Small is beautiful: The analysis of nanogram-sized astromaterials Mefcorr/rc.r K. /'/ane/ar,y Science 3 5 , 9-29 (2000) '0 Meteoritical Society, 2000. Printed in USA Invited Review Small is beautiful: The analysis of nanogram-sized astromaterials M. E. ZOLENSKYl*, C. PIETERS2, B. CLARK3 AND J. J . PAPIKE4 'Planetary Science Branch, NASA, Johnson Space Center, Houston, Texas 77058, USA 2Department of Geological Sciences, Brown University, Providence, Rhode Island 029 12, USA 3Planetary Protection Laboratory, Lockheed Martin Astronautics, Denver, Colorado 8020 1, USA 41nstitute of Meteoritics, Department of Earth and Planetary Sciences, University of New Mexico, Albuquerque, New Mexico 8713 1, USA *Correspondence author's e-mail address: michael.e.zolensky1 @jsc.nasa.gov (Received 1999 February 26; accepted in revised form 1999 October 5) Abstract-The capability of modem methods to characterize ultra-small samples is well established from analysis o f interplanetary dust particles (IDPs), interstellar grains recovered from meteorites, and other materials requiring ultra-sensitive analytical capabilities. Powerful analytical techniques are available that require, under favorable circumstances, single particles of only a few nanograms for entire suites of fairly comprehensive characterizations. A returned sample of >lo00 particles with total mass of just 1 pg permits comprehensive quantitative geochemical measurements that are impractical to carry out in situ by flight instruments. The main goal o f this paper is to describe the state-of-the-art in microanalysis of astrornaterials. Given that we can analyze fantastically small quantities of asteroids and comets, etc., we have to ask ourselves, how representative are microscopic samples of bodies that measure a few to many kilometers across? With the Galileo flybys of Gaspra and Ida, it is now recognized that even very small airless bodies have indeed developed a particulate regolith. Acquiring a sample of the bulk regolith, a simple sampling strategy, provides two critical pieces of information about the body. Regolith samples are excellent bulk samples because they normally contain all the key components of the local environment, albeit in particulate form, Furthermore, because this fine fraction dominates remote measurements, regolith samples also provide information about surface alteration processes and are a key link to remote sensing of other bodies. Studies indicate that a statistically significant number of nanogram-sized particles should be able to characterize the regolith of a primitive asteroid, although the presence of larger components ( e . g . , chondrules, calcium- aluminum-rich inclusions, large crystal fragments, etc.) within even primitive meteorites ( e . g . , Murchison) points out the limitations of using data obtained from nanogram-sized samples to characterize entire primi- tive asteroids. However, the most important asteroidal geological processes have lefi their mark on the matrix, because this is the finest-grained portion and therefore most sensitive to chemical and physical changes. Thus, the following information can be learned from this fine grain size fraction alone: (1) mineral paragenesis; (2) regolith processes; (3) bulk composition; (4) conditions of thermal and aqueous alteration (if any); (5) relationships to planets, comets, meteorites (via isotopic analyses, including 0); ( 6 ) abundance of water and hydrated material; (7) abundance of organics; (8) history of volatile mobility; (9) presence and origin of presolar and/or interstellar material. Most of this information can be obtained even from dust samples from bodies for which nanogram-sized samples are not truly representative. Future advances in sensitivity and accuracy of laboratory analytical techniques can be expected to enhance the science value of nano- to microgram-sized samples even further. This highlights a key advantage of sample returns-that the most advanced analysis techniques can always be applied in the laboratory and that well-preserved samples are available for future investigations. INTRODUCTION We are entering a new and golden age of sample return missions. In the coming decade, we will harvest samples from Comet P/Wild I1 and interstellar dust courtesy of the Stardust mission (Brownlee et al., 1997), asteroid 1989ML by the ISAS Muses-C mission (ISAS, 1996), and solar wind by the Genesis mission. A sample return from Mars is also envisioned as early as 2008. It is, however, sobering to realize that Muses-C aims to return 3-10 g of sample, Stardust will provide micrograms of comet and interstellar dust, and Genesis will harvest only few micrograms of atoms. The diminutive size of the returning samples may be a source of concern for petrologists used only to looking at hefty lunar rocks and meteorites. From the Apollo missions, the new resource of 380 kg of lunar samples drove development of new, more sensitive and precise sample analysis techniques. We might expect the same thing to occur for Stardust and Muses-C samples. However, we cannot assume that these developments will occur, given the different political climate for science as compared to 30 years ago. Now is the time to push developments of new analysis techniques and increase the precision and sensitivity of existing instruments. Despite the fact that some future missions will be returning gram-sized quantities of sample, not micro- or nanogram quantities, the samples will nonetheless be precious and should be treated as such. Approaching analyses this way will ensure that the samples receive the greatest possible dissemination, while at the same time guaranteeing that adequate material will remain following the preliminary classification to curate and thus be available for future instrument developments we all desire. Also, if we can conclusively tie a specific meteorite type to any returned sample, then we can always turn to meteorites for further characterization of larger petro- graphic features that might be lacking in the space-returned samples. 9 10 Zolensky et al. cn 01 W I- W z 0 01 0 5 0 T Solar Exposure History Mineralogy, Petrography, Composition Composition Origin and History of Elements Atomic and Magnetic Structure Molecular Structure History of Carbon, Origin of Life FIG. 1. A schematic showing the incredible amount of information that can be gained from careful dissection (by ultramicrotome) and consortium study of a single grain measuring 1 0 p m . Not all applicable techniques are even shown. In Fig. 1, we present a schematic showing the incredible amount of information that can be gained from careful dissection (by ultra- microtome) and consortium study of a single grain measuring 10 p m (-1 ng) as an introduction to the state-of-the-art of study of fine- grained materials. Since 1981. NASA has supported asteroid and comet science by collecting dust grains from these bodies in the stratosphere and making them available for analysis in laboratories worldwide (Warren and Zolensky, 1994). Over the succeeding 17 years, many new techniques have been developed for these pain- staking analyses by at least 24 different laboratories across the globe. Despite the fact that the particle supply has always exceeded the demand, the painstaking efforts required for most of the nanoscale analyses have resulted in only 1520 grains having been analyzed, with a total mass of only 0.52 pg. The work reported by Thomas et al. ( 1 995) is a perfect example of this consortium mode of interplanetary dust particle (IDP) research, wherein six different analytical techniques in different laboratories were applied to a single, complex particle. The purpose of this paper is to answer the following fundamental question: How much sample is really needed to achieve prime science objectives, while maintaining a cost-effective mission (Discovery class)? The range of geological processes that we will want to address with these samples is staggering, encompassing not merely the entire history of the solar system, but the history of the elements themselves. The interstellar processes include element formation, production and interactions with radiation, formation of organics, grain condensation and evolution, and interactions with magnetic fields. In the preaccretionary (nebular) environment, we wish to understand grain condensation, evaporation and recondensation, shock, radiation processing, solar energetic particle implantation, gas composition, the magnetic environment, and the evolution of organics. Finally, for solid bodies, we wish to examine accretion history, shock, brecciation, impact gardening, metamorphism, aqueous alter- ation, weathering, exposure history, volcanism, fumarolic activity, differentiation, the magnetic environment, atmosphere evolution, and the evolution of organics. SAMPLING AND ANALYSIS MISSIONS Missions In Preparation There are several funded ( i . e . , "real") missions at some stage of development that will return samples for analysis back on Earth over the next eight years. These are described here in the order of their delivery date to Earth. Genesis-Genesis is a NASA Discovery mission to collect and return to Earth -5 p g of solar wind atoms (for C through U, as the lighter atoms are of little interest here). Although the spacecraft is scheduled to l i f t off in 2001 and return to Earth in 2004, the launch period is very flexible, because the Sun is relatively fixed. The spacecraft will be inserted into a halo orbit about the L1 Lagrangean point (0.01 AU from Earth) where collector arrays will be exposed to the solar wind. During an approximately two year exposure period, solar wind atoms will impact and be implanted into ultrapure Si wafers, as well as a few other materials. Considerable efforts are being made to ensure low contamination levels both before and following solar wind collection. Following collection, the Si wafers will be stowed into a sample return capsule for return to Earth at the Utah Test and Training Range (UTTR). These samples will then be transported to a new curation facility located at NASA's Johnson Space Center (JSC) and will be handled, dissected, and curated in dry nitrogen. This is not the first return to Earth of solar wind material, having been done on the surface of the Moon during the Apollo missions. However, the collection duration will be orders of magnitude longer for Genesis, and contamination concerns are (this time around) paramount. The highest priority measurement is stated to be the solar wind 0-isotopic ratios, which will be measured to ? I % (Wiens et al., 1999). Also, while collecting solar wind, the collec- tion surfaces and surrounding structures will also be impacted by interplanetary dust particles (IDPs) and P-meteoroids. Efforts will be made to study the impact residues resulting from these impacting Small is beautiful: The analysis of nanogram-sized astromaterials 11 asteroidal and cometary particles, although nothing has been done to mitigate the detrimental effects these particles suffer during impact. Stardust-Another NASA Discovery mission, Stardust will be the first sample return from a comet. Grains from a comet's coma will be collected into high-purity silica aerogel. The mission was launched on 1999 February 7. Thus, it launched well before Genesis; however, it returns later. The Stardust spacecraft will perform two swing-by orbits of the Earth to gather sufficient speed to reach the comet under optimal encounter conditions. The spacecraft reaches Comet Wild I1 on 2004 January 10 (or more properly, the comet, being faster, passes the spacecraft at this time). During passage through the cometary coma, a tray of silica aerogel is exposed, and coma grains impact on it and are captured (Fig. 2). At the encounter velocity of 6 k d s , the grains will be decelerated as they pass into the aerogel and come to rest there in a reasonably intact state (Barrett et al., 1992; Horz et al., 1998). It is anticipated that -1000 grains measuring en