Presolar Grains from Meteorites: Remnants from the Early Times of the Solar System

Transcription

1 Presolar Grains from Meteorites: Remnants from the Early Times of the Solar System Katharina Lodders and Sachiko Amari (Washington University, St. Louis, Missouri) Review for Chemie der Erde Abstract This review provides an introduction to presolar grains preserved stardust from in the interstellar molecular cloud from which our solar system formed - found in primitive meteorites. We describe the search for the presolar components, the currently known presolar mineral populations, and the chemical and isotopic characteristics of the grains and of dust-forming stars to identify the grains most probable stellar sources. 1 Introduction The history of our solar system started with the gravitational collapse of an interstellar molecular cloud laden with gas and dust supplied from dying stars. The dust from this molecular cloud is the topic of this review. As it turns out, a small fraction of this dust escaped destruction during the many processes that happened after molecular cloud collapse about 4.55 Ga ago. We define presolar grains as stardust that formed in stellar outflows or ejecta, and remained intact throughout its journey into the solar system where it was preserved in meteorites. The survival and presence of genuine stardust in meteorites was not expected in the early years of meteorite studies. In the 1950s and 1960s models of solar system formation predicted a different fate for presolar solids, and many aspects of these models remain until today. It was (and occasionally still is) believed that, before winding up in the Sun or planetary bodies, the matter from the presolar molecular cloud was processed and homogenized which would erase the mineralogy of any presolar solids. Most matter of the presolar cloud accreted to the Sun and less than about one percent remained to form the planets, their satellites, and other small objects (asteroids, Kuiper- Edgeworth-belt objects). During collapse and accretion of matter towards the center of the presolar cloud, gravitational heating vaporized presolar solids, and it was generally assumed that this process resulted in a relatively homogeneous solar nebular gas made of both evaporated presolar solids and presolar gas. Upon cooling of the solar nebula, new condensates appeared which accumulated to the solid bodies in the solar system (see cartoon in Figure 1). In this very simplified picture, all matter from the presolar molecular cloud would be chemically and isotopically homogenized and no record about the mineralogy of presolar solids would remain. All we would know is that the presolar molecular cloud had essentially the same overall chemical elemental composition as the Sun, but nothing would be known about how the elements were distributed between the different solids and the gas phase within the molecular cloud. Long before presolar grains were discovered, Cameron (1973) speculated on the question Interstellar grains in museums? and concluded that primitive carbonaceous chondrites may harbor presolar grains. Indeed, presolar grains were incorporated into meteorite parent bodies (small asteroid-size objects). Chemical and metamorphic 1

2 processes on the least metamorphosed meteorite parent bodies apparently were mild and more or less non-destructive to the grains, so upon meteorite delivery from a parent body to Earth, the presolar grains awaited discovery. There are several incentives to study presolar dust. Fresh dust and gas are continuously supplied to the interstellar medium (ISM), mainly by mass loss from red giant stars and by exploding novae and supernovae, which is the way such stars enrich the ISM with their nucleosynthetic products over time. Hence the presolar grains from meteorites could provide a glimpse into the dust population of the presolar molecular cloud. However, the known presolar minerals are very likely a biased sample of solids from the presolar molecular cloud because of their different stabilities against physical and chemical processing in the ISM, in the solar nebula, on meteorite parent bodies, and especially in the laboratory during grain isolation procedures. Another reason to study presolar grains is that their physical, chemical and isotopic signatures record nucleosynthetic and grain formation processes in a variety of stars. Grain morphologies and compositions may reflect formation conditions in the stellar environments and the grains chemical and isotopic compositions are firm tests of stellar evolution and nucleosynthesis models. Hence the microscopic grains reveal much more details about these processes than currently possible astronomical observations with even the best telescopes. Figure 1. The end of red giant stars and supernovae is accompanied by production of dust grains that also entered the molecular cloud from which our solar system formed. A very small portion of original stardust survived the passage through the ISM and the subsequent events during formation of the solar nebula. After extraction of presolar dust from meteorites by chemical and physical separation techniques and examination by various types of instruments, we obtain information about the parent stars retained in presolar dust. But who to find the nm- to µm-size presolar grains in a meteorite? One way is to search for variations in isotopic compositions, which revealed the presence of presolar grains in meteorites to begin with. The isotopic composition of several elements in certain meteoritic components is clearly different than the terrestrial isotopic reference composition. Many of these isotope anomalies cannot easily be explained by massfractionation processes or by decay of 2

3 longer-lived radioactive isotopes. Therefore the isotope anomalies suggest the presence of exotic, possibly presolar, phases. In the 1960s there were already hints from noble gases that meteoritic material is not isotopically homogeneous. However, it was the discovery of widespread isotopic variations in oxygen, the major rock-forming element, by Clayton et al. (1973) that provided strong evidence of incomplete homogenization of matter in the solar nebula. In particular, the so-called calcium aluminum-rich inclusions (CAIs) found in chondritic meteorites show characteristic enrichments of around five percent in 16 O when compared to terrestrial rocks and other major meteorite components. These enrichments cannot be derived by normal mass-dependent fractionation processes in the solar nebula and require another explanation. Because 16 O is a major product from supernovae, Clayton et al. (1973) suggested that 16 O from a supernova source was present in a reservoir in the solar nebula (see, however, alternative explanations of the 16 O enrichments by non-mass dependent fractionation processes by Thiemens and Heidenreich 1983; Clayton 2002). Further support that supernova and other stellar debris may have been present in the presolar molecular cloud came from observations of isotopic variations in other abundant rock-forming elements such as calcium, titanium, and chromium in CAIs (see Clayton et al for a summary). The variations in Ca and Ti isotopic compositions in CAIs are typically observed for neutron-rich isotopes such as 48 Ca and 50 Ti, which are signatures from nucleosynthesis operating in supernovae, but the size of these anomalies (per-mil to tenths of per-mil) is quite small (Clayton et al. 1988). Thus although CAIs often carry isotopic anomalies, many researchers do not regard them as pure presolar phases, and the origin of isotopic anomalies in CAIs is rather vaguely assigned to a possible incorporation of some presolar components. In contrast, bona-fide presolar grains are identified by their often huge, orders of magnitude ranging excesses or deficits in isotopic compositions (relative to normal terrestrial isotopic abundances). A presolar phase may have an outstanding isotopic anomaly in at least one element, but often isotope anomalies are observed simultaneously in several major elements such as C, N, O, and Si within a single presolar grain. Essentially in all cases the observed isotopic anomalies can only be explained by nucleosynthetic processes, which means that these grains formed near the sites of nucleosynthesis. This leaves the stars to imprint their chemical and isotopic signatures onto the grains. The principal environments for grain formation are the circumstellar shells of red giant stars and asymptotic giant branch (AGB) stars, and supernova ejecta, because these stellar sources are the most prolific providers of dust to the ISM. Until recently it was thought that currently AGB stars contribute most dust to the ISM, because large amounts of cold dust in supernova remnants went undetected in infrared observations. Now it seems that giant stars and supernovae contribute about equally to the interstellar dust. In addition to isotopic compositions, the major and trace element chemistry can be used to identify presolar grains. For example, the occurrence of reduced grains such as graphite and silicon carbide in meteorites consisting mainly of oxidized rock and hydrous silicates (e.g., CI and CM carbonaceous chondrites) is a rather unusual paragenesis, and is most easily explained by an external source of reduced grains. However, the presolar grains are rather small and carbonaceous dust also may have formed in the solar nebula so that major element chemistry alone cannot provide a strong constraint on the origin of 3

4 the reduced dust. On the other hand, trace element abundances in some reduced grains cannot be explained by chemical fractionation during condensation from a gas of solar composition and trace elements in non-solar proportions are required at the grain sources. Several types of stars have non-solar trace element abundances due to nucleosynthesis, so trace elements in presolar grains can provide a link to dust producing stars. This review is organized as follows. We describe some of the history of the search and discovery of presolar dust, the minerals already identified, and what other minerals are to be expected. We then describe dust producing stars and how certain grain types can be related to them. Since the discovery and isolation of presolar grains in 1987 by Lewis et al. (1987b), a large body of work on presolar grains has followed, and several reviews cover the progress in presolar grain research and its different directions (Anders and Zinner 1993; Bernatowicz and Zinner 1997; Ott 1993; Zinner 1998; 2004). ADD refs? 2 The search for presolar grains As noted in the introduction, in the 1950s and 1960s the cosmochemists view was that all dust evaporated during the collapse of the presolar molecular cloud and that mixing homogenized the chemical and isotopic composition of the solar nebular gas. However, even then there were indications that the latter was not the case. For example, Boato (1953; 1954) and Briggs (1963) found deuterium enrichments in carbonaceous chondrites that were not easy to explain by chemical mass-fractionation processes. Clayton (1963) encountered a similar problem to explain large 13 C enrichments in carbonate from the Orgueil meteorite and thought that incomplete homogenization of matter from different nucleosynthetic sources could be responsible. Unusual isotopic compositions in noble gases from meteorites were discovered by Reynolds and Turner (1964) for xenon, and by Black and Pepin (1969) for neon, which mark the onset of presolar grain studies. Historically, noble gas studies of extra-terrestrial materials played an important role in cosmochemistry. The noble - or rare -gases are literally rare in many meteorites but even a small addition of a trapped or adsorbed component whose isotopic composition is vastly different from normal is easily detected. Because several of the noble gases have more than two stable isotopes and an anomalous composition may not be restricted to a single isotope, the term component is used to describe an isotopic mixture that shows a certain characteristic isotopic composition. A technique commonly applied in noble gas studies to distinguish the various components is called stepwise heating, where a sample is heated in incremental temperature steps and the isotopic composition of the noble gases released during each step is measured. The idea is that components of different origin reside in different phases and/or have been trapped in different sites by different mechanisms, so that they are released at different temperatures. The studies by Reynolds and Turner (1964) and Black and Pepin (1969) revealed some unusual Ne and Xe components with extreme isotopic compositions during stepwise heating. In subsequent studies these persisted even more clearly after other components that partially masked the unusual ones, were removed by chemical treatments. This led to the questions if it were possible to isolate the pure unusual gas components and to identify the carrier phases. The detective work for Ne and Xe is described next. 4

5 2.1 Presolar signatures in neon isotopes: Ne-E Neon has three stable isotopes, 20 Ne, 21 Ne, and 22 Ne. Until the study by Black and Pepin (1969), the Ne-isotopic composition in meteorites was explained by mixing of three major components, historically called Ne-A, Ne-B, and Ne-S, each of which possess characteristic 21 Ne/ 22 Ne and 20 Ne/ 22 Ne ratios. Neon-A, or planetary Ne, has been observed in primitive meteorites. The name planetary Ne came from the notion that it must be representative of the Ne isotopic composition of the solar nebula gas that was trapped when meteorites and planets formed. (It turned out, however, that the major portion of Ne-A is carried by diamond, one of the presolar grain types.) Neon-B is observed in particularly gas-rich meteorites and is thought to be implanted solar wind or solar energetic particles. Neon-S, or cosmogenic Ne, is made by cosmic ray spallation, which produces all three Ne isotopes in about the same amounts. If Ne in meteorites is a mixture of the three components, the observed compositions should plot in a triangle bounded by the components Ne-A, Ne-B, and Ne-S in a Ne three-isotope plot, where 20 Ne/ 22 Ne and 21 Ne/ 22 Ne are the ordinate and the abscissa, respectively (see Anders 1988 for more details). When Black and Pepin (1969) analyzed six carbonaceous chondrites by stepwise heating, the Ne released between 900 C and 1000 C plotted below the triangle spanned by the known end-member compositions. This component was poor in 21 Ne, and had 20 Ne/ 22 Ne <3.4, much below the 20 Ne/ 22 Ne of ~8 and ~13 for Ne-A and Ne-B, respectively. This indicated there was a previously unknown component very rich in 22 Ne. Black (1972) named it Ne-E, as the letters C and D were already taken for other minor Ne components. The subsequent studies (Eberhardt et al. 1979; Lewis et al. 1979; Jungck 1982) showed that there are two kinds of Ne-E that reside in different density fractions of meteorites. One kind, Ne-E(L), was released at low temperatures ( C) and the carrier phase was concentrated in low-density fractions ( g/cm 3 ), whereas the other kind, Ne-E(H), was released at high temperatures ( C) and the carrier phase was concentrated in high-density fractions ( g/cm 3 ), Upper limits to the 20 Ne/ 22 Ne ratios became even lower [0.008 for Ne-E(L), 0.2 for Ne-E(H)] when Ne was measured in separates from the Orgueil meteorite (Jungck 1982). These measurements indicated that almost pure 22 Ne could be present in some phase of the separated meteorite fractions. This supported the idea that Ne-E is of nucleosynthetic origin, which was already suggested by Black (1972). A possible source of pure 22 Ne is 22 Na, which is made in novae and supernovae and decays to 22 Ne (T 1/2 =2.6 years). With such a short half-life, 22 Na must have been incorporated into a carrier near its stellar source to allow in-situ decay (Black 1972; Clayton 1975; Eberhardt et al. 1981; Jungck 1982). Jungck (1982) proposed a light element compound for the carrier of Ne-E(L), and apatite and spinel as the carriers of Ne-E(H), but neither of them is a carrier. It took until 1987 to identify the carrier phase of Ne-E(H) as silicon carbide (Bernatowicz et al. 1987; Tang and Anders 1988) and that of Ne-E(L) as graphite (Amari et al. 1990). It is now known that the 22 Ne in Ne-E(H) in silicon carbide is a direct nucleosynthetic product made in low-mass (~1-3 M? ) AGB stars, whereas the 22 Ne in Ne-E(L) is mainly from the decay of 22 Na plausibly produced in novae or supernovae (Clayton 1975) with possibly some 22 Ne from the He shell of AGB stars. 5

