(Received 12 December 2008; revision accepted 30 September 2010)

Transcription

1 Meteoritics & Planetary Science 46, Nr 1, (2011) doi: /j x Disturbance of isotope systematics during experimental shock and thermal metamorphism of a lunar basalt with implications for Martian meteorite chronology Amy M. GAFFNEY 1*, Lars E. BORG 1, Yemane ASMEROM 2, Charles K. SHEARER 3, and Paul V. BURGER 3 1 Lawrence Livermore National Laboratory, Physical and Life Sciences, Institute of Geophysics and Planetary Physics, Livermore, California 94550, USA 2 Department of Earth and Planetary Sciences, University of New Mexico, Albuquerque, New Mexico 87131, USA 3 Institute of Meteoritics, University of New Mexico, Albuquerque, New Mexico 87131, USA * Corresponding author. gaffney1@llnl.gov (Received 12 December 2008; revision accepted 30 September 2010) Abstract To better determine the effects of impact-related processes on radiometric chronometers in meteorites, we undertook an isotopic study of experimentally shocked and heated samples of lunar basalt Shock experiments at 55 GPa were completed on one subsample, and a second subsample was heated in an evacuated quartz tube at 1000 C for 170 h. A third subsample was maintained as a control. Samarium-neodymium, Rb-Sr, 238 U- 206 Pb, and 206 Pb- 207 Pb isotopic analyses were completed on mineral fractions (leached and unleached), leached whole rocks, and complementary acid leachates. Disturbance in the shocked and heated samples was evaluated through comparison of their isochron diagrams with those of the control sample. The Sm-Nd isotope system was the least disturbed, the Rb-Sr isotope system was more disturbed, and the 238 U- 206 Pb and 206 Pb- 207 Pb isotope systems were the most disturbed by shock and annealing. Samples that experienced extended heating demonstrated greater isotopic disturbances than shocked samples. In some cases, the true crystallization age was preserved, and in others, age information was degraded or destroyed. In no case did the experiments generate isochrons that maintained linearity while being rotated or completely reset. Although our results show that neither experimental shock nor thermal metamorphism alone can account for the discordant ages represented by different isotope systems in some Martian meteorites, we postulate that shock metamorphism may render a meteorite more susceptible than its unshocked counterpart to subsequent disturbance during extended impact-related heating or aqueous alteration. The combination of these processes may result in the disparate chronometric information preserved in some meteorites. INTRODUCTION A principal goal of achondrite meteorite studies is to establish the geologic history of the meteorite s parent body. Meteorites from differentiated bodies such as Mars or the Moon potentially record information on the timing and duration of geologic processes, including planetary differentiation, volcanism, and hydrothermal activity. Isotopic analyses of meteorites are used to establish the chronology of events and constrain the compositional characteristics of the source from which an individual meteorite is derived. The most commonly used method for determining the crystallization age and initial isotopic composition of a meteorite involves measuring parent daughter radionuclide pairs, such as 147 Sm- 143 Nd or 87 Rb- 87 Sr, in various mineral fractions to produce an internal isochron. A requirement of the mineral isochron technique is that the isotope systematics of the meteorite have remained undisturbed since the time that the minerals crystallized from a melt. Other radiometric dating techniques such as 40 Ar- 39 Ar may record the time of crystallization, but are also important for dating subsequent thermal events related to impacts that may disturb the isotope systematics in a 35 Ó The Meteoritical Society, 2011.

2 36 A. M. Gaffney et al. meteorite and thus result in complete resetting of the chronometer. In the case of some Martian and lunar samples, the isotopic compositions of various mineral and wholerock fractions either fail to yield isochrons, or yield regression lines in different isotope systems from which calculated ages are discordant, indicating that these samples have experienced some disturbance since the time of crystallization (e.g., Lugmair et al. 1976; Papanastassiou and Wasserburg 1976; Shih et al. 1982; Chen and Wasserburg 1986; Borg et al. 1997). The discordant ages in Martian meteorites in particular have led to fundamentally contrasting interpretations of the timing of Martian magmatism (e.g., Bouvier et al. 2008; Nyquist et al. 2009). Among the shergottites, there are individual samples that yield internally well-defined isochrons with highly discordant ages. Specifically, Rb-Sr and Sm-Nd isotope systems yield concordant ages that have been interpreted to indicate relatively recent crystallization ( Ma; Shih et al. 1982; Borg et al. 2001; Morikawa et al. 2001; Nyquist et al. 2001a; Brandon et al. 2004; Symes et al. 2008; Nyquist et al. 2009), whereas the 206 Pb- 207 Pb isotope system has been interpreted to reflect crystallization at a relatively ancient time (4 Ga; Bouvier et al. 2005, 2008). Furthermore, many samples exhibit scatter of individual mineral fractions on internal isochron diagrams, providing clear evidence for postcrystallization disturbances (e.g., Chen and Wasserburg 1986; Borg et al. 1997; Shih et al. 2003). Thus, establishing the absolute chronology of the geologic history of Martian meteorites is hampered by disturbances occurring on the surface of Mars or Earth that modified or destroyed chronologic information in the sample. Deciphering the chronology of the Martian meteorites requires separating the effects of secondary disturbance from the isotopic record of primary crystallization. There are a number of processes that could potentially disturb isotope chronometers in the Martian meteorites. One process is impact metamorphism. This includes shock with durations of 1 s (Beck et al. 2005), accompanied by transient heating, as well as postshock heating of longer duration (days to years or longer). Impact-related shock and heating both affect target rocks in a large impact event. Other possible processes that can disturb chronometers are alteration (i.e., reactions that decompose the minerals to form new ones) and contamination (i.e., addition of extraneous components to the rock). On Mars, in contrast to the Moon, water may play a significant role in disturbing isotope chronometers via alteration or contamination on the parent body. Petrologic and geochemical evidence indicates that alteration and contamination affect many of the Martian meteorites (e.g., Treiman et al. 1993; Crozaz et al. 2003), whereas every meteorite experiences at least one impact event, related to the ejection of the meteorite from Mars. Shock pressures experienced by the Martian meteorites during the ejection event are estimated from 5 to 55 GPa (Nyquist et al. 2001b, and references therein; Fritz et al. 2005). The range and extent of isotopic disturbance that can result from impact metamorphism and the modification that this can cause to isotope chronometers are not well established. From studies on terrestrial meteorite impact sites, it is known that melting of target rock can reset isotope chronometers so that the time of the impact is recorded in this impact-related material (e.g., Sudbury: Davis 2008; Manicouagan: Hodych and Dunning 1992). Confidently dated materials include impact melt rocks, tektites, glass, suevite, and recrystallized minerals (summarized by Deutsch and Scha rer 1994; Jourdan et al. 2009). Only rarely does a target rock record the impact age in the absence of complete melting (e.g., Sudbury: Deutsch et al. 1989). However, terrestrial impact deposits are rarely ideal for investigating the specific isotopic effects of different shock-related processes, such as pure thermal metamorphism, or shock accompanied only by transient shock-related heating, because it is difficult to control for variables such as initial lithologic heterogeneity in the target rock, duration of thermal metamorphism, and hydrothermal or other alteration. Furthermore, there are few examples of terrestrial impacts in target lithologies that are compositionally analogous to shergottites (e.g., Lonar crater). Experimental studies provide an alternative approach for evaluating the isotopic effects of impact metamorphism in which it is possible to control many of the variables that are present in a natural setting. A preliminary experimental study on a lunar basalt found Rb loss as well as a minor degree of Sm-Nd isochron rotation in an experimentally heated sample (Nyquist et al. 1988, 1991). By contrast, no effect was observed in the Rb-Sr isotope systematics of another experimentally shocked sample (Nyquist et al. 1987). To expand this small database of experiments on basaltic materials and characterize the effects of impact metamorphism on Sm-Nd, Rb-Sr, U-Pb, and Pb-Pb chronometry, we have undertaken a study of experimentally shocked and heated basalts. We investigated two impact-related processes: (1) shock accompanied only by transient shock-related heating and (2) pure thermal metamorphism. A lunar basalt was selected for this study because this material is sufficiently old that it contains significant and highly variable amounts of radiogenic Sr, Nd, and Pb in the mineral fractions, and is essentially free of alteration.

3 Isotopic disturbance from experimental shock and heat 37 The particular sample used in this study, Apollo basalt 10017, is petrographically, geochemically, and chronologically well characterized (e.g., Beaty and Albee 1978; Gaffney et al. 2007a). One piece of the sample was used as an unshocked and unheated control for the experiment. A second piece was heated in a manner to simulate the effects of postimpact thermal metamorphism. A third sample of was shocked at 55 GPa in the course of another experiment (Nyquist et al. 1987), and we used this sample to investigate the effects of impact-related shock. In this article, we first present detailed results from these experiments. We then apply these results to the case of Martian meteorites, and evaluate the possible causes of discordant ages reflected by different chronometers in several Martian meteorites. EXPERIMENTAL PROCEDURES Our experiments investigated two endmember effects of an impact: (1) shock at 55 GPa, accompanied only by the transient shock heating; and (2) heating of unshocked material at 1000 C for 1 week. Target material at the center of an impact may experience temperatures and pressures up to 1000 C and 60 GPa (shock stage IV; Deutsch and Scha rer 1994); at higher T P conditions the target rock may be melted or vaporized. Thus, the shock pressure of our experiment replicates the pressure conditions at the high end of the range expected in a natural impact setting. This pressure is also equal to the maximum pressure experienced by any of the Martian meteorites (Nyquist et al. 2001b, and references therein; Fritz et al. 2005). Thermal metamorphism of target rock can result from contact with an impact melt sheet within the crater, or from heating by a continuous breccia deposit located within and outside of the crater, to a distance of two crater radii of the crater rim (Deutsch and Scha rer 1994). Miller and Wagner (1979) used zircon and apatite fission tracks from basement rocks and crystalline blocks in the impact breccia at the Ries impact crater, Germany, to determine the thermal history. They found the maximum temperature experienced by basement rocks to be approximately C, with a duration of <1 h. The lowest allowable temperature was approximately 200 C, with a duration of 1000 yr. Rates of diffusion and chemical reaction, and therefore potential isochron disturbance, are strongly dependent on the time as well as the temperature to which target rock is heated in an impact. However, it was not possible to run an experiment on a long (>year) time scale. In the attempt to maximize the possible extent of disturbance produced in our experiment, we conducted the experiment at a higher temperature than would generally be expected to affect the basement rock in a natural impact setting (1000 C), and ran the experiment for 1 week. Therefore, the results of our heating experiment approach one extreme in the range of possible outcomes of thermal metamorphism resulting from an impact. Samples of lunar basalt were shocked at 54.6 GPa, using a 20 mm flat plate accelerator, by F. Ho rz at NASA