Motor ' incident The electron microprobe analyzer (EMPA), the Slits workhorse of the modern mineralogy lab, can be 18 Zolensky et a1 a / . (1995). These authors examined the oxidation state of Fe in chondritic lDPs and chondrite matrix, using the National Synchro- tron Light Source (NSLS) Brookhaven x-ray beam line. The mass spectroscopy of secondary ions by a time-of-flight instrument offers attractive advantages over conventional ion microprobes using double-focusing magnetic mass spectrometers (Stephan et a/., 1994). New generation time-of-flight secondary ion mass spectrometry (TOF-SIMS) instruments have a primary beam only -0.1 p m in diameter; and when ionization is made by laser. this technique can provide almost complete elemental and isotopic analyses using only 108 atoms (assuming chondritic composition) (Jessberger, 1991a). It has also been applied to the elucidation of the surface chemistry of chondritic IDPs to provide information on the degree of contamination and nature of surface reactions (Rost et al., 1999) The TOF-SIMS technique has significant sample preparation requirements and is considered destructive. Time-of-flight secondary ion mass spectrometry permits simultaneous detection of all ions with the same charge sign and is characterized by high transmission through the spectrometer (20-80%), by high mass resolution (&Am I 2 0 000 at low and m/Am I 6 000 at high lateral resolution), and by low sample con- sumption (just monolayers in favorable situations). Quantification problems persist with this as for all SIMS analyses. Also, because negative ions must be analyzed separately from positive ions, and each analysis consumes some sample, it can be difficult to properly register the negative and positive ion images. However, in general, it is possible to study elemental correlations in samples on a submicron scale and, if combined with TEM or other mineralogic analyses, with sample mineralogy. This technique has been applied to the analyses of individual chondritic IDPs for some years now, and a good review of the results are given by Jessberger (1991a). Laser microprobes have been used for some time for mass spectrometry of geological materials. For example, Alonso-Azarate et al. (1999) have recently described application of this technique to determination of S isotopes in sample volumes 100 p m in diameter. This technique will no doubt be applied to planetary materials in quick order. A promising new technique for in situ trace element analysis of 10-50 p m diameter spots is laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS). With the very low detection limits characteristic of ICP-MS, coupled with the in s i f u analytical capabilities of laser ablation, this technique is particularly appropriate for high-precision analysis of elements such as Y , REE, Zr, Hf, Nb, Ta, and other lithophile elements that characteristically show no fractionation during laser ablation (Taylor et a/., 1997). The laser ablation microprobe uses a focused YAG laser to ablate a tiny sample in a closed cell, with the ablated material being carried by Ar into an inductively-coupled plasma- mass spectrometer. The use of frequency quadrupling hardware has reduced the ablated pit to a minimum of 10 p m in recent work on silicates (Taylor el al., 1997). Current detection limits for this instrument for elements with atomic mass >85 are typically < I ppm for 10 p m sampling resolution, and subparts-per-billion for 30 p m sampling resolution, and subparts-per-million detection limits for many lithophile elements (Gunther et al., 1995). Addition of a multiple collector to the ICP technique is the latest advance (Halliday et a/., 1998). In this technique, superior peak shapes are obtained due to the ion optical focal plane of a large dispersion magnetic sector mass spectrometer, permitting multiple collection of elements, particularly for elements with a high first- ionization potential. Although still new, the multiple collector-ICP- MS technique, especially when combined with laser ablation, has already been applied to Lu-Hf systematics, 182Hf-182W dating, and the first high-sensitivity measurements of isotopes of In, Cd, Te, Cu, Zn, U, Th, and Pt-group elements. Enthusiasts for this technique predict that it will quickly supplant now standard trace element analytical techniques, including spark source mass spectrometry, x-ray fluorescence, neutron activation analysis, and conventional ICP emission spectroscopy. Isotopic studies are among the most powerful tools available to the planetary scientist. For example, many meteorite groups plot in unique positions on the three-isotope plot for 0, although these trends are smeared out for separated minerals as opposed to bulk samples (Clayton, 1993). Similarly, oxidation state shows a huge variation according to meteorite type, owing to differences established both during pre- and postaccretionary periods (Brearley and Jones, 1998). Thus, it is in principle possible to tie specific grains to specific known meteorite types, although ambiguities are reduced if bulk or, at least, polymineralic grains are used. Recent improvements in sensitivity and spatial resolution are available for double-focusing secondary ion mass spectrometry (SIMS). In SIMS, a primary ion beam, such as 3 H e + , 1 6 0 + , or 40Ar+, is accelerated and focused onto the surface of a sample and sputters material into the gas phase. Approximately 1 % of the sputtered material comes off as ions, which can then be analyzed by a mass spectrometer. Secondary ion mass spectrometry has the advantage that material can be continually sputtered from a surface to determine analyte concentrations as a function of distance from the original surface (depth profiling). Also, in situ analyses are available in the newest generation of instruments (i.e., analyses can be done on grains within thin sections). Secondary ion mass spectrometry provides information on H, C, N, 0, Mg, Ca, Ti, S, and Si isotopes, as well as some trace elements, including the REE (Papike, 1996), at a minimum spatial scale of 2-3 p m (Fig. 5) (though often up to 100 p m in reality), with a maximum precision on the order of 1-10 ppm or, when presented on an isotopic ratio diagram, much less than 1 % ~ . However, precision is more typically 4-lox these values (Zinner et a / . , 1983; McKeegan et al., 1985; McKeegan, 1987; Stadermann et al., 1990; Paterson et a/., 1997; Leshin e t a / . , 1998; Goswami et a / . , 1998). The discussion of inter- instrument analysis comparisons for two SIMS techniques (for analysis of S) given by Paterson et a/. ( 1 997) is particularly valuable and points out the need for rigorous interlaboratory calibration, particularly for SIMS where instrumental factors are so important. This critical activity should be performed before the return of the Stardust and Muses-C samples in 2006, in order to provide maximum utility and minimum confusion. With these data, it is indeed possible to discriminate between material formed in the nebula and presolar grains (Zinner, 1991; Nittler et al., 1998) (Fig. 6). In interstellar grains recovered from unequilibrated chondrites, isotopic compositions of H, C, N, Mg, Si, Ca, Ti, and Zr have been measured by SIMS (Anders and Zinner, 1993; Hoppe el a/., 1993, 1996a.b), and noble gases by sensitive mass spectrometry, and these analyses have proved sufficient to tie specific grains to various carbon stars, Type I1 supernovae, 0-rich red giant stars, and (possibly) Wolf-Rayet stars. All this from diamond, carbide, nitride, oxide, and graphite grains individually measuring no more than 2 0 p m , and usually a good deal smaller. Small is beautiful: The analysis c if nanogram-sized astromaterials 19 FIG 5. Scanning electron hackscattered image of a carbonate occurrence in ALH84001. showing an ion microprobe pit (center) resulting from analysis of 0 isotopes. The image shows the small (15 pm) size of the analyzed area. Figure provided by Laurie Leshin. Just on the horizon is a new generation SIMS, called the nano- SIMS (Stadermann et al., 1999). The first of these instruments will find a home at Washington University in the coming year. Its unique design features a normal incidence primary beam, and a reduced working distance, resulting in a substantially smaller primary beam spot and high secondary ion collection efficiency. The prototype instrument has achieved a beam diameter as small as 30 nm, with significantly higher ion yields that the ims3F and ims1270 SIMS instruments at mass resolutions up to 6000. The applications of such an instrument are obvious. The best current analytical precision of in situ 0-isotopic analyses ( I%o) just permits resolution of martian from terrestrial or asteroidal materials (Clayton, 1993; Leshin et al., 1998), a funda- mental goal of the proposed Aladdin mission to the martian moons (Pieters et al., 1997). Secondary negative ion images can be made with a resolution of 1 pm, permitting location of grains with unusual isotopic compositions from within a fine-grained mineral assemblage or from among a large collection of separate grains (McKeegan et al., 1985). Young and Russell (1998) have recently reported success with a new UV laser ablation and fluorination method for in situ analysis of 1sO/160 and I7O/I6O ratios in meteoritic components. The increase in sensitivity is achieved by preconcentrating 0 from a fluorination line for analysis by isotope ratio monitoring gas chromatography mass spectrometry (irm-GCMS). This technique requires 10-20 nmol of 0 (-I p g of a typical silicate) to be successful but then produces data with an accuracy of 20.2% or better, and precision between 20.1 and 2 0 . 3 . The technique has been applied to in situ analysis of CAI and should find more general application (Young et al., 1998). However, these authors note that laser ablation in a fluorinating environment relies on the presence and distribution of 0 $ h 3 1 O2 I O3 ......__............__......... 7 Solar i System 165 I I I : I O5 I O4 I O3 1 o2 FIG. 6 . Three-isotope plot of 0, showing values obtained from micron-sized and smaller interstellar grains separated from chondrites. This diagram shows the precision possible from such analyses and also demonstrates that material from different sources (red giants, solar system, type I I supemovae) can be distinguished. Figure provided by Larry Nittler. crystalline defects in the mineral surface and is complicated by dynamical interactions between the plasma plume and ambient reagent gas. This means that results will vary depending on compo- sition as well as the structural state of the sample. Although the 0 mass requirement of this techniques are order of magnitude smatler than for other fluorination methods yielding similar analytical precision and accuracy, the sample mass requirements of this technique are still greater than those of SIMS (which, however, has less accuracy and precision). Thus, one can obtain very high-quality 0-isotopic data for submicrogram samples, but SIMS is still required for masses of a few nanograms. Resonance ion mass spectrometry (RIMS) uses a laser beam focused to - 1 p m to promote an atom or molecule above its ionization potential to create an ion. Ablated atoms are then resonantly ionized with two or three tuned lasers. This ionizes only the element of interest, which is then accelerated and mass analyzed in a time-of-flight mass spectrometer. Because each element h a s a unique energy level structure, RIMS provides a selective ionization method. Resonance ion mass spectrometry is useful for studying the electronic structure of atoms or molecules and to make quantitative measurements of analyte concentrations. The sensitivity is excellent-ane can count a few percent of the atoms removed from the sample, compared with -1% for SIMS. The selectivity is also excellent-for example, one can easily ionize Mo without ionizing Zr (which overlaps Mo isotopes at three masses). Meteoriticists are currently using RIMS to analyze presolar grains, where the isotopic anomalies are huge and very interesting. Thus far, isotopes of Ca, Sr, Zr, and MO have been variously determined in S i c and graphite (Nicolussi et al., 1997a,b, 1998). Thermal ionization mass spectrometry (TIMS) has been used to determine Mg isotopes in some IDPs, with a spatial resolution of -10 p m (Esat and Taylor, 1987). However, this technique does not appear to be as versatile as some of the other MS techniques, because entire grains must be placed onto filaments and destroyed to be analyzed. 