Oxygen isotope heterogeneity in chondrules from the Mokoia CV3 carbonaceous chondrite

We report a study of the oxygen isotope ratios of chondrules and their constituent mineral grains from the Mokoia, oxidized CV3 chondrite. Bulk oxygen isotope ratios of 23 individual chondrules were determined by laser ablation fluorination, and oxygen isotope ratios of individual grains, mostly olivine, were obtained in situ on polished mounts using secondary ion mass spectrometry (SIMS). Our results can be compared with data obtained previously for the oxidized CV3 chondrite, Allende. Bulk oxygen isotope ratios of Mokoia chondrules form an array on an oxygen three-isotope plot that is subparallel to, and slightly displaced from, the CCAM (carbonaceous chondrite anhydrous minerals) line. The best-fit line for all CV3 chondrite chondrules has a slope of 0.99, and is displaced significantly (by δ¹⁷O ∼ −2.5‰) from the Young and Russell slope-one line for unaltered calcium-aluminum-rich inclusion (CAI) minerals. Oxygen isotope ratios of many bulk CAIs also lie on the CV-chondrule line, which is the most relevant oxygen isotope array for most CV chondrite components. Bulk oxygen isotope ratios of most chondrules in Mokoia have δ¹⁸O values around 0‰, and olivine grains in these chondrules have similar oxygen isotope ratios to their bulk values. In general, it appears that chondrule mesostases have higher δ¹⁸O values than olivines in the same chondrules. Our bulk chondrule data spread to lower δ¹⁸O values than any ferromagnesian chondrules that have been measured previously. Two chondrules with the lowest bulk δ¹⁸O values (−7.5‰ and −11.7‰) contain olivine grains that display an extremely wide range of oxygen isotope ratios, down to δ¹⁷O, δ¹⁸O around -50‰ in one chondrule. In these chondrules, there are no apparent relict grains, and essentially no relationships between olivine compositions, which are homogeneous, and oxygen isotopic compositions of individual grains. Heterogeneity of oxygen isotope ratios within these chondrules may be the result of incorporation of relict grains from objects such as amoeboid olivine aggregates, followed by solid-state chemical diffusion without concomitant oxygen equilibration. Alternatively, oxygen isotope exchange between an ¹⁶O-rich precursor and an ¹⁶O-poor gas may have taken place during chondrule formation, and these chondrules may represent partially equilibrated systems in which isotopic heterogeneities became frozen into the crystallizing olivine grains. If this is the case, we can infer that the earliest nebular solids from which chondrules formed had δ¹⁷O and δ¹⁸O values around -50‰, similar to those observed in refractory inclusions.     

Controls on iron-isotope fractionation in organic-rich sediments (Kimmeridge Clay, Upper Jurassic, Southern England)

This study explores the fractionation of iron isotopes (⁵⁷Fe/⁵⁴Fe) in an organic-rich mudstone succession, focusing on core and outcrop material sampled from the Upper Jurassic Kimmeridge Clay Formation type locality in south Dorset, UK. The organic-rich environments recorded by the succession provide an excellent setting for an investigation of the mechanisms by which iron isotopes are partitioned among mineral phases during biogeochemical sedimentary processes.Two main types of iron-bearing assemblage are defined in the core material: mudstones with calcite ± pyrite ± siderite mineralogy, and ferroan dolomite (dolostone) bands. A cyclic data distribution is apparent, which reflects variations in isotopic composition from a lower range of δ⁵⁷Fe values associated with the pyrite/siderite mudstone samples to the generally higher values of the adjacent dolostone samples. Most pyrite/siderite mudstones vary between −0.4 and 0.1‰ while dolostones range between −0.1 and 0.5‰, although in very organic-rich shale samples below 360 m core depth higher δ⁵⁷Fe values are noted. Pyrite nodules and pyritized ammonites from the type exposure yield δ⁵⁷Fe values of −0.3 to −0.45‰. A fractionation model consistent with the δ⁵⁷Fe variations relates the lower δ⁵⁷Fe pyrite and siderite ± pyrite mudstones values to the production of isotopically depleted Fe(II) during biogenic reduction of the isotopically heavier lithogenic Fe(III) oxides. A consequence of this reductive dissolution is that a ⁵⁷Fe-enriched iron species must be produced that potentially becomes available for the formation of the higher δ⁵⁷Fe dolostones. An isotopic profile across a dolostone band reveals distinct zonal variations in δ⁵⁷Fe, characterized by two peaks, respectively located above and below the central part of the band, and decoupling of the isotopic composition from the iron content. This form of isotopic zoning is shown to be consistent with a one-dimensional model of diffusional-chromatographic Fe-isotope exchange between dolomite and isotopically enriched pore water. An alternative mechanism envisages the infiltration of dissolved ferrous iron from variable (high and low) δ⁵⁷Fe sources during coprecipitation of Fe(II) ion with dolomite. The study provides clear evidence that iron isotopes are cycled during the formation and diagenesis of organic carbon-rich sediments.     