6 2.2 Presolar signatures in xenon isotopes: Xe-HL, Xe-S With nine stable isotopes xenon is the most complex element among the noble gases. Xenon components include a radiogenic component ( 129 Xe from the decay of 129 I with T 1/2 = years), a spontaneous fission component from 235,238 U and 244 Pu, a cosmicray spallation component, and so-called trapped components. With the complexity of the Xe system in meteorites (as well as in planetary atmospheres), Reynolds (1963) coined the Xe studies Xenology. Reynolds and Turner (1964) observed enrichments of the heavy isotopes Xe in the C fractions released from the Renazzo CR-chondrite, and that the trend in Xe composition was akin to that produced from spontaneous fission of heavy actinides. Rowe and Kuroda (1965) reported similar observations. Subsequently this component was dubbed CCF-Xe (carbonaceous chondrite fission) but the ensuing debate in the late 1960s about the possible presence of super-heavy elements in meteorites implied by CCF-Xe did not last (see Anders 1988). One objection was that the enrichments of heavy Xe isotopes were accompanied by enrichments in the lightest ones, 124 Xe and 126 Xe, which is inconsistent with a fission origin. The long search for the carrier of the unusual Xe component started when Lewis et al. (1975) treated the Allende meteorite with HF-HCl mixtures to dissolve silicates. They found that essentially all trapped Xe in the meteorite was in the residue, which comprised 0.5 mass% of the bulk meteorite. They further processed the residue with HNO 3, which resulted in the loss of only 6% of the residue s mass. All trapped Xe had vanished but a Xe component (Xe-HL) enriched in both and heavy ( 134 Xe and 136 Xe) and light ( 124 Xe and 126 Xe) isotopes emerged. The isotopic anomalies in light and heavy isotopes were always correlated, although their nucleosynthetic production mechanisms are different. The neutron-poor isotopes 124 Xe and 126 Xe are produced by the p-process, whereas the neutron-rich 132 Xe and 136 Xe isotopes are made by the r-process (section 7). Because the p- and r-process are believed to take place in supernovae, the correlation suggested that the carrier of Xe-HL formed in supernova ejecta. Another component characterized by its high 130 Xe/ 132 Xe ratio was accidentally found when Srinivasan and Anders (1978) tried to characterize Xe-HL in the Murchison meteorite. They considered the possibility that the carrier of Xe-HL in this meteorite might be different from that in the Allende meteorite (Anders 1988). It was necessary to treat the sample with additional oxidants to remove organic matter, which is more abundant in Murchison than in Allende. When the residue was analyzed by stepwise heating, they found the new component with a high 130 Xe/ 132 Xe ratio. This component was enriched in the even-numbered isotopes ( 128 Xe, 130 Xe, and 132 Xe), and a comparison to nucleosynthesis theory revealed that this component bore a signature of the slow neutron capture process (s-process), thus it was named Xe-S. Typically, Xe-S is accompanied by a krypton component also rich in s-process isotopes (Kr-S). 3 Isolation and discovery of presolar grains Although the exotic noble gas components (section 2) were found during stepwise heating experiments, their abundances relative to the total noble gas content are extremely low. For example, the s-process 132 Xe comprises only 0.006% of the total 132 Xe in the Murchison meteorite. Hence the abundances of the carrier minerals (what we now 6

7 call presolar grains) of the anomalous noble gases were also expected to be quite low. Lewis et al. (1975) demonstrated that the carrier of Xe-HL comprises less than 0.5% by mass of the whole Allende meteorite. Such low abundances made the identification of the carriers challenging and it took about two decades since the detection of anomalous noble gas components to the identification of the first presolar mineral in 1987 (see Table 1 for early results). Table 1. Early Results on Presolar Grain Identifications Around 1988 Working C-α C-β a C-ε a C-δ C-θ Designation Identified Phase amorphous carbon SiC SiC diamond amorphous carbon Noble Gas Identifier Ne-E(L) e Xe-S Ne-E(H) Xe-H(L) no noble gases Grain Size µm Average Density to 2.33 <2.2 g/cm 3 Abundance b ppm < δ 13 C, per-mil d ~ δ 15 N, per-mil d > +252 ~ -500 ~ -375 Possible Stellar Source d Novae, SN, AGB? AGB AGB SN SN? Sources: Lewis et al. (1987b), Anders (1988), Tang and Anders (1988; 1988), Anders and Zinner (1993) a Originally it was thought that C-β and C-ε are two different carriers. It was believed that C-β carries Xe-S, and that C-ε, associated with spinel because of similar density, carries Ne-E(H). (e.g., Anders 1988). b Abundance (ppm by mass) in CM2 chondrites c Stellar sources. AGB = asymptotic giant branch star (section 6), SN = Supernova (section 7) d Values are for carrier-enriched fractions, not for the pure carrier phase e Ne-E(L) = pure 22 Ne is mainly from 22 Na decay but may have some 22 Ne from AGB stars The group lead by Edward Anders and Roy S. Lewis finally succeeded to isolate and identify the carrier minerals, after many years of developing an isolation procedure. At the time the anomalous noble gas components were discovered, the carrier minerals were not known, but subsequent studies indicated that they seemed to be carbonaceous (e.g., Eberhardt et al. 1981, Jungck 1982, see summary by Anders 1987, 1988). During their search, Anders and colleagues named the carriers alphabetical like C-α and C-β. In order to nail down the carrier, meteorite fragments were processed chemically and physically, and divided into several separates. The noble gases were measured in each separate to examine which of them were enriched in the anomalous noble gas component(s), and these separates were treated further to concentrate the carriers. Hence the anomalous noble components served as beacons during the separation process. By 1987, Lewis et al. (1987b) succeeded to isolate diamond, the carrier of Xe-HL. This discovery was followed by the isolation of SiC, the carrier of Kr-S, Xe-S, and Ne-E(H) (Bernatowicz et al. 1987; Tang and Anders 1988), and graphite, the carrier of Ne-E(L) (Amari et al. 1990). Luckily all carriers of the anomalous noble gas components are carbonaceous and can withstand harsh chemicals - otherwise, it would not have been possible to isolate the carriers in this way. 7

8 Figure 2 outlines a standard procedure to separate presolar grains (Amari et al. 1994). First, silicates, which comprise a major part of stony meteorites (~96%), are removed by HF. Part of the organic matter - aromatic polymers collectively called reactive kerogen which is abundant in primitive meteorites - is destroyed by oxidants (H 2 O 2, Cr 2 O 7 2- ). At this point, nearly 99% of the meteorite is dissolved. Presolar diamond is extracted by colloidal separation, where the ph of the diamond suspension is raised so that diamond particles with weakly acidic groups on the surface are negatively charged, repulsing each Figure 2. The steps of the chemical isolation procedure and the resulting presolar grain size- and density-fractions from the Murchison meteorite by Amari et al. (1994). 8

9 other. Since presolar graphite has similar chemical properties to other forms of carbonaceous matter that still remains in the residue, a density separation is applied to extract presolar graphite from the remaining carbonaceous matter and other minerals with higher densities (>2.2g/cm 3 ). The separate with density higher than 2.2g/cm 3 is purified with HClO 4, which leaves minerals such as SiC and oxides (e.g., corundum and spinel). Most of the grains were isolated from meteorites by progressively harsher acid dissolution of the meteorite host rock, and subsequently analyzed. The advantage of this method is that individual grains can be studied for their overall morphology and crystal structure. The disadvantage of the dissolution process is that other potential presolar minerals are destroyed in the process. Another desired piece of information is how presolar grains interact with the meteorite host during metamorphism, because decreases in presolar grain abundances with metamorphic type are observed (see below). Locating the grains in situ is necessary to study the process of grain destruction in meteorite parent bodi es and to identify their reaction products. The first in-situ detection of presolar grains in meteorites was reported by Alexander et al. (1990). 4 Characterization techniques The techniques used to analyze presolar grains are listed in Table 2. Morphology and chemical compositions of grains are examined by scanning electron microscopy, SEM. Structural information is obtained by transmission electron microscopy, TEM, and Raman spectroscopy. There are two ways to prepare thin-sections of graphite and SiC grains for structural studies by TEM. One way is to embed grains in resin and to slice them into sections with a nominal 70 nm thickness 1 with an ultramicrotome equipped with a diamond knife (e.g., Bernatowicz et al. 1991). Another method is focused ion beam lift-out, where a ~3µm-thick Pt-layer is deposited onto a grain to protect it from the subsequent sputtering to cut parallel trenches by a high-energy Ga beam in order to make a ~100 nm thin section (e.g., Stroud et al. 2002). Most light element isotopic data have been obtained by ion probe. As described below, presolar oxides are a very minor population of all oxides in meteorites, so the majority of oxide grains are isotopically normal. To efficiently locate presolar oxide grains, ion imaging techniques have been established, pioneered by P. Hoppe and further developed by L. Nittler (1996, 1997). The concept is to use the signal strengths of isotopic ratios from e.g., 16 O and 18 O to produce isotopic maps of grains on a sample mount ( µm/image). Any grains with isotope ratios different than the standard then can be located from the isotope map of the mount for further analyses. Abundance and isotopic measurements of reasonable precision for several elements by conventional ion probe requires grain sizes of ~1µm or larger and relatively high concentrations of trace elements. The recent development of a new type of ion probe, the NanoSIMS, makes it possible to analyze submicron grains with much higher precision, which already led to new discoveries (e.g., Messenger et al. 2003; Nguyen and Zinner 2004). The Cs + primary beam size of the new ion probe can be as small as 30 nm (as opposed to a few µm of CAMECA IMS-3f) and achieve high spatial resolution. Furthermore, the NanoSIMS has higher sensitivity at high-mass resolution (e.g., 30?(or 1 For comparison, on average, a human hair is about 90 microns thick. 9

10 50?) times higher than the IMS-3f for Si isotopic ana lysis) and a multi-detection 5 mobile electron system with multipliers. Table 2. Analytical Methods Applied in Presolar Grain Studies Analytical quantity a b Method References c Elemental abundances SiC (single/bulk): Mg, Al, Ca, Ti, V, Fe, SIMS Amari et al. (1995d) Sr, Y, Zr, Ba, Ce graphite (single): H, N, O Al, Si SIMS Hoppe et al. (1995) diamond (bulk): Sc, Cr, Fe, Co, Ni, Ru, Os, Ir INAA Lewis et al. (1991) Isotopes of light elements SiC (single/bulk): C, N, O, Al-Mg, Si, SIMS Hoppe et al. (1994), Huss et al. Ca, Ti, Fe (1997), Amari et al. (2000a) graphite (single/bulk): C, N, O, Al-Mg, SIMS Amari et al. (1993), Hoppe et al. Si, Ca, Ti (1995), Travaglio et al. (1999) diamond (bulk): C, N, MS Russell et al. (1996) Si3N 4 (single): C, N, Si SIMS Nittler et al. (1995b) oxides (single): O, Al-Mg (Ca, Ti) SIMS Huss et al. (1994), Hutcheon et al. (1994), Nittler et al. (1997), Choi et al. (1998b; 1999) silicates (single): O, Al-Mg SIMS Messenger et al. (2003 in IDPs), Nguyen & Zinner (2004), Nagashima et al. (2004) Isotopes of heavy elements SiC (bulk): Sr, Ba, Nd, Sm TIMS, SIMS Ott et al. (1990), Zinner et al. (1991), Prombo et al. (1993) Sr. Zr, Mo, Ba, Ru RIMS Nicolussi et al. (1997; 1998c), Savina et al. (2003b; 2004) graphite (single): Zr, Mo RIMS Nicolussi et al. (1998b) diamond (bulk): Te TIMS Richter et al. (1998) Noble gases SiC ( bulk): He, Ne, Ar, Kr, Xe NGMS Lewis et al. (1990; 1994) graphite (bulk): Ne, Ar, Kr, Xe NGMS Amari et al. (1995a) SiC & graphite (single): He, Ne NGMS Nichols et al. (2004) Crystal structure SiC TEM, Raman Virag et al. (1992), Bernatowicz et al. (1992) graphite TEM, Raman Zinner et al. (1995), Bernatowicz et al. (1991; 1996), Croat et al. (2003) diamond TEM, EELS Bernatowicz et al. (1990), Daulton et al. (2002; 2003) Multiple properties (grain size, morphology, SEM Hoppe et al. (1994, 1995) elemental compositions) a Notes. single: individual grain analysis. bulk: analysis of aggregate grain samples b EELS: Electron energy loss spectrometry. INAA: Instrumental neutron activation analysis. - MS: Mass spectrometry. -NGMS: Noble gas mass spectrometry. - SEM: Scanning electron microscopy. - SIMS: Secondary ion mass spectrometry. - TEM: Transmission electron microscopy. - Raman: Raman spectroscopy. - RIMS: Resonant ion mass spectrometry c Only a few references are listed here to provide a starting point to analytical details. 10

11 The isotopic composition of heavy elements (Sr and Ba) in aggregate grain samples has been analyzed by conventional thermal ionization mass spectroscopy, TIMS, which provides data of very high precision. The sample (e.g., SiC grains) is directly loaded onto a filament and gradually heated which ionizes different elements at different steps. With this method, elements within similar mass ranges can be separated. Since isotopic abundances of elements heavier than iron can be modified by neutron capture reactions in certain stars, the isotopic ratios of heavy elements are very informative in identifying stellar sources. Analyses of heavy element isotopes on single grains have been performed by resonant ionization mass spectrometry (RIMS), namely the CHARISMA instrument at Argonne National Laboratory in Chicago (e.g., Nicolussi et al. 1998a). First, a plume of neutral atoms and molecules is generated by laser-induced thermal desorption. Then the atoms are resonantly ionized by tuned laser beams, and subsequently analyzed by a time-of-flight mass spectrometer. Although ionization schemes must be developed for each element, a great advantage of this instrument is that isotopes of interest can be analyzed without interference from other elements. 5 The presolar grain zoo Since 1987 the list of known presolar minerals expanded quite substantially as seen from Table 3. In meteorites the more abundant presolar minerals are diamond, SiC, graphite, corundum, and spinel; less frequently encountered are Si 3 N 4, hibonite, silicates, and TiO 2. As a bonus, presolar graphite grains often enclose small trace element carbide- and Fe-Ni metal particles. By now, several thousand individual SiC and a few hundred graphite grains have been analyzed. Despite the facts that diamond was discovered first and is the most abundant presolar mineral, its nm-size prevented individual grain analyses, and isotopic measurements are restricted to samples consisting of collections of grains (Lewis et al. 1987b; 1991a; Richter et al. 1998). Most of the several hundred presolar oxide grains analyzed are corundum and spinel, and only some dozen are hibonite (Huss et al. 1994; Hutcheon et al. 1994; Nittler et al. 1994; 1997; 1998; Choi et al. 1998; 1999; Nittler and Alexander 1999; Krestina et al. 2002; Nguyen et al. 2003; Zinner et al. 2003). The acid residues containing aluminous phases after chemical isolation procedures mainly consist of aluminous phases from the host meteorite and the ion imaging technique has proven to be valuable to locate the presolar oxides among them (e.g., Zinner et al. 2003). The first presolar silicates (olivine and pyroxene) in meteorites were detected by Nguyen and Zinner (2004). After dis-aggregation and size-sorting of the Acfer 094 carbonaceous chondrite, sub-micron size fractions were analyzed by ion-imaging with the NanoSIMS to detect isotopically anomalous silicates. Recently, Nagashima et al. (2004) located presolar silicates in thin sections of two primitive meteorites. Presolar grains are essentially ubiquitous in all types of primitive chondritic meteorites. The observed abundance of a presolar mineral group depends on the resistance during chemical acid processing which leaves abundances of diamond, graphite, and SiC essentially unaffected, depending on the specifics of the acid treatment (Amari et al. 1994), but also on grain survival during metamorphism on meteorite parent bodies. Estimated abundances of presolar diamonds, SiC and graphite in carbonaceous, unequilibrat ed ordinary, and enstatite ch ondrites are given in Table 4. 11