20 Zolensky e t a / Organic Analyses Reviews of organic chemistry of meteorites and IDPs show that more than 400 different compounds have been definitively identified-many thousands undoubtedly await detection by the more sensitive techniques that will be available in the future (Hayatsu and Anders, 1981; Mullie and Reisse, 1987; Cronin e t a / . , 1988; Anders, 1991). Mixing and secondary processing of the original interstellar and proto-solar organics is expected to make analysis and interpretation of results from any analyses very messy. The mass spectrometric results from the Giotto and Vega missions to comet Halley have been interpreted to indicate that at least half of the organics there are interstellar in origin (Kissel and Krueger, 1987; Anders, 1991). Important questions to be answered during further analysis of cometary or primitive asteroidal organics include ( I ) for the interstellar organics, what was the relative contributions from ion-molecule reactions, grain surface reactions, UV photolysis of ices, circumstellar condensation, and shock chemistry (Peterson et a/.. 1997); and (2) what was the origin of the remaining 50% of the organics? (Anders, 1991). A severe limitation of the existing techniques is the need for analysis of polymers, which are destroyed during most current analyses. We need information particularly regarding polymers on the graphite-kerogen-PAH continuum, including information on morphology; structure; bonding of C, H, 0, and N ; molecular weights; structural subunits; and reactivities. We will also need to check for the effects of secondary alteration processes, including radiation, heat, and aqueous alteration (Anders, 1991). Because of the enormous complexity of organic matter in comets and asteroids, that probably consist of thousands of molecules which cannot be separated and analyzed individually, it may be more fruitful to obtain an elemental composition of the bulk organics and then use optically- and acoustically-excited phonon spectroscopy to provide an overall view of the material (Jessberger, 1991b). The D/I-I ratio is the marker tor ion-molecule reactions and needs to be detcrmined in all organic materials. Also, the carrier of the D nccds to be determined in all cases. If possible, the carriers of the interstellar D should be separated from the proto-solar D, and the two samples analyzed separately, because the interstellar cloud environment should have produced different populations of organic compounds than the proto-solar nebular cloud (Jessberger, 1991 b). This effort should be facilitated by the Genesis mission, which will provide a much improved IYH determination for the solar wind. Micro Raman spectroscopy provides the molecular structure of a limited number of important inorganics and organics for samples measuring 1-2 p m and has been applied to the characterization of individual IDPs (Wopenka, 1988; Munro et a / . , 1996). However, this technique needs multi-channel capability to lessen sample damage from the intense, focused laser beam (Jessberger, 1991b). I t should be more appropriate for rcfractory organic species and inorganics. Stepped combustion and static mass spectrometry are the most commonly employed techniques for isotopic analysis of organics and associated stable isotope species. However, the large sample sizes generally required for these bulk techniques ( e . g . , 6-100 p g for C and 2 p g for N ; Carr et a/., 1986; Wright and Pillinger, 1989; Wright ef a/., 1997) highlight the increases in sensitivity required for the future of this technique. At present, only individual chondritic grains measuring 50-100 pin in diameter can be analyzed by these techniques. Two-stage laser desorptionllaser multiphoton ionization mass spectrometry b L 2 M S ) is a relatively new technique enabling direct in situ analysis with a spatial resolution of about 10-100 p m for selected organic molecules in complex mixtures. In the first step of this technique, neutral molecules from the sample surface are desorbed intact with a pulsed, focused infrared (IR) laser. These desorbed molecules are then ionized with a pulsed, tunable ultraviolet (UV) laser, by resonance-enhanced two-photon ionization of the desorbed species; this soil ionization scheme prevents fragmentation. The resulting ions are swept into a reflection time-of-flight mass spectrometer (Zenobi et a / . , 1989; Kovalenko et a / . , 1991). In the first step, desorption occurs without decomposition; whereas in the next step, the desorbed molecules are ionized "softly," resulting in mass spectra consisting mainly of parent ion peaks. The mass spectra are dominated by intact parent ions of those mixture components that strongly absorb the selected ionization laser wavelength. Under some instrument configurations, only molecules with an excited state in resonance with the photon energy are ionized, enabling selective detection of a chosen class of compounds for analysis. Thus far the PAWS have been best analyzed by this technique in IDPs (Fig. 7) and meteorites (Hahn et a/., 1988; Clemett et a/., 1993). Although nowhere near as precise as SIMS, pL2MS is also capable of providing information on D/H and I3C/I2C ratios (Scott Sandford, pers. comni., 1998). Two-stage laser desorptiordlaser multiphoton ionization mass spectrometry offers several advantages over conventional methods for analysis of organic in diminutive samples. Little o r no sample preparation is necessary, and the direct analysis of complex environmental samples is possible. Furthermore, a measurement is performed within a few minutes. The detection limit is only -1 attomole (500000 molecules), a million times lower than for most conventional methods. Two remaining problems have prevented p L 2 M S from finding broader application in analytical chemistry until now: mass isomers could not be separated in a satisfactory way and quantitative analysis in complex mixtures was difficult or impossible. However. recent work has concentrated on overcoming these impediments (Haefliger and Zenobi, 1998). Transmission and reflectance infrared-visible spectroscopy techniques are described b e l o ~ i under the section concerning Mineralogy and Atomic Structure. Florianus A 2 1 I I . I Aurelian * B 5 3 "I Caligula 2 '0 100 200 300 400 500 600 700 Mass (amu) FIG 7 The micro-L2MS organic analysis of three individual chondritic IDPs, named Florianus, Aurelian, and Caligula The peak groupings have been identified as including the polycyclic aromatic hydrocarbons napthalene (128 amu), phenanthrene (178 amu), pvrene (202 amu), chrysene (228 amu), benzopyrene (252 a m ) , and pentacene (278 amu), and their alkylated series Figure provided by Simon Clemett Small is beautiful: The analysis of nanogram-sized astromaterials 21 Fluorescence behavior of organic molecules can be used as a gross identification technique (ie., that fluorescence can reveal the prcscncc o f organics but cannot permit characterization). Briggs and Mamikunian (1963) and Murae (1997) have used the fluorescence behavior of some organics to suggest the presence of PAHs and relatcd heavier organics in CM2 carbonaceous chondrites. Obviously, this is a simplc, nondcstructive technique that can be applied to nanogram-sizcd samples. I lowevcr, the reported results suggest that specific organic characterization is not possible by this technique. In addition, intcrfcrencc by inorganic fluorescing minerals (some carbonates, phosphates, Fc-poor silicates being common examples) would be a severe impediment to the useful application of this technique for organic Characterization. Carbon has bcen mapped within chondritic IDPs using XANES by I:lynn et al. (1998a.b). with a spatial resolution of a few hundred nanometers. This technique can be useful in distinguishing organic liom amorphous C. bccause the former exhibits several pre-edge peaks from C-C. C-II, and C-0 bonds; whereas most forms of elemental C havc only a single pre-edge peak. Noble Gases and Exposure History Noble gases display diffcrences between chondrite, planetary, and solar wind origins. Origin on specific planets can be distinguished owing to differences in the atmospheric evolution for each body (Ott and Begcman, 1985). Sensitive step-hcating measurements of He and N e isotopes using a high-performancc double-focusing mass spectrometer havc been made for individual chondritic IDPs by Nier and Schlutter (1992, 1993). This information can also be used to gauge heating in a regolith environment, bccause the quantity of gas released at each tcinpcrature step can hc used to infer the degree of preanalysis heating, as clcgantly shown by Nier and Schluttcr (1993). Allowance has also to bc made for thc possible effects of noble gas loss due to shock (Nakamura ef a/.. 1997). Recently, newer mass spectrometers arc being constructed that will permit measurement of isotopes of all noble gases in nanogram-sized samples (Tomoki Nakamura, pers. comm., 1998), and thcsc instruments are slated to be available beforc the turn o f t h e century. Solar flare tracks, imaged by TEM, can be used to constrain grain origins. Track densities are indicative of the exposure duration to solar wind, cither as a free floating object or during residence in a parcnt body regolith (Bradley et a[., 1984; Sandford, 1986). Sandford ( 1 986) further used track densities in lDPs to constrain the heliocentric distance during exposure and used this information to distinguish, on a statistical basis, between asteroidal and cometary grains. This technique requires the presence of competent silicates, like olivine and pyroxene, in crystals large enough to preserve the tracks. This requires crystals on the order of 0. I p m ; the grains have to be larger than the tracks they arc recording. Fluid Inclusions Because so many mctcorites show pervasive effects of aqueous fluid processing, it is rcasonable to expect to find fluid inclusions in extratcrrestrial samples. In fact, thcse have recently been recognized in the ordinary chondrite Monahans (1998) and are receiving attention at this moment (Zolensky et al., 1999). The failure to find thcsc inclusions morc frequently may be due to decrepitation of thcse inclusions during the shock events that launched meteorites from their parcnt asteroids. If fluid inclusions are present in recovered samples, it will prescnt us with opportunities to directly analyze extraterrestrial mineralizing solutions. Upon recognizing inclusions, one would want to perform the conventional heatinglfreezing work using a petrographic microscope in order to learn trapping temperatures and possibly solution salinities (Roedder, 1984). It can be expected that the gas and liquid compositions of such inclusions will be analyzable by Raman and mass spectrometry (Miller and Pillinger, 1997) and that any solid daughter crystals would also be suitable for characterization by Raman microsampling spectrometry (Pasteris and Chou, 1998), analytical electron microscopy, and microparticle x-ray diffraction techniques (Zolensky and Bodnar, 1982; Ohsumi and Zolensky, 1998). It may also be possible to measure the isotopic composition of 0 in the fluid (assuming it is water) by a sensitive laser ablation technique. Raman microsampling spectrometry deserves additional comment here, because it is a nondestructive, in situ technique not normally applied to meteorites (for an exception, see Wopenka, 1988). The technique is easy to use and involves laboratory-scale