Unique Meteorite from Early Amazonian Mars: Water-Rich Basaltic Breccia Northwest Africa 7034


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Unique Meteorite from Early Amazonian Mars: Water-Rich Basaltic Breccia Northwest Africa 7034

  1. 1. Research Articles Unique Meteorite from Early (4.9 ± 1.3%), and apatite (3.7 ± 2.6%). The x-ray data also indicate a minor amount of iron-sulfide and chromite.Amazonian Mars: Water-Rich Basaltic The data are also consistent with mag- netite and maghemite making up ~70%Breccia Northwest Africa 7034 and ~30%, respectively, of the iron oxide detected (8). Numerous clasts and textural varie- 1,2 1,2 1,2 1 ties are present in NWA 7034 thatCarl B. Agee, * Nicole V. Wilson, Francis M. McCubbin, Karen Ziegler, include gabbros, quenched melts, andVictor J. Polyak,2 Zachary D. Sharp,2 Yemane Asmerom,2 Morgan H. Nunn,3 iron oxide-ilmenite-rich reaction 3 3 4 4Robina Shaheen, Mark H. Thiemens, Andrew Steele, Marilyn L. Fogel, spherules (figs. S1 to S4) (8), however 4 4 3,5 1,2Roxane Bowden, Mihaela Glamoclija, Zhisheng Zhang, Stephen M. Elardo the dominant textural type is a fine-1 2 Institute of Meteoritics, University of New Mexico, Albuquerque, NM 87131, USA. Department of Earth grained basaltic porphyry with feldspar 3and Planetary Sciences, University of New Mexico, Albuquerque, NM 87131, USA. Department of and pyroxene phenocrysts. NWA 7034 4Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA 92093, USA. Geophysical is a monomict brecciated porphyritic 5Lab, Carnegie Institution of Washington, Washington, DC 20005, USA. School of Environmental Science basalt that is texturally unlike any SNCand Engineering, Sun Yat-Sen University, Guangzhou 510275, China. meteorite. Basaltic breccias are com-*To whom correspondence should be addressed. E-mail: agee@unm.edu mon in Apollo samples, lunar meteor- Downloaded from www.sciencemag.org on January 3, 2013 ites, and HED meteorites, but whollyWe report data on the martian meteorite, Northwest Africa (NWA) 7034, which absent in the world’s collection of SNCshares some petrologic and geochemical characteristics with known martian (SNC, meteorites (9). Absence of shocked-i.e., Shergottite, Nakhlite, and Chassignite) meteorites, but also possesses some produced SNC breccias seems curiousunique characteristics that would exclude it from the current SNC grouping. NWA at face value, since nearly all of them7034 is a geochemically enriched crustal rock compositionally similar to basalts and show evidence of being subjected toaverage martian crust measured by recent rover and orbiter missions. It formed high shock pressures, with feldspar2.089 ± 0.081 Ga, during the early Amazonian epoch in Mars’ geologic history. NWA commonly converted to maskelynite.7034 has an order of magnitude more indigenous water than most SNC meteorites, Martian volcanic breccias are probablywith up to 6000 ppm extraterrestrial H2O released during stepped heating. It also has not rare given the observed widespreadbulk oxygen isotope values of Δ17O = 0.58 ± 0.05‰ and a heat-released water occurrence of volcanism on Mars.oxygen isotope average value of Δ17O = 0.330 ± 0.011‰ suggesting the existence of However launch and delivery of suchmultiple oxygen reservoirs on Mars. materials to Earth as meteorites has not been observed (9). Although NWA 7034 is texturally heterogeneous bothThe only tangible samples of the planet Mars that are available for study in hand sample and microscopically (Fig. 1), it can be considered ain Earth-based laboratories, have up to now, been limited to the so-called monomict breccia because it shows a continuous range of feldspar andSNC (1) meteorites and a single cumulate orthopyroxenite (Allan Hills pyroxene compositions that are consistent with a common petrologic84001). The SNCs currently number 110 named stones and have provid- origin (figs. S5 and S6). We find no outlier minerals or compositionsed a treasure trove for elucidating the geologic history of Mars (2). But that would indicate the existence of multiple lithologies or exotic com-because of their unknown field context and geographic origin on Mars, ponents. We also see no evidence for polymict lithologies in either thetheir fairly narrow range of igneous rock types and formation ages (3), it radiogenic or stable isotope ratios of NWA 7034 solids. However, manyis uncertain to what extent SNC meteorites sample the crustal diversity clasts and some of the fine-grained groundmass have phases that appearof Mars. In fact, geochemical data from NASA’s orbiter and lander mis- to have been affected by secondary processes to form reaction zones. Wesions suggest that the SNC meteorites are a mismatch for much of the observed numerous reaction textures, some with a ferric oxide hydroxidemartian crust exposed at the surface (4). For example, the basalts ana- phase, which along with apatite, are the main hosts of the water in NWAlyzed by the Mars Exploration Rover Spirit at Gusev Crater (5, 6) are 7034 (fig. S2). Impact processes are likely to have affected NWA 7034distinctly different from SNC meteorites, and the Odyssey Orbiter gam- by virtue of the fact that this meteorite was launched off of Mars, ex-ma ray spectrometer (7) (GRS) data show that the average martian crust ceeding the escape velocity – presumably by an impact–although thecomposition does not closely resemble SNC. shock pressures did not produce maskelynite. One large (1-cm) quench NWA 7034, on deposit at the Institute of