Johnson Space Center (Schaal and Ho rz 1977; Nyquist et al. 1987; Ho rz, personal communication). In preparation for the shock experiment, the sample was cored using gaseous nitrogen, and the core was then cut into wafers using a diamond blade saw. The wafers were polished with diamond abrasives. The final size of the wafers was 0.5 mm thick 5 mm diameter. Rubber gloves were used for all sample handling. In the effort to avoid introducing water to the sample prior to the experiment, only ethyl alcohol was used to clean the core and wafers. The experiment was conducted at 5 mbar pressure of terrestrial atmosphere. The shock pulse duration was 0.8 ls, and the shock-induced temperature was estimated at approximately 800 C. Following the experiment, the samples were pried loose from the tungsten sample holder with a stainless steel pick, with the samples breaking into 5 10 fragments during this process, and stored in a glass vial (in ambient atmosphere) until the time of isotopic analysis. Four sample wafers were combined for the isotopic analysis, and an additional wafer was used for the thin section. The heating experiment was conducted using an unshocked subsample of that was flame-sealed in an evacuated (1 10 )5 torr) quartz tube, and heated to 1000 C for 170 h. Additional details of this experiment are given in Chaklader et al. (2006). The sample was heated in a vacuum to eliminate the possibility that atmospheric contamination could be added to the sample during heating (e.g., terrestrial Pb), and this temperature was chosen so that the results would illustrate the maximum extent of disturbance that can be attributed to heating, without initiating melting. SAMPLE DESCRIPTION AND PETROGRAPHY Lunar sample 10017,328 is a high-k, high-ti lunar basalt collected on the southwest part of Mare Tranquilitatis. Adler et al. (1970), Brown et al. (1970), Dence et al. (1970), French et al. (1970), Kushiro and Nakamura (1970), Schmitt et al. (1970), Papike et al. (1976), McGee et al. (1977), and Beaty and Albee (1978) provided the earliest detailed petrographic descriptions of An extensive collection of petrographic and geochemical data for is available in the Lunar Sample Compendium

4 38 A. M. Gaffney et al. Fig. 1. Backscattered electron image of mare basalt 10017, from JEOL 8200 electron microprobe at the University of New Mexico. PL = plagioclase; PX = pyroxene; ILM = ilmenite; Mes = mesostasis. ( The basalt is fine grained with a vesicular to vuggy subophitic texture (Fig. 1). Vesicles are circular to irregular in shape, and are devoid of fillings or latestage reaction products and have smooth inner walls. Vesicles range from 0.2 to 0.5 mm in diameter and constitute <5 vol% of the sample. Continuously zoned, subhedral clinopyroxene is the dominant phase, making up 45 60% of the basalt. The earliest-crystallized pyroxene have compositions of Wo 40 En 44 Fs 16 and Wo 10 En 65 Fs 25 and are zoned to Ca-poor, Fe-rich rims (Wo 11 En 21 Fs 68 ). Pyroxene ranges in size from <50 to 400 lm. Ilmenite is lath-like to anhedral, has an average length of 100 lm and a modal abundance of 14 24%. Pyroxene and ilmenite are poikilitically enclosed by anhedral to lath-shaped plagioclase (An ). Plagioclase is 2 3 mm in length and has a modal abundance of 18 35%. The mesostasis is complex and composed of Fe-rich pyroxene, plagioclase, K-feldspar, Fe-metal, ilmenite, silica, K-rich glass, Fe-rich basaltic glass, apatite, and troilite. The mesostasis makes up approximately 8% of the basalt. Based on texture and mineral chemistry, the crystallization sequence is pyroxene fi ilmenite fi plagioclase. This crystallization sequence progressed under an oxygen fugacity of approximately ironwu stite ) 1. Basalt shows no significant petrographic evidence for shock, with pyroxene and plagioclase lacking significant fracturing and ilmenite remaining untwinned (Chaklader et al. 2006). The high ilmenite content of this sample is unique to lunar basalts, and therefore introduces a compositional variable to the experimental work that is not represented in the shergottites. However, its age, pristine nature, and the prior shock experiments on this sample made it otherwise ideal for this study (Schaal and Ho rz 1977; Nyquist et al. 1987; Chaklader et al. 2006). Textural and mineralogical responses to shock over the range of GPa have been described by Schaal and Ho rz (1977) and Chaklader et al. (2006). At 54.6 GPa, the subophitic texture is still recognizable (Fig. 2), although it is partially disrupted by remobilized mesostasis (Fig. 2b) and frothy glass (Fig. 2c). At this pressure, plagioclase undergoes conversion to maskelynite, pyroxene is fractured, ilmenite is shock twinned and fragmentary disjointed, and cristobalite is isotropic and diaplectic. The composition of the shocked pyroxene overlaps with that of the pyroxene in the unshocked sample (Chaklader et al. 2006). The heated sample retained most of its subophitic texture (Fig. 3). This is probably due to the temperature of 1000 C being approximately 100 below the solidus (Ringwood and Essene 1970; O Hara et al. 1974). Chaklader et al. (2006) concluded that the major element compositions of the pyroxene and plagioclase in the heated sample are similar to those in the pristine sample. However, they observed a redistribution of Li and B among the mesostasis, pyroxene, and plagioclase in the heated sample. ANALYTICAL PROCEDURES Because of the high percentage of incompatible element-enriched mesostasis present in this sample (8%), there is a potential for heterogeneous distribution of incompatible elements between the three subsamples. To minimize this concern, the subsamples were made as large as possible (739 mg for the control sample, 260 mg for the shocked sample, and 871 mg for the heated sample). Subsequently, all three subsamples were processed with the same initial sample preparation and mineral separation procedures, so that the resulting mineral fractions would be directly comparable among the three subsamples (Fig. 4; details following). Upon inspection under binocular microscope (98 magnification), no differences were observed among the magnetic separates made using the same magnetic field for the three different samples, indicating that, at least at this level, the separates were mineralogically comparable. The specific mineral separation techniques employed were chosen because they replicate those used to date basaltic meteorites (e.g., Gaffney et al. 2007b). Each sample was crushed with a sapphire mortar and pestle, and sieved to separate the lm grain size fraction. These fractions were passed through a Frantz

