Boron in chert and Precambrian siliceous iron formations

In order to assess the importance of siliceous sediments as a sink for oceanic B and to determine the effect of diagenesis on the mobilization of B, samples were analysed from chert nodules, bedded cherts, and siliceous banded iron formations from a variety of sedimentary environments and geologic ages. Boron analyses on bulk samples were made by prompt gamma neutron activation analysis. The distribution of B in rocks was mapped using α-track methods.Nodular Phanerozoic cherts typically contain 50–150 ppm B, and bedded cherts somewhat less. The B is initially concentrated in tests of silica-secreting organisms, but some is lost in early diagenesis as silica progressively recrystallises to quartz.Banded iron formation silica of Archean and Proterozoic age usually contains < 2 ppm B. This conforms with the view that such silica is not of biogenic origin but, since many iron formations are undoubtedly of marine origin, raises the question whether Precambrian oceans were impoverished in B. Analyses of Precambrian marine argillaceous sediments, averaging 70 ppm B, do not resolve this question.     

Geochemistry and petrogenesis of a basalt-benmoreite-trachyte suite from the southern part of the Gregory Rift,Kenya

In the southern Gregory Rift valley a series of transitional basalt, ferrobasalt, and benmoreite flows (1.65–1.4 Myr) is overlain by flood trachyte lavas (1.3–0.9 Myr). Mass balance calculations for major element compositions of rocks of this suite and their phenocrysts and microphenocrysts suggest that the ferrobasalts and benmoreites formed from magma resembling the most primitive basalt by closed system fractionation of plagioclase, clinopyroxene, olivine, titanomagnetite, and apatite. The trachytes formed from evolved magmas largely by alkali feldspar fractionation. Estimates of phenocryst and liquid densities and Rayleigh-law modelling of trace element contents support these conclusions. From Rayleigh-law modelling, we derived a set of effective distribution coefficients. Partial melting of crustal rocks or volatile transfer processes had no significant effect on the petrogenesis of this suite. The duration of the eruptive cycle, cooling time calculations, and mass balance calculations suggest that fractionation occurred in a magma reservoir with volume of at least 3 × 10⁴ km³ during an interval of about 0.8 Myr. Temperatures during fractionation probably ranged from about 1200 °C to 900 °C, and pressures may have been roughly 5 to 8 Kb. We suggest that rift development was accompanied by large-scale injection of basaltic magma and dilation of the crust, extensive fractionation, preferential eruption of low-density and fluid trachytic flood lavas, and by several episodes of normal faulting.     

Twentieth century simulation of the southern hemisphere climate in coupled models. Part II: sea ice conditions and variability

We examine the representation of the mean state and interannual variability of Antarctic sea ice in six simulations of the twentieth century from coupled models participating in the Intergovernmental Panel on Climate Change fourth assessment report. The simulations exhibit a largely seasonal southern hemisphere ice cover, as observed. There is a considerable scatter in the monthly simulated climatological ice extent among different models, but no consistent bias when compared to observations. The scatter in maximum winter ice extent among different models is correlated to the strength of the climatological zonal winds suggesting that wind forced ice transport is responsible for much of this scatter. Observations show that the leading mode of southern hemisphere ice variability exhibits a dipole structure with anomalies of one sign in the Atlantic sector associated with anomalies of the opposite sign in the Pacific sector. The observed ice anomalies also exhibit eastward propagation with the Antarctic circumpolar current, as part of the documented Antarctic circumpolar wave phenomenon. Many of the models do simulate dipole-like behavior in sea ice anomalies as the leading mode of ice variability, but there is a large discrepancy in the eastward propagation of these anomalies among the different models. Consistent with observations, the simulated Antarctic dipole-like variations in the ice cover are led by sea-level pressure anomalies in the Amundsen/ Bellingshausen Sea. These are associated, to different degrees in different models, with both the southern annular mode and the El Nino-Southern Oscillation (ENSO). There are indications that the magnitude of the influence of ENSO on the southern hemisphere ice cover is related to the strength of ENSO events simulated by the different models.     

