Noble gases in ureilites: cosmogenic, radiogenic, and trapped components

Abundances and isotopic compositions of Ne (in bulk samples only), Ar, Kr, and Xe have been investigated in 6 monomict, 3 polymict, and the diamond-free ureilite ALH78019 and their acid-resistant, C-rich residues. Isotopic ratios of Kr and Xe are very uniform and agree with data for ureilites from the literature. The measured ratio ³⁸Ar/³⁶Ar showed large variations due to an experimental artifact. This is shown to be connected to the pressure dependence of the instrumental mass discrimination, which for ureilites with their low abundance of ⁴⁰Ar is different from that of the usual air standard. This observation necessitates a reassessment for the recently reported ³⁶Ar excesses due to possible decay of extinct ³⁶Cl in the Efremovka meteorite.Trapped ²²Ne in the range of (1.4-2.5) × 10⁻⁸ cc STP/g is present in bulk ureilites. A Ne three-isotope plot for polymict ureilites indicates the presence of solar Ne. ²¹Ne-based cosmic ray exposure ages for the 10 ureilites studied range from 0.1 Ma (for ALH78019) to 46.8 Ma (for EET83309)All ureilites may have started with nearly the same initial elemental ratio (¹³²Xe/³⁶Ar)₀, established in the nebula during gas trapping into their carbon carrier phases (diamond, amorphous C) by ion implantation. Whereas diamonds are highly retentive, amorphous C has suffered gas loss due to parent body metamorphism. The correlation of the elemental ratios ¹³²Xe/³⁶Ar and ⁸⁴Kr/³⁶Ar along the mass fractionation line could be understood as a two-component mixture of the unaffected diamond gases and the fractionated (to varying degrees) gases from amorphous C. In this view, the initial ratio (¹³²Xe/³⁶Ar)₀ is a measure of the plasma temperature in the nebula at the formation location of the carbon phases. Its lack of correlation with Δ¹⁷O (a signature of the silicate formation location) indicates that carbon phases and silicates formed independently in the nebula, and not from a carbon-rich magmaThe elemental ratios ¹³²Xe/³⁶Ar and ⁸⁴Kr/³⁶Ar in carbon-rich acid residues show a decreasing trend with depth (inferred from carbon consumption during combustion), which can be interpreted as a consequence of the ion implantation mechanism of gas trapping that leads to greater depth of implantation for lighter mass ionThe similarity between trapped gases in phase Q in primitive chondrites and the C phases in ureilites—for both elemental and isotopic compositions—strongly suggests that phase Q might also have received its noble gases by ion implantation from the nebula. The slight differences in the elemental ratios can be explained by a plasma temperature at the location of phase Q gas loading that was about 2000 K lower than for ureilite C phases. This inference is also consistent with the finding that the trapped ratio ¹²⁹Xe/¹³²Xe (1.042 ± 0.002) in phase Q is slightly higher, compared to that of ureilite C phases (1.035 ± 0.002), as a consequence of in situ decay of ¹²⁹I, and becomes observable due to higher value of I/Xe in phase Q as a result of ion implantation at about 2000 K lower plasma temperature.     

Evidence from polymict ureilite meteorites for a disrupted and re-accreted single ureilite parent asteroid gardened by several distinct impactors

Ureilites are ultramafic achondrites that exhibit heterogeneity in mg# and oxygen isotope ratios between different meteorites. Polymict ureilites represent near-surface material of the ureilite parent asteroid(s). Electron microprobe analyses of >500 olivine and pyroxene clasts in several polymict ureilites reveal a statistically identical range of compositions to that shown by unbrecciated ureilites, suggesting derivation from a single parent asteroid. Many ureilitic clasts have identical compositions to the anomalously high Mn/Mg olivines and pyroxenes from the Hughes 009 unbrecciated ureilite (here termed the “Hughes cluster”). Some polymict samples also contain lithic clasts derived from oxidized impactors. The presence of several common distinctive lithologies within polymict ureilites is additional evidence that ureilites were derived from a single parent asteroid.In situ oxygen three isotope analyses were made on individual ureilite minerals and lithic clasts, using a secondary ion mass spectrometer (SIMS) with precision typically better than 0.2-0.4‰ (2SD) for δ¹⁸O and δ¹⁷O. Oxygen isotope ratios of ureilitic clasts fall on a narrow trend along the CCAM line, covering the range for unbrecciated ureilites, and show a good anti-correlation with mineral mg#. SIMS analysis identifies one ferroan lithic clast as an R-chondrite, while a second ferroan clast is unlike any known meteorite. An exotic enstatite grain is derived from an enstatite chondrite or aubrite, and another pyroxene grain with Δ¹⁷O of −0.4 ± 0.2‰ is unrelated to any known meteorite type.Ureilitic olivine clasts with mg#s < 85 are much more common than those with mg# > 85 which include the melt-inclusion-bearing “Hughes cluster” ureilites. Thus melt was present in regions of the parent ureilite asteroid with a bulk mg# > 85 when the asteroid was disrupted by impact, giving rise to two types of ureilites: common ferroan ones that were residual after melting and less common magnesian ones that were still partially molten when disruption occurred. One or more daughter asteroids re-accreted from the remnants of the mantle of the proto-ureilite asteroid. Polymict ureilite meteorites represent regolith that subsequently formed on the surface of a daughter asteroid, including impact-derived material from at least six different meteoritic sources.     