equipment. This vibrational spectroscopic technique examines the inelastic scattering of monochromatic visible light as it interacts with covalent bonds in minerals, liquids, and gases. Thus although applicable to three of the four states of matter, it is limited to materials containing covalent bonds. For these materials, Raman spectrometry can be used to identify compounds, characterize composition and degree of crystallinity, and study bonding modes (Wopenka, 1988; Pasteris and Chou, 1998). In addition, careful analysis of the Raman scattered line shape can give insight into the dynamics of displasive phase changes (McMillan, 1989). The monochromatic laser can be focused to 1 p m diameter and can be used to study materials embedded as far as 100 p m deep into transparent materials. It is possible that thermal effects are produced in the sample during such fine focusing-this effect has yet to be adequately addressed. In the past, the structures of such materials as graphite and PAHs have been profitably studied. The technique has been successfully applied to qualitative and quantitative analysis of molecular species (including CO, C 0 2 , CH4 and other hydrocarbons, N2, H2, 02, and H2S) in liquid and glass inclusions down to only a few micrometers in diameter (McMillan, 1989). Clathrates can also be studied by Raman spectroscopy (Dubessy et a / . , 1982; Seitz et al., 1987). It is possible to complement the Raman analyses of gases and daughter minerals with in situ SXRF analyses of the fluid-inclusion solution composition. This nondestructive technique can be applied immediately following the Raman work and leaves the inclusion available for later isotopic characterization. Age Dating It seems likely that some components of both comets and asteroids predate the formation of the solar system. Detection of extinct radionuclides would provide an important picture of the pre- accretion and accretion stage of the nebula. Cosmic-ray exposure clocks could also be used to distinguish between mineralogic processes occurring during irradiation within a comet as opposed to that occurring before this stage. It should ultimately be possible to distinguish between irradiation occurring before the nebula in interstellar space. This is not currently possible. The most commonly used radionuclide clocks are based on lithophile elements such as K, Rb, Sm, Th, U, and Pb. For iron meteorites derived from asteroidal cores, the high concentration of noble metals makes it possible to use the P-decay of Is7Re to Is7Os, although the uncertain half life of this reaction renders results 22 Zolensky et al. ambiguous (Mittlefehldt et al., 1998). Chronological information can also be obtained from extinct radionuclide systems, if the isotopic signature of the early radioactive decay has been preserved. These systems include Io7Pd, 182Hf, 205Pb, 244Pu, 146Sm, 53Mn, and ' Z 9 I , and can be used to measure the time after accretion when the important geologic processes of magmatism, core formation, and metamorphism occurred (Rowe et al., 1970; Mittlefehldt et al., 1998). A severe limitation on analysis of the required elements for age dating is the availability of reliable blanks at the subpicogram level. For example, at CI abundance, in order to determine the concentra- tions of the critical elements Rb, Sr, Sm, Nd, U, and Pb, 1-10 p g of sample are required just to equal the elemental concentrations present in the best available blanks (Turner, 1991). It is clear that heroic work is required in the essential, though unexciting, effort to improve the quality of blanks. The brightest candidate in this otherwise dim picture is 39Ar-40Ar dating by laser ablation mass spectrometry, due principally to the relatively high abundance of K in chondritic samples (566 ppm), and also to the small required mass for analysis (1 pg). Metamorphism and impact ages are probably best determined by the 39Ar/40Ar method (Bogard and Garrison, 1995). This technique uses 39Ar produced by 39K by (n, p) reactions by fast neutrons from a nuclear reactor to establish the amount of parent 40K in the sample. A major technical advantage of this technique over conventional K-Ar dating is that only one aliquot of sample needs to be analyzed, therefore reducing problems of sample heterogeneity (Reddy et al., 1997). The current limitation by interference from absorbed atmospheric 40Ar could be circumvented by returning the sample to Earth in a pressurized canister (as is planned for Muses-C), but another interference by organic matter at mass 39 will continue to be a problem. A serious impediment to 39Ar-40Ar dating sensitivity improvement is 39Ar recoil (Villa, 1997), which should be a serious problem for submicron masses or aggregates of smaller grains (Turner, 1991). However, a technique has recently been developed to vacuum encapsulate the ultra-small sample during analysis, preventing loss of 39Ar gas (Foland et al., 1992; Smith et al., 1993). This technique has been modified and applied to in situ dating of illite grains of microgram mass within thin sections (Dong et al., 1997). This mass corresponds to volumes on the order of 60 p m on a side. There is promise that the analytical sensitivity can be further reduced to permit in situ dating of nanogram-sized samples in the foreseeable future. Nevertheless, it must be borne in mind that, to be successfully dated, a mineral must contain essential K and have remained competent (no degassing) for its lifetime; these are not simple limitations. Few minerals will be found to satisfy these requirements; however, the recent discovery of sylvite (KCI) within an ordinary chondrite by one author (M. E. Z.) demonstrates that these K-bearing phases can be found. The greatest spatial resolution for 39Ar-40Ar dating is possible when an IR or UV laser is used to release the Ar. The advantages of this approach include ( I ) low blank levels, because only the area impinged by the laser is heated, and (2) high spatial resolution, permitting minerals of different generations or with varying textural or petrographic relationships to be analyzed separately (Kelley, 1995). Ion probe techniques promise solutions to the age dating problem but so far have only been applied to U-Pb studies of relatively U-rich mineral grains. Such grains will be extremely rare in anticipated cometary or asteroidal samples (Turner, 1991). Mineralogy and Atomic Structure Transmission electron microscopy has already been discussed. The combination of TEM with electron energy loss spectroscopy (EELS) has proven to be a powerful tool for qualitative to quantitative chemical analyses at the nanometer scale. With EELS one studies the primary processes of electron excitation, in which an electron looses a characteristic amount of energy (Garvie et al., 1994; Egerton, 1996). The apparatus for this analysis is attached to a TEM and is used in conjunction with imaging of ultra-thin slices of a sample. Electron energy loss spectroscopy is particularly sensitive to the presence of molecular species in minerals, such as C03*- and B033-. This is because molecular units show charac- teristic spectral peaks due to excitation of oxygen K-shell electrons (called 0 - K near edge structure) (Wirth, 1997). In fact, Wirth (1997) has shown that a small peak at -528 eV in EELS spectra is correlated with water and/or OH content. This observation promises to permit water determination in some minerals at the nanometer scale, which is several orders of magnitude higher spatial resolution than possible with optical spectroscopy. Recently, Garvie and Buseck (1 998) have reported a procedure for determining Fe3+Z1Fe in rock-forming minerals at nanomater- scale resolution using EELS. They find that spectra for particular minerals show Fe L2,3 edges with constant shapes for given oxidation states, which permits calculation of Fe3+Z1Fe for a mineral provided that suitable standards have been previously characterized. Apparently, this procedure will work also for noncrystalline materials. The results of this EELS study appear to be more precise than those for the EMPA techniques reported above (Hofer et al., 1996; Sobolev e f al., 1999); certainly they are applicable to much smaller samples. Electron energy-loss near edge structure (ELNES) analysis can be used to investigate the local solid-state environment of certain elements in crystalline and amorphous materials, including valency, coordination, and site symmetry of excited atoms (Garvie et al., 1994). The apparatus for this analysis is also attached to a TEM. Bradley (1994) used ELNES in tandem with TEM imaging to characterize the structural and compositional state of amorphous materials within chondritic IDPs. Electron energy-loss near edge structure has also been applied to determination of the spectroscopy of mixed Si coordination in minerals, such as the silica polymorphs (Poe et al., 1997). This would be very useful in characterization of silica phases formed during impact processes (i.e., stishovite, coesite, and keatite), although silica is not a common phase away from the Earth. This technique should also be applicable to majorite and some garnets (Poe e f al., 1997). Usual x-ray diffraction techniques cannot be applied to nanogram-sized mineral grains (measuring only few a few microns at most). However, the crystal structure of such diminutive samples can be fully characterized using synchrotron x-ray diffraction (SXRD) (Ohsumi and Zolensky, 1998). In this Laue technique, an extremely bright x-ray beam (-10 orders of magnitude brighter than conventional x-rays provided by a rotating anode instrument) is collimated down to -3 pm, permitting collection of a full three- dimensional x-ray intensity data set for a grain measuring at least this size, in only 1-6 h. The procedure can be performed on separated crystals or on grains in situ and is nondestructive. Most recently, Ivanov et al. (2000) collected single-crystal Laue patterns of a new meteoritic mineral (FeTiP) present in only one thin section as three grains measuring a maximum of 10 p m in dimension (Fig. 8). The x-ray data set was used to perform a full three-dimensional Small is beautiful: The analysis o n FIG. 8 . (a) Backscattered electron image of a rounded grain of cronstedtite from the Kaidun chondrite, containing three small crystals of the new phase FeTiP (arrowed). Scale bar measures 10 pm. (b) Single-crystal Laue pattern obtained from the middle FeTiP crystal in (a) by synchrotron x-ray diffraction. A few of the retlections are labeled with miller indices. Each reflection consists of four separate spots, indicating that the crystal actually consists of four domains in nearly parallel growth. Even with this imperfection, the data set was sufficient to permit a full three-dimensional crystal structure analysis to be performed. crystal structure refinement of the new mineral, yielding valuable clues regarding the genesis of the host meteorite. Because this analysis was performed in situ, the grains remain in the section, available for further study. The short-range atomic structure of noncrystalline materials (phases lacking long-range order) can be investigated by non-Bragg scattering methods and spectroscopic methods using synchrotron x-rays. X-ray scattering from such materials is about two orders of magnitude less intense than normal Bragg scattering from crystalline materials, and thus difficult to observe without the intense synchrotron x-ray source (Basset and Brown, 1990). This technique might prove to be one of the most important for cometary and space- weathered samples, where we may encounter abundant amorphous phases. A key clement in understanding cosmochemical and physical processes to all size scales is the dependence of physical and chemical properties of extraterrestrial materials on molecular structure, chemical bonding, and composition. Spectroscopic studies of minerals can provide much of this information. However, because of the small sample volumes, low concentrations