Initial Al/Al in carbonaceous-chondrite chondrules: too little Al to melt asteroids

We report ²⁶Mg excesses correlated with Al/Mg ratios in five chondrules from the primitive CO3.0 chondrite Yamato 81020 that yield a mean initial ²⁶Al/²⁷Al ratio of only (3.8 ± 0.7) × 10⁻⁶, about half that of ordinary chondrite (OC) chondrules. Even if asteroids formed immediately after chondrule formation, this ratio and the mean Al content of CO chondrites is only capable of raising the temperature of a well-insulated CO asteroid to 940 K, which is more than 560 K too low to produce differentiation. The same ratio combined with the higher Al content of CV chondrites results in a CV asteroid temperature of 1100 K. We calculate that the mean initial ²⁶Al/²⁷Al ratio of about 7.4 × 10⁻⁶ found in LL chondrules is only able to produce small amounts of melting, too little to produce differentiation. These results cast serious doubt on the viability of ²⁶Al as the heat source responsible for asteroid differentiation. Inclusion of ⁶⁰Fe raises temperatures about 160 K, but this increment is not enough to cause differentiation, even of an LL-chondrite asteroid.     

Genetic significance of fluid inclusions in the CSA Cu–Pb–Zn deposit, Cobar, Australia

CSA mine exploits a ‘Cobar-type’ Cu–Pb–Zn±Au±Ag deposit within a cleaved and metamorphosed portion of the Cobar Supergroup, central New South Wales. The deposit comprises systems of ‘lenses’ that encompass veins, disseminations and semi-massive to massive Cu–Pb–Zn ores. The systems and contained lenses truncate bedding, are approximately coplanar with regional cleavage and similarly oriented shear zones and plunge parallel to the elongation lineation. Systems have extreme vertical continuity (>1000 m), short strike length (400 m) and narrow width (100 m), exhibit vertical and lateral ore-type variation and have alteration haloes. Models of ore formation include classical hydrothermalism, structurally controlled remobilisation and polymodal concepts; syntectonic emplacement now holds sway.Fluid inclusions were examined from quartz±sulphide veins adjacent to now-extracted ore, from coexisting quartz–sulphide within ore, and from vughs in barren quartz veins. Lack of early primary inclusions precluded direct determination of fluids associated with D₂–D₃ ore and vein emplacement. Similarly, decrepitation (by near-isobaric heating) of the two oldest secondary populations precluded direct determination of fluid phases immediately following D₂–D₃ ore and vein emplacement. Post-decrepitation outflow (late D₃ to early post-D₃) is recorded by monophase CH₄ inclusions. Entrained outflow of deeply circulated meteoric fluid modified the CH₄ system; modification is recorded by H₂O+CH₄ and H₂O+(trace CH₄) secondary populations and by an H₂O+(trace CH₄) primary population. The contractional tectonics (D₂–D₃) of ore emplacement was superseded by relaxational tectonics (D_4P) that facilitated meteoric water penetration and return flow.Under D₂ prograde metamorphism, entrapment temperatures (Tt) and pressures (Pt) for pre-decrepitation secondary inclusions are estimated as Tt300–330 °C and Pt1.5–2 kbar≈Plith (the lithostatic pressure). Decrepitation accompanied peak metamorphism (T350–380 °C) in mid- to late-D₃, while in late-D₃ to early post-D₃, essentially monophase CH₄ secondary inclusions were entrapped at Tt350 °C and Pt=1.5–2 kbar≈Plith. Subsequently, abundant CH₄ and entrained meteoric water were entrapped as H₂O+CH₄ secondaries under slowly decreasing temperature (Tt330–350 °C) and constant pressure (Pt1.5–2 kbar). Finally, with increasingly dominant meteoric outflow, H₂O+(trace CH₄) populations record decreasing temperatures (Tt>300 to <350 down to 275–300 °C) at pressures of Phydrostatic<Pt (1 kbar) <Plith (1.5 kbar).The populations of inclusions provide insight into fluid types, flow regimes and P–T conditions during parts of the deposit's evolution. They indirectly support the role of basin-derived CH₄ fluids in ore formation, but provide no insight into a basement-sourced ore-forming fluid. They fully support post-ore involvement of meteoric water. The poorly constrained entrapment history is believed to span 10 Ma from 395 to 385 Ma.     