Highly siderophile elements in ureilites

The abundances of the highly siderophile elements (HSE) Ru, Pd, Re, Os, Ir, and Pt were determined by isotope dilution mass spectrometry for 22 ureilite bulk rock samples, including monomict, augite-bearing, and polymict lithologies. This report adds significantly to the quantity of available Pt and Pd abundances in ureilites, as these elements were rarely determined in previous neutron activation studies. The CI-normalized HSE abundance patterns of all ureilites analyzed here except ALHA 81101 show marked depletions in the more volatile Pd, with CI chondrite-normalized Pd/Os ratios (excluding ALHA 81101) averaging 0.19 ± 0.23 (2σ). This value is too low to be directly derived from any known chondrite group. Instead, the HSE bulk rock abundances and HSE interelement ratios in ureilites can be understood as physical mixtures of two end member compositions. One component, best represented by sample ALHA 78019, is characterized by superchondritic abundances of refractory HSE (RHSE—Ru, Re, Os, Ir, and Pt), but subchondritic Pd/RHSE, and is consistent with residual metal after extraction of a S-bearing metallic partial melt from carbonaceous chondrite-like precursor materials. The other component, best represented by sample ALHA 81101, is RHSE-poor and has HSE abundances in chondritic proportions. The genesis of the second component is unclear. It could represent regions within the ureilite parent body (UPB), in which metallic phases were completely molten and partially drained, or it might represent chondritic contamination that was added during disruption and brecciation of the UPB. Removal of carbon-rich melts does not seem to play an important role in ureilite petrogenesis. Removal of such melts would quickly deplete the ureilite precursors in Re/Os and As/Au, which is inconsistent with measured osmium isotope abundances, and also with literature As/Au data for the ureilites. Removal of ²⁶Al during silicate melting may have acted as a switch that turned off further metal extraction from ureilite source regions.     

Origin of isotopically light nitrogen in meteorites

Bulk meteorite samples of various chemical classes and petrologic types (mainly carbonaceous chondrites) were systematically investigated by the stepped combustion method with the simultaneous isotopic analysis of carbon, nitrogen, and noble gases. A correlation was revealed between planetary noble gases associating with the Q phase and isotopically light nitrogen (δ¹⁵N up to –150‰). The analysis of this correlation showed that the isotopically light nitrogen (ILN) is carried by Q. In most meteorites, isotopically heavy nitrogen (IHN) of organic compounds (macromolecular material) is dominant. The ILN of presolar grains (diamond and SiC) and Q can be detected after separation from dominant IHN. Such a separation of nitrogen from Q and macromolecular material occurs under natural conditions and during laboratory stepped combustion owing to Q shielding from direct contact with oxygen, which results in Q oxidation at temperatures higher than the temperatures of the release of most IHN. There are arguments that ILN released at high temperature cannot be related to nanodiamond and SiC. The separation effect allowed us to constrain the contents of noble gases in Q, assuming that this phase is carbon-dominated. The directly measured ³⁶Ar/C and ¹³²Xe/C ratios in ILN-rich temperature fractions are up to 0.1 and 1 × 10^–4 cm³/g, respectively. These are only lower constraints on the contents. The analysis of the obtained data on the three-isotope diagram δ¹⁵N–³⁶Ar/¹⁴N showed that Q noble gases were lost to a large extent from most meteorites during the metamorphism of their parent bodies. Hence, the initial contents of noble gases in Q could be more than an order of magnitude higher than those directly measured. Compared with other carbon phases, Q was predominantly transformed to diamond in ureilites affected by shock metamorphism. The analysis of their Ar–N systematics showed that, similar to carbonaceous chondrites, noble gases were lost from Q probably before its transformation to diamond.     

On the possibility of a kinetic fractionation of nitrogen stable isotopes during natural diamond growth

In a diamond from New South Wales (Australia), cubic and octahedral growth sectors, as identified by cathodoluminescence (CL), show slight differences in N-contents of 29 and 42 ppm respectively but no significant differences in either δ¹³C, δ¹⁵N and nitrogen aggregation state with values at +1.96‰, +19.4‰, and 25% Type IaAB aggregation, respectively.Two gem cubes from the Orapa kimberlite (Botswana) were studied by CL revealing a nonfaceted cubic growth. Accordingly, nine other gem cubes were combusted and yielded δ¹³C-values from -5.33‰ to -6.63‰, δ¹⁵N from -1.0‰ to -5.5‰, and nitrogen contents from 914 to 1168 ppm, with nitrogen aggregation state being only Type IaA (zero % B). The gem cubes show striking similarities to fibrous/coated diamonds, not only in both δ¹³C ranges (less than 3‰ from -5 to -8‰), but also in the high levels of nitrogen (≈ 1000 ppm), suggesting that the two diamond types are related. Additionally, no δ¹⁵N variation was detected between the cube and octahedral growth sectors of the Australian diamond, in the cube sectors of the nine gem cubes from Botswana, nor in fibrous/coated diamonds previously studied. These analyses contrast with an earlier study on a synthetic diamond, which reported a strong kinetic fractionation of N-isotopes of about 40‰ between cube and octahedral growth. The present evidence, therefore, suggests that kinetic fractionation of N-isotopes does not operate during natural diamond formation.     