5 Isotopic disturbance from experimental shock and heat 39 Fig. 3. Backscattered electron image of mare basalt that was heated to 1000 C. There appears to be limited evidence of mesostasis remobilization. PL = plagioclase; PX = pyroxene; ILM = ilmenite; Mes = mesostasis. Fig. 2. a) Backscattered electron image of mare basalt shocked at 56.4 GPa. PL = plagioclase; PX = pyroxene; ILM = ilmenite. b) Detail of area outlined in large rectangle in (a). Image illustrates remobilized mesostasis that consists of a variety of mineral fragments (including SiO 2 rimmed with K-feldspar or plagioclase) and heterogeneous glass. c) Detail of area outlined in small rectangle in (a). Image illustrates heterogeneous, frothy glass. isodynamic magnetic separator to isolate plagioclase maskelynite-rich, pyroxene-rich, and ilmenite-rich mineral separates. For ease of comparison among the three samples, throughout the remainder of the article we use the term plagioclase to refer to plagioclase in the heated and control samples, as well as maskelynite in the shocked sample. For the heated and control samples, purified plagioclase and pyroxene mineral separates were generated from the magnetic fractions by hand-picking. Portions of the mineral separates rejected during hand-picking are designated with the suffix -rej. The ilmenite-rich magnetic separates were not further purified by hand-picking. The ilmenite-rich fractions also contain a large proportion of mesostasis. There was insufficient material in the shocked sample magnetic separates to further purify with handpicking. Separate whole-rock fractions were obtained from homogenized powders of each of the three samples. As part of the analytical procedure, all whole-rock and most mineral fractions were leached in 2 N HCl, to remove terrestrial contamination from the grain surfaces. This leaching step is very important when analyzing meteorites that have undergone a period of residence on Earth s surface. This procedure is also used to remove rare earth element (REE)-rich phosphate minerals from Martian meteorites and thereby help to generate compositional spread among Sm Nd ratios of mineral fractions that would otherwise be dominated by REE from phosphates. Therefore, although the leaching procedure is not strictly necessary for Apollo lunar samples, we included this step in the experimental

6 40 A. M. Gaffney et al. with the residue mineral fractions. Fractions that have been leached are designated with the suffix (R), and leachates are designated with the suffix (L). In total, there are nine analyzed fractions for each of the heated and control samples, and seven analyzed fractions for the shocked sample. The mineral, whole-rock, and leachate fractions were spiked with mixed 87 Rb- 84 Sr, 149 Sm- 150 Nd, and 233 U- 236 U- 205 Pb tracers, and digested with a combination of HF, HCl, and HNO 3. Sequential separations of U, Pb, Rb, Sr, Sm, and Nd follow the procedures described by Borg et al. (2005). Isotope ratios were measured using the VG Sector 54 thermal ionization mass spectrometer at the University of New Mexico. ISOTOPE SYSTEMATICS OF THE CONTROL SAMPLE Fig. 4. Mineral separation schemes for a) shocked aliquot and b) heated aliquot. Shaded boxes indicate the fractions analyzed. WR = whole rock; Px = pyroxene; Plag = plagioclase; Ilm = ilmenite- and mesostasis-rich fraction; (R) = leached residue; (L) = leachate; rej = portion of magnetic separate rejected during handpicking. procedures to simulate the treatment that a Martian meteorite would receive in the course of geochemical analysis. Prior to leaching, mineral and whole-rock fractions were washed in 0.5 N acetic acid, for 10 min in an ultrasonic bath, and rinsed with quartz-distilled water. These wash and rinse solutions were discarded. With the exception of the pyroxene-reject, plagioclase-reject, and ilmenite-rich fractions, all of the mineral and whole-rock fractions were leached in 2 N HCl, for 10 min, in an ultrasonic bath at room temperature. After the leachates were decanted from the solid fractions and reserved for analysis, the fractions were rinsed with quartz-distilled water. The water rinse for each fraction was combined with the corresponding HCl leachate, and these were processed and analyzed along The Sm-Nd, Rb-Sr, 238 U- 206 Pb, and 206 Pb- 207 Pb data for the unshocked, unheated sample of are reported and discussed in detail by Gaffney et al. (2007a), and shown in Table 1 and Figs The relevant results are summarized here. The Rb-Sr, Sm- Nd, and 238 U- 206 Pb isotope systems record concordant ages for The Rb-Sr isochron yields an age of ± Ga (MSWD = 4.8) and an initial isotopic composition of 87 Sr 86 Sr i = ± (Gaffney et al. 2007a). Previously reported Rb-Sr ages of include (all corrected to k 87 Rb = Ga )1 ; Minster et al. 1982; Begemann et al. 2001): 3.56 ± 0.05 Ga (Papanastassiou et al. 1970), 3.54 ± 0.22 Ga (Gopalan et al. 1970), and 3.67 ± 0.07 Ga (Nyquist et al. 1987). The Sm-Nd age of is ± Ga (MSWD = 0.55), and the initial Nd isotopic composition is e Ndi = ± The 238 U- 206 Pb isotope system preserves an age of ± Ma (MSWD = 86) with an initial isotopic composition of 206 Pb 204 Pb i = 31 ± 11. The 235 U- 207 Pb isotope system yields an age of 3.80 ± 0.12 Ga (MSWD = 455). The 206 Pb- 207 Pb isotope system does not yield a coherent age. Gaffney et al. (2007a) attribute the apparent disturbance of 207 Pb, evident from the large uncertainty and MSWD of the 235 U- 207 Pb age and the lack of a 206 Pb- 207 Pb age, to contamination of glassy mesostasis in with ancient, radiogenic Pb derived from the lunar surface, via Pb volatilization and recondensation resulting from impacts. This contamination was not sufficient to disturb significantly the 238 U- 206 Pb isotope systematics. Additional disturbance to the 206 Pb- 207 Pb system by the heating and shock experiments can be at least partially assessed by comparison with the control sample.

