermediate between the high- and middle-grade specimens’ sizes. Mean porphyroblast size does not correlate with peak temperatures from garnet-biotite Fe-Mg exchange thermometry, nor is post-crystallization annealing (Ostwald Ripening) required to produce the observed textures, as was previously proposed for these rocks. Robust pseudosection calculations fail to reproduce the observed garnet core compositions for two specimens, suggesting that these calc-pelites experienced metasomatism. For each of these two specimens, Monte Carlo calculations suggest potential pre-metasomatism bulk compositions that replicate garnet core compositions. Pseudosection analyses allow the estimation of the critical temperatures for garnet growth: ∼481, ∼477, and ∼485°C for the lowest-garnet-zone, middle-garnet-zone, and sillimanite-zone specimens, respectively. Porphyroblast size appears to be determined in this case by a combination of the heating rate during garnet crystallization, the critical temperature for the garnet-forming reaction and the kinetics of nucleation. Numerical simulations of thermally accelerated, diffusion-controlled nucleation, and growth for the three samples closely match measured crystal size distributions. These observations and simulations suggest that previous hypotheses linking the garnet size primarily to the temperature at the onset of porphyroblast nucleation can only partially explain the observed textures. Also important in determining porphyroblast size are the heating rate and the distribution of favorable nucleation sites.     

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.     

Core formation and the oxidation state of the Earth: Additional constraints from Nb, V and Cr partitioning

We have combined metal-silicate partitioning data from the literature with new experimental results at 1.5-8 GPa and 1480-2000 °C to parameterize the effects of pressure, temperature and composition on the partitioning of V, Cr and Nb between liquid Fe metal (with low S and C content) and silicate melt.Using information from the steelmaking literature to correct for interactions in the metal phase, we find that, for peridotitic silicate melts, metal-silicate partition coefficients are given by:

     

Experimental constraints on the parental liquid of the Chassigny meteorite: A possible link between the Chassigny meteorite and a Martian Gusev basalt

Most magmas proposed as parental to the Martian SNC meteorites are high in iron and low in alumina. Yet, experiments at low pressures on such liquids have not produced the cumulate or melt-inclusion assemblages seen in the chassignite meteorites. Therefore, elevated pressure experiments under anhydrous and hydrous (water-undersaturated) conditions were conducted on a high-Fe, low-Al liquid proposed to be parental to the Chassigny meteorite. These experiments failed to produce the most magnesian cumulate phases, as well as the olivine hosted kaersutite-bearing melt-inclusion assemblage, of the chassignites. These results suggest that the parental liquid to the chassignite meteorites is both more magnesium and aluminum-rich than the previously considered composition (A^∗; Johnson et al., 1991). The proposed composition is similar to the Martian Adirondack class Gusev basalt Humphrey and suggests a link between the Chassigny meteorite and rocks on the surface of Mars.     

Kinetics of Cd sorption, desorption and fixation by calcite: A long-term radiotracer study

Time-dependent sorption and desorption of Cd on calcite was studied over 210 days utilizing ¹⁰⁹Cd as a tracer to distinguish between ‘labile’ and ‘non-labile’ forms of sorbed Cd. Stabilizing the calcite suspensions for 12 months under atmospheric P_CO2 and controlled temperature was necessary to reliably follow Cd dynamics following initial sorption. Results revealed time-dependant Cd sorption and marked desorption hysteresis by calcite under environmentally relevant conditions. Data obtained were fitted to a first-order kinetic model and a concentric shell diffusion model. Both models described the progressive transfer of Cd²⁺ to a less reactive form within calcite and subsequent desorption of Cd subject to different initial contact times. The kinetic model provided a better fit to the combined sorption and desorption data (R² = 0.992). It differentiates between two ‘pools’ of sorbed Cd²⁺ on calcite, ‘labile’ and ‘non-labile’, in which labile sorbed Cd is in immediate equilibrium with the free Cd²⁺ ion activity in solution whereas non-labile Cd is kinetically restricted. For the diffusion model (R² = 0.959), the rate constants describing Cd dynamics in calcite produced a half-life for Cd desorption of ∼175 d, for release to a ‘zero-sink’ solution. Results from this study allow comment on the likely mechanisms occurring at the calcite surface following long-term Cd sorption.