Enhanced trapping of molybdenum by sulfurized marine organic matter of marine origin in Mesozoic limestones and shales

There have been many studies devoted to trace metals and their value in assessing the paleoredox conditions of ancient marine deposition. Among them, molybdenum (Mo) is frequently cited as an effective proxy for sediments and sedimentary rocks. Recently, Helz et al. (Helz, G.R., Miller, C.V., Charnock, J.M., Mosselmans, J.L.W., Pattrick, R.A.D., Garner, C.D., Vaughan, D.J., 1996. Mechanisms of molybdenum removal from the sea and its concentration in black shales: EXAFS evidences. Geochim. Cosmochim. Acta, 60, 3631-3642) and Adelson et al. (Adelson, J. M., Helz, G. R., Miller, C. V., 2001. Reconstructing the rise of recent coastal anoxia; molybdenum in Chesapeake Bay sediments. Geochim. Cosmochim. Acta, 65, 237-252.) suggested that Mo does not behave conservatively in the water column when H₂S reaches a threshold concentration. Above this concentration, a “switch” operates, and Mo is scavenged by forming bonds with metal-rich (notably iron) particles, sulfur-rich organic molecules and pyrite. In this paper, Mo-trapping by sulfur-rich organic matter (OM) in ancient marine deposits is emphasized. The following Mesozoic geological formations were selected for study because of their relatively high concentration of sulfurized OM: the Akkuyu Formation (Turkey), the Calcaires d'Orbagnoux (France) and Kimmeridge Clay (UK) and its timeequivalent in Boulonnais (France), the Kashpir oil shales (Russia), and the La Luna Formation (Venezuela). The sulfur-rich OM is identified by either measured organic-S abundance or kerogen microscope observation. Our results show that Mo is systematically more enriched relative to the other redox-sensitive/sulfide-forming elements studied (U, V, Ni, Cu, Zn, Cr), and Mo enrichment is positively correlated with the amount of sulfurized OM but not with pyrite abundance. These results illuminate the role played by sulfurized OM in geologic-scale Mo capture and retention, but they also underline the role played by reactive iron. Significant OM sulfurization is only possible when reactive iron is limited. Nevertheless, pyrite formation, though limited, could act as an initial Mo trap, prior to Mo uptake by OM that is sulfurized after the pyritization step. In future paleoenvironmental reconstructions, attention must be paid to this enhanced Mo enrichment in the presence of sulfurized organic matter. In such cases, the use of Mo could lead to overestimation of the reducing conditions of the depositional environment.     

New data on the abundance of palladium in meteorites

The concentration of Pd in 7 carbonaceous chondrites, 18 ordinary chondrites, 3 achondrites, 29 iron meteorites and other samples has been determined by stable isotope dilution using solid source mass spectrometry. The Cl chondrite Orgueil gives a ‘cosmic’ abundance for Pd of 1.5 (Si = 10⁶ atoms), in good agreement with the currently accepted value.The concentration of Pd shows little variation among the carbonaceous chondrites, but in ordinary chondrites decreases from the H to L to LL groups. Pd in achondrites is approx 100 times lower than in chondrites. Data for iron meteorites plot around the ‘cosmic’ $\text{Pd}\text{Ni}$ ratio; however the Pd data falls into distinct groups, corresponding to the chemical group classification. These results support the hypothesis that at least two fractionation processes have occurred during the formation of iron meteorites.     