of some important trace elements, and eternal need for high signal-to-noise ratio data, extremely high photon fluxes are required for many of these studies. Synchrotron-based analytical techniques have recently permitted use If nanogram-sized astromaterials 23 of these techniques to very small sample volumes, and ppb-level trace element concentrations. Probably, the most important of these are x-ray absorption spectroscopy (XAS) methods, including extended x-ray absorption fine structure (EXAFS) and XANES, which can provide information on the local structure (<5 A radius around a selected atom) and bonding for atoms in all types of solids (Bassett and Brown, 1990). Again, using synchrotron light sources, these techniques are applicable to nanogram-sized sample volumes. The EXAFS spectra can yield the distance, number, and identity of first- and second-nearest neighbors surrounding an absorber atom in a sample, and can be applied to almost all elements. The XANES spectra can provide information on the absorber atom's local environment and its valence (oxidation state) (Bajt et al., 1995). Thus, this technique would yield critical data on the valence and spin state of Fe, Ti, Co, Ni, Cu, or Mn in a mineral. X-ray absorption near-edge structure has recently been used to map the distribution of K and C within chondritic IDPs (Flynn et ul., 1998a,b). Sutton and Flynn report that the new APS beamline can be used to measure Fe- oxidation state on samples containing as little as 1 femtogram of Fe (Sutton and Flynn, 1999). Thus, EXAFS and XANES complement x-ray diffraction studies by providing details of the local structure rather than the average structure. This is particularly important in studies of minerals where more than one element may occupy one type of crystallographic site, which is to say, practically all important rock-forming minerals. Examples of the use of these spectra are legion. For example, knowledge of the oxidation state of Fe in minerals provide information on the 0 fugacity of a planetary object's interior or its past atmosphere, and its degree of aqueous alteration (Browning et al., 1996). The site geometry of Ti4+, for example, cannot be studied by any other technique (Waychunas, 1987). The cation environments in silicate glasses can also be characterized, which can reveal critical details of their formation processes-radiation damage vs. igneous, for example. Transmission IR-Vis spectra have been successfidly made from individual nanogram-sized IDPs, over the range 2.5-25 pm, for grains >5 p m (Sandford and Walker, 1985; Bradley et al., 1992). In addition, Bradley et al. (1996) have collected IR-Vis reflectance spectra of -10 p m in diameter IDPs in the laboratory using a specially-fitted micro FTIR instrument, over the range 380 to 1 100 nm (Fig. 9). The high-intensity 1R beamline at the Brookhaven NSLS is well suited for characterization of subnanogram-sized objects, because it provides an IR beam spot >1OOx brighter than laboratory IR spectrometers and can cover the entire range from 2-25 p m in wavelength (Reffner et al., 1994). Using IR-Vis spectroscopy, workers have identified similarities for some particles to reflectance spectra collected from asteroids. This work is of fundamental importance, because it ties together laboratory-collected data for samples with remote sensing information of probable parent bodies. Atomic force microscopy (AFM) (discussed above) is currently being applied to interplanetary dust by Wolfgang Klock, Jens Romstedt, and their collaborators in Europe as they prepare for the European Space Agency's Rosetta mission, which will include AFM on the payload. This instrument is also planned for the payload of the Mars 2001 mission. Although this technique is promising, the results from analyses of the dust have been somewhat disappointing (Klock, pers. comm., 1998). This is probably due to the widely varying electrical properties making up these materials. It is clear that this technique will be applicable to some natural materials. 24 Zolensky et al. 70 60 -50 s 40 8 30 v z 8 3 20 J u, 10 0 .. I I - 0 0 0 400 500 600 700 800 WAVELENGTH (nm) 1 2 3 4 5 0 6 8 9 X I 0 + 0 x 4- FIG. 9. Reflectance spectra of 10 individual chondritic IDPs. The spectrum at the top, with the steepest rise, resembles those for P and D-class asteroids, which are believed to be rich in organics. This particular IDP, L2006 cluster 4, has a bulk C content of -50 wt%. Spectra collected by John Bradley and Lindsey Keller. Cathodoluminescence (CL) is the emission of light from a material following electron irradiation. Cathodoluminescence microscopy and spectroscopy in an SEM is a nondestructive technique for characterization of defect centers in materials with high sensitivity and spatial resolution (Yacobi and Hoyt, 1990). Although CL spectroscopy can be used to characterize the nature of impurity ions within materials, it is a point technique. Therefore, a quantitative correlation between CL integrated intensities and bulk trace element analyses by any other technique should not be expected. In addition, the observed CL spectra may be reduced by competitive nonradiative de-excitation processes in some samples, or when impurities are present in nonluminescent structural configurations. It is most effective to use a trace element analysis to assist in identification and interpretation of the CL spectra (Stevens Kalceff et al., 1997). Physical properties Magnetic force microscopy (MFM) permits imaging of the magnetic structure of materials, using much of the same equipment as AFM (Cloete et al., 1998, 1999). In this technique, the AFM tip interacts with the stray magnetic field emanating from the sample. Submicron-resolution imaging of the magnetic orientation and domain structure of the sample is obtained (Fig. 10). In fact, this technique is facilitated by small (submicron), single domain samples, because these are very efficient carriers of remnant magnetization signatures; larger crystals develop a multidomain character. Another application of the AFM technique is the investigation of mechanical properties by force spectroscopy (Burnham and Colton, 1993). In this technique, the tip indents the sample surface. If the indentation force is periodically moduhted, the amplitude of the tip position is a function of the material elasticity. Density measurements may be made of individual nanogram- sized grains by three techniques, a:; shown by work on IDPs. Direct weighing of IDPs has been performed using a glass fiber balance (Fraundorf et al., 1982). Flynn and Sutton (1991) have used the synchrotron x-ray excitation of some elements ( i e . , Fe) within chondritic IDPs, having calibrated this using standards of known mass and composition. Corrigan et al. (1997) performed image processing of carefully sliced IDPs, again with reference to a known density standard. Sample Analysis Flow Charts A major goal is to maximize the science return from the smallest possible sample mass. Analyses should be as nondestructive as possible. The analysis plan has to be flexible because of the still unknown nature of the samples, especially for the comets and interstellar grains. One can use Table 1 to construct analyses flow charts, taking full advantage of the nondestructive analyses before proceeding to the more destructive ones. The critical thing is to be aware of the full universe of applicable analyses before launching into the sample preliminary investigation, to ensure that maximum information is obtained from the precious returned sample. Small is beautiful: The analysis of nanogram-sized astromaterials 25 momaq netite F I G I0 (a) Backscattered electron image of titanomagnetite, magnetite, and quartz of a granite-gneiss, Vredefort, South Africa (b) Magnetic force microscope image of the same area as in (a), showing the multidomain magnetic structure of the magnetite and the nonmagnetic nature of the titanomagnetite and quartz The width of field of view is 20 pm Image provided by Thinus Cloete HOW REPRESENTATIVE OF PRIMITIVE OR EVOLVED SOLAR SYSTEM OBJECTS ARE NANOGRAM-SIZED SAMPLES? A key question to then ask is how representative are microscopic samplcs of bodies that measure a few to many kilometers across? A dccadc of work by persistent IDPs workers has demonstrated that carefully organized, sequential analyses permit a comprehensive series of measurements to be obtained even from individual nanogram-sized particles (-10 p m in diameter). From such analyses of a grand total of 0.5 pg of chondritic IDPs (-1500 particles), inultiplc compositional types have been identified, and their geochemistry has been determined sufficiently to infer key aspects of their origins and histories. The gross similarities of these nanogram-sized chondritic IDPs reveal that their parent comets and primitive asteroids have exceedingly fine-grained regoliths (Lindstrom et al., 1990). Comets are certainly not homogeneous at the femtogram grain scale (Clark et al., 1987) but perhaps are homogeneous at the nanogram mass scale. With the Galileo flybys of Gaspra and Ida, and Mars Global Surveyer's observations of Phobos, it is now recognized that small airless bodies have indeed developed a particulate regolith. Acquiring a sample of the bulk regolith, a simple sampling strategy, provides two critical pieces of information about the body. Regolith samples are excellent bulk samples because they normally contain all the key components of the local environment, albeit in particulate and somewhat processed form. Furthermore, because this fine fraction dominates remote measurements (Pieters et al., 1993), regolith samples also provide information about surface alteration processes and are a key link to remote sensing of other bodies. Of course, regoliths are also the places where foreign materials (meteorites, micrometeorites) will reside, and one will have to be ever vigilant to recognize non-indigenous materials among regolith grains. The lunar experience tells us that this can be done, although the problem will be more acute with purely fine-grained sample returns. The lunar regolith was demonstrated to contain 1-4 wtYo foreign (predominantly chondritic) material, which was recognized early on through a comparison of the siderophile composition of the lunar regolith vs. lunar basalts, and this posed no significant problems for characterization of the Moon (Wasson et al., 1975). If one wished to obtain a bulk composition of another regolith, one could make a similar correction, subtracting out 1 4 wt% chondritic composition materials, as a first approximation. For most elements, this should not introduce significant analytical uncertainty. However, if one is characterizing the mineralogy or more detailed nature of individual particles, one will probably have to measure the 0-isotopic composition of suspect grains (or make some similar diagnostic measurement) in order to weed out interlopers, at least until one understands the sample well enough to recognize foreign material more readily. Meteorite studies indicate that a statistically significant number of nanogram-sized particles should be able to characterize the regolith of a primitive asteroid. The carbonaceous chondrite Murchison, for example, contains both fine-grained matrix as well as larger components such as chondrules, CAIs, large crystal fragments, etc. An INAA study of grains from the carbonaceous chondrite Murchison found that the matrix component of this meteorite is homogenous to the nanogram scale (Lindstrom et al., 1990). However, the presence of larger components within Murchison ( e . g . , chondrules, CAIs, large crystal fragments, e t c . ) points out the limitations of using data obtained from nanogram-sized samples to characterize entire primitive asteroids. Analyses of Allende bulk material indicate that gram-sized quantities are required to yield bulk chemical analyses accurate to within 1%; for 100 mg, accuracy is degraded to 3% (Jarosewich et al., 1987). However, the most