A search for nickel isotopic anomalies in iron meteorites and chondrites

We report Ni isotopic data, for ^58,60-62Ni, on (1) FeNi metal and sulfides in different groups of iron meteorites, (2) sulfides and a whole rock sample of the St. Séverin chondrite, and (3) chondrules from the Chainpur chondrite. We have developed improved, Multiple-Collector, Positive ion Thermal Ionization Mass Spectrometric (MC-PTIMS) techniques, with Ni⁺ ionization efficiency at 1‰, and chemical separation techniques for Ni which reduce mass interferences to the 1 ppm level, so that no mass interference corrections need be applied, except for ⁶⁴Ni (from ⁶⁴Zn, at the 0.1‰ level), for which we do not report results. We normalize the data to ⁶²Ni/⁵⁸Ni to correct for mass dependent isotope fractionation. No evidence was found for resolved radiogenic or general Ni isotope anomalies at the resolution levels of 0.2 and 0.5 εu (εu = 0.01%) for ⁶⁰Ni/⁵⁸Ni and ⁶¹Ni/⁵⁸Ni, respectively. From the ⁵⁶Fe/⁵⁸Ni ratios and ε(⁶⁰Ni/⁵⁸Ni) values, we calculate upper limits for the initial value of (⁶⁰Fe/⁵⁶Fe)₀ of (a) <2.7 × 10⁻⁷ for Chainpur chondrules, (b) <10⁻⁸ for the St. Séverin sulfide, and (c) <4 × 10⁻⁹ for sulfides from iron meteorites. We measured some of the same meteorites measured by other workers, who reported isotopic anomalies in Ni, using Multiple-Collector, Inductively-Coupled Mass Spectrometry. Our results do not support the previous reports of Ni isotopic anomalies in sulfide samples from Mundrabilla by Cook et al. [Cook D. L., Clayton R. N., Wadhwa M., Janney P. E., and Davis A. M. (2008). Nickel isotopic anomalies in troilite from iron meteorites. Geophy. Res. Lett. 35, L01203] and in sulfides from Toluca and Odessa by Quitté et al. [Quitté G., Meier M., Latkoczy C., Halliday A. N., and Gunther D., (2006). Nickel isotopes in iron meteorites-nucleosynthetic anomalies in sulfides with no effects in metals and no trace of ⁶⁰Fe. Earth Planet. Sci. Lett. 242, 16-25]. Hence, we find no need for specialized physical-chemical planetary processes for the preservation of different Ni isotope compositions, between FeNi metal and sulfides in the same iron meteorites, as proposed by the above reports nor for complex astrophysical scenarios to provide the very peculiar Ni isotope anomalies reported by these workers for sulfides.     

The effect of aqueous diffusion on the fractionation of chlorine and bromine stable isotopes

Diffusive isotopic fractionation factors are important in order to understand natural processes and have practical application in radioactive waste storage and carbon dioxide sequestration. We determined the isotope fractionation factors and the effective diffusion coefficients of chloride and bromide ions during aqueous diffusion in polyacrylamide gel. Diffusion was determined as functions of temperature, time and concentration. The effect of temperature is relatively large on the diffusion coefficient (D) but only small on isotope fractionation. For chlorine, the ratio, D_³⁵Cl/D_³⁷Cl varied from 1.00128 ± 0.00017 (1σ) at 2 °C to 1.00192 ± 0.00015 at 80 °C. For bromine, D_⁷⁹Br/D_⁸¹Br varied from 1.00098 ± 0.00009 at 2 °C to 1.0064 ± 0.00013 at 21 °C and 1.00078 ± 0.00018 (1σ) at 80 °C. There were no significant effects on the isotope fractionation due to concentration. The lack of sensitivity of the diffusive isotope fractionation to anything at the most common temperatures (0 to 30 °C) makes it particularly valuable for application to understanding processes in geological environments and an important natural tracer in order to understand fluid transport processes.     