Hydrogen isotope evidence for the origin and evolution of the carbonaceous chondrites

We present new hydrogen isotope data for separated matrix, hydrated chondrules, and other hydrated coarse silicate fragments from nine carbonaceous chondrites. These data were generated using a micro-analytical method involving stepped combustion of tens to hundreds of micrograms of hydrous solids. We also re-evaluate hydrogen isotope data from previous conventional stepped combustion experiments on these and other carbonaceous chondrites.Hydrogen isotope compositions of matrix and whole-rock samples of CM chondrites are correlated with oxygen isotope indices, major and minor-element abundances, and abundance and isotope ratios of other highly volatile elements. These correlations include a monotonic decrease in δD with increasing extent of aqueous alteration and decreasing abundances of highly volatile elements (including C, N and Ar), between extremes of ∼0‰ (least altered, most volatile rich) and −200‰ (most altered, least volatile rich). In plots involving only abundances and/or isotope ratios of highly volatile elements, CI chondrites fall on the high-δD, volatile rich end of the trends defined by CM chondrites; i.e., CI chondrites resemble the least altered CM chondrites in these respects. These trends suggest the protoliths of the CM chondrites (i.e., before aqueous alteration) contained an assemblage of volatiles having many things in common with those in the CI chondrites. If so, then the volatile-element inventory of the CI chondrites was a more widespread component of early solar system objects than suggested by the scarcity of recognized CI meteorites. Differences in volatile-element chemistry between the CI and average CM chondrites can be attributed to aqueous alteration of the latter.Previous models of carbonaceous chondrite aqueous alteration have suggested: (1) the protoliths of the CM chondrites are volatile poor objects like the CO or CV chondrites; and (2) the CI chondrites are more altered products of the same process producing the CM chondrites. Both suggestions appear to be inconsistent with hydrogen isotope data and other aspects of the volatile-element geochemistry of these rocks. We present a model for aqueous alteration of the CM chondrites that reconciles these inconsistencies and suggests revised relationships among the major subtypes of carbonaceous chondrites. Our model requires, among other things, that the water infiltrating CM chondrites had a δD value of ∼−158‰, consistent with initial accretion of CM parent bodies at ∼4 AU.     

Trace elements in primitive meteorites—V. Abundance patterns of thirteen trace elements and interelement relationships in enstatite chondrites

Neutron activation analysis was used to determine As, Au, Bi, Cd, Co, Cu, Ga, In, Sb, Se, Te, Tl and Zn in 11 samples representing 9 chondrites of grades E4–6. These chondrites exhibit systematic intra- and inter-grade differences particularly for highly-variable elements, the differences being E4 ? E3 > E6 ? E5. The abundance pattern for these 13 and an additional 16 elements in E3-6 chondrites differs from those of other primitive meteorites—the carbonaceous and unequilibrated ordinary chondrites. A search for statistically-significant interelement relationships among the 13 elements (for grades E4–6) reveal that 40 elementpairs are linearly and/or exponentially correlated. Similar consideration of data for 37 elements in 12 chondrites (grades E3–6) reveals that 191 element-pairs exhibit such relationships, 170 involving linear and/or exponential correlations, the remainder involving anti-correlations. The patterns depicting these relationships—i.e. the correlation profiles—and elemental abundance patterns, factor analysis and two-element correlation diagrams are consistent with all enstatite chondrites representing a single evolutionary sequence. The primary process responsible for the chemical trends of these chondrites involved thermal fractionation accompanied by geochemical fractionation of sulfide-plus-metal from silicate, probably during condensation and accretion of solid material from the solar nebula. Chalcophile elements may have been fractionated during condensation or, after accretion, during thermal metamorphism in the parent body. No genetic model proposed thus far accounts for the detailed chemical trends, although the constrained equilibrium theory and two-component condensation theories qualitatively seem most satisfactory. The correlation profiles of enstatite, carbonaceous and unequilibrated ordinary chondrites are distinctly different, pointing to major differences in the formation conditions of these different sorts of primitive meteorites.     