The origin of iron silicides in ureilite meteorites

Ureilite meteorites contain iron silicide minerals including suessite (Fe,Ni)₃Si, hapkeite (Fe₂Si) and xifengite (Fe₅Si₃). Despite occurring mostly in brecciated varieties presumed to be derived from the regolith of the ureilite parent asteroid, suessite has also been confirmed in one lithology of a dimict ureilite (NWA 1241). In contrast, Si-bearing Fe-metals occur in both brecciated and unbrecciated ureilites, implying that they were formed throughout the ureilite parent asteroid. We examined major, minor and trace element data of Fe-metals in seven brecciated ureilites (DaG 319, DaG 999, DaG 1000, DaG 1023, DaG 1047, EET 83309, and EET 87720) in addition to the dimict ureilite NWA 1241.In this study we show that the silicides and Si-bearing metals in ureilites have similar siderophile trace element patterns; therefore, the precursors to the silicides were indigenous to the ureilite parent body. Si-free kamacite grains in brecciated ureilites show flatter, more chondritic siderophile element patterns. They may also be derived from the interior of the ureilite parent body, but some may be of exogenous origin (impactor debris), as are rare taenite grains.On Earth, iron silicides are often formed under high-temperature and strongly reducing conditions (e.g. blast furnaces, lightning strikes). On the Moon, hapkeite (Fe₂Si) and other silicides have been found in the regolith where they were formed by impact-induced space weathering. In the Stardust aerogel, iron silicides derived from comet Wild2 were also formed by an impact-related reduction process. Silicides in ureilite regolith breccias may have formed by similar processes but ureilites additionally contain abundant elemental carbon which probably acted as a reducing agent, thus larger and more abundant silicide grains were formed than in the lunar regolith or cometary material. The origin of suessite in NWA 1241 may be analogous to that of reduced lithologies in the terrestrial mantle, although a regolith origin may also be possible since this sample is shown here to be a dimict breccia.     

Feldspathic clast populations in polymict ureilites: Stalking the missing basalts from the ureilite parent body

Polymict ureilites DaG 164/165, DaG 319, DaG 665, and EET 83309 are regolith breccias composed mainly of monomict ureilite-like material, but containing ∼2 vol% of feldspathic components. We characterized 171 feldspathic clasts in these meteorites in terms of texture, mineralogy, and mineral compositions. Based on this characterization we identified three populations of clasts, each of which appears to represent a common igneous (generally basaltic) lithology and whose mafic minerals show a normal igneous fractionation trend of near-constant Fe/Mn ratio over a range of Fe/Mg ratios that extend to much higher values than those in monomict ureilites. The melts represented by these populations are unlikely to be impact melts, because the ubiquitous presence of carbon in polymict ureilites (the regolith of the ureilite parent body) implies that impact melts would have crystallized under conditions of carbon redox control and therefore have highly magnesian mafic mineral compositions with constant Mn/Mg ratio. Therefore, these melts appear to be indigenous products of igneous differentiation on the ureilite parent body (UPB), complementary to the olivine-pigeonite residues represented by the majority of monomict ureilites.The most abundant population is characterized by albitic plagioclase in association with pyroxenes, phosphates, ilmenite, silica, and incompatible-element enriched glass. Model calculations suggest that it formed by extensive fractional crystallization of the earliest melt(s) of precursor materials from which the most magnesian (shallowest) olivine-pigeonite ureilites formed. A less abundant population, characterized by labradoritic plagioclase, may have formed from melts complementary to more ferroan olivine-pigeonite ureilites, and derived from deeper in the UPB. The third population, characterized by the presence of olivine and augite, could only have formed from melts produced at greater depths in the UPB than the olivine-pigeonite ureilites. Many other feldspathic clasts cannot be positively associated with any of these three populations, because their mafic mineral compositions exhibit carbon redox control. However, they may be products of early crystallization of basaltic melts produced on the UPB, before carbon was exhausted by reduction.Partial melting on the ureilite parent body was a fractional (or incremental) process. Melts were produced early in UPB history, and most likely extracted rapidly, thus preserving primitive chemical and oxygen isotopic signatures in the residues.     