Mass-independent fractionation of oxygen isotopes in the mesostasis of a chondrule from the Semarkona LL3.0 ordinary chondrite

A large chondrule from Semarkona, the most primitive ordinary chondrite known, has been discovered to contain a record of mass transport during its formation. In most respects, it is a normal Type I, group A1, low-FeO chondrule that was produced by reduction and mass-loss during the unidentified flash-heating event that produced the chondrules, the most abundant structural component in primitive meteorites. We have previously measured elemental abundances and abundance profiles in this chondrule. We here report oxygen isotope ratio abundances and ratio abundance profiles. We have found that the mesostasis is zoned in oxygen isotope ratio, with the center of the chondrule containing isotopically heavier oxygen than the outer regions, the outer regions being volatile rich from the diffusion of volatiles into the chondrule during cooling. The δ¹⁷O values range from −2.0‰ to 9.9‰, while δ¹⁸O range from −1.9‰ to 9.6‰. More importantly, a plot of δ¹⁷O against δ¹⁸O has a slope of 1.1 ± 0.2 (1σ) and 0.88 ± 0.10 (1σ) when measured by two independent methods. Co-variation of δ¹⁷O with δ¹⁸O that does not follow mass-dependent fractionation has often been seen in primitive solar system materials and is usually ascribed to the mixing of different oxygen reservoirs. We argue that petrographic and compositional data indicate that this chondrule was completely melted at the time of its formation so that relic grains could not have survived. Furthermore, there is petrographic and compositional evidence that there was no aqueous alteration of this chondrule subsequent to its formation. Although it is possible to formulate a series of exchanges between the chondrule and external ¹⁶O-rich and ¹⁶O-poor reservoirs that may explain the detailed oxygen isotope systematics of this chondrule, such a sequence of events looks very contrived. We therefore hypothesize that reduction, devolatilization, and crystallization of the chondrule melt may have produced ¹⁶O-rich olivines and ¹⁶O-poor mesostasis plotting on a slope-one line as part of the chondrule-forming process in an analogous fashion to known chemical mass-independent isotopic fractionation mechanisms. During cooling, volatiles and oxygen near the terrestrial line in oxygen isotope composition produced the outer zone of volatile rich and ¹⁶O-rich mesostasis. The chondrule therefore not only retains a record of considerable mass transport accompanying formation, but also may indicate that the isotopes of oxygen underwent mass-independent fractionation during the process.     

Weathering of ilmenite from Chavara deposit and its comparison with Manavalakurichi placer ilmenite,southwestern India

The magnetic fractions of ilmenite from the beach placer deposit of Chavara, southwest India have been studied for mineralogical and chemical composition to assess the range of their physical and chemical variations with weathering. Chavara deposit represents a highly weathered and relatively homogenous concentration. Significant variation in composition has been documented with alteration. The most magnetic of the fractions of ilmenite, separated at 0.15 Å, and with a susceptibility of 3.2 × 10^?6 m³ kg^?1, indicates the presence of haematite–ilmenite intergrowth. An iron-poor, titanium-rich component of the ilmenite ore has been identified from among the magnetic fractions of the Chavara ilmenite albeit with an undesirably high Nb₂O₅ (0.28%), Cr₂O₃ (0.23%) and Th (149 ppm) contents. The ilmenite from Chavara is compared with that from the nearby Manavalakurichi deposit of similar geological setting and provenance. The lower ferrous iron oxide (2.32–14.22%) and higher TiO₂ (56.31–66.45%) contents highlight the advanced state of alteration of Chavara. This is also evidenced by the relatively higher Fe³⁺/Fe²⁺ ratio compared to Manavalakurichi ilmenite. In fact, the ilmenite has significantly been converted to pseudorutile/leucoxene.     