The composition of the Earth

Compositional models of the Earth are critically dependent on three main sources of information: the seismic profile of the Earth and its interpretation, comparisons between primitive meteorites and the solar nebula composition, and chemical and petrological models of peridotite-basalt melting relationships. Whereas a family of compositional models for the Earth are permissible based on these methods, the model that is most consistent with the seismological and geodynamic structure of the Earth comprises an upper and lower mantle of similar composition, an Fe---Ni core having between 5% and 15% of a low-atomic-weight element, and a mantle which, when compared to CI carbonaceous chondrites, is depleted in Mg and Si relative to the refractory lithophile elements.The absolute and relative abundances of the refractory elements in carbonaceous, ordinary, and enstatite chondritic meteorites are compared. The bulk composition of an average CI carbonaceous chondrite is defined from previous compilations and from the refractory element compositions of different groups of chondrites. The absolute uncertainties in their refractory element compositions are evaluated by comparing ratios of these elements. These data are then used to evaluate existing models of the composition of the Silicate Earth.The systematic behavior of major and trace elements during differentiation of the mantle is used to constrain the Silicate Earth composition. Seemingly fertile peridotites have experienced a previous melting event that must be accounted for when developing these models. The approach taken here avoids unnecessary assumptions inherent in several existing models, and results in an internally consistent Silicate Earth composition having chondritic proportions of the refractory lithophile elements at 2.75 times that in CI carbonaceous chondrites. Element ratios in peridotites, komatiites, basalts and various crustal rocks are used to assess the abundances of both non-lithophile and non-refractory elements in the Silicate Earth. These data provide insights into the accretion processes of the Earth, the chemical evolution of the Earth's mantle, the effect of core formation, and indicate negligible exchange between the core and mantle throughout the geologic record (the last 3.5 Ga).The composition of the Earth's core is poorly constrained beyond its major constituents (i.e. an Fe---Ni alloy). Density contrasts between the inner and outer core boundary are used to suggest the presence ( 10 ± 5%) of a light element or a combination of elements (e.g., O, S, Si) in the outer core. The core is the dominant repository of siderophile elements in the Earth. The limits of our understanding of the core's composition (including the light-element component) depend on models of core formation and the class of chondritic meteorites we have chosen when constructing models of the bulk Earth's composition.The Earth has a bulk Fe/Al of 20 ± 2, established by assuming that the Earth's budget of Al is stored entirely within the Silicate Earth and Fe is partitioned between the Silicate Earth ( 14%) and the core ( 86%). Chondritic meteorites display a range of Fe/Al ratios, with many having a value close to 20. A comparison of the bulk composition of the Earth and chondritic meteorites reveals both similarities and differences, with the Earth being more strongly depleted in the more volatile elements. There is no group of meteorites that has a bulk composition matching that of the Earth's.     

The significance of meteorite density and porosity

Non-destructive, non-contaminating, and relatively simple procedures can be used to measure the bulk density, grain density, and porosity of meteorites. Most stony meteorites show a relatively narrow range of densities, but differences within this range can be useful indicators of the abundance and oxidation state of iron and the presence or absence of volatiles. Typically, ordinary chondrites have a porosity of just under 10%, while most carbonaceous chondrites (with notable exceptions) are more than 20% porous. Such measurements provide important clues to the nature of the physical processes that formed and evolved both the meteorites themselves and their parent bodies. When compared with the densities of small solar system bodies, one can deduce the nature of asteroid and comet interiors, which in turn reflect the accretional and collisional environment of the early solar system.     

Chromite alteration processes within Vourinos ophiolite

The renewed interest in chromite ore deposits is directly related to the increase in Cr price ruled by international market trends. Chromite, an accessory mineral in peridotites, is considered to be a petrogenetic indicator because its composition reflects the degree of partial melting that the mantle experienced while producing the chromium spinel-bearing rock (Burkhard in Geochim Cosmochim Acta 57:1297–1306, 1993). However, the understanding of chromite alteration and metamorphic modification is still controversial (e.g. Evans and Frost in Geochim Cosmochim Acta 39:959–972, 1975; Burkhard in Geochim Cosmochim Acta 57:1297–1306, 1993; Oze et al. in Am J Sci 304:67–101, 2004). Metamorphic alteration leads to major changes in chromite chemistry and to the growth of secondary phases such as ferritchromite and chlorite. In this study, we investigate the Vourinos complex chromitites (from the mines of Rizo, Aetoraches, Xerolivado and Potamia) with respect to textural and chemical analyses in order to highlight the most important trend of alteration related to chromite transformation. The present study has been partially funded by the Aliakmon project in collaboration between the Public Power Corporation of Greece and Institute of Geology and Mineral Exploration of Kozani.     