The carbon and nitrogen isotopic composition of ureilites: Implications for their genesis

Fourteen ureilites were analyzed for stable C isotopic composition using stepped combustion. The δ¹³C values over the temperature range 500 to 1000°C are fairly constant for any particular meteorite although there are differences between samples. The similarity in combustion temperatures of pure diamond (600–1000δC) and pure graphite (600–800°C) makes it difficult to ascertain the relative proportions of either component within each sample. However, the constant δ¹³C values observed over the range 500 to 1000°C strongly suggests that ureilite diamond and graphite have the same isotopic composition. This would seem to confirm that the diamond in ureilites formed from the graphite during a process, presumably an impact event, which did not fractionate C isotopes.There is a variation in C isotopic composition of graphite/diamond intergrowths among ureilites, which is not continuous—the samples fall into two groups, with δ¹³C values clustered around ?10%. and ?2%. PDB. These groups are also distinguishable on the basis of the Fe content of their olivines, which may reflect the existence of more than one ureilite parent body. The brecciated ureilite North Haig has a δ¹³C value of ?6.5%. and it is thus possible that this sample contains components from mixed parent materials.Nitrogen abundance and stable isotope measurements were made on five samples using stepped combustion analysis. Nitrogen concentrations range from 25 to 150 ppm and $\text{C}\text{N}$ ratios are substantially less than for carbonaceous chondrites. Variation in N isotopic composition is wide and there is evidence of different ratios in diamond/graphite, silicate and metal.     

Chronology and shock history of the Bencubbin meteorite: A nitrogen, noble gas, and Ar-Ar investigation of silicates, metal and fluid inclusions

We have investigated the distribution and isotopic composition of nitrogen and noble gases, and the Ar-Ar chronology of the Bencubbin meteorite. Gases were extracted from different lithologies by both stepwise heating and vacuum crushing. Significant amounts of gases were found to be trapped within vesicles present in silicate clasts. Results indicate a global redistribution of volatile elements during a shock event caused by an impactor that collided with a planetary regolith. A transient atmosphere was created that interacted with partially or totally melted silicates and metal clasts. This atmosphere contained ¹⁵N-rich nitrogen with a pressure ?3 × 10⁵ hPa, noble gases, and probably, although not analyzed here, other volatile species. Nitrogen and noble gases were re-distributed among bubbles, metal, and partly or totally melted silicates, according to their partition coefficients among these different phases. The occurrence of N₂ trapped in vesicles and dissolved in silicates indicates that the oxygen fugacity (f_O2) was greater than the iron-wüstite buffer during the shock event. Ar-Ar dating of Bencubbin glass gives an age of 4.20 ± 0.05 Ga, which probably dates this impact event. The cosmic-ray exposure age is estimated at ∼40 Ma with two different methods. Noble gases present isotopic signatures similar to those of “phase Q” (the major host of noble gases trapped in chondrites) but elemental patterns enriched in light noble gases (He, Ne and Ar) relative to Kr and Xe, normalized to the phase Q composition. Nitrogen isotopic data together with ⁴⁰Ar/³⁶Ar ratios indicate mixing between a ¹⁵N-rich component (δ¹⁵N = +1000‰), terrestrial N, and an isotopically normal, chondritic N.Bencubbin and related ¹⁵N-rich meteorites of the CR clan do not show stable isotope (H and C) anomalies, precluding contribution of a nucleosynthetic component as the source of ¹⁵N enrichments. This leaves two possibilities, trapping of an ancient, highly fractionated atmosphere, or degassing of a primitive, isotopically unequilibrated, nitrogen component. Although the first possibility cannot be excluded, we favor the contribution of primitive material in the light of the recent finding of extremely ¹⁵N-rich anhydrous clasts in the CB/CH Isheyevo meteorite. This unequilibrated material, probably carried by the impactor, could have been insoluble organic matter extremely rich in ¹⁵N and hosting isotopically Q-like noble gases, possibly from the outer solar system.     

Volatile composition of microinclusions in diamonds from the Panda kimberlite, Canada: Implications for chemical and isotopic heterogeneity in the mantle

In order to better investigate the compositions and the origins of fluids associated with diamond growth, we have carried-out combined noble gas (He and Ar), C and N isotope, K, Ca and halogen (Cl, Br, I) determinations on fragments of individual microinclusion-bearing diamonds from the Panda kimberlite, North West Territories, Canada. The fluid concentrations of halogens and noble gases in Panda diamonds are enriched by several orders of magnitude over typical upper mantle abundances. However, noble gas, C and N isotopic ratios (³He/⁴He = 4-6 Ra, ⁴⁰Ar/³⁶Ar = 20,000-30,000, δ¹³C = −4.5‰ to −6.9‰ and δ¹⁵N = −1.2‰ to −8.8‰) are within the worldwide range determined for fibrous diamonds and similar to the mid ocean ridge basalt (MORB) source value. The high ³⁶Ar content of the diamonds (>1 × 10⁻⁹ cm³/g) is at least an order of magnitude higher than any previously reported mantle sample and enables the ³⁶Ar content of the subcontinental lithospheric mantle to be estimated at ∼0.6 × 10⁻¹² cm³/g, again similar to estimates for the MORB source. Three fluid types distinguished on the basis of Ca-K-Cl compositions are consistent with carbonatitic, silicic and saline end-members identified in previous studies of diamonds from worldwide sources. These fluid end-members also have distinct halogen ratios (Br/Cl and I/Cl). The role of subducted seawater-derived halogens, originally invoked to explain some of the halogen ratio variations in diamonds, is not considered an essential component in the formation of the fluids. In contrast, it is considered that large halogen fractionation of a primitive mantle ratio occurs during fluid-melt partitioning in forming silicic fluids, and during separation of an immiscible saline fluid.     