Carbonate abundances and isotopic compositions in chondrites

We report the bulk C abundances, and C and O isotopic compositions of carbonates in 64 CM chondrites, 14 CR chondrites, 2 CI chondrites, LEW 85332 (C2), Kaba (CV3), and Semarkona (LL3.0). For the unheated CMs, the total ranges of carbonate isotopic compositions are δ¹³C ≈ 25–75‰ and δ¹⁸O ≈ 15–35‰, and bulk carbonate C contents range from 0.03 to 0.60 wt%. There is no simple correlation between carbonate abundance and isotopic composition, or between either of these parameters and the extent of alteration. Unless accretion was very heterogeneous, the uncorrelated variations in extent of alteration and carbonate abundance suggests that there was a period of open system behavior in the CM parent body, probably prior to or at the start of aqueous alteration. Most of the ranges in CM carbonate isotopic compositions can be explained by their formation at different temperatures (0–130 °C) from a single fluid in which the carbonate O isotopes were controlled by equilibrium with water (δ¹⁸O ≈ 5‰) and the C isotopes were controlled by equilibrium with CO and/or CH₄ (δ¹³C ≈ ?33‰ or ?20‰ for CO‐ or CH₄‐dominated systems, respectively). However, carbonate formation would have to have been inefficient, otherwise carbonate compositions would have resembled those of the starting fluid. A quite similar fluid composition (δ¹⁸O ≈ ?5.5‰, and δ¹³C ≈ ?31‰ or ?17‰ for CO‐ or CH₄‐dominated systems, respectively) can explain the carbonate compositions of the CIs, although the formation temperatures would have been lower (~10–40 °C) and the relative abundances of calcite and dolomite may play a more important role in determining bulk carbonate compositions than in the CMs. The CR carbonates exhibit a similar range of O isotopes, but an almost bimodal distribution of C isotopes between more (δ¹³C ≈ 65–80‰) and less altered samples (δ¹³C ≈ 30–40‰). This bimodality can still be explained by precipitation from fluids with the same isotopic composition (δ¹⁸O ≈ ?9.25‰, and δ¹³C ≈ ?21‰ or ?8‰ for CO‐ or CH₄‐dominated systems, respectively) if the less altered CRs had higher mole fractions of CO₂ in their fluids. Semarkona and Kaba carbonates have some of the lightest C isotopic compositions of the meteorites studied here, probably because they formed at higher temperatures and/or from more CO₂‐rich fluids. The fluids responsible for the alteration of chondrites and from which the carbonates formed were almost certainly accreted as ices. By analogy with cometary ices, CO₂ and/or CO would have dominated the trapped volatile species in the ices. The chondrites studied are too oxidized for CO‐dominated fluids to have formed in their parent bodies. If CH₄ was the dominant C species in the fluids during carbonate formation, it would have to have been generated in the parent bodies from CO and/or CO₂ when oxidation of metal by water created high partial pressures of H₂. The fact that the chondrite carbonate C/H₂O mole ratios are of the order predicted for CO/CO₂‐H₂O ices that experienced temperatures of >50–100 K suggests that the chondrites formed at radial distances of <4–15 AU.     

A molecular and isotopic study of the macromolecular organic matter of the ungrouped C2 WIS 91600 and its relationship to Tagish Lake and PCA 91008