The Confirmation of a New Type of Chondrites and Their Cosmochemical Significance

The data available show that some Antarctic carbonaceous chondrites are similar to Cl meteorites.Tehy contain a lot of phyllosilicate aggregates and the oxygen isotopic composition of the whole-rock samples is approximate to that of C1 chondrites,so they are named after quasi-C1(Q-C1)chondrites Unlike Cl metcorites,the Q-Cl chondites possess chondrule structrue,and the compositions of hih temperature condensates(chondrule fragments,mineral grains or aggregates)show that the oxygen fugacity varied within a wide range in the surroundings where they were formed,similar to the variation range from E.H.L,LL to C group chondrites.It is inferred that the Q-C1 chondrites could be formed at the edges far from the equator in the whole asteroid region of the solar nebular disk.where the nebula was lower in density and the condensates were lower in accretion velocity,so that the hydration of chon drules and matrix occurred during the late stage of nebular condensation.The discovery of the Q-Cl chondrites and the fact that the earth and other terrestrial planets contain water indicate that at the edges far from the equator in the terrestrial reigion of the solar nebular disk,a large amount of water was incorporated into the lattice of minerals in the condensates as a result of hydration during nebular condensation,and then found its way into the interior parts of the Earth and other terrestrial planets due to accretion.     

Carbon,hydrogen and nitrogen in carbonaceous chondrites: Abundances and isotopic compositions in bulk samples

Whole-rock samples of 25 carbonaceous chondrites were analysed for contents of C, H and N and δ¹³C, δD and δ¹⁵N. Inhomogeneous distribution of these isotopes within individual meteorites is pronounced in several cases. Few systematic intermeteorite trends were observed; N data are suggestive of isotopic inhomogeneity in the early solar system. Several chondrites revealed unusual compositions which would repay further, more detailed study. The data are also useful for classification of carbonaceous chondrites; N abundance and isotopic compositions can differentiate existing taxonomic groups with close to 100% reliability; Al Rais and Renazzo clearly constitute a discrete “grouplet”; and there are hints that both CI and CM groups may each be divisible into two subgroups.     

Assessment of the Re decay constant by cross calibration of Re-Os molybdenite and U-Pb zircon chronometers in magmatic ore systems

The past decade has seen renewed interest in ¹⁸⁷Re-¹⁸⁷Os geochronology using a variety of matrices including sulfide minerals, shales and meteorites. The most widely used value of the ¹⁸⁷Re decay constant (λ¹⁸⁷Re) is 1.666 ± 0.005 × 10⁻¹¹ a⁻¹ (±0.31%), which is based on cross calibration of Re-Os and Pb-Pb chronometers for certain meteorites [Smoliar M. I., Walker R. J., and Morgan J. W. (1996) Re-Os isotope constraints on the age of Group IIA, IIIA, IVA, and IVB iron meteorites. Science271, 1099-1102]. However, other recent studies have yielded alternate values of λ¹⁸⁷Re, based upon either direct counting experiments or analysis of meteorites. Here, we provide an independent assessment of λ¹⁸⁷Re, using methodology, sample materials, and preparation of Os standard solutions different from those of Smoliar et al. (1996). Combining Re-Os age data for molybdenite formed in magmatic ore deposits, with the U-Pb zircon age of the magmatic rocks, a refined λ¹⁸⁷Re value is determined by averaging 11 individual cross-calibration experiments spanning ca. 2700 Ma of Earth history. Using the U decay constants of Jaffey [Jaffey A. H., Flynn K. F., Glendenin L. E., Bentley W. C., and Essling A. M. (1971) Precision measurement of half-lives and specific activities of 235U and 238U. Phys. Rev.4, 1889-1906], a value for λ¹⁸⁷Re of 1.6668 ± 0.0034 × 10⁻¹¹ a⁻¹ is determined. Using the λ²³⁸U value of Jaffey et al. (1971) and λ²³⁵U value of Schoene [Schoene B., Crowley J. L., Condon D. J., Schmitz M. D., and Bowring S. A. (2006) Reassessing the uranium decay constants for geochronology using ID-TIMS U-Pb data. Geochim. Cosmochim. Acta70, 426-445], a value for λ¹⁸⁷Re of 1.6689 ± 0.0031 × 10⁻¹¹ a⁻¹ is determined. These values are nominally higher (ca. 0.1 and ca. 0.2%) than the value determined by Smoliar et al. [Smoliar M. I., Walker R. J., and Morgan J. W. (1996) Re-Os isotope constraints on the age of Group IIA, IIIA, IVA, and IVB iron meteorites. Science271, 1099-1102], but within calculated uncertainty. Further refinement of λ¹⁸⁷Re by cross calibrating the molybdenite and U-Pb zircon chronometers should be possible by utilizing high precision, single-grain, chemical abrasion zircon U-Pb analyses.     