Osmium isotope systematics of ureilites

The ¹⁸⁷Os/¹⁸⁸Os for 22 ureilite whole rock samples, including monomict, augite-bearing, and polymict lithologies, were examined in order to constrain the provenance and subsequent magmatic processing of the ureilite parent body (or bodies). The Re/Os ratios of most ureilites show evidence for a recent disturbance, probably related to Re mobility during weathering, and no meaningful chronological information can be extracted from the present data set. The ureilite ¹⁸⁷Os/¹⁸⁸Os ratios span a range from 0.11739 to 0.13018, with an average of 0.1258 ± 0.0023 (1σ), similar to typical carbonaceous chondrites, and distinct from ordinary or enstatite chondrites. The similar mean of ¹⁸⁷Os/¹⁸⁸Os measured for the ureilites and carbonaceous chondrites suggests that the ureilite parent body probably formed within the same region of the solar nebula as carbonaceous chondrites. From the narrow range of the ¹⁸⁷Os/¹⁸⁸Os distribution in ureilite meteorites it is further concluded that Re was not significantly fractionated from Os during planetary differentiation and was not lost along with the missing ureilitic melt component. The lack of large Re/Os fractionations requires that Re/Os partitioning was controlled by a metal phase, and thus metal had to be stable throughout the interval of magmatic processing on the ureilite parent body.     

Nitrogen isotope fractionations during progressive metamorphism: A case study from the Paleozoic Cooma metasedimentary complex, southeastern Australia

The well-studied Paleozoic Cooma metamorphic complex in southeastern Australia is characterized by a uniform siliciclastic protolith, of uniform age, with a continuous range of metamorphic grade from subgreenschist- to upper amphibolite-facies, and migmatite-grade in an annular pattern around the Cooma granodiorite. Those conditions are optimal for investigating variations of N concentrations and δ¹⁵N values during progressive metamorphism. Nitrogen concentrations decrease and δ¹⁵N increases with increasing metamorphic grade (sub-chlorite zone: 120 ppm N, δ¹⁵N = 2.3‰; chlorite zone: 110 ppm N, δ¹⁵N = 3.0‰; biotite and andalusite zone: 85 ppm N, δ¹⁵N = 3.8 ‰; sillimanite and migmatite zones: 40 ppm N, δ¹⁵N = 10.7‰). Covariation of K and N contents is consistent with N substituting for K as NH₄⁺ in micas. Observed trends of increasing δ¹⁵N values with decreasing nitrogen concentrations can be explained by a continuous release of nitrogen depleted in ¹⁵N with progressive metamorphism, which causes an enrichment of ¹⁵N in the residual nitrogen of the rock. Equilibrium models for Rayleigh distillation and batch volatilisation for data of the greenschist and amphibolite facies metasedimentary rocks can be explained by N₂-NH₄⁺ exchange at temperatures of 300-600 °C, whereas observed large fractionations for the upper amphibolite-facies and melt products in the migmatite-grade samples may be interpreted as NH₃-NH₄⁺ exchanges at temperature of 650-730 °C. Lower values in the highest grade zones may also stem in part from input of ¹⁵N-depleted fluids from the granodiorite.The magnitude of isotope fractionation of nitrogen is about 1-2‰ during progressive metamorphism of metasedimentary rocks from sub-chlorite zone to biotite-andalusite zone, which is consistent with previous studies. Consequently, the large spread of δ¹⁵N values in Archean greenschist-facies metasedimentary rocks of −6‰ to 30‰ can be accounted for by variable mixtures of mantle plume-dominated volatiles with a δ¹⁵N of −5‰, and a ¹⁵N-enriched marine sedimentary kerogen component inherited from a CI chondrite veneer having δ¹⁵N of 30‰ to 42‰.     

Diamond growth from oxidized carbon sources beneath the Northern Slave Craton, Canada: A δC-N study of eclogite-hosted diamonds from the Jericho kimberlite