Abstract– Insight into the chemical history of an ungrouped type 2 carbonaceous chondrite meteorite, Wisconsin Range (WIS) 91600, is gained through molecular analyses of insoluble organic matter (IOM) using solid‐state ¹³C nuclear magnetic resonance (NMR) spectroscopy, X‐ray absorption near edge structure spectroscopy (XANES), and pyrolysis‐gas chromatography coupled with mass spectrometry (pyr‐GC/MS), and our previous bulk elemental and isotopic data. The IOM from WIS 91600 exhibits similarities in its abundance and bulk δ¹⁵N value with IOM from another ungrouped carbonaceous chondrite Tagish Lake, while it exhibits H/C, δ¹³C, and δD values that are more similar to IOM from the heated CM, Pecora Escarpment (PCA) 91008. The ¹³C NMR spectra of IOM of WIS 91600 and Tagish Lake are similar, except for a greater abundance of CH_xO species in the latter and sharper carbonyl absorption in the former. Unusual cross‐polarization (CP) dynamics is observed for WIS 91600 that indicate the presence of two physically distinct organic domains, in which the degrees of aromatic condensation are distinctly different. The presence of two different organic domains in WIS 91600 is consistent with its brecciated nature. The formation of more condensed aromatics is the likely result of short duration thermal excursions during impacts. The fact that both WIS 91600 and PCA 91008 were subjected to short duration heating that is distinct from the thermal history of type 3 chondrites is confirmed by Carbon‐XANES. Finally, after being briefly heated (400 °C for 10 s), the pyrolysis behavior of Tagish Lake IOM is similar to that of WIS 91600 and PCA 91008. We conclude that WIS 91600 experienced very moderate, short duration heating at low temperatures (<500 °C) after an episode of aqueous alteration under conditions that were similar to those experienced by Tagish Lake.     

Isotopic fractionation associated with biosynthesis of fatty acids by a marine bacterium under oxic and anoxic conditions

Shewanella putrefaciens (Strain MR-4), a gram negative facultative marine bacterium, was grown to stationary phase under both aerobic and anaerobic conditions using lactate as the sole carbon source. Aerobically-produced cells were slightly enriched in ¹³C (+1.5‰) relative to the lactate carbon source, whereas those from anaerobic growth were depleted in ¹³C (−2.2‰). The distribution of fatty acids produced under aerobic conditions was similar to that resulting from anaerobic growth, being dominated by C_16:1 ω7 and C_16:0 fatty acids with a lesser amount of the C_18:1 ω7 component. Low concentrations of saturated even numbered normal fatty acids in the C₁₄ to C₁₈ range, and iso-C_15:0 were synthesized under both conditions. Fatty acids from anaerobic cultures (average δ¹³C=−37.8‰) were considerably depleted in ¹³C relative to their aerobically-synthesized counterparts (−28.8‰). The distinct differences in isotopic composition of both whole cells and individual fatty acid components result from differences in assimilation pathways. Under aerobic conditions, the primary route of assimilation involves the pyruvate dehydrogenase enzyme complex which produces acetyl-CoA, the precursor to lipid synthesis. In contrast, under anaerobic conditions formate, and not acetate, is the central intermediate in carbon assimilation with the precursors to fatty acid synthesis being produced via the serine pathway. Anaerobically-produced bacterial fatty acids were depleted by up to 12‰ relative to the carbon source. Therefore, detection of isotopically depleted fatty acids in sediments may be falsely attributed to a terrestrial origin, when in fact they are the result of bacterial resynthesis.     

Consortium study of the unusual H chondrite regolith breccia,Noblesville

Abstract— The Noblesville meteorite is a genomict, regolith breccia (H6 clasts in H4 matrix). Mössbauer analysis confirms that Noblesville is unusually fresh, not surprising in view of its recovery immediately after its fall. It resembles “normal” H4–6 chondrites in its chemical composition and induced thermoluminescence (TL) levels. Thus, at least in its contents of volatile trace elements, Noblesville differs from other H chondrite, class A regolith breccias. Noblesville's small pre-atmospheric mass and fall near Solar maximum and/or its peculiar orbit (with perihelion <0.8 AU as shown by natural TL intensity) may partly explain its levels of cosmogenic radionuclides. Its cosmic ray exposure age of ～ 44 Ma, is long, is equalled or exceeded by <3% of all H chondrites, and also differs from the 33 ± 3 Ma mean exposure age peak of other H chondrite regolith breccias. One whole-rock aliquot has a high, but not unmatched, ¹²⁹Xe/¹³²Xe of 1.88. While Noblesville is now among the chondritic regolithic breccias richest in solar gases, elemental ratios indicate some loss, especially of He, perhaps b; impacts in the regolith that heated individual grains. While general shock-loading levels in Noblesville did not exceed 4 GPa, individual clasts record shock levels of 5–10 GPa, doubtless acquired prior to lithification of the whole-rock meteoroid.     

