A. V. Fisenko

Populations of nanodiamond grains in meteorites from the data on isotopic composition and content of nitrogen

The present study has shown that the dependence of the isotopic composition of nitrogen on the N/C ratio, revealed from the data for bulk samples of meteoritic nanodiamond, can be obtained within the framework of the following model of the composition of populations of nanodiamond grains: (a) initial nanodiamond, i.e., the nanodiamond in the protoplanetary cloud before the accretion of the meteorite parent bodies, was composed mainly of grains of two populations (denoted as CN and CF), the ratio of which changed in meteorites depending on the degree of hydrothermal metamorphism; (b) only the grains of one of these populations (CN) contain volume-bound nitrogen with δ15N = −350‰; (c) the grains of both populations contain surface-bound nitrogen (δ15N ≡ 0). The calculations revealed the following properties of population grains in this model. (1) The grains of the CN and CF populations are most likely the same in isotopic composition of carbon and heterogeneous in distribution of its isotopes: the central part of grains is enriched with the δ12C isotope relative to the remainder of the grain. While the value of δ13C is −37.3 ± 1.1‰ for carbon in the central part, it is −32.8 ± 1.5‰ for the whole volume of the grains. (2) The noble gases of the HL component, specifically Xe-HL, are anomalous in isotopic composition and are most likely contained in the third population of nanodiamond grains (denoted as CHL), the mass fraction of which is negligible relative to that for other grain populations. Only the grains of the CHL population have an undoubtedly presolar origin, while the grains of the other nanodiamond populations could have formed at the early stages of the evolution of the protoplanetary cloud material before the accretion of the meteoritic parent bodies.

Photoluminescence of silicon-vacancy defects in nanodiamonds of different chondrites

Photoluminescence spectra show that silicon impurity is present in lattice of some nanodiamond grains (ND) of various chondrites as a silicon-vacancy (SiV) defect. The relative intensity of the SiV band in the diamond-rich separates depends on chemical composition of meteorites and on size of ND grains. The strongest signal is found for the size separates enriched in small grains; thus confirming our earlier conclusion that the SiV defects preferentially reside in the smallest (less than 2 nm) grains. The difference in relative intensities of the SiV luminescence in the diamond-rich separates of individual meteorites are due to variable conditions of thermal metamorphism of their parent bodies and/or uneven sampling of nanodiamonds populations. Annealing of separates in air eliminates surface sp2-carbon, consequently, the SiV luminescence is enhanced. Strong and well-defined luminescence and absorption of the SiV defect is a promising feature to locate cold (< 250 {\deg}C) nanodiamonds in space.

A numerical model of ion implantation into presolar grains

Pre-solar grains such as diamond and silicon carbide (found in primitive chondritic meteorites), contain isotopically anomalous noble gases. There are two ways that these could have been incorporated into the grains: direct assimilation during grain formation and growth, or subsequent addition after the grains had formed. Herein we investigate the latter possibililty and explore the role of ion implementation within the interstellar medium (i.e. into pre-existing grains distributed in free space). Numerical models are derived to address the issue of how ion implantation would affect the grain population.

On nature of bimodal release of noble gases during pyrolysis of the meteoritic nanodiamonds

Analysis of noble gas proportions and their release kinetics during stepped pyrolysis and oxidation of meteoritic nanodiamonds, as well as their core-shell structure led to the following conclusions: (1) Noble gases of HL component with anomalous isotopic composition were presumably formed prior to implantation in the nanodiamonds owing to mixing of nucleosynthetic products of p- and r- process associated with explosion of type-II supernova with noble gases having “normal” isotopic composition; (2) isotopically normal P3 noble gases in the nanodiamonds grains are confined to the nondiamond (for instance, graphite-like) phase in the surface layer. The “layer” structure of nanodiamonds grains resulted from heating up to 800–900°C. Observed increase in contents of P3 noble gases with increasing grain sizes of meteoritic nanodiamonds is caused by the dependence of the degree of graphitization of the superfical layer at given temperature on the grain size and surface defect density; (3) bimodal release of noble gases during pyrolysis of the meteoritic nanodiamonds from weakly metamorphosed meteorites was caused by P3 and HL components, which are comparable in abundance but sharply differ in their release temperature.

Heterogeneity of the interstellar diamond in the CV3 meteorite efremovka

Based on the heterogeneity in the contents and isotopic compositions of carbon, nitrogen, and rare gases found in different (in grain size) interstellar diamond fractions of the meteorite Efremovka, we discuss issues associated with the nature of the diamond, the distribution of the isotopic components of impurity chemical elements in it, and the kinetics of their release.

Kinetics of C, N and Xe release during the quasi-isothermal pyrolysis and subsequent oxidation of nanodiamond from the Orgueil CI meteorite

Analysis of the C, N, and Xe release kinetics of intermediate-sized nanodiamond fraction from the Orgueil CI meteorite during isothermal pyrolysis conducted for the first time and subsequent oxidation indicates that (a) the rate of C, N, and Xe release at pyrolysis at a constant temperature decreases with time; (b) the relative amount of released Xe, which mostly has a normal isotopic composition (Xe-P3) at various pyrolysis time up to 800°C, is controlled, first of all, by the heating temperature, whereas the amount of N is controlled by both the temperature and heating time; and (c) prolonged pyrolysis notably modifies the distribution of nitrogen of normal (δ15N = 0) and anomalous (δ15N= −350‰) isotopic composition in diamond grains. The identified features of the C and N release kinetics are explained by differences in the binding energy of chemically adsorbed O with C atoms and the accommodation of the main amounts of N in extended defects of the crystal structure of nanodiamond. The major factors of the decrease in the Xe-P3 release rate during the isothermal pyrolysis of nanodiamond are either the differences between the Xe desorption parameters of the traps in graphite-like phases containing Xe-P3 or the differences between the radiation-induced defectiveness of grains of the population containing implanted Xe-P3. Our results led us to conclude that (1) meteoritic nanodiamond contains relatively low amounts of a phases carrying the P3 component of noble gases, regardless of the nature of this component, and (2) the population of nanodiamond grains containing most of isotopically anomalous nitrogen was produced at a high rate to preserve this nitrogen, first of all, at extended defects in the diamond crystal structure.