Meteoritics, purchased by melt clast that was found could originate from shock processes (fig. S3).Jay Piatek from Aziz Habibi, a Moroccan meteorite dealer, in 2011, is a On the other hand, the very fine groundmass with the large phenocrystic319.8 g single stone, porphyritic basaltic monomict breccia, with a few feldspars and pyroxenes strongly suggests an eruptive volcanic origin foreuhedral phenocrysts up to several millimeters and many phenocryst NWA 7034, thus it is likely that volcanic processes are a source of thefragments of dominant andesine, low-Ca pyroxene, pigeonite, and augite brecciation.set in a very fine-grained, clastic to plumose, groundmass with abundant It has been shown (10) that Fe-Mn systematics of pyroxenes andmagnetite and maghemite; accessory sanidine, anorthoclase, Cl-rich olivines are an excellent diagnostic for classifying planetary basalts. Fe-apatite, ilmenite, rutile, chromite, pyrite, a ferric oxide hydroxide phase, Mn of NWA 7034 pyroxenes, as determined by electron microprobeand a calcium carbonate identified by electron microprobe analyses on analyses, most resemble the trend of the SNC meteorites from Mars (Fig.eight different sections at the University of New Mexico (UNM). X-ray 2); other planetary pyroxenes such as in lunar samples and basalts fromdiffraction analyses conducted at UNM on a powdered sample and on a Earth are poor matches for NWA 7034. Furthermore, feldspar composi-polished surface show that plagioclase feldspar is the most abundant tions (fig. S5) (8) and compositions of other accessory phases in NWAphase (38.0 ± 1.2%), followed by low-Ca pyroxene (25.4 ± 8.1%), 7034 are consistent with mineralogies commonly found in SNC meteor-clinopyroxenes (18.2 ± 4.0%), iron-oxides (9.7 ± 1.3%), alkali feldspars ites (11), but not with any other known achondrite group. However, the / http://www.sciencemag.org/content/early/recent / 3 January 2013 / Page 1/ 10.1126/science.1228858
  2. 2. average bulk chemical composition of NWA 7034 does not overlap in partial melting. Due to the instability of plagioclase at high pressuremajor element space with SNC, instead it is remarkably similar to the (25), these processes would have necessarily occurred in the crust orgeochemistry of the rocks and soils at Gusev Crater and the average upper mantle of Mars. Consequently, the geochemically enriched sourcemartian crust composition from the Odyssey Orbiter gamma ray spec- that produced NWA 7034 could have originated from the martian crusttrometer (GRS) (Fig. 3 and figs. S7 and S8). NWA 7034, Gusev rocks, or mantle, much like the geochemically enriched reservoir(s) that areand the GRS average martian crust all have higher concentrations of the recorded in the shergottites (26–30).alkali elements sodium and potassium in comparison to SNC meteorites. Confocal Raman imaging spectroscopy (CRIS) conducted at the Ge-Other major and minor element ratios such as Mg/Si, Al/Si, and Ni/Mg ophysical Laboratory, Carnegie Institution, in Washington DC (Carne-have similarly good matches between NWA 7034 and Gusev Crater gie) identified the presence of macromolecular carbon (MMC) withinrocks (figs. S7 and S8). Although some experimental work has been mineral inclusions in the groundmass minerals of NWA 7034 (8). Thisconducted to link martian meteorites to surface rocks analyzed by the MMC is spectrally similar to reduced organic macromolecular carbonMars Exploration Rovers (12–14), and aside from the exotic “Bounce that has been identified in several shergottites and a single nakhlite me-Rock” (15) at Meridiani Planum, and hypothesized martian soil compo- teorite (fig. S15) (30), indicating that the production of organic carbonnent in Tissint melt pockets (16), there has been no direct link between from abiogenic processes in the martian interior may not be unique tothe bulk chemical compositions of martian meteorites and surface rocks SNC-like source regions in Mars. Steele et al. (31) also demonstratedto date. that the formation mechanism of MMC requires reducing magmatic The rare earth element (REE) abundances of NWA 7034 were de- conditions consistent with oxygen fugacities below the fayalite-termined by multi-collector inductively coupled plasma mass spectrome- magnetite-quartz (FMQ) buffer. Consequently, much of the ferric iron intry (Neptune MC-ICP-MS) at UNM. They are significantly enriched the oxides of NWA 7034, as evidenced by EPMA and XRD analyses, Downloaded from www.sciencemag.org on January 3, 2013relative to chondritric abundances with a marked negative europium was likely a product of oxidation subsequent to igneous activity as aanomaly (Eu/Eu* = 0.67) (fig. S9 and table S2). The REE pattern has a result of secondary processes.negative slope and light rare earth elements (LREE) are elevated relative Bulk carbon and carbon isotopic measurements on NWA 7034 wereto the heavy rare earth elements (HREE) (La/Yb)N = 2.3. Bulk SNC also carried out at Carnegie using combustion in an elemental analyzermeteorites are much less enriched in REE (17) than NWA 7034 (fig. (Carlo Erba NC 2500) interfaced through a ConfloIII to a Delta V PlusS10), although LREE enrichment relative to HREE and REE patterns isotope ratio mass spectrometer (ThermoFisher) in the same manner aswith negative slopes are seen in nakhlites, only magmatic inclusions and the data reported by (31, 32) (8). These data indicate that at least 22 ± 10mesostasis in nakhlites and estimated nakhlite parent magmas have ppm carbon is