7 Isotopic disturbance from experimental shock and heat 41 Table 1. Ages calculated from control, shocked, and heated samples of Age (Ga) MSWD Initial isotopic composition a Fractions used in age calculation Control sample Sm-Nd ± e Nd = ± 0.39 All minerals and WR(R) Rb-Sr ± Sr 86 Sr = ± 65 All minerals and WR(R) 238 U- 206 Pb ± Pb 204 Pb = 31 ± 11 All minerals and WR(R) Shocked sample Sm-Nd 3.65 ± e Nd = ± 0.64 Plag(R), WR(R), Ilm Rb-Sr 3.61 ± Sr 86 Sr = ± 29 All minerals and WR(R) Rb-Sr 3.61 ± Sr 86 Sr = ± 18 Recombined fractions + Ilm 238 U- 206 Pb 3.48 ± Pb 204 Pb = 26 ± 21 Px(R), WR(R), Ilm Heated sample Sm-Nd 3.51 ± e Nd = +1.6 ± 3.7 All minerals and WR(R) Sm-Nd ± e Nd = ± 0.37 All minerals Sm-Nd 3.63 ± e Nd = ± 0.45 Recombined fractions + Ilm Rb-Sr 3.29 ± Sr 86 Sr = ± 32 All minerals and WR(R) Rb-Sr 3.59 ± Sr 86 Sr = ± 68 All minerals Rb-Sr 3.76 ± Sr 86 Sr = ± 42 Recombined fractions + Ilm Method Age (Ga) b Reference Previously reported ages of Rb-Sr 3.56 ± 0.05 Papanastassiou et al. (1970) Rb-Sr 3.54 ± 0.22 Gopalan et al. (1970) Rb-Sr 3.67 ± 0.07 Nyquist et al. (1987) a e Nd =10 4 [(( 143 Nd 144 Nd sample t ) ( 143 Nd 144 Nd CHUR t )) ) 1]. CHUR parameters used in calculation of initial e Nd values are: 143 Nd 144 Nd (0) = and 147 Sm 144 Nd (0) = b Ages corrected to k 87 Rb = Ga )1 (Minster et al. 1982; Begemann et al. 2001). EFFECTS OF 55 GPA SHOCK ON THE ISOTOPE SYSTEMATICS OF Element Mobility in the Shocked Sample The abundances of Rb, Sr, Sm, Nd, U, and Pb in 2 N HCl whole-rock leachates are not significantly different in the control and shocked samples, suggesting that shock does not cause a substantial change in mobility of these elements (Fig. 9). Rubidium, Sm, and Nd show slightly increased mobility, whereas Sr, U, and Pb show slightly decreased mobility. In all cases, these slight differences in mobility most likely reflect small degrees of heterogeneity among the subsamples. Isotope Systematics of the Shocked Sample Samarium-Neodymium All of the analyzed fractions of the shocked sample, with the exception of Plag(L), plot within uncertainty of the Sm-Nd isochron defined by the control sample (Fig. 5b; Table 2). Unfortunately, the Nd isotopic analysis for the shocked Px(R) mineral separate failed. The recombined shocked WR(R + L) fraction lies on the control isochron, but the recombined shocked Plag(R + L + rej) fraction falls slightly to the left of the control isochron. The values for these recombined points were calculated from the isotopic compositions of the (R), (L), and rej fractions for each lithology (WR, Plag, etc.), weighted according to the total amount of each element in the fractions, to reconstruct the composition of the bulk fraction prior to hand-picking and leaching. The line regressed through the three mineral and whole-rock fractions (Plag(R), Ilm, and WR(R)) yields an age of 3.65 ± 0.19 Ma (MSWD = 1.2), with an initial e Nd of ± 0.64 (Table 1; Fig. 10). The large uncertainty associated with this age is in part due to the small spread in 147 Sm 144 Nd values among the fractions, resulting from the absence of a Px(R) analysis. Nyquist et al. (1988) present Sm-Nd isotopic results for density and magnetic separates of a sample of basalt shocked at 35 GPa and a corresponding control sample. However, their data show a much smaller range of 147 Sm 144 Nd ratios than is evident in our shocked and control samples. This most likely reflects the different mineral separation procedures used in the two studies. The small range of 147 Sm 144 Nd ratios in the Nyquist et al. (1988) study precludes the calculation of an Sm-Nd age. However, the fractions analyzed by Nyquist et al. (1988) are shifted off the control isochron, reflecting a difference in the Sm Nd ratios of the shocked fractions of up to approximately 3%. The disturbance is greatest in the most mesostasis-rich fractions, suggesting that the glassy mesostasis is more susceptible to disturbance.

8 42 A. M. Gaffney et al. Fig. 5. Sm-Nd isochron diagrams for a) Control aliquot (Gaffney et al. 2007a). b) Shocked aliquot. c) Heated aliquot. Ages and initial isotopic compositions are given in Table 1. (See Fig. 4 caption for abbreviations.) Rubidium-Strontium The shocked sample does not exhibit substantial disturbance in the Rb-Sr isotope system (Fig. 6b; Table 3). The slight displacement of the WR(L) fraction to the left of the control isochron is similar to that observed in the control sample, and therefore appears to reflect a disturbance that is not related to the experimental procedures. The one notable difference between the shocked and control sample is that the ilmenite-rich fraction in the shocked sample has a much lower Rb Sr ratio, and a correspondingly lower Fig. 6. Rb-Sr isochron diagrams for 10017: a) Control aliquot (Gaffney et al. 2007a). b) Shocked aliquot. c) Heated aliquot. Ages and initial isotopic compositions are given in Table 1. (See Fig. 4 caption for abbreviations.) The radiogenic nature of the ilmenite-rich fraction reflects the abundance of incompatible element-enriched mesostasis in this fraction. 87 Sr 86 Sr. This effect probably results from a smaller proportion of incompatible element-enriched mesostasis in the shocked ilmenite-rich fraction (Gaffney et al. 2007a). The four mineral and whole-rock fractions from the shocked sample yield a regression line corresponding to an age of 3.61 ± 0.19 Ma (MSWD = 8.8), with an initial 87 Sr 86 Sr of ± (Table 1; Fig. 10). The Ilm + recombined mineral fractions yield similar results: age = 3.60 ± 0.14 Ma (MSWD = 5.2) and