Organic matter and metamorphic history of CO chondrites

The metamorphic grades of a series of eight CO3 chondrites (ALHA77307, Colony, Kainsaz, Felix, Lancé, Ornans, Warrenton and Isna) have been quantified. The method used was based on the structural grade of the organic matter trapped in the matrix, which is irreversibly transformed by thermal metamorphism. The maturation of the organic matter is independent with respect to the mineralogical context and aqueous alteration. This metamorphic tracer is thus valid whatever the chemical class of chondrites. Moreover, it is sensitive to the peak metamorphic temperature.The structural grade of the organic matter was used along with other metamorphic tracers such as petrography of opaque minerals, Fa and Fs silicate composition in type I chondrules, presolar grains and noble gas (P3 component) abundance. The deduced metamorphic hierarchy and the attributed petrographic types are the following: ALHA77307 (3.03) < Colony (3.1) < Kainsaz (3.6) < Felix (3.6 (1)) < Ornans (3.6 (2)) < Lancé (3.6 (3)) < Warrenton (3.7 (1)) < Isna (3.7 (2)).For most metamorphosed objects, the peak metamorphic temperature can be estimated using a geothermometer calibrated with terrestrial metasediments [Beyssac O., Goffe B., Chopin C., and Rouzaud J. N. (2002) Raman spectrum of carbonaceous material in metasediments: a new geothermometer. J. Metamorph. Geol., 20, 859-871]. A value of 330 °C was obtained for Allende (CV chondrite), Warrenton and Isna, consistent with temperatures estimated from Fe diffusion [Weinbruch S., Armstrong J., and Palme H. (1994). Constraints on the thermal history of the Allende parent body as derive from olivine-spinel thermometry and Fe/Mg interdiffusion in olivine. Geochim. Cosmochim. Acta58(2), 1019-1030.], from the Ni content in sulfide-metal assemblages [Zanda B., Bourot-Denise M., and Hewins R. (1995) Condensate sulfide and its metamorphic transformations in primitive chondrites. Meteorit. Planet. Sci.30, A605.] and from the d₀₀₂ interlayer spacing in poorly graphitized carbon [Rietmeijer, F., and MacKinnon, I. (1985) Poorly graphitized carbon as a new cosmothermometer for primitive extraterrestrial materials. Nature, 315, 733-736]. The trapped noble gas and C content appear to be sensitive but not precise metamorphic tracers, indicating that the “Ornans paradox” does not exist. Major problems with the current petrologic types derived from Induced ThermoLuminescence are pointed out.     