12 Table 3. Currently Known Presolar Minerals Mineral Characteristic Possible Stellar Discovery Papers Size Source a check ref list Diamond 2 nm AGB?, SN? Lewis et al. 1987b SiC µm AGB, SN, novae Bernatowicz et al. 1987; Tang & Anders 1988; Zinner et al. graphite 1 20 µm ABG, SN 1987 Amari et al carbides in graphite nm AGB, SN Bernatowicz et al. 1991, 1996; metal grains in graphite nm SN Croat et al.2003 Si 3 N µm AGB?, SN Nittler et al corundum µm RGB, AGB, SN? Hutcheon et al Nittler et al spinel µm RGB, AGB, SN? Nittler et al. 1997, Choi et al hibonite µm RGB, AGB, SN? Choi et al TiO 2 Nittler & Alexander 1999 silicates ( olivine, pyroxene) µm AGB?, SN? Messenger et al (IDPs) Nguyen & Zinner 2004 (in chondrites) Notes. a AGB asymptotic giant branch stars. RGB: red giant branch stars. SN: supernovae. An? indicates not known/uncertain. Abundance estimates for corundum, spinel, silicates, and Si 3 N 4 are only available for a few meteorite groups. Corundum in unequilibrated H chondrites is about 0.03 ppm (by mass) and 0.13 ppm in CM chondrites. The CM chondrites also contain 1-2 ppm spinel and ppm Si 3 N 4. A first lower abundance limit of ~25 ppm for presolar silicates in a very primitive carbonaceous chondrite is reported by Nguyen and Zinner (2004). In addition to primitive meteorites, presolar silicate grains were found in interplanetary dust particles (IDPs), where presolar silicates apparently occur in much larger abundance than in me teorites. Abundance estimates are ~5500 ppm in cluster IDPs ( Messenger et al. 2003) and 450 ppm in IDPs with N-isotopic anom alies (Floss and Stader mann 2004). Table 4 Abundance Estimates of Presolar Grain Types in Different Meteorite s (ppm by mass) Chondrite Group Diamond SiC Graphite CI CM CR CO <0.15? CV-reduced below detection limit CV-oxidized < 0.20 CH H 3.4 (<?) ~ L 3.4/ LL3.0/ EH Sources: Huss (1990, 1997), Huss et al. (2003), Ott (1993), Zinner et al. (2003) Primitive meteorites of low petrographic type that never experienced high metamorphic temperatures or aqueous alterations (e.g., unequilibrated ordinary 12

13 chondrites) provide the best time capsules for preserving presolar grains. Early studies showed that the C-isotopic compositions in the most primitive ordinary chondrites (petrologic type 3) varied more than those of higher petrologic types (4-6) (Swart et al. 1983). This suggests selective destruction of presolar grain populations in ordinary chondr ites of higher-metamorphic type. This is also indicated by noble gas measurements of diamond separates from different types of chondrites and provides useful measure of meteorite parent body metamorphism (e.g., Huss and Lewis 1994a; 1995). 5.1 Sorting the presolar grain record This section describes properties of the major presolar minerals. The chemical and isotopic compositions of individual presolar grains from the major mineral groups - graphite, SiC, and oxides - indicate that different types of stars produced grains of similar mineralogy. Some characteristics of the SiC, graphite and oxide grain populations are given in Tables 5-7, and for comparison, similar characteristics of the major potential stellar sources are listed in Table Silicon carbide Silicon carbide is the most extensively studied presolar mineral, both in the form of aggregated bulk samples and of single grains, for several reasons. First, the separation procedure of SiC is less complicated than that of graphite. Second, SiC is present in several classes of meteorites (Table 4). Third, although most SiC grains in meteorites are sub-micron in size, there are grains larger than one micron that are suitable for correlated isotopic analyses in single grains. Fourth, trace element concentrations are high enough to make elemental abundance and isotopic measurements with reasonable precision. Figure 3. Secondary electron images of silicon carbide grains extracted from the Murchison meteorite. Most SiC grains are submicron in size and larger grains such as shown are relatively rare. Scale bars are 1 µm. (a) The fluffy surface structure is common in SiC grains, and most likely due to the harsh chemical treatments during the extraction from meteorites. The 12 C/ 13 C ratio of this grain is 55 (cf. solar = 89). (b) A SiC grain with a smooth surface. The 12 C/ 13 C ratio of this grain is

14 The average size of individual SiC is about 0.5 microns with sizes ranging up to 20 microns, although grains larger than 10 microns are extremely rare. The size distribution of SiC in different types of meteorites vary, e.g., the Murchison CM-chondrite typically has larger-size SiC on average than other meteorites for reasons that are unknown (Amari et al. 1994; Huss et al. 1997; Russell et al. 1997). The morphology of most SiC grains extracted from meteorites by the chemical isolation procedure shows euhedral shapes with more or less fluffy surfaces (Figure 3a,b). In order to examine pristine SiC grains not subjected to chemicals Bernatowicz et al. (2003) dispersed matrix material excavated from the interior of the Murchison meteorite onto polished graphite planchets and examined them by SEM. The pristine grains have less surface pits than grains isolated by chemical procedures, indicating that etching of surface defect structures occurs during chemical isolation. Of the 81 pristine grains studied by Bernatowicz et al. (2003), ~60% are coated with an amorphous, possibly organic phase. No other differences in morphology than caused by sample extraction procedures have been observed among SiC grains. Synthetic SiC occurs in several hundred different crystallographic modifications but presol ar SiC only occurs in the cubic 3C and the hexagonal 2H modification and intergrowths of these two forms (Daulton et al. 2002). The limited polytype distribution in presolar SiC probably reflects condensation of SiC at relatively low total pressures in circumstellar outflows (Daulton et al. 2002) Chemical and isotopic compositions bulk SiC aggregates The analyses of bulk samples have the advantage that data with high precision can be obtained. This provides well defined average properties for whole suites of separates to Figure 4. Noble gas components in aggregates of SiC grain compared to solar composition. The data are from Lewis et al. 1990, 1994 (see also Ott 2002) normalized to the solar isotopic composition taken from Wieler (2002). The isotope ratios are further normalized to 20 Ne, 36 Ar, 84 Kr, and 132 Xe, respectively. The dotted line indicates the solar composition. The components were derived assuming that the noble gases in SiC grains are a mix of a normal component and a component that resembles abundance ratios from nucleosynthesis by the s-process. 14

15 examine systematic differences as a function of average grain size. On the other hand, there is the potential problem that aggregates may contain some contaminant, which can hamper the interpretation of bulk elemental abundances. However, any isotopic anomalies would only be diluted by contamination with normal material, and large overall isotopic anomalies can still be detected. The following describes the isotopic compositions of the noble gases, Sr, and Ba in SiC aggregates. Silicon carbide is the carrier of Ne-E(H), Kr-S and Xe-S, which had prompted the search for presolar grains in meteorites. Lewis et al. (1990; 1994) analyzed all noble gases in the size-sorted SiC fractions (average size: µm) extracted from the Murchison meteorite. They found that the measured noble gas compositions can be modeled a mixture of two-components which they designated N component for normal, and G component for AGB (Figure 4). The G component of Kr was found to be similar to the theoretical composition from nucleosynthesis by the s-process in AGB stars (Gallino et al. 1990; 1997), hence the name. Initially the terms G and N component were only used for noble gases but were extended to other trace elements. The isotopic composition of Sr (Podosek et al. 2004) and Ba (Ott and Begemann 1990; Zinner et al. 1991; Prombo et al. 1993) was also analyzed for the same size-sorted SiC fractions (but for different suites) by TIMS and SIMS. In all cases the G component was prevalent which indicated that a large fraction of presolar SiC grains originated from stars in which the s-process responsible for the G component operates Individual SiC grains: Clues to SiC sub-populations Isotopic and trace element analyses of single grains by ion probe revealed the presence of sub-populations for SiC grains. Most information about the different types of SiC comes from isotopic studies of C, N, and silicon, which leads to the five major subtypes called mainstream, A+B, X, Y, and Z, currently known. The distinguishing characteristics of the SiC types are listed in Table 5. The C- and N-isotopic ratios of individual SiC grains in Figure 5 define at least three specific types of SiC grains. Figure 6 shows the Si-isotopic composition of individual SiC grains 2 in a three-isotope plot, reveals distinct compositional arrays. The number of grains plotted in Figures 5 and 6 does not represent their true distribution among the sub-populations because grains from certain subpopulations were preferentially searched for by ion imaging and then studied. The true population distribution is noted in the legends of Figures 5 and 6, and in Table 5. About 93% of presolar SiC grains, the mainstream grains, have lower 12 C/ 13 C and higher 14 N/ 15 N ratios than the respective solar ratios of 12 C/ 13 C =89 and 14 N/ 15 N = 272. Their Si-isotopic composition is slightly 29 Si- and 30 Si-rich ( 29 Si/ 28 Si and 30 Si/ 28 Si ratios up to 1.2 times solar). In the three Si-isotope plot mainstream grains defined a line with δ 29 Si = δ 30 Si (Lugaro et al. 1999). There is some variance in the fit parameters depending on the number of data points included in the regressions, e.g., Hoppe et al. (1994) find δ 29 Si = δ 30 Si, and Nittler and Alexander (2003) obtained δ 29 Si = 18.3(±0.6) +1.35(±0.01) δ 30 Si. 2 Here and elsewhere the delta notation is used to describe the derivation of an isotope ratio ( i N/ j N) of a sample from the (terrestrial) standard ratio in per-mil units. The δ notation is defined as δ i N ( ) = [( i N/ j N) sample /( i N/ j N) standard 1]

16 Figure 5 Individual SiC grains fall into different populations based on their C and N isotopic ratios. Most grains are mainstream grains. The number of grains in the minor populations is over-represented because they were preferentially studied after their identification by ion imaging techniques. Real abundances of the populations are shown in the legend. The dotted lines indicate the solar isotopic ratios. Data are from Alexander (1993), Amari et al. (2001-a-c), Hoppe et al. (1994, 1996a), Huss et al. (1997), Lin et al. (2002), Nittler et al. (1995). Grains with 12 C/ 13 C < 10 and 14 N/ 15 N ratios from about 40 to 12,000 are called A+B grains (Amari et al. 2001a). Originally it was thought that two distinct populations A and B exist, but these two belong to the same compositional continuum spanned by C- and N-isotopes (Figure 5). The Si-isotopes of A+B grains are similar to those of mainstream grains (Figure 6). In the three Si-isotope plot A+B grains define a line with δ 29 Si = 34.1(±1.6) (±0.03) δ 30 Si (Amari et al. 2000b) with a small off-set in slope compared to the mainstream grains. The A+B grains constitute 3-4% of all SiC grains and are the second largest one among the SiC populations. The SiC of type X about ~1% of all SiC is characterized by higher 12 C/ 13 C and lower 14 N/ 15 N ratios than the respective solar values. The X grains show low δ 29 Si and δ 30 Si values, and 28 Si excesses reach up to five times solar (Amari et al. 1992; Hoppe et al. 2000; Amari and Zinner 1997). About one percent of all SiC grains have 12 C/ 13 C >100 and 14 N/ 15 N ratios higher than the solar ratio (Amari et al. 2001b, Hoppe et al. 1994). These Y grains appear to be very 12 C-rich mainstream grains, but their slightly larger 30 Si/ 28 Si ratios than that of mainstream grains merits to place them into a separate group. The Z grains make up to 3% of all SiC, particularly among smaller size grain fractions. Their 12 C/ 13 C and 14 N/ 15 N ratios are indistinguishable from those in mainstream grains but Z grains have large excesses in 30 Si (Alexander 1993; Hoppe et al. 1997). The mainstream, Y and Z grains are believed to come from AGB stars with different initial 16

17 Figure 6. Silicon isotope ratios are useful to classify the different SiC populations. The silicon isotopic composition is given in the δ notation (see footnote 1). The mainstream and A+B grains are not very well resolved. References to the data are the same as in Figure 5. contents of heavy elements, which may lead to the observed differences in isotopic compositions. Only a few nova SiC grains have been identified (Amari et al. 2001c; José et al. 2004; Nittler and Hoppe 2004a). They are characterized by low 12 C/ 13 C ratios ranging from 4 to 9, and low 14 N/ 15 N ratios between 5 and 20. Nova grains have close-tosolar 29 Si/ 28 Si ratios but 30 Si excesses. The isotopic compositions of other elements provide further hints on the grains origins. Many SiC grains have large 26 Mg/ 24 Mg ratios when compared to the solar ratio (Amari et al. 1992; 2001a; 2001b; 2001c; Hoppe et al. 1994; 2000; Huss et al. 1997). In contrast, the 25 Mg/ 24 Mg isotopic ratios are solar within 10%. Some SiC X grains contain almost pure 26 Mg which indicates that 26 Mg excesses were most likely introduced by insitu decay of 26 Al (t 1/2 = years) that was incorporated into the grains at their stellar sources. The inferred 26 Al/ 27 Al ratios are shown in Figure 7. The X grains have the largest 26 Al/ 27 Al ratios of up to ~0.6, whereas ratios in A+B and mainstream grains typically do not exceed 0.01 (Hoppe et al. 1994; Amari et al. 2001a). In SiC grains the isotopic compositions have also been measured for Ca and Ti (Ireland et al. 1991; Amari et al. 1992; 2001b; 2001a; Hoppe et al. 1994; 1996; 2000; Nittler et al. 1996; Alexander and Nittler 1999; Hoppe and Besmehn 2002; Besmehn and Hoppe 2003) and Fe, Zr, Mo, Sr, Ba, and Ru (Nicolussi et al. 1997; 1998a; 1998c; Pellin et al. 1999; 2000a; 2000b; 2001; 2002; Tripa et al. 2002; Davis et al. 2002; Savina et al. 2003a; 2003b; 2004). 17

18 Table 5. Some Characteristics of Presolar Silicon Carbide Populations Designation Mainstream MS X Y Z A+B a Nova Grains Crystal type 3C, 2H b 3C, 2H b 3C, 2H b 3C, 2H b 3C, 2H b 3C, 2H? b Heavy trace ~10-20 c highly ~ 10 c NA solar or NA elements c variable c 12 C/ 13 C < 3.5 (A) < (B) 14 N/ 15 N < Si/ 28 Si c Si-rich solar Si/ 28 Si c Si-rich 30 Si-rich 30 Si-rich Si rich 26 Al/ 27 Al 10-3 to to 0.6 similar to similar to <0.06 up to 0.4 MS MS Other isotopic markers c 44 Ca excess K excess 47 Ti-rich excess in 46 Ti, 49 Ti, 50 Ti over 48 Ti excess in 46 Ti, 49 Ti, 50 Ti over 48 Ti excess in 46 Ti, 47 Ti, 49 Ti over 48 Ti excess in 46 Ti, 49 Ti, 50 Ti over 22 Ne d yes NA NA NA NA NA Abundance 87-94% 1% 1 2% 0 3% 2 5% << 1% Notes: a Group A and B grains were initially separated but later found to form a continuum in compositions. - b cubic 3C, hexagonal 2H. - c abundance compared to solar composition. - d 22 Ne = Ne-E(H) = Ne(G). - NA: not analyzed Sources: Amari et al. (2001b; 2001a); Hoppe and Ott (1997), Hoppe and Zinner (2000), Ott (2003), Zinner (1998), Nittler and Hoppe (2004a; 2004b) 48 Ti Figure 7. Inferred 26 Al/ 27 Al ratios vs. 12 C/ 13 C ratios in individual SiC and graphite grains. The SiC type X and low-density graphite grains have the largest 26 Al/ 27 Al. See text for data sources. 18