Diamonds from high- and low-MgO groups of eclogite xenoliths from the Jericho kimberlite, Slave Craton, Canada were analyzed for carbon isotope compositions and nitrogen contents. Diamonds extracted from the two groups show remarkably different nitrogen abundances and δ¹³C values. While diamonds from high-MgO eclogites have low nitrogen contents (5-82 ppm) and extremely low δ¹³C values clustering at ∼−40‰, diamonds from the low-MgO eclogites have high nitrogen contents (>1200 ppm) and δ¹³C values from −3.5‰ to −5.3‰.Coupled cathodoluminescence (CL) imaging and SIMS analysis of the Jericho diamonds provides insight into diamond growth processes. Diamonds from the high-MgO eclogites display little CL structure and generally have constant δ¹³C values and nitrogen contents. Some of these diamonds have secondary rims with increasing δ¹³C values from −40‰ to ∼−34‰, which suggests secondary diamond growth occurred from an oxidized growth medium. The extreme negative δ¹³C values of the high-MgO eclogite diamonds cannot be produced by Rayleigh isotopic fractionation of average mantle-derived carbon (−5‰) or carbon derived from typical organic matter (∼−25‰). However, excursions in δ¹³C values to −60‰ are known in the organic sedimentary record at ca. 2.7 and 2.0 Ga, such that diamonds from the high-MgO eclogites could have formed from similar organic matter brought into the Slave lithospheric mantle by subduction.SIMS analyses of a diamond from a low-MgO eclogite show an outer core with systematic rimwards increases in δ¹³C values coupled with decreases in nitrogen contents, and a rim with pronounced alternating growth zones. The coupled δ¹³C-nitrogen data suggest that the diamond precipitated during fractional crystallization from an oxidized fluid/melt from which nitrogen was progressively depleted during growth. Model calculations of the co-variation of δ¹³C-N yielded a partition coefficient (K_N) value of 5, indicating that nitrogen is strongly compatible in diamond relative to the growth medium. δ¹³C values of diamond cores (−4‰) dictate the growth medium had higher δ¹³C values than primary mantle-derived carbon. Therefore, possible carbon sources for the low-MgO eclogite diamonds include oxidized mantle-derived (e.g. protokimberlite or carbonatite) fluids/melts that underwent some fractionation during migration or, devolatilized subducted carbonates.     

Complex trajectories of aquatic and terrestrial ecosystem shifts caused by multiple human-induced environmental stresses

Large shifts in the isotopic compositions of organic matter (OM) in lake sediments, over the last few hundred years, are commonly interpreted as representing changes in photosynthetic productivity corresponding to eutrophication or in the input of terrestrial OM due to human disturbances. Based on multiple-proxy data (C:N ratio, δ¹³C and δ¹⁵N of OM, δ¹³C of calcite, lithology and fossil pollen) from a 700-year sediment core at White Lake, New Jersey (USA), we propose a new explanation that relates these large shifts in OM δ¹³C and δ¹⁵N to human-induced changes in aquatic OM producers. Combined records of geochronology, fossil pollen and lithology from White Lake reveal that the upland forest was cleared by European settlers for farmland beginning around 1745 A.D. and has gradually reforested since 1930 after the abandonment of the farmlands. For the pre-agricultural period, OM had relatively constant but extremely low δ¹³C_VPDB (−35.8 to −34.5‰) and δ¹⁵N_Air (−3.5 to −2.5‰) and high atomic C:N ratios (13.7 to 16.7), indicating a stable anoxic lake environment with prominent microbial producers. Following the human disturbance (since 1745), high OM mass accumulation rates and abundances of the green alga Pediastrum indicate an increase in aquatic photosynthetic productivity due to enhanced nutrient input from disturbed uplands. However, carbonate δ¹³C remains constant or even decreases during this period, implying that increasing productivity did not elevate the δ¹³C of dissolved inorganic carbon and thus cannot explain the observed large increase in OM δ¹³C (7.4‰) and δ¹⁵N (5.8‰) over this period. Instead, δ¹³C, δ¹⁵N and C:N ratios of OM and differences in δ¹³C between calcite and OM suggest that the large increase in OM δ¹³C and δ¹⁵N can be attributed to a human-induced ecological shift in the predominant organic source from anaerobic bacteria to autotrophic phytoplankton. During the post-agricultural period, mass accumulation rates of OM, carbonate and silicate, and the δ¹³C of OM and calcite all decreased significantly, corresponding to stabilization of the uplands. However, over the last 70 years, an intensifying aquatic stress from the deposition of ¹⁵N-enriched industrial pollutants has resulted in a steady increase of 1.9‰ in δ¹⁵N. Proxy records for lake (δ¹³C and δ¹⁵N of OM) and upland conditions (pollen and silicates) at White Lake show complex trajectories of the aquatic and terrestrial ecosystems in response to past human disturbances.     

Rare gases and fossil particle tracks in the Kenna ureilite

Fossil particle tracks and spallation-produced He and Ne in the Kenna ureilite indicate that it existed in space as a small object for 23 m.y. In our study of Kenna, we found no evidence of trapped He or Ne. Large amounts of heavy rare gases occur in Kenna in concentrations typical of ureilites. In a step-wise release of gases, the isotopic compositions of Kr and Xe were found to be constant above 600°C, revealing the presence of a single retentively sited component. The Xe isotopic abundances are characterized by 124:126:128:129:130:131:132:134:136 = 0.471:0.414:8.280:103.61: 16.296:81.92:100:37.70:31.23. This isotopic composition is distinct from AVCC (average carbonaceous chondritic), but similar to compositions known for some time in certain temperature fractions of Renazzo, Murray and Murchison. Kenna-type Xe appears to be one of the several components found in carbonaceous chondrites.

Binz et al. (Geochim. Cosmochim. Acta 39, 1576–1579, 1975) have recently found that many volatile trace elements are strongly depleted in ureilites. Thus, the relatively large amounts of heavy rare gases present in ureilites did not result from a mixture of a volatile-rich component with the ureilite host. It appears that some material rich in carbon and heavy rare gases was incorporated into a differentiated ureilite host. All current hypotheses which purport to explain the origin of trapped gases in meteorites encounter difficulty in accounting for trapped gases in ureilites in a straightforward manner.     