9 Isotopic disturbance from experimental shock and heat 43 Fig U- 206 Pb isochron diagrams for a) Control aliquot (Gaffney et al. 2007a). b) Shocked aliquot. c) Heated aliquot. Inset panel in (a) shows the position of the Ilm and WR(R) fractions relative to the rest of the fractions. Ages and initial isotopic compositions are given in Table 1. (See Fig. 4 caption for abbreviations.) The position of the WR(R) fraction at the radiogenic end of the control isochron reflects the fact the whole rock contains a highly radiogenic component that was not included in the mineral separates, which were obtained by tuning the magnetic field of the Frantz to optimize separation of plagioclase, pyroxene, and ilmenite only. The 235 U- 207 Pb isochron diagram is not plotted because mineral fractions demonstrate the same relative relationships on this diagram as the on the 238 U- 206 Pb isochron diagram. initial 87 Sr 86 Sr = ± These results are consistent with the results of Nyquist et al. (1987) for a sample of shocked to 35 GPa, who also found minimal disturbance in the Rb-Sr systematics. Fig U- 207 Pb isochron diagrams for a) Control aliquot (Gaffney et al. 2007a). b) Shocked aliquot. c) Heated aliquot. Inset panel in (a) shows the position of the Ilm and WR(R) fractions relative to the rest of the fractions. (See Fig. 4 caption for abbreviations.) Uranium-Lead The shock experiments disturbed the 238 U- 206 Pb systematics of (Fig. 7b; Table 4). With the exception of the WR(L) fraction, all of the measured fractions fall below the 238 U- 206 Pb control isochron, and taken together, the fractions demonstrate much more scatter than is evident in the control sample (Fig. 7). Correspondingly, ages calculated from lines regressed through different subsets of mineral, whole-rock, and leachate fractions from the shocked sample have large

10 44 A. M. Gaffney et al. Fig. 9. Relative element mobility during leaching of control, shocked, and heated samples of Percent of each element in leachate calculated in the basis of the whole-rock fraction, as: 100 (ng element in WR(L)) (ng element in WR(L) + ng element in WR(R)). uncertainties. The Px(R), WR(R), and Ilm fractions correspond to an age of 3.48 ± 0.63 Ga (MSWD = 24). The four mineral and whole-rock fractions together correspond to an age of 4.1 ± 2.7 Ga (MSWD = 161), and all seven fractions correspond to an age of 3.58 ± 0.92 Ga (MSWD = 1065). The age derived from the recombined fractions and ilmenite is 4.0 ± 1.6 Ga (MSWD = 1002). The disturbance apparent in this sample precludes the assignment of any significance to these calculated ages. Disturbance is most apparent in the Plag(R) and Plag(L) fractions, which fall farther below the control isochron than any of the other fractions, suggesting that the U-Pb systematics of plagioclase are particularly susceptible to disturbance during shock. The WR(R) and Ilm fractions in the shocked sample have much lower U Pb ratios, and correspondingly less radiogenic 206 Pb 204 Pb, than in the control sample. This probably reflects heterogeneous distribution of a trace phase with high U Pb (mesostasis) among the three initial whole-rock subsamples of The lower bulk U Pb of the subsample used for the shock experiment results in a smaller overall spread in the U Pb and 206 Pb 204 Pb values of the shocked mineral fractions. However, the scatter in the data is attributed to shock-related disturbance. Lead-Lead Unlike in the U-Pb system, there are no apparent systematic effects of disturbance in the 206 Pb- 207 Pb system (Fig. 8b). The relative positions of the shocked fractions mimic the positions in the control sample. However, the overall spread of the shocked data defines a more narrow range than in the control sample. This Fig. 10. Summary diagram of ages determined from Sm-Nd, Rb-Sr, and 238 U- 206 Pb isotope systems, for control (Gaffney et al. 2007a), shocked, and heated samples of Also shown are previously published Rb-Sr ages for 10017, corrected to k 87 Rb = Ga )1 (Minster et al. 1982; Begemann et al. 2001). can most likely be attributed to heterogeneity of the bulk sample, as suggested by the U-Pb systematics. As in the control sample, the shocked WR(R) fraction is more radiogenic than the Ilm fraction. However, in contrast to the control sample, the recombined shocked WR fraction is more radiogenic than the Ilm fraction. This is an additional indication of heterogeneous distribution of radiogenic Pb-rich mesostasis among the three subsamples. EFFECTS OF HEATING ON THE ISOTOPE SYSTEMATICS OF Element Mobility in the Heated Sample During leaching of the heated sample, Rb, Sr, Sm, Nd, and U show extents of mobility that are similar to those in the control sample (Fig. 9). By contrast, the mobility of Pb during leaching is substantially increased in the heated sample. Approximately 30% of the Pb is removed from the control whole rock by leaching, whereas nearly 70% of the Pb is removed from the heated whole rock by leaching. The positions of the WR(L) and WR(R) fractions above and below, respectively, the 238 U- 206 Pb control isochron are