19 5.2.3 Trace elements in individual SiC grains Silicon carbide grains contain several trace elements, some of them in considerable amounts. Magnesium concentrations are typically around 100 ppm and Al abundances Figure 8. Trace element abundances in individual SiC grains normalized to solar abundances and Si. Relative depletions or enrichments in Sr and Ba are most notable. Mainstream grains are shown by black symbols, open symbols are for A+B grains, and type Y grains are shown in grey. Abundances in two X type SiC grains are shown in a separate panel. The letters marked by a star refer to the original groupings in Figure 1 by Amari et al. (1995). 19

20 can reach several mass-percent (e.g., Hoppe et al. 1994). Nitrogen, probably substituting for carbon in the SiC lattice, shows relatively high concentrations so the N-isotopic ratios can be analyzed with reasonable precision. However, determination of the absolute concentration of nitrogen is difficult: it does not form a stable negative ion and carbon must be present to produce the CN - which is used to analyze N by the ion probe (Zinner et al. 1989). In addition to Al and Mg, concentrations of Ca, Ti, V, Fe, Sr, Y, Zr, Nb, Ba, Ce, and Nd were measured in 60 SiC grains (average grain size: 4.6µm) and in three sizesorted SiC aggregates ( µm) with the ion probe (Amari et al. 1995c). The general problem in determining multiple trace element abundances in presolar grains is that the grains are partially consumed during the measurements. The first measurements are generally for C, N, and Si isotopic ratios to identify the grain s membership among the SiC populations. After this, only initially large grains have enough mass left to make additional trace element analyses. This situation will improve once NanoSIMS analyses are extended to trace element data in smaller SiC grains. Trace element measurements of 34 mainstream grains define at least 8-9 different normalized abundance patterns (Figure 8) and only 4 of these grains had unique abundances (Amari et al. 1995c). In mainstream grains element/si ratios of elements heavier than iron (Y, Zr, Nb, Ba, La, Ce, and Nd) are up to 35 times the solar ratio. These enrichments most likely reflect the composition at the stellar sources. However, the source composition can be fractionated during trace element condensation into SiC. In many grains Sr and Ba, which are s-process elements that should be similarly enriched as the other heavy elements, are often less abundant when compared to the abundances of their neighbors (Figure 8). These depletions result from volatile fractionations of Sr and Ba, as described in section 6. The enrichment of s-process elements in Y grains (Figure 8) fosters their close relationship to mainstream SiC. Trace elements have not yet been reported for the Z type SiC grains. Most of the trace element abundances measured in the two X grains are very low and only upper limits for e.g., Zr and Sr were obtained. The trace elements of twenty A+B SiC grains (Figure 8) give 4 separate types of abundance patterns (Amari et al. 1995c; 2001a). These provided a surprise for the A+B grains at least two types of stellar sources with different characteristic bulk abundances of heavy elements are needed to explain the elemental abundances, which was not indicated by their isotopic compositions. In one of the patterns all elements plot near the solar abundance ratio and only Sr shows a relative depletion. The other 3 patterns show higher relative abundances of the heavy elements and various volatility related fractionations, which makes these A+B grains more similar to mainstream grains. 5.3 Silicon nitride The few known Si 3 N 4 grains share many properties of the SiC X grains, and their C, N, Si, and Al isotopic compositions are shown together with the SiC grain data (Figures 5-7). More information about these rare grains can be found in Amari et al. 2002, Besmehn and Hoppe 2003, Lin et al. 2002, Nittler and Alexander 1998, and Nittler et al. 1995b. 20

21 5.4 Graphite Presolar graphite is present only in primitive meteorites (Huss and Lewis 1995, see also Table 4). It is not as chemically resistant as SiC or the oxides corundum and spinel. The identification of presolar graphite is complicated because other carbonaceous compounds with similar chemical and physical properties are present in primitive meteorites. Thus the separation of graphite, which is achieved by a combination of mild oxidation and density separation, is far more elaborate than that of other presolar grains and essentially all studies of presolar graphite have been performed on four graphite-rich fractions extracted from the Murchison meteorite. These four fractions (designated by capital letters and numbers) differ in their densities as follows: KE1 and KE3: g/cm 3, KFA1: g/cm 3, KFB1: g/cm 3, KFC1: g/cm 3 (Amari et al. 1994). Some properties of these fractions are listed in Table 6. Table 6. Some Characteristics of Presolar Graphite Density Fractions a Designation KE1, KE3 KFA1 KFB1 KFC1 Density (g/cm -3 ) Morphology mainly cauliflower mainly onion 12 C/ 13 C N/ 15 N mostly solar mostly solar mostly solar mostly solar b (28-306) ( ) ( ) 18 O/ 16 O up to 184 solar up to 6.6 solar solar solar 29 Si/ 28 Si solar solar ± solar c solar c 30 Si/ 28 Si solar solar ± solar c ± solar c,d 26 Al/ 27 Al up to up to up to Major sources: Hoppe et al. (1995), Travaglio et al. (1999) a Amari et al. (1994). - b one grain in KFC1 with 14 N/ 15 N = 730±64. - c very large uncertainties d one nova grain with 30 Si/ 28 Si = 1.76 solar. Some structural, elemental, and isotopic features of presolar graphite grains vary with density. On average, the low-density separates contain more larger grains (Hoppe et al. 1995). Amari et al. (1995a) and Hoppe et al. (1995) describe correlations between density Figure 9. Presolar graphite grains show two morphologies. (a) A graphite grain of the onion type, with a layered surface structure. (b) A graphite grain of the cauliflower type, which appears as aggregates of small grains. 21

22 Figure 10. Carbon and N isotopic composition of individual graphite grains from four different density fractions. The density increases in alphabetical order (E<FA<FB<FC). In all fractions 12 C/ 13 C ratios vary more than 3 orders of magnitude, but 14 N/ 15 N ratios are surprisingly normal in most grains. and isotopic compositions of the noble gases and carbon. This is in marked contrast to SiC grains where observed isotopic features in Kr, N, Sr, and Ba were found to depend only on grain size. Graphite grains are much larger, typically >1µm, with sizes ranging up to 20 µm, while most SiC grains are sub-micron in size. This is a huge advantage for single grain analyses. Investigation by SEM and TEM show different external and internal structure of the graphite grains. Two morphological types shown in Figure 9 and dubbed cauliflower and onion are distinguished (Bernatowicz et al. 1991; 1996; Hoppe et al. 1995; Bernatowicz and Cowsik 1997). The TEM work shows that grains of the onion type have a concentriclayered structure 3 of well-graphitized carbon and a core of randomly oriented, fine-grained crystalline aggregates (Bernatowicz et al. 1996). On the other hand, cauliflower type grains appear to be aggregates of small grains and consist entirely of turbostratic graphite (i.e., graphite with contorted layers not having long-range continuity) (Bernatowicz et al. 1991; 1996). The onion type graphite is more abundant in the high-density fractions, and the cauliflower type is more abundant in the low-density fractions. Figure 10 shows the C- and N-isotopic composition of individual graphite grains from the four density fractions. Overall, the 12 C/ 13 C ratios in graphite grains range from 2.1 to 7223, demonstrating their presolar origin. Grains with higher 12 C/ 13 C ratios than the solar ratio are most abundant (~75%) in the highest density separate KFC1 ( g/cm 3 ). In contrast the isotopic composition of nitrogen, one of the most abundant trace elements in graphite, is bewilderingly solar in many grains. This has been interpreted that at least part of the indigenous N in graphite equilibrated with air (Hoppe et al. 1995). The graphite from the lowest density separate (KE3, density g/cm 3 ) is a possible exception because a slight decrease in the 14 N/ 15 N ratio with increasing 12 C/ 13 C ratio (see Figure 10). In this 3 The onion like morphology of these graphite grains is reminiscent to that of hailstone, although on a different absolute scale. 22

23 respect it is interesting to note that an outstanding feature of graphite grains is the presence of almost pure 22 Ne (the Ne-E(L)). If nitrogen isotopically equilibrated with air the noble gases should also equilibrate thus erasing any isotopic anomalies. In particular neon should be affected because it has similar adsorption properties as nitrogen but Ne is anomalous. This compounds the mystery of the normal N-isotopic composition in presolar graphite and requires more investigation. Abundances of H, O, N, Al, and Si in individual graphite grains are typically around one-mass percent (Hoppe et al. 1995). With increasing density of the grain fractions the concentrations of H, N, O, and Si decrease. The isotopic composition of O, Mg, Al, Si, Ca, Ti, Zr and Mo in several individual graphite grains from the KE3, KFA1 and KFC1 low-density fractions were measured by e.g., Hoppe et al. (1995), Amari et al. (1995b, 1996), Nicolussi et al. (1998b), and Travaglio et al. (1999). The Si isotopes in graphite grains (Figure 11) are similar to those observed among the different SiC populations. Most graphite grains, particularly from the lowest density Figure 11. Silicon isotopes in presolar graphite grains from the lowdensity fractions define arrays similar to those given by presolar SiC grains (compare to Figure 6). fraction KE3, are similar to the SiC X grains rich in 28 Si (Figure 6). This kinship also follows from the 26 Al/ 27 Al ratios in graphite (Figure 7). 23

24 Oxygen isotopes in graphite grains (Figure 12) from the lowdensity fractions KE3 (Travaglio et al. 1999) and KFA1 (Amari et al. 2004) appear normal in 17 O/ 16 O but show large enrichments in 18 O/ 16 O relative to the solar ratio. The O- isotopic composition in the graphite grains is remarkably different from that in presolar oxide grains (see Figure 14 below). Low-density graphite grains - the KE3 grains, and a few of the KFA1 grains - are believed to have formed in supernovae, while high-density grains - KFC1 grains - most likely formed in low-metallicity AGB stars. In addition, novae can account for isotopic features of a few grains. There are no equivalent designations for the different Figure 12. Oxygen isotopes in graphite grains from the low-density fractions KE3 (black symbols; Travaglio et al. 1999) and KFA1 (grey symbols, Amari et al. 2004). Dotted lines indicate solar oxygen isotopic composition graphite populations as for the mainstream, A+B, X, Y, and Z populations of silicon carbide. It is still unknown how many presolar graphite populations exist, and how many types of stars are required to account for the presolar graphite. The C-isotope ratios alone are not diagnostic to distinguish the possible stellar sources and the isotopic compositions of other elements is needed to identify the graphite grains parent stars. However, with the exception of the KE3 grains, the generally low trace element contents make isotopic analyses challenging. 5.5 Sub-Grains in Graphite and SiC Figure 13. A TEM image of two TiC sub-grains in presolar graphite. Figure courtesy K. Croat and T. Bernatowicz. Sometimes surprises come in small packages. Nanometer size sub-grains hidden in presolar graphite and SiC grains made their debut during TEM studies by Bernatowicz et al. (1991; 1992). A SiC grain about 5.3 micron in size of clear presolar origin as shown by its low 12 C/ 13 C = 51.6±0.4 contained several sub-grains ranging in size from nm. Diffraction patterns and EDS analysis confirmed that they are TiC. An epitaxial relationship between the TiC and the SiC host suggests that SiC and TiC either grew simultaneously, or that TiC exsolved from SiC (Bernatowicz et al. 1992). Much more extensive studies have been performed on inclusions in graphite grains from the lowest density separate KE3 (Croat et al. 2003) and the 24

25 highest density separate KFC1 (Bernatowicz et al. 1996; Croat et al. 2004). The tiny subgrains in graphite are shown in Figure 13. The sub-grains in KFC1 graphite are smaller (5-200 nm) than those in KE3 graphite which contain ~10 to ~400 nm-size TiC grains. The sub-grains appear to have an independent origin from the graphite because the size distributions of the subgrains do not correlate with the size of the host graphite. In addition, the varying V content (V/Ti= ) of the TiC sub-grains favors an independent origin. About 30 % of the TiC grains have partially amorphous rims (3 to 15 nm thick) that could be the result of atom bombardment when the grains were at drift with respect to the ambient gas before they were embedded into the growing graphite grains (Croat et al. 2003). In contrast to sub-grains in SiC, those in graphite show no crystallographic (epitaxial) relationship with the host graphite, suggesting that they formed prior to graphite and were randomly incorporated into graphite grains later. Many graphite grains from the high-density KFC1 fraction contain sub-grains consisting of refractory carbides with compositions ranging from nearly pure TiC to nearly pure Zr-Mo carbides (Bernatowicz et al. 1996; Croat et al. 2004). In a few graphite grains a carbide grain is located in the center of the graphite grains, indicating that the carbide served as a nucleation site (see Figure 13 and the Figure 7(a) in Bernatowicz et al. 1996). However, there are also graphite grains with sub-grains of TiC, iron-nickel metal, and cohenite, but no Mo-Zr carbides, which points to different stellar sources, possibly supernovae, of these graphite grains (Croat et al. 2003). 5.6 Presolar oxide grains: Corundum, spinel, hibonite Oxide grains are resistant to chemicals used to isolate carbonaceous presolar grains, thus oxide grains concentrate in SiC-rich residues. The problem of identifying presolar oxide grains is that the vast majority of oxide grains left in meteoritic residues is isotopically normal because of its origin in the solar system. For example, in the Tieschitz (H3.6) ordinary chondrite presolar Al 2 O 3 is estimated to be 0.03 ppm (Nittler et al. 1997), and in CM2 chondrites less than 1% of all corundum grains are expected to be presolar (Zinner et al. 2003). In contrast, essentially all SiC grains in meteorites are presolar. Hence it becomes necessary to analyze the isotopic composition of a large amount of oxides after isolation in order to identify any presolar grains among them. The first presolar oxide grains were found during ion probe studies on individual grain analysis (Huss et al. 1994; Hutcheon et al. 1994). The majority of known presolar oxide grains was found by ion imaging, and these grains were subsequently analyzed by conventional high-mass-resolution ion probe. The oxides are mainly corundum and spinel (Huss et al. 1994; Hutcheon et al. 1994; Nittler et al. 1994; 1997; 1998; Nittler and Alexander 1999; Choi et al. 1998; 1999; Krestina et al. 2002). Other presolar oxide minerals are a few hibonite grains (Choi et al. 1999; Krestina et al. 2002) and one TiO 2 grain (Nittler and Alexander 1999). Corundum was the dominant mineral of presolar oxides until Zinner et al. (2003) analyzed individual spinel grains from the spinel-rich separates CF (mean diameter 0.15 µm) and CG (mean diameter 0.45 µm) from the Murray meteorite with the NanoSIMS. Ion probe analyses of aggregates of CF grains had shown O-isotope anomalies, suggesting that up to one percent of the grains may be presolar (Zinner and Tang 1988). Presolar spinel is more abundant among oxide grains of less than 0.5µm (see Table 2 by Zinner et al. 2003). Nguyen et al. (2003) obtained O isotopic images of tightly packed CF 25