important asteroidal geological processes have left their mark on the matrix, becauce this is the finest-grained portion and therefore most sensitive to chemical and physical changes. Thus, the following information can be learned from this tine grain size fraction alone: ( I ) mineral paragenesis and igneous processes; (2) regolith processes; (3) bulk composition; (4) conditions of thermal and aqueous alteration (if any); ( 5 ) relationships to planets, comets, meteorites (via isotopic analyses, including 0); (6) abundance of water; 2 6 Zolensky et a1 (7) abundance of organics; (8) history of volatile mobility; and (9) presence and origin of presolar material. CONTAMINATION CONCERNS A significant constraint on any sample return is the absolute requirement for a contamination-free sample container. Calculations indicate that for a chondritic composition sample weighing 1 pg, the total permitted contamination levels for inorganic elements on the walls o f the sample container vary from to g for instrumental and radiochemical neutron activation analyses (INAA and RNAA). For nanogram-sized grains, the requirements are significantly more stringent. Accordingly, smaller-scale techniques such as ion probery, PIXE, and RIMS require even more care in contamination control. For organic compounds, contamination control requirements are not only hard to achieve but currently often difficult to usefully define. Blank levels must be decreased, as the necessary developments in sample handling are accomplished. This is well described by Miller and Pillinger (1997). The experiences of A l Nier are instructive in this regard. In his initial attempts to measure noble gas contents of individual chondritic IDPs, he discovered that the metal foils he was using for sample containment contained hitherto unrecognized, and rather high, amounts of these same noble gases (A1 Nier, pers. comm., 1990). He was therefore led into a tedious side-investigation of the noble gas contents of many laboratory materials. Similar fates undoubtedly await other careful analysts. In summary, current technology allows even the tiniest samples to provide major breakthroughs in understanding the origin and compositional evolution of the solar system. Fortunately, further advances in sensitivity and accuracy of laboratory analytical techniques can be expected to enhance the science value of nano- to microgram-sized samples further. This factor highlights a key advantage of sample returns-that the most advanced analysis techniques can always be applied in the laboratory and that a well- preserved sample is available for future investigations. SAMPLE DEGRADATION Although it would be most informative to have as returned samples undisturbed, pristine materials maintained at the exact environmental conditions as they existed on the parent body (temperature, atmosphere, etc.), this is not practical at this time. Even where great pains were taken to ensure this sampling fidelity, for the Apollo lunar samples, many samples were exposed to pure 0 and the humid environment of the lunar excursion module and return capsule (Freidman et al., 1970; Epstein and Taylor, 1974). We have to understand how the returned samples will have been affected by heating, shock, disaggregation, and pulverization. Sometimes the samples will be flooded with terrestrial air (albeit clean air) upon reentry, as will happen for Stardust. For low-cost missions, it may not be practical to return samples without some degradation. By careful control of contamination sources and the .judicious employment of thermal control, we generally can preserve samples such that a very large fraction of science objectives can be met. CONCLUSIONS Thus, the following information can be learned from this fine- grain size fraction alone: ( 1 ) mineral paragenesis; (2) regolith processes; (3) bulk composition; (4) conditions of thermal and aqueous alteration (if any); ( 5 ) relationships to planets, comets, meteorites (via isotopic analyses, including 0); (6) abundance of water; (7) abundance of organics; (8) history of volatile mobility; and (9) presence and origin of presolar and/or interstellar material. Therefore, current technology allows even the tiniest samples to provide major breakthroughs in understanding the origin and com- positional evolution of the solar system. Fortunately, further advances in sensitivity and accuracy of laboratory analytical techniques can be expected to enhance the science value of nano- to microgram-sized samples further. This factor highlights a key advantage of sample returns-that the most advanced analysis techniques can always be applied in the laboratory and that a well-preserved reservoir of samples remain available for future investigations. Acknowledgements-Many investigators shared details of their painstaking analyses and offered critical advice on sections of the manuscript. We thank in particular Andy Davis, Laurie Leshin, Thinus Cloete, Simon Clemett, Larry Nittler, Ronny Bemhard, Fred HOrz, Paul Buchanan, David Mittlefehldt, and Hajime Yano. John Bradley and George Flynn provided thorough reviews of the entire manuscript. Part of this paper was written while M. E. Z. was a visiting scienlist at the Mineralogical Institute of the University of Tokyo, and at the Institute for Space and Astronautical Science; M. E. 2. is grateful to Masamichi Miyamoto and Akira Fujiwara for the opportunity to work there. Editorial handling: S. A. Sandford REFERENCES ALONSO-AZARATE J . , BOYCE A. J., BOTTRELL S. H., MACAULAY C. I., RODAS M , FALLICK A. E. A N D MAS J . R. (1999) Development and use of in situ laser sulfur isotope analyses for pyrite-anhydrite geothermometry: An example from the pyrite deposits of the Cameros Basin, NE Spain. Geochim. Cosmochim. Acta 63,509-5 13 ANDERS E. (1991) Organic matter in meteorites and comets' Possible origins. Space Sci. Rev. 56, 157--166. ANDERS E. A N D ZINNER E. (1993) Interstellar grains in primitive meteorites: Diamond, silicon carbide and graphite. Meteoritics 28,490-5 14. ARNDT P., BOHSUNG J., MAETZ M. A N D JESSBERGER E. K . (1996) The elemental abundances in interplanetary dust particles Meteorrt. Planet. Sci. 31,817-833. Fe oxidation states in interplanetary dust particles and matrix fragments of primitive chondrites (abstract). Lunar Planet. Scr. 26,67-68. BARRETT R. A,, ZOLENSKY M. E., M O M F., LINDSTROM D. J. A N D GIBSON E. K. (1992) Suitability of silica aerogel as a capture medium for interplanetary dust. Proc. Lunar Planet. Sci. Conf: 19th, 203-212. BASSETT W. A. AND BROWN G. E., JR. (1990) Synchrotron radiation: Applications in the Earth Sciences. In Annual Revrews of Earth and Planetary Science (eds. G. Wetherill, A. Albee and F. Stehli), pp. 3 8 7 4 7 . Annual Reviews Inc., Palo Alto, California, USA. BENCE A. E. A N D PAPIKE J. J. (1972) Pyroxenes as recorders of lunar basalt petrogenesis: Chemical trends due to crystal-liquid interaction Proc. Lunar Sci. ConJ 3rd, 431-469. BINNING G. A N D ROHRER H. (1987) Scanning Tunneling Microscopy from Birth to Adolescence. Rev. Mod. Phys. 59,615-635. BOGARD D. D. A N D GARRISON D. H. (1995) 39Ar-40Ar age of the lbitira eucrite and constraints on the time of pyroxene equilibration. Geochim. Cosmochrm. Acta 5 9 , 4 3 1 7 4 3 2 2 . BRADLEY J . P. (1994) Nanometer-scale mineralogy and petrography of fine- grained aggregates in anhydrous interplanetary dust particles. Geochirn. Cosmochrm. Acta 58,2123-21 34. BRADLEY J . P., BROWNLEE D. E. A N D FRAUNDORF P. (1984) Discovery of nuclear tracks in interplanetary dust Science 226, 1432-1434. BRADLEY J . P., GERMANI M. S. A N D BROWNLEE D. E. (1989) Automated thin-film analyses of anhydrous interplanetary dust particles in the analytical electron microscope. .Earth Planet. Sci. Lett. 93, 1-1 3 . BRADLEY J. P., HUMECKI H. J . AND GERMANI M. S. (1992) Combined infrared and analytical electron microscope studies in interplanetary dust particles. Appl. J. 3 9 4 , 6 4 3 4 5 1 BRADLEY J. P., KELLER L. P., BROWNLEE D. E. AND THOMAS K. L. (1996) Reflectance spectroscopy of interplanetary dust particles. Meteorit. Planet. Scr. 3 1 , 3 9 4 4 0 2 . BEARLEY A. A N D JONES R. (1998) Chondritic meteorites. In Planetary Marerrals (ed. J . J . Papike), pp. 3-1 to 3-298. Mineral. SOC. America, Washington, D.C., USA. BAJT S., FLY" G. J , SUTTON S R. AND KLOCK W. (1995) Comparison Of Small is beautiful: The analysis o f nanogram-sized astrornaterials 27 BRIGGS M. H. A N D M A M I K U N I A N G. (1963) Organic constituents of the carbonaceous chondrites. Space Sci. Rev. I, 6 4 7 4 8 2 . BROWNING L., MCSWEEN H. Y., JR. ANDZOLENSKY M. E. (1996) Correlated alteration effects in CM carbonaceous chondrites. Geochim. Cosmochrm. Acta 60,2621-2633. BROWNLEE D. /rr~/,. (1997) The Stardust mission: Returning comet samples to Earth (ahstract). Meteorit. Planet. Sci. 32 (Suppl.), A22. RSVP (BASALTIC VOLCANISM STUDY PROJECT) (1981) Basaltic Volcanism on the Terrestrial Planets. Pergamon, New York, New York, USA. 1286 pp. BURNETT D. S. A N D WOOLUM D. S. (1983) In situ trace element micro- analysis. I n Annual Reviews of Earth and Planetary Science (eds. G. Wetherill, A. Albee and F. Stehli), pp. 329-358. Annual Reviews Inc., Palo Alto, California, USA. BURNHAM N . A. AND COLTON R. J . (1993) Force microscopy. In Scanning Tunneling Microscopy and Spectroscopy (ed. D. A. Bonnell), p. 191. VCH Publishers, New York, New York, USA. CARR R. H , WRIGHT 1. P, JONES A. W. A N D PlLLlNGER c. T. (1986) Measurement of carbon stable isotopes at the nanomole level: A static mass spectrometer and sample preparation technique. J . Phys. Ec Sci. Instrum 19,798. CLARK B. C., MASON L. W. A N D KISSEL J . (1987) Systematics Of the "Cl ION" and other light-element particle populations in comet P/Halley. Astron. Astrophys. 187,779-784. CLAYTON R. N. (1993) Oxygen isotopes in meteorites. In Annual Review of Earth and Planetary Science (eds. G. W. Wetherill, A. L. Albee and K. C Burke), pp. 1 15-149. Annual Reviews Inc., Palo Alto, California, USA. CLEMETT S. J , M A E C H L I N G C . R., ZARE R. N . , SWAN P. D. A N D WALKER R M (1993) Identification of complex aromatic molecules in individual interplanetary dust particles. Science 262,721-723. CLOETE M., HART R. J., SCHMIDT H. K., DEMANET C., SANKAR V., MARE L. A N D D R U R Y M. (1998) Crystallographic and magnetite particles in shocked quartz, Vredefort, South Africa (abstract). Int. Mineral. Assoc. Annual Meet. 17th, A21. CLOETE M., HART R. J., S C H M I D H. K., DRURY M., DEMANET C. M. A N D V I J A Y A SANKAR K. (1999) Characterization of magnetite particles in shocked quartz by means of electron and magnetic force microscopy: Vredefort, South Africa. Contrib. Mineral. Petrol,, in press. (1997) The porosity and permeability of chondritic meteorites and interplanetary dust particles. Meteorrt. Planet. Sci. 32,509-51 5 . CRONIN J. R., PIZZARELLO S. A N D CRUIKSHANK D. P. (1988) Organic matter in carbonaceous chondrites, planetary satellites, asteroids and comets. I n Meteorites and the Early Solar System (eds. J. F. Kerridge and M. S Matthews), pp. 819-857. Univ. Arizona Press, Tucson, Arizona, USA. CROZAZ G. A N D MCKAY G . A. (1989) Minor and major element microdis- tributions in Angra dos Reis and LEW 86010: Similarities and differences (abstract) Lunar Planet. Sci. 20,208-209. DIXON J . R. A N D PAPIKE J. J . (1975) Petrology of anorthosites from the Descartes region of the Moon: Apollo 16. Proc. Lunar Science Con! DONG H., HALL C . M , HALLIDAY A N. A N D PEACOR D. R. (1997) Laser 40Ar-39Ar dating of microgram-size illite samples and implications for thin section dating. Geochrm. Cosmochim. Acta 61,3803-3808. DRAKE M. J., NEWSOM H. E. A N D CAPOBIANCO C. J . (1989) V, Cr, and Mn i n the Earth, Moon, EPB and SPB and the origin of the Moon: Experimental studies Geochrm. Cosmochrm. Acta 53,2101-21 11. DUBESSY J., AUDEOULD D., WlLKlNS R. AND KOSZTOLYANYI C. (1982) The use of the Raman microprobe MOLE in the determination of the electrolytes dissolved in the aqueous phase of fluid inclusions. Chem. Geol. 37,137-50 EGERTON R. F. (1996) Electron Energy-Loss Spectroscopy In The Electron Microscope. Plenum Press, New York, New York, USA. 479 pp. EL GORESY A., TAYLOR L. A A N D RAMDOHR P. (1972) Fra Mauro crystalline rocks: Mineralogy, geochemistry, and subsolidus reduction of opaque minerals. Proc. Lunar Science Con! 3rd, 333-349. EPSTEIN S. A N D TAYLOR H P. (1974) D/H and l80/I6O ratios of H 2 0 in the "rusty" breccia 66095 and the origin of "lunar water". Proc. Lunar Planet. Scr. Con! Sth, 1839-1854. ESAT T. M. A N D TAYLOR S. R. (1987) Mg isotopic composition of some interplanetary dust particles (abstract). Lunar P lanef. Sci. 18,269-270. FlALlN M., REMY H., RICHARD C. AND WAGNER C. (1999) Trace element analysis with the electron microprobe: New data and perspectives. Am. Mineral. 