The origin and evolution of chondrites recorded in the elemental and isotopic compositions of their macromolecular organic matter

Extraterrestrial organic matter in meteorites potentially retains a unique record of synthesis and chemical/thermal modification by parent body, nebular and even presolar processes. In a survey of the elemental and isotopic compositions of insoluble organic matter (IOM) from 75 carbonaceous, ordinary and enstatite chondrites, we find dramatic variations within and between chondrite classes. There is no evidence that these variations correlate with the time and/or location of chondrite formation, or with any primary petrologic or bulk compositional features that are associated with nebular processes (e.g., chondrule and volatile trace element abundances). Nor is there evidence for the formation of the IOM by Fischer-Tropsch-Type synthesis in the nebula or in the parent bodies. The elemental variations are consistent with thermal maturation and/or oxidation of a common precursor. For reasons that are unclear, there are large variations in isotopic composition within and between chondrite classes that do not correlate in a simple way with elemental composition or petrologic type. Nevertheless, because of the pattern of elemental variations with petrologic type and the lack of any correlation with the primary features of the chondrite classes, at present the most likely explanation is that all IOM compositional variations are the result of parent body processing of a common precursor. If correct, the range of isotopic compositions within and between chondrite classes implies that the IOM is composed of several isotopically distinct components whose relative stability varied with parent body conditions. The most primitive IOM is found in the CR chondrites and Bells (CM2). Isotopically, the IOM from these meteorites resembles the IOM in interplanetary dust particles. Chemically, their IOM resembles the CHON particles of comet Halley. Despite the large isotopic anomalies in the IOM from these meteorites, it is uncertain whether the IOM formed in the interstellar medium or the outer Solar System, although the former is preferred here.     

Twentieth century simulation of the southern hemisphere climate in coupled models. Part 1: large scale circulation variability

The ability of five, global coupled climate models to simulate important atmospheric circulation characteristics in the Southern Hemisphere for the period 1960–1999 is assessed. The circulation features examined are the Southern Hemisphere annular mode (SAM), the semi-annual oscillation (SAO) and the quasi-stationary zonal wave 3 (ZW3). The models assessed are the National Center for Atmospheric Research Community Climate System Model Version 3 (CCSM3), the Commonwealth Scientific and Industrial Research Organisation Mark 3, the Geophysical Fluid Dynamics Laboratory Model, the Goddard Institute for Space Studies Model ER (GISS-ER) and the UK Meteorological Office Hadley Center Coupled Model Version 3. The simulations were compared to the NCAR–NCEP reanalyses. The models simulate a SAO which differs spatially from the observed over the Pacific and Indian oceans. The amplitudes are too high over the southern ocean and too low over the midlatitudes. These differences are attributed to a circumpolar trough which is too deep and extends too far north, and to the inability of the models to simulate the middle to high latitude temperature gradient. The SAM is well-represented spatially by most models but there are important differences which may influence the flow over the Pacific and in the region extending from the Ross to Weddell Seas. The observed trend towards positive polarity in the SAM is apparent in the ensemble averages of the GISS-ER and CCSM3 simulations, suggesting that the trend is due to external forcing by changes in the concentration of ozone and greenhouse gases. ZW3 is well-represented by the models but the observed trend towards positive phases of ZW3 is not apparent in the simulations suggesting that the observed trend may be due to natural variability, not external forcing.