26 and CG grains and found about 84 presolar oxide grains by ion imaging, capitalizing on the high spatial resolution from the small beam diameter of the NanoSIMS. However, isotopic anomalies in very small grains tend to be diluted by normal, surrounding grains but ion imaging still remains an efficient method to quickly locate anomalous grains Classification of presolar oxide grains Oxygen isotopes are the obvious choice not only to identify but also to classify the oxide grains. Four oxide groups are distinguished according to their 17 O/ 16 O and 18 O/ 16 O isotopic ratios (see Table 7, Nittler et al. 1997). Table 7. Isotopic Characteristics of Presolar Oxides Designation Group I Group II Group III Group IV Range in 17 O/ 16 O Range in 18 O/ 16 O < Mean initial 26 Al/ 27 Al Sources: Nittler et al. (1997), Nguyen et al. (2003), Zinner et al. (2003) Figure 14 shows the resolution of these four groups in the three-isotope plot for oxygen. Grains in group I exhibit 17 O excesses and/or modest 18 O deficiencies relative to the SMOW 4 standard. Grains in group II are characterized by large 18 O deficiencies ( 18 O/ 16 O < 0.5 solar) and 17 O excesses (up to 3.5 solar). Grains with moderate depletions in 17 O and 18 O (equivalent to small 16 O excesses) belong to group III, and those with 17 O and 18 O excesses are in group IV. Corundum and spinel are present in all four groups. The few hibonite grains known plot within the fields of groups I to III. The 26 Al/ 27 Al ratios inferred from 26 Mg excesses measured in many oxide grains are useful to further classify the oxide grains (Nittler et al. 1994; 1995a; 1997; Hutcheon et al. 1994). This is shown in Figure 15 where the symbol colors indicate the 26 Al/ 27 Al content of the oxide grains inferred from Figure 14. Oxygen isotopic ratios in presolar oxide and silicate grains are used to define 4 characteristic groups. The dotted lines indicate the solar ratios (for data sources see text). excesses in 26 Mg. Black symbols indicate grains with 26 Al/ 27 Al > 0.03, 4 Standard Mean Ocean Water, generally taken to be representative of the solar O-isotopic composition. 26

27 grey symbols are for grains with 0.03 < 26 Al/ 27 Al < 10-4, and white symbols indicate grains with 26 Al/ 27 Al < 10-4 and grains for which only upper limits were determined. Many grains in group II of the O-isotopic classification also show the highest 26 Al/ 27 Al ratios. 5.7 Presolar Silicates Not many presolar silicate grains are known because of two major difficulties. Silicates are more susceptible to metamorphism and chemical processing than presolar carbonaceous and oxide grains, thus it is not clear how many presolar silicates are preserved in meteorites. For example, CI chondrites, which show the highest level of carbonaceous presolar grains, have experienced aqueous alteration on their parent bodies, which transformed silicates into hydrous silicates. This process also erases any presolar isotopic signatures in the silicates. Therefore meteorites from parent bodies that never experienced (much) aqueous alterations are the best choices to search for presolar Figure 15. Same as Figure 14, but here symbol colors indicate the 26 Al/ 27 Al content of the oxide grains. Black symbols show grains with 26 Al/ 27 Al > 0.03, grey symbols are for grains with 0.03 < 26 Al/ 27 Al < 10-4, and white symbols indicate grains with 26 Al/ 27 Al < 10-4 and grains for which only upper limits have been determined. silicates. The second difficulty in finding presolar silicates is that they must be located among boundlessly abundant solar system silicates that are major constituents of meteorites. The ion imaging technique was applied to search for presolar silicates in the Murchison CM-chondrite (Nittler, private communication) and Acfer 094, a unique carbonaceous chondrite with high abundances of other presolar minerals, (Messenger and Bernatowicz 2000) but with no avail. The first identification of six presolar silicates of microns in diameter was in interplanetary dust particles (IDPs) by O-isotope ion imaging with the NanoSIMS (Messenger et al. 2003). One of them is forsterite and two are amorphous silicates called GEMS (glass with embedded metal and sulfides). Subsequently, Nguyen and Zinner (2004) identified 9 presolar silicate grains ranging in size between 0.2 and 0.6µm in a size-separated disaggregated matrix from the Acfer 094 meteorite that has experienced minimal thermal or aqueous processing (Newton et al. 1995). The grains are tentatively identified (because of interference from underlying or surrounding grains) as pyroxene, olivine, and Al-rich silicate. Nagashima et al. (2004) searched for presolar silicates on thin sections of the Acfer 094 and NWA530 meteorites and identified one olivine and five mineralogically uncharacterized presolar silicate grains. The O-isotopic ratios of presolar silicates from IDPs and meteorites are similar to 27

28 those of presolar oxides (Figure 14). The abundance of presolar silicates is estimated to be 25 ppm in Acfer 094 (Nguyen and Zinner 2004). 5.8 Diamond Diamond was the first presolar mineral identified in meteorites in 1987 (Lewis et al. 1987b) and it has the highest relative abundance among the carbonaceous presolar grains in meteorites. Still, it remains the least understood mainly because the diamond grains are only 1-3 Ǻngstroms in size (Lewis et al. 1987a; Daulton et al. 1996) which makes them too small for individual analysis. Presolar diamond aggregates for analysis are obtained by colloidal separation at elevated ph which holds the in diamond suspension, as shown in Figure 16. The diamond separates obtained by chemical acid treatment from meteorites are not 100% pure carbon, and are of lower density than normal crystalline diamond (3.51 g/cm 3 ). The diamonds contain nitrogen and oxygen, probably as chemical functional groups on their surfaces as inferred from infrared spectra (e.g., Lewis et al. 1989; Mutschke et al. 1995; Andersen et al. 1998; Jones et al. 2004). Nitrogen abundances in diamonds from ordinary-, enstatite and CV chondrites range from 2200 to ppm (by mass) whereas diamonds from CI and CM chondrites show a range of 7500 to 9200 ppm (Russell et al.1991). In addition to nitrogen and oxygen, diamonds contain noble gases (see below), hydrogen enriched in deuterium by % (Carey et al. 1987; Virag et al. 1989), and various heavy trace elements (Lewis et al. 1991b). Figure 16. A test tube with nano-diamonds suspended in basic solution. The diamonds seem to have weakly acidic groups such as COOH on their surface which dissociate in basic solution (diamond-cooh diamond- COO - + H + ) and charge the diamond particles negatively so that they repulse each other. Photo courtesy of XXXXXX The 12 C/ 13 C ratio of of bulk diamond in primitive meteorites (Lewis et al. 1987b; Virag et al. 1989; Russell et al. 1991, 1996) is surprisingly close to the solar ratio of 89, considering the wide range in C-isotopic compositions of presolar SiC and graphite grains. The δ 15 N in diamonds ranges from 330 to 350 (Lewis et al. 1987b; Russell et al. 1996), also relatively close to the terrestrial value and to the N-isotopic composition of presolar graphite. The range in δ 15 N of the diamonds is below the values observed in various types of meteorites (~ 100 to +200 ). However, the diamond values are close to the upper limit of δ 15 N < 240 from measurements of nitrogen implanted by solar wind into the lunar regolith and to the N-isotopic composition of Jupiter (δ 15 N = -374, Owen et al. 2001). The Jovian value is probably more representative for the solar system than the value of the terrestrial atmosphere which is influenced by atmospheric escape processes. 28

29 The similarity of C- and N-isotopes in presolar diamonds and the solar system supports the idea that a larger diamond fraction originated within the solar system and by definition - is not presolar. However, the complexity of the carbon release patterns and C/N ratios observed during stepwise heating by Russell et al. (1996) suggests the presence of more than one type of diamond. It also cannot be excluded that another phase remained in the diamond separate after chemical and physical diamond isolation. Detailed studies show that at least two clearly resolved noble gas components, called P3 and HL, are present in meteoritic nano-diamonds. In addition, there is a less clearly resolved component called P6 which is released at the highest temperatures from diamond separates (Tang et al. 1988; Tang and Anders 1988; Huss and Lewis 1994b, see also Ott 2002). Figure 17 shows the noble gas isotopic compositions of the two major components. The first component, P3 is released around 500 C. Except for Figure 17. The noble gas isotopic composition in diamonds. Data are from Huss and Lewis 1994a (see also Ott 2002) normalized to the solar isotopic composition from Wieler (2002). The isotope ratios are further normalized to 20 Ne, 36 Ar, 84 Kr, and 132 Xe, respectively. The dotted line indicates solar composition. neon, the isotopic ratios in P3 are close to solar and without any major fractionations among individual isotopes of a given element. The second component, HL, released at temperatures around 1300 C shows stronger fractionations relative to solar. The most prominent feature is the relative enrichment in the light and heavy Xe-isotopes, the Xe- HL. The Kr isotopic ratios increase with increasing mass number. The 38 Ar/ 36 Ar is higher than solar, and the Ne isotopic composition is probably a mixture of true Ne-HL and neon from a third noble gas component P6 which is not well characterized (see Huss and Lewis 1994b; Ott 2002). In contrast to the neon in the P3 component, the normalized 21 Ne/ 20 Ne ratio in the high temperature release fraction is larger than the 22 Ne/ 20 Ne ratio. The presence of the low temperature component P3 is mainly seen in diamond separates from CI- and CM chondrites and is only marginally present in CV, ordinary-, 29

30 and enstatite chondrites (Huss and Lewis 1994b; Ott 2002). This may reflect the preferred destruction of the P3 carrier during thermal metamorphism on meteorite parent bodies. The presence or absence of the P3 component is used to estimate the degree of metamorphism of meteorite parent bodies (Huss and Lewis 1994a; 1995). The two major noble gas components suggests that at least two different populations of diamond exist, but the reason of why one diamond population is less thermally stable than the other is not entirely clear. However, the nitrogen concentrations in the diamonds of CI and CM chondrites are also higher than in diamond from CV-, ordinary-, and enstatite chondrites. If the diamonds carrying the low temperature P3 component have more nitrogen as impurity in solid solution, their crystal structure stability is plausibly decreased against thermal destruction. The tracer to presolar diamond, Xe-HL, indicates a supernova origin of diamonds, and isotopic anomalies of other heavy elements, i.e., Te and Pd (Richter et al. 1998; Maas et al. 2001) also point to supernova nucleosynthesis. On the other hand, the C- and N- isotopic signatures indicate that not all presolar diamonds originate from supernovae and that the supernova contribution to the diamonds is probably not very large. A huge isotopic anomaly in Xe-HL within a small grain fraction can easily dominate the overall observed Xe-isotopic composition but not the C- and N-isotopic composition. Carbon (and likely N) is present in all diamonds grains and the C and N signatures from a few supernova grains are easily masked by those from more abundant grains. In contrast, the absolute noble gas content in the diamond fractions is quite small: Only one to three in a million diamond grains contain a Xe atom. Thus, a tiny amount carrying an anomalous Xe component is less likely to be masked. There is no shortage of suggested origins of presolar diamonds, which remains enigmatic. In addition to an origin in supernovae (Clayton 1989; Clayton et al. 1995) and within the solar system itself (Dai et al. 2002), suggestions of the diamonds origin include novae (Clayton et al. 1995), carbon-rich giant stars (Clayton 1975; Lewis et al. 1987a; Andersen et al. 1998), Wolf-Rayet stars (Tielens 1990; Arnould et al. 1993), and binary star scenarios where mass from a carbon-rich giant star is transferred onto a white dwarf which then explodes as a type Ia supernova (Jørgensen 1988). 6 Giant stars and their grains The majority of known presolar grains apparently came from giant stars, and we describe some aspects of the nucleosynthetic processes during the evolution of these stars because the nucleosynthetic products are incorporated into the grains when grains condense in the giant stars circumstellar shells. In the following one should keep in mind that the broad theoretical picture of nucleosynthesis and evolution of giant stars is consistent with astronomical observations and measurements of presolar grains, but that many details are not yet completely understood in the models. Indeed the observations from giant stars and presolar grains often lead to revisions of these models. Some observed properties of giant stars are summarized in Table 8 below. 6.1 Chemical and isotopic markers of giant star evolution Observationally the different stages of stellar evolution are tracked in the Hertzsprung- Russell (HR) diagram (Figure 18). This diagram is a plot of the difference in the flux of 30

31 star light between certain optical wavelengths (the so-called color difference), versus absolute magnitude. The color difference is a measure of stellar effective ( surface ) temperatures. The absolute magnitude is the energy flux at a given wavelength normalized to a standard distance to take distance-related dimming of starlight into account, and provides a measure for stellar brightness or luminosity. In the HR diagram, cool stars plot on the right side, and the brightest stars plot at the top. The band of stars plotting from the bottom right towards the left top is the main sequence and consists of dwarf stars (including the Sun) of increasing mass. The branches moving off the main sequence are occupied by giant stars. Red giants are low- to intermediate mass stars in late stages of stellar evolution that have evolved from dwarfs with main sequence masses of ~1 to ~8 M? 5. Stars at the giant stage become steady dust contributors to the ISM. The evolution of low- to intermediate mass stars is sketched in Figure 19 and in the following text. Many more details about the various aspects of these processes can be found in the reviews by Iben and Renzini (1983), Iben (1991), Busso et al. (1995), Wallerstein et al. (1997), Lattanzio and Forestini (1999) and in the texts by Arnett (1996) and Pagel (1997). Stars on the main-sequence burn hydrogen to helium in their cores. This hydrostatic burning lasts about 10 billion years in a 1 M? star, but is shorter in more massive stars. After exhaustion of hydrogen in the core, the remaining helium-rich core (the He-core ) contracts, and rising temperatures ignite hydrogen burning in a shell around the helium-rich core. The star Figure 18. The Hertzsprung-Russell diagram shows the separation of dwarf stars on the main-sequence from and giant stars occupying the giant star branches. The data are from the HIPPARCHOS catalogue and are for stars within 100 parsec for which distance measurements have less than 5% uncertainty. expands its outer envelope to sizes of times the solar radius (e.g., Jura 1999), and the more luminous star moves onto the red giant branch (RGB). Hydrogen burning proceeds through the proton-proton (pp)-chain, and, more important in more massive stars, through the carbon-nitrogen-(cn) -bicycle or carbon-nitrogen-oxygen-(cno) tricycle where isotopes of carbon, nitrogen, and oxygen act as catalysts to convert four protons into helium. Compared to the solar main-sequence composition (usually taken as reference standard) processing by the CNO cycle reduces 5 The subscript? refers to units in reference to the sun, e.g., 1 M? = 1 solar mass. 31