Chemical and petrographic constraints on the origin of chondrules and inclusions in carbonaceous chondrites

Bulk chemical compositions of the various petrographie types of chondrules and inclusions in Type 3 carbonaceous chondrites (excluding those affected by metamorphism) have been determined by microprobe defocused beam analysis. Inclusion compositions follow approximately the theoretical compositional trajectory for equilibrium condensation. Analyses of chondrules occurring in the same meteorites have higher silica contents and show only slight overlap with inclusion compositions. Dust fusion is apparently an inadequate mechanism for producing the wide chemical variations observed among chondrules. Impact melting models require sampling of complex target rocks which are unknown as components of meteorites; this mechanism also demands efficient mechanical processing of chondrules before accretion. A genetic relationship between chondrules and inclusions in carbonaceous chondrites is suggested by the compositional continuum between these objects. A condensation sequence which dips into the liquid stability field at lower temperatures is advocated for the production of both inclusions and chondrules. Textural relationships between intergrown chondrules and inclusions support such a sequence. This model suggests that the assembled components (inclusions and chondrules) of carbonaceous chondrites are related by a common process.     

Composition and origin of the volatile components released from the Pesyanoe aubrite by stepwise crushing and heating

Aubrites are achondritic meteorites (enstatite pyroxenites) that were formed in highly reduced magmatic environments on a differentiated parent body sharing a common oxygen isotope reservoir with enstatite chondrites (EC), Earth and Moon, and could be considered as a geochemical model of the early proto-Earth. Some pyroxenes of the Pesyanoe aubrite have high abundance of gaseous inclusions, captured during the crystallization of the rocks. Investigation of the inclusions by IR spectroscopy reveals presence of OH⁻ groups and C–H bonds. The former are assigned to protonated point defects in enstatite lattice and the latter to compounds occupying void walls. Molecular water and CO₂ were not observed. Volatile components released from the samples of the Pesyanoe enstatite by stepwise crushing and heating are composed of CO₂, H₂O and a non-condensable phase. Hydrogen isotopic composition of volatiles extracted in form of molecular water in Px-separates varies in the range δD = −61 – −84‰ with mean value of δD = −73 ± 16‰ VSMOW and is within the ranges of ECs and Earth’s mantle. The total abundance of H₂ in the pyroxene of Pesyanoe were estimated as at least 0.047 ppm that is too low in comparison with that of enstatite chondrites (≥30 ppm H₂) and could indicate nearly complete degassing of the Pesyanoe primitive precursor material during the Pesyanoe parent body accretion or a mantle degassing in igneous differentiation process. In a last case a primitive precursor could have D/H ratio different from that of enstatite chondrites.     

Early core formation in asteroids and late accretion of chondrite parent bodies: Evidence from Hf-W in CAIs, metal-rich chondrites, and iron meteorites

The ¹⁸²Hf-¹⁸²W isotopic systematics of Ca-Al-rich inclusions (CAIs), metal-rich chondrites, and iron meteorites were investigated to constrain the relative timing of accretion of their parent asteroids. A regression of the Hf-W data for two bulk CAIs, various fragments of a single CAI, and carbonaceous chondrites constrains the ¹⁸²Hf/¹⁸⁰Hf and ε_W at the time of CAI formation to (1.07 ± 0.10) × 10⁻⁴ and −3.47 ± 0.20, respectively. All magmatic iron meteorites examined here have initial ε_W values that are similar to or slightly lower than the initial value of CAIs. These low ε_W values may in part reflect ¹⁸²W-burnout caused by the prolonged cosmic ray exposure of iron meteorites, but this effect is estimated to be less than ∼0.3 ε units for an exposure age of 600 Ma. The W isotope data, after correction for cosmic ray induced effects, indicate that core formation in the parent asteroids of the magmatic iron meteorites occurred less than ∼1.5 Myr after formation of CAIs. The nonmagmatic IAB-IIICD irons and the metal-rich CB chondrites have more radiogenic W isotope compositions, indicating formation several Myr after the oldest metal cores had segregated in some asteroids.Chondrule formation ∼2-5 Myr after CAIs, as constrained by published Pb-Pb and Al-Mg ages, postdates core formation in planetesimals, and indicates that chondrites do not represent the precursor material from which asteroids accreted and then differentiated. Chondrites instead derive from asteroids that accreted late, either farther from the Sun than the parent bodies of magmatic iron meteorites or by reaccretion of debris produced during collisional disruption of older asteroids. Alternatively, chondrites may represent material from the outermost layers of differentiated asteroids. The early thermal and chemical evolution of asteroids appears to be controlled by the decay of ²⁶Al, which was sufficiently abundant (initial ²⁶Al/²⁷Al >1.4 × 10⁻⁵) to rapidly melt early-formed planetesimals but could not raise the temperatures in the late-formed chondrite parent asteroids high enough to cause differentiation. The preservation of the primitive appearance of chondrites thus at least partially reflects their late formation rather than their early and primitive origin.     