present within mineral inclusions in NWA 7034, and theLREE enrichments comparable to NWA 7034 (17, 18). We observed δ13C isotopic value of this carbon is –23.4 ± 0.73‰, which is very simi-ubiquitous, relatively large (up to ~100 μm) Cl-rich apatite grains in lar to previous bulk C and δ13C analyses of carbon included inNWA 7034 which presumably harbor a substantial fraction of the REEs shergottite meteorites analyzed in the same manner (31, 32). These datain this meteorite, as merrillite/whitlockite was not identified in any of the indicate that multiple geochemical reservoirs in the martian interior mayinvestigated thin sections or probe mounts. have similarly light δ13C values. The bulk C concentration in the untreat- A five-point isochron gives an Rb-Sr age for NWA 7034 of 2.089 ± ed sample performed in these measurements was 2080 ± 80 ppm C, with0.081 Ga (2σ) (MSWD = 6.6), an initial 87Sr/86Sr ratio of 0.71359 ± 54 corresponding δ13C value of –3.0 ± 0.16‰. Scattered carbonate veinlets(Fig. 4), and a calculated source 87Rb/86Sr ratio of 0.405 ± 0.028 (Fig. 5). from desert weathering were observed by BSE imaging and elementThe Sm-Nd data for the same samples result in an isochron of 2.19 ± 1.4 mapping with the electron microprobe–especially in the near-surfaceGa (2σ). The high uncertainty in the latter is due to minimal separation material, but rarer in the deeper interior slices of NWA 7034. Althoughbetween the data points generated from analysis of mineral separates. this carbonate is a minor phase within the meteorite, being below theThe small error on the Rb-Sr age may come from the abundance and detection of our XRD-analyses of the bulk sample, we believe thisvariety of feldspar compositions in NWA 7034 (fig. S5). Furthermore, weathering product is sampled in our bulk carbon and carbonate anal-we are confident that the Rb-Sr isochron and variations in the 87Sr/86Sr yses (8) (fig. S16).values are the result of the time-integrated radiogenic growth from 87Rb Measurements of oxygen isotopic composition were performed byand not the results of mixing between end-members with different laser fluorination at UNM on acid- and non-acid-washed bulk sample87 Sr/86Sr values (figs. S11 to S14). The combined REE and isotopic data and at the University of California, San Diego (UCSD) on vacuum pre-show that NWA 7034 is an enriched martian crustal rock (Fig. 5). The heated (1000°C) bulk sample (table S4). The triple oxygen isotope preci-whole rock has 143Nd/144Nd = 0.511756 and 147Sm/144Nd = 0.1664, giv- sion on San Carlos olivine standard (δ18O = 5.2‰ vs. SMOW; Δ17O =ing a calculated initial (source value) 143Nd/144Nd = 0.509467 ± 0‰) analyzed during sessions at UNM was Δ17O = ±0.03‰, precision at0.000192 (initial εNd = –9.1 ± 1.7, calculated using the Rb-Sr age) which UCSD using NBS-28 quartz standard (δ18O = 9.62‰) was also Δ17O =requires that it be derived from an enriched martian reservoir (19), with ±0.03‰. In total, twenty-one analyses of bulk NWA 7034 were carriedan inferred time-integrated 147Sm/144Nd = 0.1680 ± 0.0061, assuming out (Fig. 6). The mean value obtained at UNM was Δ17O = 0.58 ±separation from a chondrite-like martian mantle at 4.513 Ga (18). Data 0.05‰ n = 13 for acid washed samples and Δ17O = 0.60 ± 0.02‰ n = 6for each of our analyses is available in table S3. An age of ~2.1 Ga for for non-acid-washed samples; at UCSD the mean value was Δ17O = 0.50NWA 7034 would make it the only dated meteorite sample from the ± 0.03‰ n = 2 for vacuum pre-heated samples that were dewatered andearly Amazonian (19) epoch in Mars’ geologic history. NWA 7034 is decarbonated. The combined data give Δ17O = 0.58 ± 0.05‰ n = 21.derived from the most enriched martian source identified to-date; even These interlab values of bulk samples are in good agreement, but aremore enriched than the most enriched shergottites (20–23) (Fig. 5). significantly higher than literature values for SNC meteorites (Δ17OBased on the REE enrichment, isotopic values, and match to rover ele- range 0.15-0.45‰) (33–36). Figure 6 shows that the δ18O values (5.5 tomental data, NWA 7034 may better represent the composition of Mars’ 7.0‰ vs. SMOW) of NWA 7034 are higher than any determination fromcrust than other martian meteorites. Although NWA 7034 may not be the SNC group. The Δ17O values of the non-acid-washed samples meas-representative of a magmatic liquid, the negative europium anomaly and ured at UNM are similar to and within error of the acid-washed samplesabsence of merrillite or whitlockite (24) is suggestive that the magma(s) indicating that NWA 7034 has, at most, only minor terrestrial weather-parental to basaltic breccia NWA 7034 either underwent plagioclase ing products which would drive the non-acid-washed values closer tofractionation prior to eruption or feldspar was left in the residuum during Δ17O = 0.00. The slope of the best-fit line to the combined UNM acid- / http://www.sciencemag.org/content/early/recent / 3 January 2013 / Page 2/ 10.1126/science.1228858