32 the carbon and oxygen abundances and increases in the nitrogen abundance, but overall the sum of C, N, and O nuclei remains more or less constant. During the RGB stage, lasting about 500 million years for a solar mass star, the outer envelope becomes convective and penetrates into the region where partial H-burning takes place. Thereby the unprocessed envelope material becomes polluted with the byproducts of the CNO-cycle (the first dredge-up ) and the atmospheres of RGB stars show higher N-, and reduced C and O abundances relative to solar. The steady-state (or equilibrium ) values of the CNO cycle are 12 C/ 13 C ~3.5, and, depending on temperature 14 N/ 15 N ~30,000 (at low T) to 14 N/ 15 N <0.1 (at high T). The observed 12 C/ 13 C ratios in RGB stars range from 6 to 20 (Table 8) and are significantly reduced from the (solar) main-sequence ratio of 12 C/ 13 C = 89. The N-isotopes are difficult to measure in stars, but the 12 C/ 13 C ratios clearly indicate that CNO-processed material is dredged-up. Measured O-isotopic compositions in RGB stars are increased from the solar value, and 18 O/ 16 O ratios are below or near the solar ratio (see Table 8 for references). Table 8 Some Properties of Dust-Producing Giant Stars and the Sun Sun M M S C J Status mainsequence red giant branch, RGB asymptotic giant branch, AGB possibly RGB? Mass (M? ) 1 < 9 <9 <9 C/O 0.5 < 0.5 ~ s-process elements a solar solar up up up solar 12 C/ 13 C < N/ 15 N 272??? >500 ~70, ~150 (4-12) O/ 16 O O/ 16 O Isotopic changes b C, + 14 N, + 17 O + 12 C, + 17 O - 18 O, + 22 Ne + 13 C, + 14 N Major sources: Dominy et al. (1986), Harris & Lambert (1984b; 1984a), Harris et al. (1985; 1987; 1988), Lambert et al. (1986), Olson & Richter (1979), Querci & Querci (1970), Smith & Lambert (1990), Harris et al. (1984a,b), Wannier et al. (1991) a relative to solar composition. b isotopic changes from solar that may be observable in presolar grains Compared to standard evolution models, stars less massive than ~2.3 M? show lower 12 C/ 13 C and Na and Al abundances than expected from the first and second dredge up (see below) of CNO processed material (Lambert 1981; Sneden et al. 1986; Gilroy 1989; Gilroy and Brown 1991; Sneden 1991; Wallerstein and Morell 1994). In order to bring the nucleosynthesis models into accord with stellar observations, an extra mixing process was postulated (Charbonnel 1994; 1995). The extra mixing is known as cool bottom processing, CBP (Wasserburg et al. 1995; Boothroyd and Sackmann 1999) and postulates that the base of the inert convective envelope cycles through the regions that are on top of the H-burning shell so that CN-processing of envelope material can occur. This way, the CN equilibrium 12 C/ 13 C = 3.5 and high 14 N/ 15 N ratios are achieved in the 32

33 observable stellar envelope. This process is also assumed to operate at later stages of stellar evolution (see below). The RGB phase terminates when the He-rich core, left behind after main-sequence burning, ignites. This violent explosion is known as the He-core flash for stars of less than 2.5 M?. He-core burning may occur concurrently with H-shell burning in stars larger than ~2.5 M?. Now the interior structure is a He-burning core, an overlying H-burning shell, and a convective envelope. This configuration lasts about 50 million years in a solar mass star. At this stage, the star moves from the RGB in the HR diagram back to near the main sequence as its luminosity drops and effective temperature slightly increases. Helium burning in the core creates 12 C by fusion of three 4 He nuclei, known as the triple-α reaction: 4 He ( 4 He,γ) 8 Be( 4 He, γ) 12 C Figure 19. A very schematic sketch of the different interior zones in giant stars. The diagrams are not to scale and the zones where nucleosynthesis takes place are much smaller. The different stages are described in the text. In the most massive giant stars (~8-9 M? ) higher core temperatures may lead to α- capture on 12 C to produce 16 O (i.e., 12 C( 4 He,γ) 16 O). This creates a carbon- and oxygenrich CO core. However, most giants with <8-9 M? have a relatively C- rich core after He-burning. After helium is exhausted in the core, the star approaches the asymptotic giant branch (AGB). This name comes from the location of these stars in the HR diagram, where AGB stars plot asymptotically to the red giant branch. Hydrogen shell burning stops, and He-shell burning sets in. In larger mass stars (>4-5 M? ) the convective envelope can penetrate deep enough to transport more CNO-processed material (rich in 4 He, 13 C, 14 N, 17 O) previously made in the H-burning shell to the stellar surface (the second dredge-up ). On the AGB, alternate burning takes place in thin H- and He-shells surrounding the inert core. The two shells are separated by an intershell region. If He-burning shell is ignited, temperatures raise and overlying zones expand. Expansion of the He-shell moves the inter-shell and the H-burning shell into cooler regions. Then H-burning is extinguished, and with time, the temperature-dependent energy production in the 33

34 expanding He-shell also drops. At some point, He burning seizes in the cooler He-shell, and subsequent contraction leads to ignition of a new H-burning shell. The successive explosive re-ignitions of He-shell burning occur in intervals of ~10 4 years and are known as thermal pulses (TP). Thermally pulsing TP-AGB stars consist of an inert carbon-oxygen-rich core, surrounded by a He-burning shell, a He-intershell layer, a H-burning shell, and the convective envelope (Figure 19). When H-shell burning is inactive, convection transports the carbon made by triple α-burning in the He-shell to the stellar surface (the third dredge-up ). This increases the observable carbon-to-oxygen (C/O) ratio and the 12 C/ 13 C ratio. The more thermal pulses and third-dredge-up episodes are proceeding, the more products from He-burning become detectable at the stellar surface. The third dredge up also brings up products made during H-shell burning, including 23 Na (the only stable Na isotope) and radioactive 26 Al (t 1/2 = years). These are made in the NeNa and Mg-Al cycles that are linked to the CNO cycle (Forestini et al. 1991; Gallino et al. 1994; Wasserburg et al. 1994; Guélin et al. 1995). The observation of 26 Al in giant stars would provide another strong link to presolar grains because many different grains show evidence of incorporated 26 Al. However, searches for 26 Al in giant stars (using the isotopic shifts from 26 Al and 27 Al in spectral bands of AlH, AlCl, or AlF, e.g., Branch and Perry 1970) give no firm results. Guelin et al. (1995) obtained 26 Al/ 27 Al < 0.04 for the closest, well-studied carbon star CW Leo (IRC ), but more measurements are required to check for the presence of 26 Al in other giant stars. Cool bottom processing may operate in low mass stars on the AGB during H shell burning. This process is invoked to explain the depletions in 18 O/ 16 O (relative to solar) in some of the presolar grains (e.g., Wasserburg et al. 1995; Nittler et al. 1997) and it may also account for the production of 26 Al (e.g., Nollett et al. 2003). The TP-AGB stars show nucleosynthesis products made by neutron capture reactions, which are of particular interest here. The neutrons necessary for this are produced by α- capture on 13 C. This requires a 13 C source in the He-burning shell, but 13 C is made by proton capture on 12 C and there are no protons in the He-shell. However, after a third dredge-up event, 12 C is left behind in the intershell region, and if protons diffuse from the H-shell into the intershell, 13 C is made via: 12 C(p,γ) 13 N(β + ν) 13 C Then 13 C diffuses into the He-burning shell where neutrons are produced by: 13 C(α,n) 16 O Similarly as 13 C, 14 N originates in the intershell and can be mixed downward to the Heshell where α-capture reactions convert 14 N to 22 Ne via: 14 N(α,γ) 18 F(β+,ν) 18 O(α,γ) 22 Ne This reaction provides the Ne-E(H), which was one of the beacons during the search for presolar grains. Lewis et al. (1990; 1994) discuss that Ne-E(H) in SiC is unlikely to originate from decay of 22 Na (which only comes from novae or supernovae), because 34

35 22 Ne correlates with 4 He which is abundant in the He-rich shell. The 22 Ne production operates in low-and intermediate mass stars, but only in more massive stars further α capture on 22 Ne provides a second neutron source from: 22 Ne(α,n) 25 Mg Neutron capture by elements around the iron peak increases the abundances of heavy elements (e.g., Iben and Renzini 1983; Gallino et al. 1990; 1997; 1998; Busso et al. 1999). In AGB stars neutron capture proceeds on a slow time scale (relative to the time scales of beta-decay of the radioactive nuclides produced) and is called the s-process. Typical elements with relatively abundant stable isotopes made by the s-process include Sr, Ba, Zr, Y, the light rare earth elements (LREE), as well as several isotopes of Kr and Xe. Thus AGB stars that experienced many third dredge-ups should show higher C/O ratios and s-process element abundances than stars like the sun or RGB stars 6. Another mechanism proposed to operate in stars of 4 7 M? at the AGB stage is hot bottom burning (HBB) or envelope burning (Becker and Iben 1980; Renzini and Voli 1981; Boothroyd et al. 1995; Lattanzio and Forestini 1999). In more massive stars the base of the convective envelope is hotter and CNO processing can occur in the portion of the envelope located above the H-burning shell. This model predicts a decrease of the 12 C/ 13 C ratio to about 3.5, and increases of 14 N/ 15 N ratios up to The freshly produced 12 C from triple α-burning in the He-shell thus is converted to 13 C and 14 N. However, this creates a problem because it may prevent an increase in the C/O ratio and the AGB star cannot become a carbon star, or, depending on timing of HBB, change a carbon star back to a oxygen-rich AGB star. 6.2 Types of cool giant stars Depending on their observed chemistry, cool giant stars fall into at least three major categories, with transitional types in-between. Starting with solar-like elemental abundances and moving to more carbon and s-process element-rich objects, the giant star sequence is M-MS-S-SC-C. The M-stars, which comprise two-thirds of giant stars, are either RGB stars (showing only products from the CNO cycle) or AGB stars whose envelopes just started to become polluted by the third dredge-up. The spectra of M giants are dominated by metal oxide bands such as VO and TiO, which also shows that these stars are relatively cool (~3000 K) near their surfaces. The S stars are clearly on the AGB because they have C/O ratios near unity and over-abundances in s-process elements relative to solar. In addition to TiO and VO bands S-star spectra show strong ZrO bands because the Zr abundance is increased by the s-process. The discovery of a pure s-process product, radioactive 99 Tc with a half-life of years by Merrill (1952) proves that the s-process indeed operates in these relative low-mass stars 7. 6 This comparison is for stars of solar metallicity, i.e., stars where elements with mass numbers between ~11 and 28 (e.g., Ca, Al, Mg, Si, and Fe) have similar element to hydrogen ratios as the sun. Often the Fe/H ratio is taken as proxy for metallicity. 7 Some S stars, however, show enrichments of s-process elements but no Tc (Little et al. 1987). Jorissen et al. (1993) call them extrinsic S stars and use intrinsic S stars for objects with Tc. The extrinsic S stars probably 35

36 In carbon stars, multiple dredge-up of carbon resulted in a C/O ratio above unity in the observable atmosphere. Instead of metal oxide bands, C stars show atomic metal lines and bands from abundant carbon-bearing molecules such as C 2, CH, and CN which was realized soon after these stars were discovered (Secchi 1868). There are several sub-types of carbon stars, e.g., the N, J, R, and CH stars but only the major group of N-type carbon stars is thought to represent true TP-AGB stars, and these are the parent stars of most of the presolar SiC grains (see section 6.4). The evolutionary status of the other types of carbon stars is not well known (see Wallerstein and Knapp 1998 for a review on C stars). They may also have contributed to the presolar grain population and we will note some of their characteristics when we compare presolar grains and different types of stars. An important property of giant stars for grain formation is stellar variability. Many AGB stars belong to the group of pulsating variable stars which show more or less regular periodic variations in brightness (e.g., Kholopov et al. 1998). The variations are caused by thermal ionization and de-ionization processes in zones of the stellar envelope relatively close to the surface (e.g., Bowen 1988). These processes affect the opacity and thus the energy transfer through the envelope, and lead to radius expansions (dimmer star) and contractions (brighter star) 8. The variability cycles from maximum to maximum are typically about 100 to 600 days, with Mira-type variables showing the most regular periods of days (Kholopov et al. 1998). Convective mixing brings the products of nucleosynthesis from the stellar interior to the stellar surface, but these products need to get into dust grains and become part of the interstellar matter. This is accomplished by stellar winds that drive mass-loss from AGB star envelopes. The accumulation of gas and condensates from the cooling gas creates circumstellar shells 9. These shells extend to large distances from the central star - several hundred stellar radii, with stellar radii themselves ranging from 100 to 500 R? (an AGB star at the center of our solar system would extend easily to Mars orbit at 1.5 AU without its circumstellar shell). The circumstellar shells are divided into an inner shell in which thermochemical (e.g., condensation) processes are more important, and an outer shell where UV-driven photochemical processes dominate (see Glassgold 1996). We focus on the inner regions of the circumstellar shells where grain formation takes place. Circumstellar shells are detected by excesses in infrared radiation as light from the central star is absorbed and re-emitted by dust at longer red and infrared wavelengths (e.g., Olnon et al. 1986; Gezari et al. 1993; Kwok et al. 1997). In some instances, enshrouded stars are only detected by the infrared radiation from their thick surrounding shells (e.g., Guglielmo et al. 1998; 1993; Volk et al. 2000). Typical mass-loss rates of M- and C-type AGB stars are ~10-4 to 10-7 M? per year, and about a factor of ten less in S stars (e.g., Loup et al. 1995; Olofsson et al. 1993). In contrast to the extensive mass loss experienced by TP-AGB stars, giants on the RGB do not show large infrared excesses received the s-process elements by accreting matter from a more massive companion star that has evolved through the AGB stage and is now a white dwarf. Extrinsic S stars may not be on the AGB. 8 Stellar variability is not related to the thermal pulses at the AGB stage, where cyclic ignitions of He-shell burning occur at a frequency of about 10 4 years. 9 In the literature the circumstellar shell is sometimes referred to as circumstellar envelope. Here throughout the text we use the term circumstellar shell to avoid confusion with the stellar envelope that directly surrounds the nuclear burning interior zones. 36