11 Isotopic disturbance from experimental shock and heat 45 Table 2. Sm-Nd data for wt. (mg) Sm (ppm) Sm (ng) Nd (ppm) Nd (ng) 147 Sm 144 Nd a 143 Nd 144 Nd b Shocked sample Plag(R) ± ± 10 Plag(L) ± ± 20 Px(L) ± ± 10 WR(R) ± ± 10 WR(L) ± ± 10 Ilm ± ± 10 Heated sample Plag(R) ± ± 10 Plag(L) ± ± 34 Plag-rej ± ± 10 Px(R) ± ± 10 Px(L) ± ± 23 Px-rej ± ± 10 WR(R) ± ± 10 WR(L) ± ± 10 Ilm ± ± 10 La Jolla (n =5) c ± 41 Note: Plag = plagioclase; Px = pyroxene; WR = whole rock; Ilm = ilmenite; (L) = HCl leachate; (R) = HCl-leached residue; rej = portion of mineral fraction rejected during hand-picking. All samples and standards run as NdO+. The Px(R) fraction for the shocked sample failed to run on the mass spectrometer. Isochrons are calculated using either 2r p (from standard runs) or 2r m (from measured isotope ratios), whichever is larger. The regression method of Fletcher and Rosman (1982) is used to calculate initial isotopic composition. a Error limits include a minimum uncertainty of 0.1% plus 50% of the blank correction for Sm and Nd added quadratically. Reported values have been corrected for Nd blank of 9 ± 3 pg with 143 Nd 144 Nd = and Sm blank of 5 ± 3 pg with a natural isotopic composition. b Normalized to 146 Nd 144 Nd = Uncertainties are 2r m calculated from the measured isotope ratios. 2r m =[R(m i ) l) 2 (n(n ) 1))] 1 2 for n ratio measurements m i with mean value l. c Error limits are 2r p.2r p =[R(M i ) p) 2 (N ) 1)] 1 2 for N measurements M i with mean value p. consistent with loss of radiogenic Pb from the WR(R) fraction, and incorporation of excess radiogenic Pb in the leachate. This Pb mobility is probably driven by the volatility of this element. This greatly increased mobilization of Pb in the heated aliquot corresponds to loss of age information in the 238 U- 206 Pb isotope system, as well as increased scatter of the mineral fractions in the 206 Pb- 207 Pb system. This demonstrates that the standard practice of leaching meteorites prior to isotopic analysis may be detrimental to the preservation of U-Pb isotopic systematics in a thermally metamorphosed sample. Isotope Systematics of the Heated Sample Samarium-Neodymium In the Sm-Nd system for the heated sample, the leachate and WR(R) fractions are most clearly disturbed (Fig. 5c; Table 2). The three leachate fractions fall above the control isochron, indicating either Sm-Nd fractionation during leaching or preferential incorporation of radiogenic Nd, mobilized from crystal lattice sites damaged by radioactive decay, in the leachates. However, neither of these possible processes appears to have had a significant effect on the position of the corresponding Plag(R) or Px(R) fractions relative to the control isochron, because the Plag(L) and Px(L) fractions contain modest amounts of Sm and Nd relative to the corresponding mineral fractions. By contrast, the WR(R) fraction falls below the control isochron. However, the recombined WR(R) + WR(L) fraction falls directly on the control isochron, indicating that the whole rock remained a closed system through the heating event. All of the mineral fractions fall on the control isochron, and yield a concordant age of ± Ga (MSWD = ) and an initial e Nd of ± The calculated age including the WR(R) fraction has a much larger uncertainty: 3.52 ± 0.52 Ga (MSWD = 53). The recombined fractions (R + L + rej) all fall on the control isochron, and preserve a concordant crystallization age, 3.63 ± 0.12 Ga (MSWD = 1.0), and an initial e Nd of ± 0.45 (Table 1; Fig. 10). Despite the apparent disturbance of the WR(R) fraction, the Sm-Nd system appears to be extremely resilient to disturbance by extensive heating. Rubidium-Strontium The Rb-Sr systematics of the whole-rock fraction in the heated sample are disturbed (Fig. 6c; Table 3). The WR(L) fraction falls far above the control isochron, and the WR(R) fraction falls a small distance below the

12 46 A. M. Gaffney et al. Table 3. Rb-Sr data for wt (mg) Rb (ppm) Rb (ng) Sr (ppm) Sr (ng) 87 Rb 86 Sr a 87 Sr 86 Sr b Shocked sample Plag(R) ± ± 10 Plag(L) ± ± 10 Px(R) ± ± 10 Px(L) ± ± 11 WR(R) ± ± 10 WR(L) ± ± 11 Ilm ± ± 10 Heated sample Plag(R) ± ± 10 Plag(L) ± ± 11 Plag-rej ± ± 10 Px(R) ± ± 10 Px(L) ± ± 14 Px-rej ± ± 10 WR(R) ± ± 10 WR(L) ± ± 10 Ilm ± ± 10 NBS 987 (n =7) c ± 30 Note: Plag = plagioclase; Px = pyroxene; WR = whole rock; Ilm = ilmenite; (L) = HCl leachate; (R) = HCl-leached residue; rej = portion of mineral fraction rejected during hand-picking. Isochrons are calculated using either 2r p (from standard runs) or 2r m (from measured isotope ratios), whichever is larger. a Error limits include a minimum uncertainty of 1% plus 50% of the blank correction for Rb and Sr added quadratically. Reported values have been corrected for Sr blank of 11 ± 4 pg with 87 Sr 86 Sr = and Rb blank of 6 ± 4 pg with a natural isotopic composition. b Normalized to 86 Sr 88 Sr = Uncertainties are 2r m calculated from the measured isotope ratios. 2r m =[R(m i ) l) 2 (n(n ) 1))] 1 2 for n ratio measurements m i with mean value l. c Error limits are 2r p.2r p =[R(M i ) p) 2 (N ) 1)] 1 2 for N measurements M i with mean value p. control isochron. However, 87 Rb 86 Sr of the heated WR(L) and WR(R) fractions are similar to the control WR(L) and WR(R), respectively, indicating that the offsets of the heated WR(L) and WR(R) fractions from the control isochron reflect preferential removal of radiogenic Sr by the HCl leachate. Although the WR(R) and WR(L) fractions fall to opposite sides of the control isochron, the recombined WR fraction falls slightly above the control isochron. This suggests that heating resulted in open-system behavior in the Rb-Sr isotope systematics of the whole rock. This open-system behavior must occur during the heating event and subsequent sample processing. The remainder of the heated leachate and residue fractions fall on or very slightly to the left of the control isochron. Although the ilmenite-rich fraction falls on the control isochron, it has lower 87 Rb 86 Sr and lower 87 Sr 86 Sr than the ilmenite fraction from either the control or shocked samples. This again suggests that incompatible element-enriched mesostasis is heterogeneously distributed among the three samples used in this study. In this sample, the WR fraction is the most