  3. 3. washed and non-acid-washed data is 0.517 ± 0.025, suggesting that the the Δ17O of the bulk SNC samples. However, their observed Δ17O-oxygen isotopic composition of NWA 7034 is the result of mass depend- relationship between bulk rock and water is reverse to the one seen inent fractionation processes. NWA 7034, with waters in general having more positive Δ17O values There are no other known achondrites or planetary samples with than their respective host-rock (Nakhla, Chassigny, Lafayette). Only twobulk oxygen isotope values similar to NWA 7034. Most achondrite shergottites (Shergotty, EETA-79001A) have waters with Δ17O valuesgroups have negative Δ17O values or near-zero values as do rocks from more negative than the host-rock, and Nakhla has water similar to itsthe Earth and Moon. The oxygen isotope composition of Venus and host-rock. Romanek (43) analyzed iddingsite, an alteration product ofMercury are currently unknown, but NWA 7034 is too oxidized and iron olivine and pyroxene, in Lafayette and found the Δ17O value is 1.37‰rich to be derived from Mercury (37–39), and it seems to be a poor for a 90% iddingsite separate, supporting the positive Δ17O shift of Lafa-match for Venus because it experienced low temperature alteration on its yette water relative to host-rock. Karlsson (41) argued that this Δ17Oparent body and has significant indigenous water, which would not per- difference suggested a lack of equilibrium between water and host rocksist with the high surface temperatures on Venus (40). with the lithosphere and hydrosphere having distinct oxygen isotopic The distinct δ18O and Δ17O values compared to other martian mete- reservoirs. Our data support this conclusion, but suggest that the Δ17Oorites can be explained by multiple reservoirs – either within the martian value of the ‘water’ reservoir is not always heavier than the rock reser-lithosphere or between the lithosphere and a surficial component (41, 42) voir– or by incorporation of exotic material. The idea of separate long-lived We determined the deuterium to hydrogen isotope ratio (δD valuesilicate reservoirs is supported by radiogenic isotope studies (21, 23). vs. SMOW) and the water content of whole-rock NWA 7034 at UNM byThe distinct Δ17O and δ18O values of the silicate fraction of NWA 7034 both bulk combustion and stepped heating in a continuous flow, heliumcompared to all SNC meteorites measured to date further supports the stream with high-T carbon reduction (49) (Fig. 8 and table S6). Six Downloaded from www.sciencemag.org on January 3, 2013idea of distinct lithospheric reservoirs that have remained unmixed whole-rock combustion measurements yielded a bulk water content ofthroughout martian history. A near-surface component with high Δ17O 6190 ± 620 ppm. The mean δD value for the bulk combustion analysesvalues has been proposed on the basis of analysis of low temperature was +46.3 ± 8.6‰. The maximum δD values in two separate stepwisealteration products (41–43), and this may, in part, explain the Δ17O dif- heating experiments were +319‰ and +327‰, reached at 804°C andferences between the bulk and ‘water-derived’ components of NWA 1014°C respectively (table S6), similar to values seen in the nakhlites7034. However, the Δ17O value of 0.58‰ for the bulk silicate is different (50). Figure 8 shows that most of the water in NWA 7034 is releasedfrom the Δ17O value of 0.3‰ found in all SNC samples measured to between approximately 150-500°C, and that there are two plateaus of δDdate. If materials with a non 0.3‰ Δ17O value are attributed to a surficial values, one around –100‰ at 50-200°C and a second around +300‰ at(atmospheric) component, then the bulk of NWA 7034 would have nec- 300-1000°C. This suggests that there are two distinct δD components inessarily undergone extensive exchange with this reservoir. This is a pos- NWA 7034, a low temperature negative value component and a highsibility, given the abundance of low-temperature iron oxides. The temperature positive value component. One possibility is that the lowramifications of distinct lithospheric reservoirs are very different from temperature negative values are from terrestrial water contamination,those attributed to a different surficial reservoir. The latter could be ex- although the Δ17O values in water released at even the lowest tempera-plained by photochemical-induced isotope fractionation and/or hydrody- ture step of 50°C has a 0.3‰ anomaly (Fig. 7). It is also possible thatnamic escape (44–46), while the former is consistent with a lack of protium-rich water is released at the lowest steps of dehydration, alt-initial planet-wide homogenization and an absence of plate tectonics hough such fractionation is not observed on terrestrial samples. Alterna-(41). Isolated lithospheric oxygen isotope reservoirs are inconsistent tively, the hydrogen, but not oxygen isotope ratios could have beenwith a global magma ocean scenario for early Mars, which would have affected by terrestrial alteration. Finally, it is possible that nearly all thevery efficiently homogenized oxygen isotopes in the planet as occurred released water from NWA 7034 is in fact martian and not terrestrial. Infor the Earth and Moon. Instead, Mars’ differentiation could have been this case, the hydrogen isotope ratios have fractionated as a function ofdominated by basin forming impacts that left regional or even hemi- temperature, or there are two distinct hydrogen isotope reservoirs.sphere scale magmatic complexes (47, 48) with distinct and varied iso- Our data show that NWA 7034 has more than an order of magnitudetopic and geochemical characteristics. more indigenous water than most SNC meteorites. The amount of water Another possibility is that NWA 7034 originally had oxygen isotope released at high temperature (>320°C) is 3280 ± 720 ppm. Leshin et al.values similar to or the same as SNC, but a cometary component with (50) measured an average of 249 ± 129 ppm H2O released above 