37 and mass loss from RGB giants is not very productive (e.g., Jura 1999). Typical mass loss rates of RGB stars are ~10-9 to10-8 M? per year (e.g., Mauron and Guilain 1995). Dust formation probably speeds-up mass loss from AGB stars because dust is accelerated by radiation pressure and dust-gas momentum coupling in the circumstellar shells (for reviews on this subject see Lafon and Berruyer 1991 and Danchi and Bester 1995). Dust formation, once initiated, may become sort of a runaway process that drags the envelope off the star. At some point, mass-loss has deprived an AGB star of its envelope, and after several 100 million years of alternating H- and He-shell burning in the inside and continuous mass loss on the outside, the AGB stage of stellar evolution comes to an end. During the post-agb stage (see review by van Winckel 2003), mass-loss rates drop since most of the envelope is already gone. The circumstellar shell continues to expand with terminal velocities of km/s. As it separates more from the central star, the veil of dust and molecular absorptions around the hot stellar remnant is lifted. The last spike of matter leaves the star in a fast wind of km/s and once this much faster wind collides with the older, slower expanding material a strong shock front is created. The shock interaction of the ejecta and the radiation from the hot central star cause the appearance of a planetary nebula 10 which continues to expand with a final velocity of ~40 km/s (Kwok et al. 1978; Kwok 1994). One can only speculate what may happen to dust grains in the older shell once they are hit by the shock wave. Grain destruction is one possibility but infrared observations show that dust is still present in planetary nebulae. What remains of a giant star is a white dwarf consisting of the carbon-oxygen-rich stellar core, surrounded by a planetary nebula created by the interaction of gas and dust ejected from the former stellar envelope. Of an initially one solar mass star, about half remains, whereas stars of initially 4-8 M? loose around 80% of their main sequence mass to the ISM (e.g., Weidemann 2000). The local mass return from M giants is estimated 1-2x 10-4 M? /year/kpc 2 and C giants provide about the same amount. The total mass returned to the galactic ISM is ~ M? /year (e.g., Knapp and Wallerstein 1998). 6.3 Dust condensation circumstellar shells The circumstellar shells around giant stars are the places where dust grains condense and from where grains enter the interstellar medium. Temperatures in the expanding gas drop by adiabatic cooling, and beyond some distance from the star, temperatures become low enough (<2000 K) for grain condensation in the circumstellar shell. The dynamic nature envelope that leads to the observed luminosity variability of giant stars also affects the radial temperature and pressure structure of the circumstellar shell. Because grain condensation is a function of temperature and total pressure, stellar variability influences the absolute distance from the central star at which grain formation occurs. Figure 20 shows how condensation may proceed during the variability cycle (see Lodders and Fegley (1997) and references therein). During maximum light, the star has the smallest radius and the highest photospheric temperature, and high temperatures within a few 10 In 1764, Messier first described these objects and in 1795, Herschel coined the term planetary nebulae for the circumstellar shells that appear as fuzzy, nebulous disks akin to the giant planets in low magnification telescopes. The historical name stuck but is unfortunate since there is no relation of planetary systems to planetary nebulae. 37

38 stellar radii do not favor condensation. When the star changes phase, the radius extends and temperatures drop in the expanding circumstellar shell and dust formation is expected to be most efficient at the lowest temperatures during minimum brightness. Because of the large expansion of the stellar radius, the absolute grain forming location is also much further away from the center of the star (but still within a few radii of the expanded star). After the star passes through the minimum light phase, effective temperatures increase and the stellar radius decreases, and gas and dust from the circumstellar shell can fall back onto the star. The temperatures at any given location in the inner circumstellar shell also increase and the dust at that location could evaporate again. However, major fallback and evaporation of dust is prevented when dust grains are accelerated in the circumstellar shell by radiation pressure from the star. In this scenario the observed periods of stellar variability (e.g., <600 days for minimum to minimum) indicate that grain formation occurs on time scales of at least half the variability period (between minimum and maximum) Major element condensates in giant stars Figure 20. A sketch of grain condensation in the circumstellar shell of giant stars during the variability cycle. During minimum light, the star has its largest radius and lowest effective temperature. Grains form at some distance from the star and incorporate trace elements according to their volatility. Once the star moves back to maximum light, it contracts and the effective temperature increases. Grains and gas fall back onto the star. However, some grains are accelerated by radiation pressure and are The nature of the gas and dust, oxidized or carbonaceous, in stellar outflows is determined by the oxidation state of the ejected envelope material, which is measured by the carbon to oxygen (C/O) ratio in the gas. In giant stars C/O ratios range from ~ 0.5 (solar) to ~1.2. Changes in other element abundances introduced by nucleosynthesis (e.g., higher N abundances in RGB stars, and higher s-process element abundances in AGB stars) should not affect the oxidation state. Long before dust was detected around giant stars, the importance of the C/O ratio on the outcome of gas chemistry was recognized by Secchi (1868), and Russell (1934) and Wildt (1933) thought about condensate formation in stellar environments. Many theoretical studies show that major element oxides and silicates condense under oxidized conditions at C/O < 1 (e.g., Lord 1965; Larimer 1969; Grossman 1972; Ebel and Grossman 2000; see also Lodders 2003), and that carbonaceous dust forms under reducing conditions at C/O > 1 from a gas of otherwise 38

39 solar elemental composition (Gilman 1969; Larimer 1975; Lattimer et al. 1978; Larimer and Bartholomay 1979; see review in Lodders and Fegley 1997). Table 9 lists expected condensates for the more abundant elements in circumstellar shells of M stars (C/O< 1) and C stars (C/O >1), the minerals identified in circumstellar shells and planetary nebulae, and the known presolar minerals. Several minerals are known in circumstellar environments and among presolar grains which fosters the conclusions of a circumstellar origin of presolar grains. The condensates in M stars are essentially the same as those for a solar composition gas because their C, N, and O abundances result in comparable oxidation states (e.g. Dominy et al. 1986, Smith and Lambert 1985, 1986, 1990, Smith et al. 1987). The major Ca and Al-bearing condensates include corundum, spinel, hibonite, gehlenite, and anorthite. Silicon and Mg condense as forsterite and enstatite, and iron forms a FeNialloy and at lower temperatures, troilite (FeS). Several of these condensates were detected in circumstellar shells and in planetary nebulae by infrared observations since the late 1960s, and recently the Infrared Space Observatory (ISO) extends observations to mid-ir wavelengths. Abundant silicate grains are expected in oxygen-rich shells and the 9.7 micron emission in M giant spectra observed by Gillett et al. (1968) was ascribed to silicates by Woolf and Ney (1969). This silicate feature is now known in many oxygen rich stars (e.g., Little-Marenin and Little 1988; 1990; Sloan et al. 1996). More definitive assignments to the mineralogy are Mgrich pyroxene and forsteritic olivine from the 20 and 28 micron emissions (Waters et al. 1996; Kemper et al. 2002b; Molster et al. 2002b; 2002a; 2002c; Suh 2002). Circumstellar silicates appear to be both crystalline and amorphous, with thicker and cooler circumstellar shells favoring the presence of crystalline silicates. Corundum (Al 2 O 3 ) dust formation in M giants was already suspected by Schmidt- Burgk and Scholz (1981). Little-Marenin and Price (1986) observed an emission feature at 13 microns which is present in 40-50% of all oxygen-rich AGB stars (Sloan et al. 1996). The source of the 13 micron emission is identified as corundum (Onaka et al. 1989; Glaccum 1995; Begemann et al. 1997; Kozasa and Sogawa 1997; Fabian et al. 2001). Begemann et al. (1997) found that corundum may show an additional emission at 21 microns, which is present in several post-agb objects. However, in post AGB stars the 21 micron feature is not accompanied by one at 13 microns and the origin of the 21 micron feature remains somewhat mysterious (see below). Another possible phase for the 13 micron source is magnesian spinel, especially if the 13 micron feature is accompanied with one at 16.8 and 32 microns (e.g., Posch et al. 1999; Fabian et al. 2001). However, the identification of spinel is not clear-cut because silicate emissions can interfere and different interpretations of the data have been suggested (see e.g., Sloan et al. 2003). Metallic iron, an expected major dust component, is infrared inactive, but Kemper et al (2002a) infer its presence in the dusty circumstellar shell of an evolved oxygen-rich giant because they need an abundant infrared opacity source to fit the spectrum. Troilite (FeS) - an abundant low-temperature condensate - is not yet identified in M giants. Also not detected in oxygen-rich circumstellar shells is perovskite (CaTiO 3 ). Posch et al. (2003) found that the infrared signatures of perovskite, other Ca-titanates, and Ti-oxides coincide with those from silicates and aluminum oxides. Titanium is less abundant than Si and Al, and their condensates likely reduce the spectral band strengths of Ti-bearing condensates so that Ti-bearing dust may not be resolvable. 39

40 Table 9. Expected and Observed Major Element Condensates * M-stars C-stars Abundance Mineral and Ideal Stellar Presolar Mineral and Ideal Formula Shell Grains Formula O oxides and silicates silicates C titanium carbide TiC graphite C silicon carbide SiC diamond? N osbornite TiN aluminum nitride AlN Mg spinel MgAl 2 O 4 forsterite Mg 2 SiO 4 enstatite MgSiO 3 niningerite MgS spinel MgAl 2 O 4 forsterite Mg 2 SiO 4 Si gehlenite Ca 2 Al 2 SiO 7 forsterite Mg 2 SiO 4 enstatite MgSiO 3 enstatite MgSiO 3 silicon carbide SiC iron silicide FeSi forsterite Mg 2 SiO 4 enstatite MgSiO 3 Fe iron alloy Fe schreibersite (Fe,Ni) 3 P iron silicide FeSi iron alloy Fe S troilite FeS oldhamite CaS niningerite MgS troilite FeS Al corundum Al 2 O 3 hibonite CaAl 12 O 19 grossite CaAl 4 O 7 gehlenite Ca 2 Al 2 SiO 7 spinel MgAl 2 O 4 anorthite CaAl 2 Si 2 O 8 Ca hibonite CaAl 12 O 19 grossite CaAl 4 O 7 gehlenite Ca 2 Al 2 SiO 7 anorthite CaAl 2 Si 2 O 8 aluminum nitride AlN corundum Al 2 O 3 spinel MgAl 2 O 4 anorthite CaAl 2 Si 2 O 8 oldhamite CaS anorthite CaAl 2 Si 2 O 8 Na albite NaAlSi 3 O 8 albite NaAlSi 3 O 8 halite NaCl (?) Ni kamacite & taenite schreibersite (Fe,Ni) 3 P kamacite & taenite schreibersite (Fe,Ni) 3 P Cr Cr in FeNi alloy daubréelite FeCr 2 S 4 Mn Mn 2 SiO 4 in olivine alabandite (Mn,Fe)S P schreibersite (Fe,Ni) 3 P schreibersite (Fe,Ni) 3 P Cl sodalite Na 4 [AlSiO 4 ] 3 Cl halite NaCl (?) K orthoclase KAlSi 3 O 8 orthoclase KAlSi 3 O 8 sylvite KCl (?) Stellar Shell (?) Presolar Grains Ti perovskite CaTiO 3 titanium carbide TiC osbornite TiN (?) * Adapted from Lodders & Fegley Elements are listed in order of decreasing solar abundance. Condensates are listed in order of appearance for each element. (?) means that entry is uncertain. solar photospheric abundances on a scale Si = atoms (Lodders 2003). 40

41 The condensates under reducing conditions (C/O > 1) listed in Table 9 are calculated for the average compositions of N-type carbon stars determined by Lambert et al. (1986). Except for carbon and oxygen, major element abundances in N-stars are close to solar 11. Major condensates are carbon and carbides (SiC, TiC), sulfides (CaS, MgS), and nitrides (AlN, TiN). Silicates also condense at C/O > 1, despite a persistent misconception among some researchers that silicates cannot form under reducing conditions. Mg-silicates are expected from thermochemical calculations and the meteorite record shows that Mg-silicates indeed form at C/O > 1. (Reduced enstatite chondrites and achondrites are mainly pure enstatite, MgSiO 3, e.g., Krot et al. 2000). Iron condenses as silicide (FeSi) and troilite. The formation of carbonaceous dust, graphite, SiC, and other carbides was anticipated by Wildt (1933), O Keefe (1939), Hoyle and Wickramasinghe (1962), Tsuji (1964), Friedemann and Schmidt (1967), Friedemann (1969a,b), and Gilman (1969), long before any of it was observed in giant stars. Most prominent in the circumstellar shells of C stars is SiC, identified by its 11.3 micron emission (e.g., Gilra 1971; Treffers and Cohen 1974; Forrest et al. 1975; Little-Marenin 1986; Little-Marenin et al. 1987). Carbon, either amorphous and/or in graphitic form, is believed to be present around many carbon stars (Rowan-Robinson and Harris 1983; Jura 1986; Martin and Rogers 1987; Orofino et al. 1987; 1990; Blanco et al. 1994). Another form of carbon, diamond, is not an expected condensate under equilibrium thermodynamic conditions. However, the characteristic emissions of surface-hydrogenated diamond at 3.43 and 3.53 microns identified by Guillois et al. (1999) have been detected in the dust shells of HR4049, a carbon-rich, very metal-poor post-agb star (Geballe et al. 1989; van Kerckhoven et al. 2002), and in the C-rich proto-planetary nebula CRL 2688 (Geballe et al. 1992). Other planetary nebulae apparently also show the characteristic diamond emissions (e.g., Roche et al. 1996). The 30 micron emission observed in carbon-rich shells of AGB stars and planetary nebulae is attributed to the presence of MgS (Goebel and Moseley 1985; Nuth et al. 1985; Hony et al. 2002a; 2003; Hony and Bouwman 2004). Another expected abundant sulfide condensate, FeS, was recently identified in planetary nebulae by Hony et al. (2002b, see also Begemann et al. 1994). The phase responsible for the 21 micron emission from several post-agb stars and planetary nebulae has been a puzzle ever since this emission feature was first described (Kwok et al. 1989). Among other suggested phases (e.g., nano-diamonds, SiS 2, polyaromatic hydrocarbons), this feature was recently ascribed to TiC nano-particles (von Helden et al. 2000). However, this assignment is highly debated and probably not correct (e.g., Hony et al. 2003; Li 2003). Although TiC is one of the first condensates to appear from a reducing gas (e.g., Lattimer et al. 1978; Lodders and Fegley 1995) the low abundance of titanium (relative to Si or C) may prevent detection of TiC in circumstellar shells. In addition, the presolar grains show that TiC serves as nucleation seed for graphite (and possibly SiC) which means that the amount of detectable TiC in circumstellar shells must be reduced because TiC is hidden within other grains. 11 One should expect higher N-abundances than solar in carbon stars from CNO processing, which is observed in M giants and planetary nebulae ( progenitors and descendants, respectively, of normal carbon stars). However, there could be problems with the determination of nitrogen abundances in N-type carbon stars, as described by Lambert et al. (1996). 41

42 Many of the major minerals identified among presolar grains and around giant stars and in planetary nebulae are the first condensates under oxidizing or reducing conditions, respectively. The condensation temperatures as a function of total pressure are shown in Figures 21 and 22. The range in total pressures shown covers the range expected in circumstellar shells, e.g., 10-5 to 10-8 bar at temperatures below 2000 K. Figure 21 shows the condensation sequence representative for M giants. Generally condensation temperatures increase with increasing total pressure. There is not much change in the relative condensation sequence except for a switch of perovskite condensing prior to hibonite at total pressures below ~10-7 bar, and a switch in forsterite and metal alloy condensation ~10-5 bars. Condensation temperatures for minerals forming at C/O =1.1 as a function of total pressure are shown in Figure 22. With the notable exception of carbon, the condensation temperatures again increase with increasing total pressure. The existence of trace metal carbides in stellar atmospheres was considered by Wildt in 1933 and more recent investigations show that many transition element carbides (e.g., TiC, ZrC, MoC) are indeed quite refractory (e.g., Lattimer et al. 1978; Lodders and Fegley 1995; 1997). Under reducing conditions the condensation temperature of the first Figure 21. Condensation temperatures as a function of total pressure for a solar composition gas (C/O < 0.5). The condensates of the major elements mainly consist of oxides and silicates. Generally condensation temperatures increase with increasing total pressure. condensate for a given major element (e.g., Si, Al, Ca, Mg) is generally lower than under oxidizing conditions (at the same total pressure). However, in both cases the first condensates are referred to as refractory condensates but it should be remembered that refractory is on a relative temperature scale defined differently for oxidizing and reducing conditions. Figure 23 illustrates the sensitivity of the carbonaceous dust condensation sequence as a function of C/O ratio and total pressure. At all C/O ratios and total pressures shown in the diagram, TiC always condenses prior to SiC. At C/O > 1, carbon also enters the condensation sequence. Taking a given C/O ratio and increasing the total pressure gives variations in the condensation sequence as C-TiC-SiC, TiC-C-SiC, and TiC-SiC-C. The reason for these changes is the decrease of the TiC and SiC condensation temperatures 42