84, 7&77. FLY" G. J. A N D SUTTON S. (1990) Synchrotron x-ray fluorescence analysis of stratospheric cosmic dust. New results for chondritic and low-nickel particles. Proc. Lunar Planet. Scr. Con! ZOth, 335-342. C O R R I G A N C. C . , ZOLENSKY M. E., DAHL J., LONG M , WEIR J. AND SAPP C. 6th. 263-291. FLY" G. J. A N D SUTTON S. R. (1991) Cosmic dust particle densities: Evidence for two populations of stony micrometeorites. Proc. Lunar Planet. Scr. ConJ21st, 541-547. FLY" G. J., FRALJNDORF P., SHIRCK J . AND WALKER R. M. (1978) Chemical and structural studies of "Brownlee" particles. Proc. Lunar Planet. Sci. Con! 9th, 1187-1208. FLY" G. J., KELLER L. P., JACOBSEN C. A N D WlRlCK S . (1998a) Carbon and potassium mapping and carbon bonding state measurements on interplanetary dust (abstract). Meteorit. Planet. Sci. 33 (Suppl.), A50. FLY" G. J., KELLER L. P., JACOBSEN C. AND WIRICK S. (1998b) Carbon mapping and carbon XANES bonding state measurements on interplanetary dust particles (abstract). Lunar P lanet. Scr. 29, # 1 159, Lunar and Planetary Institute, Houston, Texas, USA (CD-ROM). FLY" G. J., KELLER L. P., JACOBSEN C. AND WlRlCK S. (1999) Elemental mapping and X-ray absorption near-edge structure (XANES) spectroscopy with a scanning transmission X-ray microscope (abstract). Meteorrt. Planet. Sci. 34 (Suppl.), A36. FOLAND K . A,, HUBACHER F. A. AND AREHART G. B. (1992) 40Ar-39Ar dating of very fine-grained samples; an encapsulated-vial procedure to overcome the problem of 39Ar recoil loss. Chem. Geol. 102,269-276. FRAUNDORF P., BROWNLEE D. E. A N D WALKER R. M. (1982) Laboratory studies of interplanetary dust. In Comets (ed. L. L. Wilkening), pp. 383-409. Univ. Arizona Press, Tucson, Arizona, USA FREIDMAN I., GLEASON J . D. AND HARDCASTLE K. G. (1970) Water, hydrogen, deuterium, carbon, and C13 content of selected lunar material. Proc. Apollo I 1 Lunar Sci. Con! 2nd, 1 103. GARVIE L. A. J. A N D BUSECK P. R. (1998) Ratios of ferrous to ferric iron from nanometre-sized areas in minerals. Nature 396,667-670. GARVIE L. A. J., CRAVEN A. J . AND BRYDSON R. (1994) Use of electron- energy loss near-edge fine structure in the study of minerals. Am. Mineral. 79,411-425. GOSWAMI J. N., SAHIJPAL S., KEHM K., HOHENBERG C. M., SWINDLE T. A N D GROSSMAN J. N. (1998) In situ determination of iodine content and iodine-xenon systematics in silicates and troilite phases in chondrules from the LL3 chondrite Semarkona. Meteorit. Planet. Sci. GRESHAKE A. (1997) The primitive matrix components of the unique carbonaceous chondrite Acfer 094: A TEM study. Geochim. Cosmo- chim. Acta 6 1 , 4 3 7 4 5 2 . GUNTHER D., LONGERICH H. P., FORSYTHE L. A N D JACKSON S. E. (1995) Laser ablation microprobe-inductively coupled plasma-mass spectrometry. Am. Lab. June, 24-29. GRUN E. ET AL. (1993) Discovery of jovian dust streams and interstellar grains by the Ulysses spacecraft. Nature 3 6 2 , 2 8 4 3 0 HAEFLIGER 0. P. AND ZENOBI R. (1998) New Sample Preparation for Quantitative Laser Desorption Mass Spectrometry and Optical Spectro- scopy. Rev. Scr. Instrum. 69, 1828-1 832. HAHN J. H., ZENOBI R., BADA J. L. AND ZARE R. N. (1988) Application of the two-step laser mass spectrometry to cosmogeochemistry. Science HALLIDAY A. N. / f l ' A / > . (1998) Applications of multiple collector-ICPMS to cosmochemistry, geochemistry, and paleooceanography. Geochim. Cosmochrm. Acta 62,919-940. HARLOW G. E., NEHRU C. E., PRINZ M., TAYLOR G. J . A N D KEIL K. (1979) Pyroxenes in Serra de Mage: Cooling history in comparison with Moama and Moore County. Earth Planet. Scr. Lett. 43, 173-181. HAYATSU R. AND ANDERS E. (1981) Organic compounds in meteorites and their origins. Topics in Current Chemistry 99, 1-37. HOFER H. E., B U Y G P. A N D OBERHANSLI R. (1996) The determination of the oxidation state of iron in synthetic garnets by x-ray spectroscopy with the electron microprobe. Physics and Chemistry of Minerals 23, 446. HOPPE P., AMARl S . , ZlNNER E., IRELAND T. A N D LEWIS R. (1993) Carbon, nitrogen, magnesium, silicon, and titanium isotopic compositions of single interstellar silicon carbide grains from the Murchison carbonaceous chondrite. Astrophys. J . 430,870-890. HOPPE P., STREBEL R., EBERHARDT P., AMARI S . AND LEWIS R. S. (1996a) Small S i c grains and a nitride grain of circumstellar origin from the Murchison meteorite: Implications for stellar evolution and nucleo- synthesis. Geochrm. Cosmochim. Acta 60,883-907. HOPPE P., STREBEL R., EBERHARDT P., AMARI S. A N D LEWIS R. S . (1996b) Type 11 supernova matter in a silicon carbide grain from the Murchison meteorite. Science 272, 1314-1316. HORZ F., ZOLENSKY M., CRESS G., BERNHARD R. P., SEE T. H., WARREN J. H , BROWNLEE D. E. A N D TSOU P. (1998) ODC: Aerogel Particle Capture During 18 Months Exposure on MIR (abstract). Lunar Planet. Sci. 29, #1773, The Lunar and Planetary Institute, Houston, Texas, USA (CD-ROM). 33,527-534. 239, 1523-1525. 28 Zolensky et al. I k I A X . A N D BUSECK P. R. (1998) Unusual forms of magnetite in the Orgueil carbonaceous chondrite (abstract). Meteorrt. Planet. Sci. 33 (Suppl.), A2 I5-A220. ISAS (INSTITUTE FOR SPACE A N D ASTRONAUTICAL SCIENCE) (1996) Muses-C (largely in Japanese). ISAS, Institute for Space and Astronautical Science, Japan. 464 pp. I V A N O V A. V . , ZOLENSKY M. E., SAITO A,, OHSUMI K., MACPHERSON G. J., YANG S. V., KONONKOVA N . N. A N D MIKOUCHI T. (2000) Florenskyite, FeTiP. a new phosphide from the Kaidun meteorite. Am. Mineral, in press. KNOCIiEL A. (1998) The use of lead-glass capillaries for micro-focusing of highly-energetic (0-60keV) synchrotron radiation. J . Anal. At. Spectrom. 14, 117-138. J A R O S E W I C I I E., C L A R K E R. S., J R . A N D BARROWS J N. (1987) Allende Meteorite Reference Sample. Contributions to Earth Science #27, Smithsonian Institution, Washington, D.C., USA. 132 pp. JESSBERGER E. K . (1991a) Discussion: New techniques on the horizon for the analysis of the inorganic cometry components. Space Sci. Rev. 56, JESSBERGER E. K. (1991b) Discussion. What new techniques are needed for the analysis of the organic cometary components? Space Scr. Rev. 56, JESSBERGER E. K. A N D WALLENWEIN R. (1986) PlXE characterization of stratospheric micrometeorites. .4dv. Space Res. 6, 5-8. JONES R. H. (1992) On the relationship between isolated and chondrule olivine grains in the carbonaceous chondrite ALHA77307. Geochim. Cosmochim. Acta 5 6 , 4 6 7 4 8 2 , JONES R. H. A N D DANIELSON L. R. (1997) A chondrule origin for dusty relict olivine in unequilibrated chondrites. Meteorrt. Planet. Sci. 32,753-760. K E L L E Y S. P (1995) Ar-Ar dating by laser microprobe. In Microprobe Techniques in the Earth Sciences (eds. P. J . Potts, J . S. W. Bowles, S. J. B. Reed and M. R. Cave), pp. 327--358. Chapman and Hall, New York, New York, USA. KISSEL J . A N D K R U E G E R F. R . (1987) The organic component in dust from comet Halley as measured by the PUMA mass spectrometer on board Vega I . Nature 326.755-760. K O V A L E N K O L. J . , PHlLlPPOZ J-M., BUCENELL J . R., ZENOBI R. A N D ZARE R . N. (1991) Organic chemical analysis on a microscopic scale using two-step laser desorption/laser ionization mass spectrometry. Space Sci. Rev. 56, 191-196. LESHIN I,. A,, RUBIN A. E. AND MCKEEGAN K D. (1997) The oxygen isotopic composition of olivine and pyroxene from CI chondrites. Geochrm. Cosmochrm Acta 61,835-845. 1,ESHIN L. A . MCKEEGAN K . D., CARPENTER P. K . AND HARVEY R. P. (1998) Oxygen isotopic constraints on the genesis of carbonates from Martian meteorite ALH84001. Geochrm. Cosmochrm. Acta 62,3-13. LINDSTROM D. J., ZOLENSKY M. E A N D MARTINEZ R. R. (1990) Composi- tional variations in cosmic dust-sized pieces of Murchison matrix (abstract). Lunar Planet Scr. 21,698-699. MCKAY G . (1989) Analysis of rare earth elements by electron microprobe. In Microbeam Analysis-1989 (ed P E. Russell), pp. 549-553. San Francisco Press, California, US.4. MCKEEGAN K. D. (1987) Oxygen isotopes in refractory stratospheric dust particles: Proof of extraterrestrial origin. Science 237, 1468-1471. MCKEEGAN K. D., WALKER R. M. A N D ZINNER E. (1985) Ion microprobe isotopic measurements of individual interplanetary dust particles. Geochim. Cosmochim. Acta 49, 1971-1987. MCMILLAN P. F. (1989) Raman spectroscopy in mineralogy and geochemistry. In Annual Revreivs of Ear/h and Planetary Science (eds. G . Wetherill, A. Albee and F. Stehli), pp 255-283. Annual Reviews Inc., Palo Alto, California, USA CROZAZ G . (1996) QUE94201 shergottite: Crystallization of a martian basaltic magma. Geochim. Cosmochim. Acta 60,45634569. M I L L E R M. F. A N D PlLLlNGER C . T (1997) An appraisal of stepped heating release of fluid inclusion COz for isotopic analysis: A preliminary to 6I3C characterization of carbonaceous vesicles at the nanomole level. Geochim. Cosmochrm. Ac/a 61,193-205 MITTLEFEHLDT D W . MCCOY T. J., GOODRICII C . A. A N D KRACHER A. ( I 998) Non-chondritic meteorites from asteroidal bodies. In P1anetary Materials (ed. J . J . Papike). pp 4-1 to 4-195. Mineral. SOC. America, Washington, D.C., USA MUNRO C. H., W I T K O W S K I R. E , BORMETT R. W., ASHER S. A. A N D ZOLENSKY M. E. (1996) IJV Raman microspcctroscopy of carbon-rich meteorites and interplanetary dust particles (abstract). ICORS, 1nt. Conf Ranian Spectroscopy ISth, 324. JANSSENS K., VINCZE L., v M A N S B., ADAMS F., HALLER M. A N D 227-23 1 . 233-237. MCSWEEN 11. Y., J R . EISENHOUR E. E., TAYLOR L. A,, WADHWA M. A N D MORI H. A N D TAKEDA H. (1981) Evolution of the Moore County pyroxenes as viewed by an analytical transmission electron microprobe (ATEM). Meteoritics 16,263-264. MULLIE F. A N D REISSE J . (1987) Org,anic matter in carbonaceous chondrites. Topics in Current Chemistry 139,83-117. MURAE T. (1997) Search of carbonaceous fluorescent matter in carbonaceous chondrites (abstract). ISAS Planet. Scr. Conf: 30th, 123-125. NAKAMURA T., ZOLENSKY M. E , HORZ F., TAKAOKA N. A N D NAGAO K. ( 1 997) Impact-induced loss of primordial noble gases from experi- mentally shocked Allende meteorite. NlPR Con( of Antarctic Meteorites 22nd, 135-136. NEWSOM H. E. A N D DRAKE M. J. (1982) The metal content of the Eucrite parent body: Constraints from the partitioning behavior of tungsten. Geochrm. Cosmochim. Acta 46,2483-2489. NICOLUSSI G. K., DAVIS A. M., PELLIN M. J., LEWIS R. S., CLAYTON R. N. A N D A M A R I S. (1997a) s-Process zirconium in presolar silicon carbide grains. Science 277, 1281-1283. NICOLUSSI G. K., PELLIN M. J , CALAWAY W. F., LEWIS R S , DAVIS A. M . , AMARI s. A N D CLAYTON R. N (1997b) kotopic analysis of calcium from extraterrestrial micrometer-sized S i c by laser desorption and resonance ionization mass spectroscopy. Anal. Chem. 69, 1 14@1146. NICOLUSSI G. K., PELLIN M . J., LEWIS R. S., DAVIS A. M.. AMARI S. A N D CLAYTON R. N. (1998) Molybdenum isotopic composition of individual presolar silicon carbide grains from the Murchison meteorite Geochim. Cosmochrm. Acta 62, 1093-1 104. NIER A. 0. A N D SCHLUTTER D. (1992) Extraction of helium from individual interplanetary dust particles by step-heating. Me/eorrircs 27, 16G173 NIER A. 0. A N D SCHLUTTER D. (199.3) The thermal history of interplanetary dust particles collected in the Earth's stratosphere. Meteorriics 28, NITTLER L R., ALEXANDER C. M., WANC J A N D GAO X . (1998) Meteoritic 675-281. oxide grain from supernova found. Nature 393,222. (1998) The influence of natural mineral coatings on feldspar weathering. Nature 395,588-591. O H S U M I K . A N D ZOLENSKY M. E. (1998) X-ray studies on interplanetary dust particles L2005 AE6 and 1,2005 AG I7 by synchrotron radiation (abstract). In/. Mineral. Asso. Meet. 17, A19. OTT U . A N D BEGEMANN F. (1985) Are all "martian" meteorites from Mars? Nature 317,509-512. PAPIKE J . J . (1996) Pyroxene as a recorder of cummulate formational processes i n asteroids, Moon, Mars, Earth: Reading the record with the ion microprobe. Am. Mineral. 