300-higher δ18O δ17O, and Δ17O was mixed with it through impact processes 350°C in seven bulk SNC meteorites, with exception of the anomalouson Mars, thus producing a Δ17O excess relative to SNC. Until we find Lafayette nakhlite which released 1300 ppm H2O above 300°C. Theyclear evidence of such an exotic component in NWA 7034, this scenario (50) argued that some of the water released at temperatures as low asseems less likely than the other two. 250°C could in fact be from martian alteration products. Given our oxy- The oxygen isotope ratio of water released by stepped heating in a gen water analyses this could also be the case for NWA 7034 at tempera-vacuum at UCSD (table S5) show that most, if not all, of the water in tures as low as 50°C. Hence the total amount of martian water in NWANWA 7034 is extraterrestrial with Δ17O values well above the terrestrial 7034 could be in the vicinity of 6000 ppm, possibly supporting hypothe-fractionation line (Fig. 7). NWA 7034 water falls primarily within the ses that aqueous alteration of near surface materials on Mars occurredrange of values for bulk SNC meteorites with a weighted mean value of during the early Amazonian Epoch 2.1 billion years ago either byΔ17O = +0.33 ± 0.01‰, with δ18O and δ17O values giving a slope of magmatically derived or meteoric aqueous fluids (51–53).0.52, indicating mass dependent fractionation. Interestingly, the Δ17O The young 2.1 Ga crystallization age of NWA 7034 requires that it isvalue for NWA 7034 water is lower than, and outside the range of, the planetary in origin. Its major, minor, trace, and isotopic chemistry isΔ17O for bulk NWA 7034, offering clear evidence that there are multiple inconsistent with originating from Earth, Moon, Venus, or Mercury, anddistinct oxygen isotope sources for this sample. The Δ17O value of the it is most similar to rocks from Mars. Yet still, NWA 7034 is uniquewater released at the 500-1000°C range (+0.09‰) is approaching terres- from any other martian meteorites, as it is the most geochemically en-trial values, and this could be from decomposition of the terrestrial car- riched rock from Mars that has been found to date. Moreover, the bulkbonate veins in the meteorite and equilibration of the produced CO2 with chemistry of NWA 7034 is strikingly similar to recently collected orbitalthe released water. Karlsson et al. (41) reported oxygen isotope values of and lander data collected at the martian surface, allowing for a direct linkwater from several SNC meteorites and also saw that they differed from between a martian meteorite and orbital and lander spacecraft data from / http://www.sciencemag.org/content/early/recent / 3 January 2013 / Page 3/ 10.1126/science.1228858
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  6. 6. Fig. 1. (A) NWA 7034 hand specimen. (B) Backscatter electron image of porphyritic texture in NWA 7034. Large dark crystals are feldspar, large light colored crystals are pyroxene.. Portion of a gabbroic clast is shown above the scale bar. Downloaded from www.sciencemag.org on January 3, 2013 Fig. 2. Fe versus Mn (atomic formula units) showing the trend for all NWA 7034 pyroxenes (cyan dots, 349 microprobe analyses) and for comparison pyroxene trends from Mars (red), Moon (green), and Earth (blue) (10)./ http://www.sciencemag.org/content/early/recent / 3 January 2013 / Page 6/ 10.1126/science.1228858
  7. 7. Fig. 3. Volcanic rock classification scheme based on the abundance of alkali elements and SiO2, modified after McSween et al. (4). Red dots are analyses from Alpha-Proton-X- ray Spectrometer (APXS) of rocks and soils from the Spirit Rover at Gusev Crater (5, 6). Yellow rectangle is the average martian crust as measured by the Gamma Ray Spectrometer (GRS) on the Mars Odyssey Orbiter (7). The pink field is the known range of martian meteorite (SNC) compositions. The cyan dot is the mean value of bulk NWA 7034 as determined by 225 electron microprobe analyses of fine-grained groundmass with error bars giving one standard deviation. Downloaded from www.sciencemag.org on January 3, 2013 Fig. 4. Rb-Sr whole-rock-mineral isochron of NWA 7034. The mineral fractions are labeled as Light -1, Drk-1, 2, 3 based on abundance of dark magnetic minerals. Light-1, with high 87 Rb/86Sr was the least magnetic fraction. An MSWD value of 6.6 suggests the small scatter in the values cannot be explained by analytical errors and may include slight isotopic heterogeneities in the rock. 2σ measurement errors were used for the 87 Sr/86Sr data and 2% errors for the 87 Rb/86Sr data were used for age calculation. Larger errors were assigned 87 86 to the Rb/ Sr ratios because of the inability to do internal mass fraction on Rb isotopic measurements (Rb only has two isotopes). There was not enough Sm and Nd in the mineral fractions to provide a meaningful age./ http://www.sciencemag.org/content/early/recent / 3 January 2013 / Page 7/ 10.1126/science.1228858