43 Figure 22. Condensation temperatures as a function of total pressure for an N-type carbon star composition gas (C/O = 1.1). With the notable exception of carbon, condensation temperatures increase with increasing total pressure. with decreasing total pressure (Figure 22) whereas the condensation temperature of carbon is relatively insensitive to total pressure. The results from thermochemical calculations can be used to estimate the total pressure and temperature conditions under which these presolar grains formed (Bernatowicz et al. 1996; Chigai et al. 1999). Many graphite grains contain tiny inclusions of Ti, Mo, and Zr carbides located in the center that apparently acted as nucleation seed for the surrounding carbon (Bernatowicz et al. 1991; 1996). The presence of transition metal carbide inclusions in graphite, and the absence of silicon carbide corresponds to the condensation sequence TiC-C-SiC for these presolar grains (e.g., Bernatowicz et al. 1991; 1996). A detailed investigation considering equilibrium and non-equilibrium chemistry by Bernatowicz et al. (1996) shows that favorable conditions for the observed condensation sequence of metal carbides and carbon in the stellar outflows require total pressures larger than 10-7 bar and C/O > Chigai et al. (1999) Figure 23. The condensation sequence for TiC, carbon, and SiC is a sensitive function of total pressure at C/O ratios above unity. The condensation temperatures of TiC and SiC decrease with decreasing total pressure (Figure 22) while the condensation temperature of carbon is relatively insensitive to total pressure. This causes the changes in condensation sequence. The sequence TiC-C-SiC is recorded in presolar grains. 43

44 considered non-equilibrium conditions and inferred C/O ratios less than 1.26 to 1.46 and total pressures between 10-7 to bars. In presolar SiC grains, trace element abundances normalized to solar and silicon show characteristic abundance patterns (Figure 8). These patterns depend on the total elemental abundances at the stellar sources of the grains, and the volatility related abundance fractionations in circumstellar shells. Calculated trace element patterns resulting from fractional condensation into SiC from a carbon star gas are illustrated in Figure 24. Each panel shows abundances relative to solar abundances and silicon for a given temperature. An element present at solar abundances in the stellar source plots at 2 when it is completely condensed (it does not plot at unity because only half of all silicon, used for normalization, condenses as SiC). For the model here it is assumed that the s-process elements are 10 times higher in abundance than in the solar reference composition, so Figure 24. Calculated trace element abundance patterns when fully condensed, they plot in SiC at different temperatures in a circumstellar shell of at 20. The top panel shows the a carbon star. Abundances are normalized to solar highly fractionated abundance values and silicon. With decreasing temperature, more trace elements condense into solid solution with SiC. pattern at a few degrees below The complete condensation of the volatile elements Sr the temperature when SiC starts and Ba requires low temperatures of 1080 K. Figure to appear. Then only very little adapted from Lodders and Fegley (1997). Si is condensed and normalized abundances for the most refractory elements (e.g., Ti, Zr) are very high. In fact, refractory elements such as Ti and Zr condense as carbides long before SiC starts to form (Figure 22) and these refractory carbides may not become incorporated into SiC. In that case, trace element patterns in SiC are depleted in the most refractory elements. This effect was included during modeling the observed trace element patterns in SiC (Figure 8) but was not considered for Figure 24 for simplicity. With decreasing temperature, more Si condenses, and more of the less refractory trace elements are removed from the gas. The 44

45 most volatile elements Sr and Ba require the lowest temperature to be fully scavenged from the gas. 6.4 Synthesis: Presolar grains from giant stars The presolar minerals from giant stars can be summarized as follows. The RGB stars provided corundum, spinel, and silicate grains that belong to the oxide groups I and III. The AGB stars contributed corundum, spinel, and hibonite grains of oxide groups I and III; mainstream, Y, and Z SiC grains; probably graphite grains with 12 C/ 13 C ratios larger than solar, which comprise more than 70% of the high-density KFC1 graphite fraction; and possibly some diamonds Grains from red giant branch (RGB) stars Dust from RGB stars forms at C/O ratios near the solar value and therefore should consist of oxides and silicates. After the first dredge-up, diagnostic changes in isotopic compositions from solar are expected in C, N, and O because they are processed in the CNO-cycle. Oxidized condensates should not contain much C and N (maybe as impurity, if any), so only the O-isotopes are useful to sort out which of the presolar corundum, spinel, hibonite, and silicate grains could come from RGB stars. After the first (and second) dredge up, enrichments in 17 O over the solar ratio should appear, but the 18 O/ 16 O ratio should remain near the solar ratio. This indicates that grains from RGB stars are to be found in group III and I in Figure 14. However, the O-isotopic composition in M-stars on the RGB and AGB is still expected to be very similar (Table 8) and we need additional criteria to distinguish presolar oxide grains from RGB and early AGB stars. Oxide grains from RGB stars should not have 26 Al, and no isotopic variations introduced by the s-process. The oxide grains measured for Al-Mg systematics (Figure 15) show that 26 Al is absent in 64% of the grains from group III and in 30% of the grains from group I. Apparently group III grains are dominated by RGB stars where the O-isotopes are not changed by much from solar. However, the presence of grains from RGB stars in group I is also consistent with the scenario that 17 O, a by-product of the CNO cycle, appears after the first (and second) dredge-up Presolar grains from asymptotic giant branch (AGB) stars A star on the AGB may produce either oxidized or reduced condensates depending on how many third dredge-up episodes have occurred that changed the C/O ratio from the near solar RGB ratio to ratios above unity. On the AGB the major abundance changes are increases in carbon and elements that are produced by the s-process. Major isotopic changes include rising 12 C/ 13 C ratios from the observed RGB values below ~20, and increases in s-process isotopes of the heavy elements (e.g., Smith and Lambert 1985, 1986). Nitrogen rich in 14 N is mainly inherited from the RGB stage. Another distinguishing characteristic between TP-AGB and RGB (and early AGB) stars is that 26 Al (made during H shell burning) is brought to the surface during the 3 rd dredge-up episodes. Neutron capture reactions in AGB stars also modify the Ca and Ti isotopic compositions and increases in the isotopes 47 Ti, 48 Ti, 49 Ti, 50 Ti relative to 48 Ti and 42 Ca, 43 Ca, 44 Ca relative to 40 Ca (check 46Ca, 48Ca) are expected (e.g., Hoppe et al. 1994; Choi et al. 1998; Amari et al. 2000a). On the other hand, the Ca and Ti isotopic ratios in 45

46 presolar oxide grains from RGB stars reflect the unaltered initial Ca and Ti isotopic compositions of the stellar source. Oxidized dust from AGB stars The spectral features of the expected condensates corundum and spinel are most likely present in the circumstellar shells of M-giants on the AGB. As described in section , the oxide grains of groups I and III plotted the O-isotope diagram (Figures 14 and 15) represent a mix of grains from RGB 10-2 and AGB stars. The inferred presence of 26 Al shows that group I oxide grains has more grains from AGB stars RGB stars AGB stars (70%) than group III (36%). PN However, these percentages do not reflect the relative distribution of RGB and ABG stars contributing to presolar oxides because one AGB star produces much more dust than one RGB star group II The oxide grain data are compared to the O-isotopes measured in RGB and AGB stars and planetary nebulae (PN) in. Figure 25. The AGB stars only include stars that show technetium, group III which ensures that they are truly on the AGB. The RGB stars have about 17 O/ 16 O 10-4 group I group IV O/ 16 O Figure 25. A comparison of the oxygen isotopic composition of presolar oxides (cf. Figure 14) with that measured in RGB and AGB stars and planetary nebulae (PN). Note the different scales compared to Figure 14. Data for stars and PN are from Harris & Lambert (1984), Harris et al. (1984, 1985, 1987, 1988), Kahane et al. (1992), Lambert et al. (1986), Smith & Lambert (1990), Wannier and Sahai (1987). normal 18 O/ 16 O and enhanced 17 O/ 16 O as expected from the CNO cycle. They plot in the array given by grains of group I. Several AGB stars and PN plot together with group I grains, however, there is a notable shift to lower 18 O/ 16 O ratios for AGB stars (but not PN) towards group II grains. The origin of oxide grains in groups II and III of Figures 14 and 15) was also ascribed AGB stars (Nittler et al. 1997). Group II grains are slightly enriched in 17 O and heavily depleted in 18 O relative to solar, and many of these grains have the highest inferred 26 Al content among oxide grains. The depletion of 18 O and the large 26 Al abundances in group II oxide grains is plausibly due to cool bottom processing in intermediate mass giants. However, it is odd that there is no detection of 26 Al in oxygen rich AGB stars, and that the O-isotopic compositions in AGB stars do not overlap more with the field spanned by the group II grains as shown in Figure 25. None of the stellar objects shows O-isotopic compositions that overlap with grains of group III 46

47 and IV, and the overlap is marginal at best for group II grains. The lack of overlap in O- isotopes with existing observations for current AGB stars could favor the interpretation that the grains of group II and III reflect chemical galactic evolution processes (see Nittler et al for details). The O-isotopic compositions of the two hibonite grains found by Choi et al. (1999) favor an origin near low-mass (~1.7M O ) AGB stars. The hibonites also have evidence of the now extinct short-lived radioactive isotopes 26 Al and 41 Ca. The inferred initial 26 Al/ 27 Al ratios indicate that H shell burning, CBP and HBB, took place in the grains stellar source, and the 41 Ca/ 40 Ca ratio reflects neutron capture in the He intershell as expected from AGB models. Carbonaceous dust from carbon-rich AGB stars The carbon-rich circumstellar shells of AGB stars are most suitable environments to produce carbonaceous dust which is observed around such stars. The current statistics on presolar grains suggests that SiC and C are the most prevalent reduced dust next to diamonds. Indeed, most of the SiC grains are from AGB stars, but the fractions of graphite and presolar diamond contributed by AGB stars is unknown. SiC from AGB stars A little more than 90% of SiC is thought to have originated in AGB stars, mainly the mainstream grains and the closely related Y and Z grains (e.g., Hoppe et al. 1994; 1997; Hoppe and Ott 1997; Amari et al. 2001b). In addition to the reduced nature of the SiC grains, their isotopic compositions and trace elements are in accord with abundance determinations in N-type carbon stars and AGB models. Figures 26 and 27 show the C, N, and Si isotopic compositions of SiC grains (see also Figures 5 and 6, respectively) and of carbon stars and planetary nebulae. The stellar data are plotted Figure 26. Carbon and nitrogen isotopic compositions in presolar SiC grains and carbon stars. Stellar data are shown with error bars. Nitrogen isotopic ratios typically are lower limits. The N-type carbon stars, and their descendants, the planetary nebulae (squares) plot close to the array given by the mainstream SiC grains, but tend to show somewhat lower C-isotopic ratios. Data sources for presolar grains are given in Figure 7. The stellar data are from Wannier et al. (1991), Querci & Querci (1970), and Olsen and Richter (1979). with error bars. The few determinations for N-isotopes in stars are mainly lower limits only. However, within the uncertainties there is good overlap for the N-type carbon stars, and the mainstream SiC grains. Figure 26 shows that some carbon stars (the so- 47

48 called J types) overlap with the data of the A+B SiC grains. As described below, the A+B grains may originate from J stars, which, however, are unlikely to be on the AGB. The comparison for Si-isotopes is more difficult because of the paucity of Si-isotopic determinations in stars. In Figure 27, the two determinations for the N-type carbon star IRC fall into the array of the SiC mainstream grains. The other data are for red giants not yet on the AGB. Unfortunately, the measurements are quite uncertain. According to nucleosynthesis models, the Si-isotopic composition is not affected during nucleosynthesis in RGB stars, and only mildly modified in AGB stars and should essentially reflect the Si-isotopic composition with which a star was born. Leaving the uncertainties aside, the absence of SiC grains in the array spanned by RGB stars is Figure 27. Silicon isotope data for presolar SiC grains (as in Figure 6) and stars (symbols with error bars). The Si-isotopic determinations in stars are difficult and associated with large uncertainties as indicated in the graph. There are two determinations for the carbon star IRC+10216, from Cernicharo et al. (1986), and Kahane et al. (1988), which are shown as triangles. The other stellar Si isotope data (circles) are for oxygen-rich M-giants from Tsuji et al. (1994). comforting because we do not expect that ejecta from RGB stars are reduced enough for SiC condensation. However, in this context we note that future measurements of Si isotopes in presolar silicates, may show some overlap if these originate in RGB stars. In Figure 28 the distribution of 12 C/ 13 C ratios among SiC grains is compared to the many determinations in stars (e.g., Lambert et al. 1986; Ohnaka and Tsuji 1996; Schöier 48

49 and Olofsson 2000). The histogram for the distribution in 12 C/ 13 C ratios of SiC shows a good correspondence to the 12 C/ 13 C distribution among carbon stars determined by Lambert et al. (1986). The 12 C/ 13 C distributions measured in carbon stars by Ohnaka and Tsuji (1996, 1999) and Schöier and Olofsson (2000) are similar but their maxima are shifted to lower 12 C/ 13 C ratios. However, the data by Lambert et al. (1986) are regarded as more reliable. The similarity in the 12 C/ 13 C distribution of SiC grains with that of N- type carbon stars is fully consistent with the conclusion that most of the SiC grains (93%) are from evolved AGB stars. The trace element abundances in mainstream SiC grains provide a close link to N-type carbon stars because both show enhancements in s-process element abundances. The different trace element patterns for mainstream SiC grains (Figure 8) and the fractionations among the elements can be understood by considering fractional condensation as described above (Figure 24). Lodders and Fegley (1995) calculated the trace element abundance patterns observed in SiC grains (Amari et al. 1995c) with the goal to find the elemental abundances in the stellar sources that are necessary to explain the patterns by fractional condensation as this also constrains the types of carbon stars that produced the SiC grains. The patterns in Figure 8 require source abundances of the s- process elements ranging from solar up to 10 times solar, and in some cases, the removal of ultrarefractory Figure 28. Histograms of 12 C/ 13 C ratios in presolar SiC (Hoppe et al. 1994, Nittler et al. 1995), presolar graphite grains (Hoppe et al. 1995, Travaglio et al. 1999, OTHER), and in carbon star atmospheres (Lambert et al. 1986). The SiC and graphite grain data extend to 12C/13C ratios of several thousand (see Figures 7 and 10) and here only the distributions for the range that covers the observed carbon star isotope ratios is plotted. Four diagrams for the graphite density fractions are plotted, for which density increases in alphabetical order (E<FA<FB<FC). 49