太阳星云凝聚过程的岩石学模型：（Ⅱ）非球陨石、C1陨石及类C1陨石的凝聚成因和小行星区星云凝聚作用

综述了非球陨石（铁陨石,石铁陨石和无球粒陨石）在成分结构方面的非分异成因证据,推断其成因是：星云盘中心层中的星云发生气－液凝聚作用形成的熔滴,在较高温度下彼此合并形成了较大熔体,熔体固化后形成该类陨石母体。根据Ｃ１陨石不含球粒和其它成分特征,推断它们是星云只发生气－固凝聚作用的产物。对近年来新发现的一些特殊成分的碳质球粒陨石进行了综合分析,暂定名为类Ｃ１陨石。通过类Ｃ１陨石与其它球粒陨石及Ｃ１陨石成分结构特征的对比,推断它们是星云盘边缘层星云发生气－液－固和气－固联合凝聚作用,同时发生水化作用的产物。最后,在对所有陨石凝聚成因进行解释的基础上,建立了小行星区星云凝聚模型。     

Pressures of formation of iron meteorites from sphalerite compositions

The FeS content of sphalerite, a minor phase in some meteorites, is strongly dependent on pressure when the sphalerite is in equilibrium with troilite. We have determined FeS contents for sphalerite in Bogou, Gladstone, Sardis and Odessa ; these, together with published data on Odessa and Campo del Cielo, have been used to calculate pressures of formation of meteorites, assuming that FeS-diffusion in sphalerite ceases at 350°C. Calculated pressures range from 0.2 to 3.1 kbar, corresponding to formation at centres of chondritic objects from 140 to 410 km in radius, or metallic objects of from 50 to 200 km radius. Formation at shallower depths would require the objects to have been correspondingly larger.All meteorites in this study are members of Ga-Ge group I. Inverse correlation between Ge content and pressure of formation suggests formation at various depths in a compositionally zoned (fractionated?) object. Comparison between our pressure estimates and radii estimated from cooling rates (Frickeret al., 1970, Geochim. Cosmochim. Acta34, 475–492) suggests that Odessa, Bogou and possibly other Group I meteorites formed in a single object with a radius between 400 and 180 km and an overall composition richer in metal than average chondrites.     

Evidence from Ar/Ar ages of lunar impact glasses for an increase in the impact rate ∼800 Ma ago