Kinetic nitrogen isotope fractionation associated with thermal decomposition of NH3: Experimental results and potential applications to trace the origin of N2 in natural gas and hydrothermal systems

Ammonia (NH₃) is the major intermediate phase in the pathway of nitrogen (N) transfer from the fixed N phases (e.g., in crustal material) to free N₂ (e.g., in natural gas reservoirs and volcanic gases). Yet the N isotopic behavior during these N-cycling processes remains poorly known. In an attempt to contribute to the understanding of N cycling using N isotopes, we carried out laboratory experiments to investigate the N isotopic effect associated with thermal decomposition of ammonia (2NH₃ → N₂ + 3H₂). Pure NH₃ (with initial δ¹⁵N_NH3 of ∼ −2‰, relative to air standard) was sealed into quartz tubes and thermally decomposed at 600, 700 or 800 °C from 2 hours to 500 days. With the progress of the reaction, the δ¹⁵N of the remaining NH₃ and the accumulated N₂ increased from −2 to +35‰ and from −20 to −2‰, respectively. The differences of the N-isotope fractionations at the three temperatures are not significant. Modeling using the Rayleigh distillation model yielded similar kinetic N-isotope fractionation factors (α_N2-NH3) of 0.983 ± 0.002 for 600, 700 and 800 °C. Applied to geological settings, this significant isotope discrimination (∼17‰) associated with partial decomposition of NH₃/NH₄⁺ from crustal sources (δ¹⁵N_average ∼ +6.3‰) can produce mantle-like (i.e. ∼ −5‰) or even lower δ¹⁵N values of N₂. This may explain the large variation of δ¹⁵N (−20 to +30‰) of N₂ in natural gas reservoirs. It can also possibly explain the extreme ¹⁵N-depletion of N₂ in some volcanic gases. This possibility has to be carefully considered when using N isotopes to trace geological N cycling across subduction zones by analysis of volcanic N₂.     

The Almahata Sitta polymict breccia and the late accretion of asteroid 2008 TC3

On October 7, 2008, a small asteroid named 2008 TC₃ was detected in space about 19 h prior to its impact on Earth. Numerous world-wide observations of the object while still in space allowed a very precise determination of its impact area: the Nubian Desert of northern Sudan, Africa. The asteroid had a pre-atmospheric diameter of ∼4 m; its weight is reported with values between ∼8 and 83 t, and the bulk density with ∼2–3 g/cm³, translating into a bulk porosity in the range of ∼20–50%. Several dedicated field campaigns in the predicted strewn field resulted in the recovery of more than 700 (monolithological) meteorite fragments with a total weight of ∼10.5 kg. These meteorites were collectively named “Almahata Sitta”, after the nearby train station 6, and initially classified as an anomalous polymict ureilite. Further work, however, showed that Almahata Sitta is not only a ureilite but a complex polymict breccia containing chemically and texturally highly variable meteorite fragments, including different ureilites, a ureilite-related andesite, metal-sulfide assemblages related to ureilites, and various chondrite classes (enstatite, ordinary, carbonaceous, Rumuruti-like). It was shown that that chondrites and ureilites derive from one parent body, i.e., asteroid 2008 TC₃, making this object, in combination with the remotely sensed physical parameters, a loosely aggregated, rubble-pile-like object. Detailed examinations have been conducted and mineral-chemical data for 110 samples have been collected, but more work on the remaining samples is mandatory.     

Stable nitrogen and carbon isotope (δN and δC) variability in shallow tropical Pacific soft coral and black coral taxa and implications for paleoceanographic reconstructions

Soft corals and black corals are useful proxy tools for paleoceanographic reconstructions. However, most work has focused on deep-water taxa and few studies have used these corals as proxy organisms in shallow water (<200 m). To facilitate the use of stable nitrogen and carbon isotope (δ¹⁵N and δ¹³C) records from shallow-water soft coral and black coral taxa for paleoceanographic reconstructions, quantification of the inherent variability in skeletal isotope values between sites, across depth, and among taxa is needed. Here, skeletal δ¹⁵N and δ¹³C values were measured in multiple colonies from eleven genera of soft corals and two genera of black corals from across a depth transect (5-105 m) at two sites in Palau located in the tropical western Pacific Ocean. Overall, no difference in skeletal δ¹⁵N and δ¹³C values between sites was present. Skeletal δ¹⁵N values significantly increased and δ¹³C values decreased with depth. This is consistent with changes in isotope values of suspended particulate organic matter (POM) across the photic zone, suggesting that the primary food source to these corals is suspended POM and that the stable isotopic composition of POM controls the skeletal isotopic composition of these corals. Thus, to compare the isotope records of corals collected across a depth range in the photic zone, first order depth corrections of −0.013‰ m⁻¹ and +0.023‰ m⁻¹ are recommended for δ¹⁵N and δ¹³C, respectively. Average depth-corrected δ¹⁵N values were similar between black corals and soft corals, indicating that corals in these orders feed at a similar trophic level. In contrast, average depth-corrected δ¹³C values of black corals were significantly lower than that of soft corals, potentially resulting from metabolic processes associated with differing skeletal compositions among the orders (i.e., gorgonin vs. chitin based). Thus, a correction of +1.0‰ is recommended for black corals when comparing their δ¹³C-based proxy records to soft corals. After correcting for both the depth and order effects, variability in δ¹⁵N values among corals within each genera was low (standard deviation (SD) of the mean <±0.5‰), with the exception of Acanthorgorgia. The calculated SD of <±0.5‰ provides a first order guideline for the amount of variability that could be expected in a δ¹⁵N record, and suggests that these corals may be useful for δ¹⁵N-based paleoceanographic reconstructions. Variability in δ¹³C values among corals within genera was also low (standard deviation of the mean <±0.5‰) with the exception of Rhipidipathes and Villogorgia. Similar to δ¹⁵N, records from the genera studied here with the exception of Rhipidipathes and Villogorgia may be useful for δ¹³C-based paleoceanographic reconstructions. Overall, using the recommendations developed here, stable isotope records from multiple sites, depths and taxa of these corals can be more rigorously compared.     