radiogenic fraction analyzed. This indicates that the whole rock contains a radiogenic component that is not represented in any of the mineral fractions, which were obtained by selectively tuning the magnetic field on a Frantz isodynamic magnetic separator to isolate highpurity plagioclase, pyroxene, and ilmenite mineral separates. The best age for the heated sample, 3.59 ± 0.14 Ga (MSWD = 7.2), is derived from the mineral fractions (Table 1). This age corresponds to an initial 87 Sr 86 Sr of ± 68, which is within uncertainty of the initial derived from the control isochron. The age calculated using the WR(R) and all mineral fractions is 3.29 ± 0.41 Ga (MSWD = 77), reflecting the disturbed WR(R) fraction. The age calculated from the recombined fractions + Ilm likewise yields a large uncertainty: 3.76 ± 0.49 Ga (MSWD = 28). Thus, the Rb-Sr system is more easily disturbed by heating than the Sm-Nd system, but can still yield reliable ages if clean mineral separates are analyzed. Uranium-Lead The heated sample shows extensive scatter on the 238 U- 206 Pb isochron diagram (Fig. 7c). The majority of the fractions are well outside of analytical uncertainty of the control isochron. The WR(R) fraction lies far to the right of the control isochron, and the remainder of the fractions lie to the left of the control isochron. The only fractions with compositions close to the control isochron are the recombined WR fraction, as well as the Px(R), Px(L), and Plag(L) fractions. The location of the recombined WR(R + L) fraction on the control

13 Isotopic disturbance from experimental shock and heat 47 Table 4. U-Pb data for wt (mg) U (ppm) U (ng) Pb (ppm) Pb (ng) 238 U 204 Pb a 206 Pb 204 Pb b 207 Pb 204 Pb b 208 Pb 204 Pb b Shocked sample Plag(R) ± ± ± ± 0.79 Plag(L) ± ± ± ± 0.15 Px(R) ± ± ± ± 0.27 Px(L) ± ± ± ± 0.15 WR(R) ± ± ± ± 0.29 WR(L) ± ± ± ± 0.36 Ilm ± ± ± ± 0.19 Heated sample Plag(R) ± ± ± ± 2.6 Plag(L) ± ± ± ± 0.30 Plag-rej ± ± ± ± 1.5 Px(R) ± ± ± ± 1.7 Px(L) ± ± ± ± 0.24 Px-rej ± ± ± ± 0.49 WR(R) ± ± ± ± 0.62 WR(L) ± ± ± ± 0.25 Ilm ± ± ± ± 0.64 All Faraday runs: NBS 981 (n = 10) c ± ± ± 0.11 Faraday Daly runs: NBS 981 (n = 17) ± ± ± 0.24 Note: Plag = plagioclase; Px = pyroxene; WR = whole rock; Ilm = ilmenite; (L) = HCl leachate; (R) = HCl-leached residue; rej = portion of mineral fraction rejected during hand-picking. Isochrons are calculated using either 2r p (from standard runs) or 2r m (from measured isotope ratios), whichever is larger. a Error limits include a minimum uncertainty of 0.1% plus 50% of the blank correction for U and Pb added quadratically. Reported values have been corrected for Pb blank of 12 ± 6 pg with 208 Pb 204 Pb = , 207 Pb 204 Pb = , and 206 Pb 204 Pb = , and U blank of 4 ± 3 pg with a natural isotopic composition. b Uncertainties are 2r m calculated from the measured isotope ratios. 2r m =[R(m i ) l) 2 (n(n ) 1))] 1 2 for n ratio measurements m i with mean value l. c Error limits are 2r p.2r p =[R(M i ) p) 2 (N ) 1)] 1 2 for N measurements M i with mean value p. The greater uncertainty on the Faraday Daly standard runs reflects the added uncertainty from the Faraday Daly gain calibration. isochron points to closed system behavior of this sample during heating. The less radiogenic Pb isotopic composition of the heated sample compared to the control sample is attributed to heterogeneous distribution of incompatible element-enriched mesostasis among the subsamples. The recombined Plag and Px fractions are nearly identical in their U Pb and Pb isotopic compositions, indicating that heating effectively homogenized the Pb isotopic and U Pb compositions of the bulk plagioclase and pyroxene portions of the sample. Thus, hand-picking and leaching are required to generate compositional spread among the (R) and -rej fractions. The recombined plagioclase and pyroxene fractions as well as the ilmenite-rich fraction fall to the left of the control isochron, indicating that these fractions have been affected by other disturbance, in addition to homogenization. Taken together, these observations indicate that while the bulk plagioclase and pyroxene fractions were affected during heating by either loss of U or gain of radiogenic Pb, this disturbance is localized in the residual mineral fractions. The acid-soluble portion of these fractions remained undisturbed, as illustrated by the observation that the leachates remain on the control isochron. Lead-Lead It is challenging to interpret experimental disturbances in the 206 Pb- 207 Pb system because the control sample itself is disturbed by impact processes on the Moon. Nevertheless, disturbance of the heated sample is identified by the changes in the relative positions of the fractions in comparison to the control sample. Disturbance mirrors many of the characteristics of the 238 U- 206 Pb system in the heated sample. Notably, the Plag(L) and Px(L) fractions have nearly identical, unradiogenic Pb isotopic compositions. In comparison, these two leachates in the control sample have compositions that, although at the unradiogenic end of the array, are nonetheless different by approximately 50%. Thus, heating appears to have homogenized the leachable Pb component in the bulk plagioclase and pyroxene fractions. In the control sample, the Plag(R), Plag-rej, and recombined Plag fractions are less radiogenic than the Px(R), Px-rej, and recombined Px fractions, respectively. By contrast, the heated sample has Plag(R) and Plag-rej fractions that are more radiogenic than the Px(R) and Px-rej fractions, respectively, and the recombined Plag and Px fractions have nearly identical Pb isotopic compositions. These