Viruses as potential regulators of regional brown tide blooms caused by the alga,Aureococcus anophagefferens

Blooms of the brown tide organismAureccoccus anophagefferens have recurred in the coastal bays in New Jersey since 1995 and in the coastal bays of Long Island since 1985. Intracellular viral-like particles (VLPs) were documented during 1999–2000 brown tide blooms in Little Egg Harbor, New Jersey, but it was not determined whether cells were infected during the termination of the bloom. The objective of this study was to determine if VLPs infected and lysed natural populations ofA. anophagefferens in coastal bays of New Jersey and New York in 2002 with the same frequency as in 1999–2000 and especially at the termination of the bloom. Our results confirmed that the highest percentage (37.5%) of VLP-infected cells occurred at the termination of the brown tide bloom in New Jersey in 2002. Intracellular VLPs were present throughout the bloom event. The percentage of visibly infected cells was higher at the beginning of the bloom than during the peak of the bloom. The intracellular VLPs in natural populations ofA. anophagefferens were consistent in size and shape (approximately 140 nm in diameter) and comparable to those in previous studies. Concentrated viral isolates, prepared from waters during brown tide blooms in New York and New Jersey in 2002, infected healthy laboratoryA. anophagefferens cultures in vitro. The viral isolates associated with the highest laboratory viral activity (lysis positive) were concentrated from water samples having the highest viral and bacteria concentrations. The intracellular viruses in these virally infected laboratory cultures ofA. anophagefferens were similar in size and shape to those found in natural populations. The successful isolation of a virus specific toA. anophagefferens from a brown tide bloom in the field, the similarity of ultrastructure of VLPs infecting both natural populations and laboratory infected cultures, and the pattern of VLP infection during bloom activity in combination with the observed high percentage of VLP-infected cells during bloom termination, supports, the hypothesis that viruses may be a major source of mortality for brown tide blooms in regional coastal bays of New Jersey and New York.     

Groundwater control of mangrove surface elevation: Shrink and swell varies with soil depth

We measured monthly soil surface elevation change and determined its relationship to groundwater changes at a mangrove forest site along Shark River, Everglades National Park, Florida. We combined the use of an original design, surface elevation table with new rod-surface elevation tables to separately track changes in the mid zone (0–4 m), the shallow root zone (0–0.35 m), and the full sediment profile (0–6 m) in response to site hydrology (daily river stage and daily groundwater piezometric pressure). We calculated expansion and contraction for each of the four constituent soil zones (surface [accretion and erosion; above 0 m], shallow zone [0–0.35 m], middle zone [0.35–4 m], and bottom zone [4–6]) that comprise the entire soil column. Changes in groundwater pressure correlated strongly, with changes in soil elevation for the entire profile (Adjusted R² = 0.90); this relationship was not proportional to the depth of the soil profile sampled. The change in thickness of the bottom soil zone accounted for the majority (R² = 0.63) of the entire soil profile expansion and contraction. The influence of hydrology on specific soil zones and absolute elevation change must be considered when evaluating the effect of disturbances, sea level rise, and water management decisions on coastal wetland systems.     

Relationships among intrinsic properties of ordinary chondrites: Oxidation state, bulk chemistry, oxygen-isotopic composition, petrologic type, and chondrule size

The properties of ordinary chondrites (OC) reflect both nebular and asteroidal processes. OC are modeled here as having acquired nebular water, probably contained within phyllosilicates, during agglomeration. This component had high Δ¹⁷O and acted like an oxidizing agent during thermal metamorphism. The nebular origin of this component is consistent with negative correlations in H, L, and LL chondrites between oxidation state (represented by olivine Fa) and bulk concentration ratios of elements involved in the metal-silicate fractionation (e.g., Ni/Si, Ir/Si, Ir/Mn, Ir/Cr, Ir/Mg, Ni/Mg, As/Mg, Ga/Mg). LL chondrites acquired the greatest abundance of phyllosilicates with high Δ¹⁷O among OC (and thus became the most oxidized group and the one with the heaviest O isotopes); H chondrites acquired the lowest abundance, becoming the most reduced OC group with the lightest O isotopes.Chondrule precursors may have grown larger and more ferroan with time in each OC agglomeration zone. Nebular turbulence may have controlled the sizes of chondrule precursors. H-chondrite chondrules (which are the smallest among OC) formed from the smallest precursors. In each OC region, low-FeO chondrules formed before high-FeO chondrules during repeated episodes of chondrule formation.During thermal metamorphism, phyllosilicates were dehydrated; the liberated water oxidized metallic Fe-Ni. This caused correlated changes with petrologic type including decreases in the modal abundance of metal, increases in olivine Fa and low-Ca pyroxene Fs, increases in the olivine/pyroxene ratio, and increases in the kamacite Co and Ni contents. As water (with its heavy O isotopes) was lost during metamorphism, inverse correlations between bulk δ¹⁸O and bulk δ¹⁷O with petrologic type were produced.The H5 chondrites that were ejected from their parent body ∼7.5 Ma ago during a major impact event probably had been within a few kilometers of each other since they accreted ∼4.5 Ga ago. There are significant differences in the olivine compositional distributions among these rocks; these reflect stochastic nebular sampling of the oxidant (i.e., phyllosilicates with high Δ¹⁷O) on a 0.1-1 km scale during agglomeration.