Constraints on the formation environment of two chondrule-like igneous particles from Comet 81P/Wild 2.

Using chemical and petrologic evidence and modeling, we deduce that two chondrule-like particles named Iris and Callie, from Stardust cometary track C2052,12,74, formed in an environment very similar to that seen for type II chondrules in meteorites. Iris was heated near liquidus, equilibrated, and cooled at ≤ 100 °C/hr and within ≈ 2 log units of the IW buffer with a high partial pressure of Na such as would be present with dust enrichments of ≈ 103. There was no detectable metamorphic, nebular or aqueous alteration. In previous work Ogliore et al. (2012) reported that Iris formed late, > 3 Myr after CAIs, assuming 26Al was homogenously distributed, and was rich in heavy oxygen. Iris may be similar to assemblages found only in interplanetary dust particles and Stardust cometary samples called Kool particles. Callie is chemically and isotopically very similar but not identical to Iris.

2D/3D Microanalysis by Energy Dispersive X-ray Absorption Spectroscopy Tomography.

X-ray spectroscopic techniques have proven to be particularly useful in elucidating the molecular and electronic structural information of chemically heterogeneous and complex micro- and nano-structured materials. However, spatially resolved chemical characterization at the micrometre scale remains a challenge. Here, we report the novel hyperspectral technique of micro Energy Dispersive X-ray Absorption Spectroscopy (µED-XAS) tomography which can resolve in both 2D and 3D the spatial distribution of chemical species through the reconstruction of XANES spectra. To document the capability of the technique in resolving chemical species, we first analyse a sample containing 2-30 µm grains of various ferrous- and ferric-iron containing minerals, including hypersthene, magnetite and hematite, distributed in a light matrix of a resin. We accurately obtain the XANES spectra at the Fe K-edge of these four standards, with spatial resolution of 3 µm. Subsequently, a sample of ~1.9 billion-year-old microfossil from the Gunflint Formation in Canada is investigated, and for the first time ever, we are able to locally identify the oxidation state of iron compounds encrusting the 5 to 10 µm microfossils. Our results highlight the potential for attaining new insights into Precambrian ecosystems and the composition of Earth's earliest life forms.

Interstellar dust. Evidence for interstellar origin of seven dust particles collected by the Stardust spacecraft.

Seven particles captured by the Stardust Interstellar Dust Collector and returned to Earth for laboratory analysis have features consistent with an origin in the contemporary interstellar dust stream. More than 50 spacecraft debris particles were also identified. The interstellar dust candidates are readily distinguished from debris impacts on the basis of elemental composition and/or impact trajectory. The seven candidate interstellar particles are diverse in elemental composition, crystal structure, and size. The presence of crystalline grains and multiple iron-bearing phases, including sulfide, in some particles indicates that individual interstellar particles diverge from any one representative model of interstellar dust inferred from astronomical observations and theory.

Determination of the Cd-bearing phases in municipal solid waste and biomass single fly ash particles using SR-microXRF spectroscopy.

By using an excitation energy of 27.0 keV, synchrotron radiation-induced micro-X-ray fluorescence (SR-microXRF) is employed to extract information regarding the composition and distribution of Cd-bearing phases in municipal solid waste (MSW) and biomass fly ashes. Significance of observation is based on statistics of totally more than 100 individual MSW and biomass fly ash particles from a fluidized bed combustion (FBC) plant. Cd concentrations in the parts-per-million range are determined. In general, although previous leaching studies have indicated Cd to be predominant in the smaller-size ash particles, in the present study Cd is more evenly distributed throughout all the particle sizes. For MSW fly ashes, results indicate the presence of Cd mainly as CdBr2 hot-spots, whereas for biomass fly ashes, which exhibit lower CdX2 concentration, a thin Cd layer on/in the particles is reported. For both ashes, Ca-containing matrixes are found to be the main Cd-bearing phases. Support for this observation is found from independent first-principles periodic density functional theory calculations. The observations are condensed into a schematic mechanism for Cd adsorption on the fly ash particles.

X-ray fluorescence tomography of individual municipal solid waste and biomass fly ash particles.

Information about Cd distribution inside single municipal solid waste and biomass fly ash particles is fundamental since it affects its leachability. The internal 2D distributions of the main and trace elements in such highly inhomogeneous matrixes were successfully determined by means of the combined synchrotron radiation induced micro X-ray fluorescence (micro-SRXRF) and tomography (micro-SRXRFT) techniques. Scanning micro-SRXRF measurements show Cd elemental distribution within single fly ash particles to be inhomogeneous, but no information can be obtained about its internal distribution. During micro-SRXRFT analysis, single fly ash particles are successively measured by a rotational-translational scan in a VH=2 x 5 microm2 microbeam. The 2D internal elemental distribution images, obtained by the modified simultaneous algebraic reconstruction technique algorithm, provide the size and the location of Cd-containing areas together with the location of other measurable elements. Results showed Cd concentration to be higher in the core of the fly ash particles analyzed rather than on the surface of the particles. Moreover, in both ashes, Ca-containing matrixes are found to be the main Cd-bearing phases. A possible mechanism for Cd adsorption on the fly ash particles is proposed based on the obtained results.

Direct determination of cadmium speciation in municipal solid waste fly ashes by synchrotron radiation induced mu-X-ray fluorescence and mu-X-ray absorption spectroscopy.

Cadmium is a toxic metal that causes environmental concern in connection with utilization and land filling of ash from combustion of municipal solid waste (MSW). Collecting information about the chemical associations of Cd in ash is fundamental since this affects its solubility and leachability from the ash material. In the work presented here, the content, distribution, and chemical forms of toxic metals especially of Cd on/in individual Municipal Solid Waste (MSW) fly ash particles have been investigated in situ by synchrotron radiation induced mu-X-ray fluorescence and absorption spectrometry. The use of an excitation energy of 27 keV made it possible to detect trace metals, such as Cd, present at ppm levels routinely. Changing the excitation energy in the vicinity of the absorption edge of Cd (26.71 keV), the absorption spectra of this element were measured for the first time in this high energy range in micron-sized spots of individual fly ash particles. The measurements indicated Cd to be preferably concentrated in some small areas ("hot-spots") with high concentration (up to 200 ppm) rather than in a homogeneous distribution or as a thin coating on the whole particle surface, making the surface-reaction the most probable mechanism of Cd enrichment during MSW combustion processes. Comparisons of XAS spectra of fly ashes and reference compounds showed that in the particles studied Cd is present in the oxidation state +2. Analyses of linear combinations of standard spectra allowed estimating the Cd presence within fly ash particles as an admixture of primarily CdSO4, CdO, and CdCl2 as well as an unidentified compound not included as a standard.