Sources of fine-sized organic matter in North Atlantic Heinrich Layers: δC and δN tracers

Organic carbon (OC) and total nitrogen (TN) concentrations and stable isotope ratios (δ¹³C, δ¹⁵N) of fine (<50 μm) size fractions of deep-sea sediments from the central North Atlantic were employed to identify changes in sources of organic matter over the past 50 ka BP. Ambient glacial sediments are characterised by values that reflect mixtures of marine and terrestrial inputs (averages ± 1σ: OC/TN = 7.6 ± 0.8; δ¹³C = −22.8 ± 1.0‰; δ¹⁵N = 5.5 ± 0.6‰). δ¹³C, OC, and TN concentrations shift to higher values during the Holocene, indicating a gradual decrease of fine terrigenous supply to the North Atlantic. The unchanged δ¹⁵N record between last glacial and Holocene stages indicates that the central North Atlantic region remained oligotrophic at least during the past 50 ka BP, but additional studies are required to support this result in terms of nitrogen oceanic budget. During the phases of enhanced ice-rafted detrital supply corresponding to prominent Heinrich events (HL₁, HL₂, HL₄, and HL₅), fine-sized sedimentary organic matter has lower OC and TN concentrations, contrasting sharply with those of ambient glacial sediments. Lower δ¹³C (down to −28‰) and δ¹⁵N (down to 1.6‰) values and high OC:TN ratios (up to 14.7 ± 1.1) are found for HL₁, HL₂, and with lesser extent for HL₄. These values reflect enhanced detrital supply originating from poorly differentiated soil horizons that characterise periglacial climate conditions and from organic matter-bearing rock sources of the underlying geological basement. During HL₅, only the δ¹³C offset records the input of fine size ice-rafted organic matter. Gradually changing soil development conditions during the time interval covering HL₅ to HL₁ (marine isotope stages 5 to 2), as well as varying erosion levels, have been hypothesized on the basis of constant δ¹³C, increasing OC/TN and decreasing δ¹⁵N values.     

Molecular and compound-specific hydrogen isotope analyses of insoluble organic matter from different carbonaceous chondrite groups

We have conducted the first systematic analyses of molecular distribution and δD values of individual compounds in pyrolysates of insoluble organic matter (IOM) from different carbonaceous chondrite groups, using flash pyrolysis coupled to gas chromatography-mass spectrometry and compound-specific D/H analysis. IOM samples from six meteorites of different classifications, Elephant Moraine (EET) 92042 (CR2), Orgueil (CI1), Allan Hills (ALH) 83100 (CM1/2), Murchison (CM2), ALH 85013 (CM2), and Tagish Lake (C2) were isolated and studied. Except for the pyrolysate of Tagish Lake IOM, pyrolysates of all five meteorite IOM samples were dominated by an extensive series of aromatic (C₁ to C₇ alkyl-substituted benzenes, C₀ to C₂ alkyl-substituted naphthalenes), with aliphatic (straight chain and branched C₁₀ to C₁₅ alkanes) hydrocarbons and several S- and O- containing compounds (C₁ to C₂ alkylthiophenes, benzothiophene, benzaldehyde) being also present. The strong similarity in the pyrolysates of different carbonaceous chondrites suggests certain common characteristics in the formation mechanisms of IOM from different meteorites. The Tagish Lake IOM sample is unique in that its pyrolysate lacks most of the alkyl-substituted aromatic hydrocarbons detected in other meteorite IOM samples, suggesting distinctively different formation processes. Both bulk δD values of meteorite IOMs and weighted-average δD values of individual compounds in pyrolysates show a decreasing trend: CR2 > CI1 > CM2 > C2 (Tagish Lake), with the EET 92042 (CR2) IOM having the highest δD values (∼2000‰ higher than other samples). We attribute the high D contents in the IOM to primitive interstellar organic sources.