Geochemical and ⁴⁰Ar/³⁹Ar data on nine impact glasses from the Apollo 14, 16, and 17 landing sites indicate at least seven distinct impact events with ages ∼800 Ma. Rock fragments analyzed by Barra et al. [Barra F., Swindle T. D., Korotev R. L., Jolliff B. L., Zeigler R. A., and Olsen E. (2006) ⁴⁰Ar-³⁹Ar dating of Apollo 12 regolith: implications for the age of Copernicus and the source of nonmare materials, Geochim. Cosmochim. Acta,70, 6016-6031] from the Apollo 12 landing site and some Apollo 12 spherules reported by Levine et al. [Levine J., Becker T. A., Muller R. A., Renne P. R. (2005) ⁴⁰Ar/³⁹Ar dating of Apollo 12 impact spherules, Geophys. Res. Let., 32, L15201, doi: 10.1029/2005GL022874.] show ∼800 Ma ages, close to the accepted age of the Copernicus event, 800 ± 15 Ma [Bogard D. D., Garrison D. H., Shih C. Y., and Nyquist L. E. (1994) ³⁹Ar-⁴⁰Ar dating of two lunar granites: The age of Copernicus, Geochim. Cosmochim. Acta, 58, 3093-3100]. These Apollo 12 samples are thought to have been affected by material from the Copernicus event since there is a Copernicus ray going through the Apollo 12 landing site. When all of these data are viewed collectively, including an Apollo 16 glass bomb [Borchardt R., Stöffler D., Spettel B., Palme H. and Wänke H. (1986) Composition, structure, and age of the Apollo 16 subregolith basement as deduced from the chemistry of post-Imbrium melt bombs. In Proceedings, 17th Lunar and Planetary Science Conference, pp. E43-E54], and in the context of diverse compositional range and sample location, there is a suggestion that there may have been a transient increase in the global lunar impact flux at ∼800 Ma. Therefore, the Copernicus impact event could have been one of many. If correct, there should be evidence for this increased impact flux around 800 Ma ago in the age statistics of terrestrial impact samples.     

A revision of the meteorite based cosmic abundance of boron

Analyses of meteorites for B abundances have shown that many chondrites are contaminated with terrestrial B, producing erroneously high meteoritic abundances of this element. Boron concentrations in freshly prepared interior samples are significantly lower than they are in samples with unknown or unspecified terrestrial histories. An estimate of the cosmic abundance based upon the analyses of 8 interior samples of 2 carbonaceous chondrites and 1 interior sample of each of 8 ordinary chondrites is a factor of 6.7 less than the previous low estimate. Our revised value, 3.0 B/10¹⁰H, is in excellent agreement with estimates based on observations of the solar photosphere. There is no longer a need to consider processes that enrich B in carbonaceous chondrites or deplete it in the sun. Relative meteoritic abundances of Li, Be and B are now in general agreement with models of nucleosynthesis of these light elements by galactic cosmic ray induced spallation.     

Comment on “Hydrolysis of neptunium(V) at variable temperatures (10-85 °C)” by L. Rao, T.G. Srinivasan, A.Yu. Garnov, P. Zanonato, P. Di Bernardo, and A. Bismondo

In a recent study [Rao, L., Srinivasan, T.G., Garnov, A.Yu., Zanonato, P., Di Bernardo, P., Bismondo, A., 2004. Hydrolysis of neptunium(V) at variable temperatures (10-85 °C). Geochim. Cosmochim. Acta68, 4821-4830.] the hydrolysis of Np(V) was investigated at 10-85 °C by absorption spectroscopy, potentiometry, and microcalorimetry along the titration of Np(V) solutions with tetramethylammonium hydroxide up to pH 10. However, there is strong evidence that the precautions to avoid competing reactions with carbonate were not sufficient and that the measured effects are not caused by the formation of Np(V) hydroxide complexes but primarily by the formation of Np(V) carbonate complexes. The reported equilibrium constants, enthalpies, entropies, and heat capacities for the complexes NpO₂OH(aq) and are severely in error and must not be used for the geochemical modeling of neptunium. If the hydrolysis constants reported by Rao et al. [Rao, L., Srinivasan, T.G., Garnov, A.Yu., Zanonato, P., Di Bernardo, P., Bismondo, A., 2004. Hydrolysis of neptunium(V) at variable temperatures (10-85 °C). Geochim. Cosmochim. Acta68, 4821-4830] are used to calculate neptunium solubilities in alkaline solutions relevant for nuclear waste repositories, the Np(V) concentrations are overestimated by orders of magnitude.     

Ocean chemistry during glacial time—a comment

The detection and measurement of CO₂ in air bubbles entrapped in ice originated with Per F. Scholander in 1954, predating the studies referred to in Broecker (1982), Geochim. Cosmochim. Acta 46, 1689–1706.