A morphological, sedimentological and geophysical investigation of the Woore Moraine, Shropshire, England

The Bar Hill-Whitchurch-Wrexham Morainic Complex is a large-scale glacial landform thought to represent either the maximum extent or the re-advance of the British-Irish Ice Sheet during the Late Devensian. The origin of the moraine remains uncertain as its key characteristics have not been studied in detail due to a lack of exposures from which its large-scale structure can be determined. The development of new technologies has enabled detailed examination of the topography and internal structure of such large-scale landforms. This paper describes a multi-disciplinary approach involving digital geomorphological mapping using enhanced resolution NextMAP™ digital surface models, geophysical imaging (electrical resistivity tomography) and conventional sedimentological analyses. This combination of techniques is useful for elucidating the origin of a large glacial landform in a region of poor exposure. Digital elevation models such as NextMAP™ offer an efficient and accurate method for landform-mapping, whilst electrical resistivity tomography was able to map the major constituent sediments of the moraine, which had in turn been identified in the single exposure available. Additional geophysical techniques should however be applied to provide further structural data and thereby enable a more detailed interpretation of the moraine's internal structure. Preliminary findings indicate that the moraine is a glaciotectonic landform composed of diamicton and glaciofluvial sediments, an origin consistent with recent suggestions that the Cheshire Plain contained an active ice lobe during the last glacial maximum.     

Rapid incorporation of lipids into macromolecules during experimental decay of invertebrates: Initiation of geopolymer formation

Diagenetic alteration is critical for the preservation of fossil cuticles of plant and animal origin and to the formation of kerogen. The process takes place over millions of years, but the stage at which it is initiated is not known. Laboratory decay experiments were carried out on shrimps, scorpions and cockroaches to monitor changes in the chitin–protein of the arthropod cuticle and associated lipids. The cockroach and scorpion exoskeleton remained largely unaltered morphologically, but the shrimp experienced rapid decomposition within a month, which progressed through the 44 week duration of the experiment as revealed using electron microscopy. Mass spectrometry and ¹³C NMR (nuclear magnetic resonance) spectroscopy revealed the association of an n-alkyl component with labile lipids, such as fatty acids with up to 24 carbon atoms, which were incorporated into the decaying macromolecule. The scorpion and cockroach cuticle did not reveal the incorporation of additional lipids, indicating that decay is important in initiating in situ lipid association. This experiment provides evidence that lipids can become associated with carbohydrate and proteinaceous macromolecules during the very early stages of decay, representing the first stage in the transformation process that contributes to the aliphatic rich composition ubiquitous in organic fossils and kerogen.     

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.     

Detrital zircon provenance of Neoproterozoic to Cenozoic deposits in Iran: Implications for chronostratigraphy and collisional tectonics

Ion-microprobe U–Pb analyses of 589 detrital zircon grains from 14 sandstones of the Alborz mountains, Zagros mountains, and central Iranian plateau provide an initial framework for understanding the Neoproterozoic to Cenozoic provenance history of Iran. The results place improved chronological constraints on the age of earliest sediment accumulation during Neoproterozoic–Cambrian time, the timing of the Mesozoic Iran–Eurasia collision and Cenozoic Arabia–Eurasia collision, and the contribution of various sediment sources of Gondwanan and Eurasian affinity during opening and closure of the Paleotethys and Neotethys oceans. The zircon age populations suggest that deposition of the extensive ~ 1 km-thick clastic sequence at the base of the cover succession commenced in latest Neoproterozoic and terminated by Middle Cambrian time. Comparison of the geochronological data with detrital zircon ages for northern Gondwana reveals that sediment principally derived from the East African orogen covered a vast region encompassing northern Africa and the Middle East. Although most previous studies propose a simple passive-margin setting for Paleozoic Iran, detrital zircon age spectra indicate Late Devonian–Early Permian and Cambrian–Ordovician magmatism. These data suggest that Iran was affiliated with Eurasian magmatic arcs or that rift-related magmatic activity during opening of Paleotethys and Neotethys was more pronounced than thought along the northern Gondwanan passive-margin. For a Triassic–Jurassic clastic overlap assemblage (Shemshak Formation) in the Alborz mountains, U–Pb zircon ages provide chronostratigraphic age control requiring collision of Iran with Eurasia by late Carnian–early Norian time (220–210 Ma). Finally, Cenozoic strata yield abundant zircons of Eocene age, consistent with derivation from arc magmatic rocks related to late-stage subduction and/or breakoff of the Neotethys slab. Together with the timing of foreland basin sedimentation in the Zagros, these detrital zircon ages help bracket the onset of the Arabia–Eurasia collision in Iran between middle Eocene and late Oligocene time.     