  8. 8. Downloaded from www.sciencemag.org on January 3, 2013Fig. 5. (A) Plot of bulk rock La/Yb ratio vs. εNd calculated at 175 Ma for NWA 7034 and basaltic Shergottites. Solid linerepresents two-component mixing line between NWA 7034 and QUE 94201. (B) Plot of calculated parent/daughter sourceratios for NWA 7034, basaltic Shergottites, Nakhlites and Chassigny (Nak/Chas), and lunar mantle sources. Solid linerepresents two-component mixing line between depleted lunar mafic cumulates and lunar KREEP. Depleted lunar maficcumulates are estimated by (54–56). Lunar KREEP is estimated by (56). Data for basaltic Shergottites, Nakhlites andChassigny are from (22, 23) and references therein.Fig. 6. Oxygen isotope plot showing the values of NWA 7034 Fig. 7. Δ17O versus temperature diagram showing the valuesfrom this study, units are per mil. Cyan dots, 13 analyses of for NWA 7034 water released by stepped heating. Verticalbulk acid-washed and 6 analyses of bulk non-acid-washed error bars are given for each data point, horizontal line(UNM), cyan squares, 2 analyses of dry, de-carbonated bulk, segments show the temperature range for each step, and thepreheated to 1000°C (UCSD). Red dots are SNC meteorites thickness of the line segment indicates the relative proportionfrom the literature (33–36, 41). TFL = terrestrial fractionation of water released at each step. Dashed line is the mean 17line, slope 0.528. value of Δ O for NWA 7034 water. Also shown are ranges of 17 Δ O for bulk NWA 7034 analyses and for bulk SNC values from the literature. TFL = terrestrial fractionation line. / http://www.sciencemag.org/content/early/recent / 3 January 2013 / Page 8/ 10.1126/science.1228858
  9. 9. Fig. 8. δD versus temperature diagrams showing the data for Downloaded from www.sciencemag.org on January 3, 2013 NWA 7034 bulk sample done by stepped heating. The horizontal solid lines represent the temperature intervals, the circle are the mid-interval temperature. The two plots represent two aliquots of NWA 7034 sample./ http://www.sciencemag.org/content/early/recent / 3 January 2013 / Page 9/ 10.1126/science.1228858
  10. 10. www.sciencemag.org/cgi/content/full/science.1228858/DC1 Supplementary Materials for Unique Meteorite from Early Amazonian Mars: Water-Rich Basaltic Breccia Northwest Africa 7034 Carl B. Agee,* Nicole V. Wilson, Francis M. McCubbin, Karen Ziegler, Victor J. Polyak, Zachary D. Sharp, Yemane Asmerom, Morgan H. Nunn, Robina Shaheen, Mark H. Thiemens, Andrew Steele, Marilyn L. Fogel, Roxane Bowden, Mihaela Glamoclija, Zhisheng Zhang, Stephen M. Elardo*To whom correspondence should be addressed. E-mail: agee@unm.edu Published 3 January 2013 on Science Express DOI: 10.1126/science.1228858This PDF file includes:Materials and MethodsFigs. S1 to S16Tables S1 to S6References
  11. 11. MethodsElectron microprobe (UNM) Electron microprobe analyses and back-scattered electron images were performedusing a JEOL 8200 Electron Probe Microanalyzer, equipped with five wavelengthdispersive spectrometers. Quantitative analyses were carried out on two thin sections andthree probe mounts of NWA 7034 taken from different locations in the stone. Analyseswere made using a tungsten filament electron gun at 15 kV accelerating voltage and20nA beam current. Most analyses were collected with 1µm-diameter beam, but feldsparanalyses were collected using a 10-20µm-diameter beam, and plumose groundmass (bulkcomposition) was analyzed with a 20µm-diameter beam.X-ray powder diffraction (UNM) One aliquot of NWA 7034 powder and one thick polished section were analyzed byX-ray diffraction (XRD) in the XRD Laboratory in the Department of Earth andPlanetary Sciences at the University of New Mexico, using a Rigaku SmartLabdiffractometer system with the SmartLab Guidance system control software for systemautomation and data collection. Cu-K-alpha radiation (40 kV, 40 mA) was used with aD/teX Ultra High Speed Silicon Strip Linear (1D) detector. The powdered sample wasprepared in a thick deep powder mount and analyzed at 40 kV and 25 mA using acontinuous scanning procedure with a n effective step size of 0.02 degrees at a scan rateof °2θ/min over the range 5–90 °2θ with incident slits set to 0.5 deg, and both receivingslits set to the maximum (20 mm). JADE® (MDI, Pleasanton, CA) analysis software wasused to determine modal abundances of the major minerals present. Peak intensityvariations were in general accord with qualitative estimates of modal abundance bypetrography, so we attempted to quantify the modal abundances of minerals in NWA7034 using the Rietveld refinement tool in the JADE® (MDI, Pleasanton, CA) analysissoftware. The variation in mineral mode between the two XRD analyses is likely a resultof the heterogeneous nature of the NWA 7034 breccia.REE analyses and Sr, Rb, Nd, and Sm isotopes (UNM) REE measurements of NWA-7034 and basalt standard BHVO-2 were made onthe Thermo X-Series II inductively coupled plasma mass spectrometer (ICPMS). Awhole rock powder was leached with 1M acetic acid for 10 minutes, and then dissolvedin an acid consisting of 20% concentrated nitric acid and 80% HF in Teflon bombs at120°C for 48 hours. The solution was transferred to a Teflon beaker and dried down. Itwas redissolved in 6M HCl and dried again, then dissolved in 0.5 ml of 7M nitric acid,then diluted in 3% nitric acid containing two internal standards (In and Re). The solutionwas analyzed against standard BHVO-2. Results are listed in Table S2 relative to valuesreported for BHVO-2 [57-58]. Subsamples of NWA-7034 were separated using a magnet. The fine-grainednature of the sample and the high concentration of magnetite made separation of mineralsdifficult. The subsample powders were leached with 1M acetic acid for 10 minutes, andthen dissolved in an acid consisting of 20% concentrated nitric acid and 80% HF inTeflon bombs at 120°C for 48 hours. The leachates were collected. The five separatesconsisted of the whole-rock aliquot, a light mineral fraction that could consist of feldspars 2