81.525-544. PAPIKE J . J. (1998) Comparative planetary mineralogy: Chemistry of melt- derived pyroxene, feldspar, and olivine. In Planetary Materials (ed. J. J . Papike), pp. 7-1 to 7-1 1. Mineral. Soc. America, Washington, D.C., USA. PAPIKE J. J . A N D BENCE A E. (1972) Apollo 14 inverse pigeonites: Possible samples of lunar plutonic rocks. Earth Planet. Sci. Lett. 14, 176.182. P A P I K E J. J., BENCE A. E., BROWN G . E., PREWITT C. .r A N D w u C. H (1971) Apollo 12 clinopyroxenes: Exsolution and epitaxy. Earth Planet. Sci. Lett. 10,307-3 15. PASTERIS J. D. A N D C H O U I-M. (1998) Fluid-deposited graphitic inclusions in quartz: Comparison between KTB (German Continental Deep- Drilling) core samples and artificially reequilibrated natural inclusions. Geochrm. Cosmochim. Acta 62, 109-122. PATERSON B. A., RICIPUTI L. R. A N D MCSWEEN H. Y., J R . (1997) A comparison of sulfur isotope ratio measurement using two ion microprobe techniques and application to analysis of troilite in ordinary chondrites. Geochim. Cosmochint. Acta 61,601-609. PETAEV M. I . A N D BREARLEY A. J . (1994) Exsolution of ferromagnesian olivine of the Divnoe meteorite. 5'cience 266, 1545-1 547. PETERSON E., HOW F. A N D CHANG S. (1997) Modification of amino acids at shock pressures of 3 5 to 32 GPa Geochim. Cosmochrm. Acia 61, PlETERS c. M., FISCHER E. M., RODE 0. A N D BASU A (1993) Optical effects of space weathering: The role of the finest fraction. J. Geophys. Res. E. PIETERS C. M., /rf AL. (1997) Aladdin: Phobos-Deimos sample Return (abstract). Lunar Plane/. Sci. 28, I 1 11-1 112. POE B., SEIFERT F , SHARP T. A N D W U Z. (1997) ELNES spectroscopy of mixed Si coordination minerals Physics and Chemrstty qf Mrnerals 24, 4 7 7 4 8 7 . REDDY s. M., K E L L E Y S. P. A N D M A G E N N I S L. (1997) A microstructural and argon laserprobe study of shear zone development at the western margin of the Nanga Parbat-Haramosh Massif, western Himalaya. C'ontrib. Mineral Petrol. 128,16-29 NUGENT M. A., BRANTLEY s. L, I'ANTANO C G. A N D M A U R I C E P. A. 3937-3950. 98,20 81 7-20 824. Small is beautiful: T h e analysis o f nanogram-sized astromaterials 29 R E F F N E R J . , C A R R G L., WILLIAMS G P , SUTTON s. A N D HEMLEY R. J. ( I 994) Infrared spectroscopy at the NSLS. Synchrotron Radration News R E U T E R K., B E R N I I A R D T .I, WEDLER H , SCHARDT J., STARKE U . A N D 7,30-37 ~ I E I N Z K ( I 997) Holographic image reconstruction from electron dilTractioii intensities of ordered superstructures. Phys. Rev. Lett. 79, 48 I 8 4 8 2 I R I N D B Y A,, ENGSTROM P. A N D J A N S S E N S K. (1997) The use of a scanning x-ray microprobe for simultaneous XRF/XRD studies of fly-ash particles. J . Synchrotron Radiation 4,228-235. ROEDDER E. ( 1 984) Fluid Inclusrons. Mineralogical Society of America, Washington, D.C., USA. 644 pp. ROST D., STEPHAN T. A N D JESSBERGER E. K. (1999) Surface analysis Of stratospheric dust particles. Meteorit. Planet. Sci. 34,637-646. R O W E M. W. (1970) Evidence for decay of extinct Pu244 and 1291 in the Kapoeta meteorite Geochim. Cosmochim. Acta 34, 1019-1025. SANDFORD S . A. (1986) Solar flare track densities in interplanetary dust particles: The determination of an asteroidal versus cometary source of the Zodiacal dust cloud lcarus 68,377-394. SANDFORD S. A. A N D WALKER R. M. (1985) Laboratory infrared transmission spectra of individual interplanetary dust particles from 2 5 to 25 microns. Astrophys. J 291, 838-851 S E i r z 1 . C., PAsrERis J D. A N D WOPENKA B. (1987) Characterization of CO-CH4-H20 fluid inclusions by microthermomeiry and laser Raman microprobe spectroscopy: Inferences for clathrate and fluid equilibria. Geochini. Cosmochim. Acta 51, 1651-1664. SMITII P E , , EVENSEN N M. A N D YORK D. (1993) First successful 40Ar-39Ar dating of glauconites: Argon recoil i n single grains of cryptocrystalline material Geology 2 1 , 4 1 4 4 . SOBOl.EV V. N . , MCCAMMON C. A , TAYLOR L. A,, SNYDER G. A. A N D SOBOLEV N. V (1999) Precise Mossbauer milliprobe determination of fcrric iron 111 rock-forming minerals and limitations of electron micro- probe analysis. Am. Mineral. 84,78-85. SPACE STUDlES BOARD (1998) Evaluating the Biological Potential in Samples Returned ,from Planetary Satellites and Small Solar System Bodies. National Academy Press, Washington, D C., USA. 100 pp. STADERMANN I:. J . , W A L K E R R . M. A N D ZINNER E. (1990) Stratospheric dust collection. An isotopic survey of terrestrial and cosmic particles (abstract). Lunar Planet Scr. 21, 1190-1 191 S'I'ADERMANN I: J , WAI.KER R M A N D ZINNER E. (1999) NanoSIMS: The next generation ion probe for the microanalysis of extraterrestrial material (abstract). Meteorit. Planet. Sci. 34 (Suppl.), A l l I-Al12. STEPHAN T., JESSBERGER E . K., KLOCK W., RULLE H. A N D ZEHNPFENNING 1 . (1994) TOF-SIMS analysis of interplanetary dust. Earth Planet. Sci. Let/. 1 2 8 , 4 5 3 4 6 7 . STEVENS KALCEFF M. A,, PHILLIPS M. R., MOON A. R. A N D SMALLWOOD A. ( 1 997) Cathdoltiminescence microanalysis of natural hydrated amorphous SiO,; opal. Physics and Chemistry of Minerals 24, 131-138. SUTTON S , FLY" G J . , R I V E R S M., ENG P. A N D NEWVILLE M. (1999) Trace element analyses of L2011 cluster particles with the new x-ray microprobe at the Advanced Photon Source (abstract). Lunar Planet. Sci. 30, #1656, I.tinar and Planetary Institute, Houston, Texas, USA (CD-ROM). TAKEDA H., MIYAMOTO M , IS1111 T. A N D LOFGREN G . E. (1975) Relative cooling rates of mare basalts at the Apollo 12 and 15 sites as estimated from pyroxene exsolution data Proc. Lunar Sci. ConJ:6th, 987-996. TAKEDA H., M I Y A M O T O M , ISHI1 T. A N D R E I D A. M. (1976) Characterization of crust formation on a parent body of achondrites and the Moon by pyroxene crystallography and chemistry. Proc. Lunar Sci. C'onf 7th, 3535-3548. TAYLOR R. P., JACKSON S. E., LONGERICH H P. A N D WEBSTER J . D. (1997) In situ trace-element analysis of individual silicate melt inclusions by laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS). Geochrm. Cosmochim Acta 61,2559-2567. TPNC H. H., DOVE P. M., O R M E C. A. A N D DE YOREO J. J . (1998) Thermo- dynamics of calcite growth: Baseline for understanding biomineral formation. Science 282, 724-727 TIIOMAS K.L. / T A / , . (1995) An asteroidal breccia. The anatomy of a cluster IDP Geochim. Cosmochim Acta 59,2797-2816. Transmission electron microscope texture and crystal chemistry of coexisting ortho- and clinopyroxene in the Antarctic ureilite Frontier Mountain 90054 Implications for thermal history. Meteorit. Planet. Sci. 32, 671-678. TURNER G . (1991) Can one date a comet and its constituents? A note. Space Sci. Rev. 56. 139-140 TRIBAUDINO M., FlORETTl A. M., MARTIGNAGO F . A N D MOLIN G. (1997) VILLA I . (1997) Direct determination of 39Ar recoil distance. Geochim. Cosmochim. Acta 61,689-691. WARREN J. L. A N D ZOLENSKY M E. (1994) Collection and curation of interplanetary dust particles recovered from the stratosphere by NASA. In Analysis of lnterplanetary Dust (eds. M. Zolensky, T. Wilson, F. Rietmeijer and G. Flynn), pp. 245-253 American Institute of Physics, Woodbury, New York, USA. WASSON J T. (1985) Meteorites: Their Record of Early Solar-System History. Freeman, New York, New York, USA. 267 pp. WASSON J . T., BOYNTON W. V., CHOU C-L. A N D BAEDECKER P. A. (1975) Compositional evidence regarding the influx of interplanetary materials onto the lunar surface. The Moon 13,121-141. WAYCHUNAS G. A. (1987) Synchrotron radiation XANES spectroscopy of Ti in minerals: Effects of Ti bonding distances, Ti valence and site geometry on absorption edge structure. Am. Mineral. 72,89-101. WESCHLER L. (1995) Mr. Wilson's Cabinet of Wonder. Vintage Books, New York, New York, USA. 163 pp. WlENs R. C., HUSS G. R. A N D BURNETT D. S. (1999) The solar oxygen- isotopic composition. Predictions and implications for solar nebula processes. Meteorit. Planet. Sci. 34,99-107. WIRTH R. (1997) Water in minerals detectable by electron energy-loss spectroscopy EELS. Physics and Chemistry of Minerals 24,561-568. WOPENKA B. (1988) Raman observations of individual interplanetary dust particles. Earth Planet. Scr. Lett. 88,221-231. WRIGHT I . P. A N D PILLINGER C T. (1989) Carbon isotopic analysis of small samples by the use of stepped-heating extraction and static mass spectrometer. In New Frontiers in Stable Isotope Research: Laser Probes, lon Probes, and Small-sample Analysis (eds. W. C Shanks and R. E. Criss). DD. 9-34. U S. Geological Survev Bulletin 1890. Washington, D C , USA I WRIGHT I P . YATES P , HUTCHISON R AND PILLINGER c T (19971 The content and stable isotopic composition of carbon in individual micro- meteorites from Greenland and Antarctica. Meteorit. Planet. Sci. 3 2 , 7 9 4 9 . YACOBI B. G. AND HOLT D. B (1990) Cathodoluminescence Microscopy of Inorganic Solrds. Plenum Press, New York, New York, USA. 292 pp. YANO H., MORISHIGE K., DESHPANDE S . P , MAEKAWA Y., K I B E S . , NEISH M. J . A N D TAYLOR E. A. (1998) Origins of micro-craters on the SFU spacecraft derived from elemental and morphological analyses (abstract). 32nd COSPAR Meeting 7, 12-19. YOUNG E. D. A N D RUSSELL S. S. (1998) Oxygen reservoirs in the early solar nebula inferred from Allende CAI. Science 282,452-455 YOUNG E. D., COUTTS D. W. A N D KAPITAN D. (1998) UV laser ablation and irm-GCMS microanalysis of i 8 0 / ' 6 0 and i 7 0 / i 6 0 with application to a calcium-aluminum-rich inclusion from the Allende meteorite. Geochim. Cosmochim. Acta 62,3161-3168. ZENOBI R., PHILIPPOZ J-M., BUSECK P. R. AND ZARE R. N. (1989) Spatially resolved organic analysis of the Allende meteorite. Science 246, 1026. ZINNER E. (1991) Cometary and interstellar dust grains: Analysis by ion microprobe mass spectrometry and other techniques. Space Sci. Rev. 56, ZINNER E. (1997) In Astrophysical lmplications of the Laboratory Study of Presolar Materials (eds. T. Bernatowicz and E. Zinner), pp. 3-26. AIP Conf. Proc. 402, AIP, Woodbury, New York, USA. ZINNER E., MCKEEGAN K. D. A N D WALKER R. M. (1983) Laboratory mea- surements of D/H ratios in interplanetary dust. Nature 305, 119-121. ZOLENSKY M. E. AND BARRETT R. (1994) Chondritic interplanetary dust particles: Basing their sources on olivine and pyroxene compositions. Meteoritics 2 9 , 6 1 6 4 2 0 . ZOLENSKY M. E. A N D BODNAR R. J. (1982) Identification of tluid inclusion daughter minerals using Gandolfi X-ray techniques. Am. Mineral. 67, 137-141. ZOLENSKY M. E. A N D LINDSTROM D. J . (1992) Mineralogy of 12 large "chondritic" interplanetary dust particles. Proc. Lunar Planet. Sci. ConJ ZOLENSKY M. E. A N D PACES J . (1986) Alteration of tephra in glacial ice by "unfrozen water". GSA Abstracts with Programs 18,801. ZOLENSKY M. E. AND THOMAS K (1995) Iron- and iron-nickel sulfides in chondritic interplanetary dust particles. Geochim. Cosmochrm. Acta 59, 47074712. Analysis of lnterplanetary Dust. American Institute of Physics, Woodbury, New York, USA. 357 pp. ZOLENSKY M. E. 117' A/,. (1999) Fluid Inclusion-Bearing Halite And Solar Gases In The Monahans 1998 H5 Chondrite (abstract). Lunar Planet. Sci. 30, #1280, Lunar and Planetary Institute, Houston, Texas, USA (CD-ROM). 147-1 56. 19th, 161-169. ZOLENSKY M. E., WILSON T L., RlETMEllER F. AND FLY" G., EDS. (1994)