Petrogenesis and paleotectonic history of the Wild Bight Group,an Ordovician rifted island arc in central Newfoundland

The Wild Bight Group (WBG) is a sequence of early and middle Ordovician volcanic, subvolcanic and epiclastic rocks, part of the Dunnage Tectonostratigraphic Zone of the Newfoundland Appalachians. A detailed geochemical and Nd-isotopic study of the volcanic and subvolcanic rocks has been carried out to determine the geochemical characteristics of the rocks, interpret their palcotectonic environments and constrain their petrogenetic history. The lower and central stratigraphic levels of the WBG contain mafic volcanic rocks with island-arc geochemical signatures, including LREE-enriched are tholeiites with _Nd(t) =-0.1 to +2.2 (type A-I), LREE-depleted arc tholeiites with _Nd(t) =+5.6 to +7.1 (type A-II) and an unusual suite of strongly incompatible-element depleted tholeiites in which _Nd(t) ranges from-0.9 to +4.6 and is negatively correlated with¹⁴⁷Sm/¹⁴⁴Nd (type A-III). High-silica, low-K rhyolites occur locally in the central part of the stratigraphy, associated with mafic rocks of arc affinity, and have _Nd(t) =+4.7 to +5.4. The upper stratigraphic levels of the WBG dominantly contain rocks with non-arc geochemical signatures, including alkalic basalts with _Nd(t) =+4.6 to +5.5 (type N-I), strongly LREE- and incompatible element-enriched tholeiites that are transitional between alkalic and non-alkalic rocks with _Nd(t) =+4.4 to +7.0 (type N-II) and rocks with flat to slightly LREE-enriched patterns and _Nd(t) =+5.1 to +7.4 (type N-III). Rocks with non-arc and arc signatures are locally interbedded near the stratigraphic type of the WBG. Nd-isotopic data in the type A-I and A-II rocks are generally compatible with mixing/partial melting models involving depleted mantle, variably contaminated by a subducted crustally-derived sediment. The petrogenesis of type A-III rocks must involve source mixing and multi-stage partial melting, but the details are not clear. The geochemistry and Nd isotope data for types N-I, N-II and N-III rocks are compatible with petrogenetic models involving variable partial melting of a source similar to that postulated for modern oceanic island basalts. Comparison of the WBG with modern analogues suggests a 3-stage developmental model: stage 1) island-arc volcanism (eruption of type mafic volcancs); stage 2) arc-rifting (continued eruption of type A-I, A-I, eruption of types A-II and A-III mafic volcanics and high-silica, low-K rhyolites); and stage 3) back-arc basin volcanism (continued minor eruption of type A-I basalts, eruption of types N-I, N-II, N-III basalts). Stages 1 and 2 volcanism involved partial melting of subduction contaminated mantle, while stage 3 volcanism utilized depleted-mantle sources not affected by the subducting slab. This model provides a basis for interpreting coeval sequences in central Newfoundland and a comparative framework for some early Paleozoic oceanic volcanic sequences elsewhere in the Appalachian orogen.     

Les gisements d'émeraude de la Cordillère Orientale de la Colombie: Nouvelles données métallogéniques

Emerald deposits of Colombia are confined to lower Cretaceous shales of the Eastern Cordillera. The tectonic pattern of the deposits is related to deep reverse and large regional fault systems. Hydrofracturing is the main factor controlling emerald mineralization. It permitted to the hydrothermal solutions to permeate through fractures but also along stratification planes forming in this case stratabound mineralizations. Emerald occurs in calcite veins, veinlets, pockets and brecciated zones associated mainly with pyrite, quartz, parisite, codazzite and fluorite. Emerald mineralization belongs to an epigenetic hydrothermal process. The alternance of arenite-shale formations in the Cretaceous probably played an important role in the accumulation of solutions and in the propagation of the hydrothermal channels. The origin of emerald involves chemical elements mobilized by the fluids in the Cr-V-Fe-Al-Si-bearing black shales. The source of beryllium remains a problem and is discussed in the paper.