  12. 12. and Cl-apatite, and three dark Fe-rich mineral fractions. The subsample powders wereleached with 1M acetic acid for 10 minutes, and then dissolved in an acid consisting of20% concentrated nitric acid and 80% HF in Teflon bombs at 120°C for 48 hours. Eachdissolved subsample was transferred to Teflon beakers and spiked with a mixed 84Sr-87Rbspike and a 146Nd-149Sm spike, and 2 drops of perchloric acid were added. Samples werefluxed and then lightly dried down and redissolved in 6M HCl with 10 drops of boricacid. After another light dry down, the subsamples were dissolved in 2M HCl and driedsoftly, and redissolved in 1M nitric acid for column chemistry. Subsamples were passedthrough Tru-spec resin to collect the REE fraction, and then through Sr-spec resin tocollect the Sr fraction. The waste included the Rb fraction and was collected for Rbcolumn chemistry. The Sr fraction was passed through the Sr-spec resin again. Twocolumn chemistry procedures were modified for Rb separation. The methods used areafter [59-60]. [59] processed microsamples and used AG50 WX8 (50-100 mesh) cationresin to separate Rb. [60] passed the Rb fraction through AG50W-X12 (200-400 mesh) toseparate the Rb. Both methods produced the same results. The REE fraction was passedthrough Ln-spec cation resin to separate both Nd and Sm after the methods of [61]. Twosubsamples of basalt standard BHVO-2 were processed through the Sr-Rb columnchemistry with the NWA-7034 subsamples. Subsample Rb, Sr, Nd, and Sm separates were analyzed on a Thermo Neptunemulti-collector inductively coupled plasma mass spectrometer (MC-ICPMS), and theseincluded three leachates. Results are listed in Tables S1 and S2. Concentrations of Rband Sr for standard BHVO-2 were 9.7 and 9.8 ug/g Rb and 398.2 and 397.9 ug/g. [62]reported 9.6 and 381 ug/g for Rb and Sr, respectively, and the USGS certify this standardas 9.8±1 and 389±23 ug/g, respectively [57]. Our 87Sr/86Sr value for BHVO-2 is0.70347, which is identical to that reported by [62], and relative to a 87Sr/86Sr value of0.71025 for NBS 987. We measured the 87Rb/85Rb for a SPEX brand ICP standard to be0.38567 normalized to 91Zr/90Zr [after 59], a value within error of the reported terrestrialvalue of 0.38570 ± 0.00060 by the IUPAC [60], and that measured by [63] of 0.38554 ±0.00030, which was normalized to 92Zr/90Zr. Recently, the calculated 87Rb/85Rb valuesbased on normalization to a Sr double-spike are higher than those normalized to 92Zr/90Zror 91Zr/90Zr by about 0.2% (0.386353 ± 0.000004; [64]). These value differences areinsignificant with respect to the errors on our Rb-Sr isochron age. Rb and Sr results fromthe three leachates that were passed through the columns fall on the isochron. Isochronages were constructed with ISOPLOT [65].Elemental and isotopic analysis of carbon (Carnegie) The chemical (ppm C) and isotopic composition (δ13C relative to V-SMOW) ofcarbon in meteorite samples was determined by combustion in an elemental analyzer(Carlo Erba NC 2500) interfaced through a ConfloIII to a Delta V Plus isotope ratio massspectrometer (ThermoFisher). Carbon concentrations were calculated using a calibrationderived from measuring a homogenous sediment sample (Peru Mud, Penn StateUniversity) containing 6.67% C (by weight). For this study, 10-100 mg of this standardwas weighed out, which corresponds to 0.6 to 6 mg C. The δ13C of Peru Mud was -19.92±0.32 ‰ (n=40) for samples in this size range. Rock powders were weighed into4x6mm Ag capsules that were pre-combusted at 599°C in air for 2 to 4 h to removeorganic carbon contamination. Blanks from capsules were 0.2±0.07 mg (n=72). Details 3
  13. 13. for this were published in [29, 66]. This same protocol was followed for the NWA 7034sample presented in this study. In general, 5-10 mg of powdered meteorite matrix wasweighed for concentration and isotopic measurements. This meteorite containedmeasurable nitrogen concentrations, which is unusual for other Martian meteoritesamples measured [31]. Therefore, in this study, we report values for NWA 7034 thatwere prepared in pre-combusted Ag boats. Samples were acidified within the boats andsoluble compounds were not washed away. Second, we acidified samples in Ag boats,then combusted the boat plus sample at 599 °C for 2 hours. Measurements are presentedwithout blank correction for isotopic composition, because blanks were below normaldetection limits with the Carlo Erba-Delta V system. The bulk C concentration in the untreated sample was 2080 ± 80 ppm C, withcorresponding δ13C value of -3.0 ± 0.16‰. Subsequent to acid washing, the bulk Cconcentration dropped to 310 ± 10 ppm, with a corresponding δ13C value of -21.6 ±0.14‰, indicating substantial carbonate in NWA 7034, which was also confirmed byoptical microscopy and back scattered electron microscopy at UNM, and by isotopicanalyses of inorganic carbonate at UCSD . The acid-washed and muffled sample yielded22 ± 10 ppm C, with an isotopic value of -23.4 ± 0.73‰, which is very similar toprevious bulk C and δ13C analyses of shergottite meteorites after acid-washing andmuffling [31-32].Raman analysis (Carnegie) Raman spectra and images were collected using a Witec α-Scanning Near-FieldOptical Microscope that has been customized to incorporate confocal Ramanspectroscopic imaging. The excitation source is a frequency-doubled solid-state YAGlaser (532nm) operating between 0.3 and 1 mW output power (dependent on objective),as measured at the sample using a laser power meter. Objective lenses used included ax100 