Heterogeneity of grain-size fractions of nanodiamonds from the Orgueil C1 meteorite

A model for the composition of meteoritic nanodiamonds is suggested based on analysis of the concentrations and isotopic compositions of C, N, and Xe in the nanodiamond-rich grain-size fractions, which were separated for the first time from the Orgueil CI chondrite. According to the model, meteoritic nanodiamond consists of two populations of grains (denoted CHL and CN). The size distributions of grains in populations in the CHL and CN populations are different: the CHL population is finer grained than CN. The grains of the CHL population are characterized by a radial gradient in the carbon isotopic composition, and they contain implanted anomalous noble gases (HL component) and the heavy nitrogen isotope 15N. Following (Clayton et al., 1995), the probable astrophysical source of this population of nanodiamond grains is thought to be the mixing helium and hydrogen shells of a Type-II supernova, and the mechanism that produced these grains was the slow CVD process. The CN population grains have homogeneous isotopic compositions of carbon (δ13C ≡–100‰) and nitrogen (δ15N ≡–400‰) and contain almost all nitrogen of the nanodiamond-rich fractions. This population of nanodiamond grains was likely formed by a fast unequilibrated process, when shock waves affected organic compounds or gas rich in C- and N-bearing compounds during the early evolution of the protosolar nebula. Calculations within the framework of the model show that the nanodiamond-rich fractions separated from the Orgueil meteorite have the CN/CHL ratios varying from 1 in the finest grained fraction to 10 in the coarse-grained one. At these proportions of the populations, weighted mean δ13C values of CHL grains in the fractions lie within the range of 42 to 394‰, and the concentrations of 132Xe-HL and 15N are (49–563) × 10–8 cm3/gC and (1.1–6.2) × 10–5 cm3/gC, respectively.

On the preservation of Xe of the isotopically normal component of noble gases in meteoritic nanodiamonds and 4He in lunar soil according to the data of gas desorption during stepped pyrolysis

The release kinetics of Xe of the isotopically normal component of noble gases (P3 component) from the coarse-grained fraction of nanodiamonds from the Orgueil (CI) meteorite and the kinetics of 4He release from lunar soil were studied by means of a numerical simulation. It is demonstrated that the release of these gases as a peak with a single pronounced maximum may not correspond to the diffusion model with a single activation energy and can in fact be controlled by a spectrum of activation energies with a number of peaks a number of peaks remaining unresolved at stepped pyrolysis. In particular, the amount of Xe-P3 preserved in nanodiamonds during thermal metamorphism of the Orgueil meteorite calculated using parameters of the diffusion process (activation energy and frequency factor) that were determined in the model with a single activation energy indicates that practically all Xe should be lost during a very short time. These losses are inconsistent with both the duration of thermal metamorphism of the meteorite parent bodies and the Xe-P3 concentrations measured in these meteorites. A much higher preservation of Xe-P3 during thermal metamorphism lasting for hundreds of years follows from calculations based on diffusion with a spectrum of activation energiesa for Xe release. The results of isothermal pyrolysis of a nanodiamonds fraction from Orgueil confirms a presence of several activation energies for Xe-P3 release from the nanodiamonds. The application of the diffusion model with a spectrum of activation energies to He release from lunar soil samples also shows that He can be retained in these samples at 20°C during a much longer time than it follows from the model with a single activation energy (Anufriev, 2010).

Isotopically anomalous neon in meteoritic nanodiamonds: Formation during type II supernova explosions

We hypothesize the formation of neon associated with isotopically anomalous xenon (Xe-HL) in meteoritic nanodiamonds and designated as Ne-X through the mixing of the Ne-HL and Ne-S subcomponents. The Ne-HL subcomponent is neon from the helium (He/C) zone of a type II supernova or a mixture of neon from this zone and its hydrogen zone, while the Ne-S subcomponent is spallation neon formed during a supernova explosion in nuclear spallation reactions induced by high-energy protons. Based on this hypothesis and the presumed abundances of neon isotopes in the zones of a high-mass (25M⊙) supernova after its explosion, we have calculated the abundances of neon components in nanodiamond separates and its grain-size fractions. Our calculations have shown the following. (1) The main source of Ne-HL is neon from the helium zone of the supernova; as a result, the 20Ne/22Ne and 21Ne/22Ne ratios for Ne-X are 0.26 ± 0.03 and 0.19 ± 0.04, respectively. The isotopic composition of Ne-X is identical to that for Ne-A2 if Ne-HL is produced by the mixing of neon from the helium and hydrogen zones in proportion 1: 1.06. (2) In meteoritic nanodiamonds, the main neon abundance is determined by neon of the P3 component (Ne-P3). Ne-P3 is retained during thermal metamorphism, because it is sited in traps of the crystal lattice of diamond with a high energy of its activation. (3) The Ne-X/Ne-P3 ratio increases with nanodiamond grain size; as a result, there is no need to invoke an additional neon component (Ne-P6) to interpret the data on neon in meteoritic nanodiamonds.