LWD and a x20 LWD with a 50µm optical fiber acting as the confocal pin hole.Spectra were collected on a Peltier-cooled Andor EMCCD chip, after passing through af/4 300mm focal length imaging spectrometer typically using a 600 lines/mm grating.The lateral resolution of the instrument is as small as 360 nm in air when using the x100LWD objective, with a focal plane depth of ~800nm. This instrument is capable ofoperating in several modes. Typically 2D imaging and single spectra modes were usedduring this study. Single spectra mode allows the acquisition of a spectrum from a singlespot on the target. Average spectra are produced typically using integration times of 30seconds per accumulation and 10 accumulations to allow verification of weak spectralfeatures. Further details on the Raman instrument used can be found in [31, 67-68]. Weused both transmitted and reflected light microscopy to locate the field of interest. Targetareas were identified on the thin section in transmitted light. The microscope was thenswitched to reflected light and refocused to the surface. At which point X, Y and Z piezosof the stage were reset. Switching back to transmitted light then allows an accuratemeasurement of the depth of the feature of interest. The height and width of the field ofinterest within the light microscopy image were then measured and divided by the lateralresolution of the lens being used, to give the number of pixels per line. The instrumentthen takes a Raman spectrum (0-3600 cm-1 using the 600 lines mm-1 grating) at each pixelusing an integration time of between 1 and 6 s per pixel. A cosmic ray reduction routinewas used to reduce the effects of stray radiation on Raman images, as was image 4
  14. 14. thresholding to reject isolated bright pixels. Fluorescence effects were inhibited by theuse of specific peak fitting in place of spectral area sums and by the confocal optics usedin this instrument. The effects of interfering peaks were removed by phase maskingroutines based on multiple peak fits as compared to standardized mineral spectra. Thisproduces an average spectrum over the number of pixels chosen in the area of interest.Standard spectra were obtained from an internal Raman database provided by the RRUFFproject (www.rruff.info).Isotopic analysis of inorganic carbonates and sulfates (UCSD)These analyses were performed by acid extraction, gas chromatography, fluorination andisotope ratio mass spectrometry. One gram of NWA7034 was ground to fine powder,evacuated to 10-6Torr with 100% phosphoric acid in reaction vessel. CO2 released uponacid digestion at 25 ± 1 oC was collected after 1, 2 and 12 hours in three successive steps.The mixture was heated at 150 oC for three hours to release CO2 from non calcium or Fe-Mn-Mg rich carbonate fractions. The step-wise CO2 extraction procedure was adopted toisolate terrestrial contamination from the Martian meteorite. C and O-triple isotopiccomposition of carbonates was measured following the method developed by Shaheen etal. [69]. Inorganic sulfate was extracted by dissolving 1 g of NWA7034 in 2 mL ofMillipore water, sonicated for 3hours and supernatant collected in a vial. The step wasrepeated twice to ensure complete removal of water soluble ions. Organic impurities wereremoved from the supernatant by treating with 30% H2O2 (1.0 mL) and further passingthrough polyvinyl pyrolydine (PVP), C18 (Alltech) resins. SO4 was separated from otheranions using liquid chromatography, converted to silver sulfate and pyrolyzed at 1050 oCfor oxygen isotope analysis. The carbonate and sulfate weathering products that were sampled in oxygen tripleisotope analyses of carbonate and sulfate done by step-wise acid dissolution at UCSDyielded values of Δ17O=-0.04±0.04‰ n=4 and Δ17O=+0.04‰ n=1, respectively, with abulk CO3=0.87 wt% (Fig, S16). O-triple isotope analysis of carbonate minerals (δ17O =19-24‰ δ18O = 37- 46‰) showed higher O-isotope enrichment compared to the desertdust samples (δ17O = 15-21‰ δ18O = 29-41‰). However, NWA7034 carbonates anddesert soil samples possess Δ17O~0. Oxygen triple isotope analysis of water solublesulfate (δ17O = 3.7‰ δ18O= 6.7‰) showed mass dependently fractionated oxygenreservoirs. The Δ17O ~ 0 of secondary minerals (carbonates and sulfates) indicates theirprecipitation from a water reservoir with no oxygen isotope anomaly suggesting eitherterrestrial origin or subaerial martian water reservoir not in contact with the martianatmosphere and decoupled from the other oxygen carrying reservoirs. The Carnegiemeasurements show that there is significant organic carbon from both indigenous andexogenous terrestrial sources. Both Carnegie and UCSD detected terrestrial carbonatecomponent in their bulk samples although they have significantly different values in thetotal measured carbon and the bulk value of δ13C. We attribute these differences toheterogeneous distribution of carbonate in NWA 7034, with a heterogeneous input oforganic material to the isotope values.Sample Treatment % CO3 δ13C δ17O δ18O Δ17O (‰) (‰) (‰) (‰)NWA7034 1st h at 25o C 0.54 0.87 24.00 46.49 0.013NWA7034 2nd h at 25o C 0.06 0.75 23.62 45.89 -0.05NWA7034 12 h at 25o C 0.2 0.56 23.72 46.09 -0.05 5
  15. 15. NWA7034 3 h at 150o C 0.07 0.17 19.23 37.43 -0.07Arizona Test Dust 12 h at 25o C 4.96 -8.97 15.10 29.48 -0.10Owen Lake Dust 12 h at 25o C 5.08 -3.64 18.21 35.60 -0.15Black Rock Desert Dust, 12 h at 25o C 7.03 -6.069 18.04 35.25 -0.15NevadaYaDan GanSu dust, China 12 h at 25o C 7.38 -13.52 16.51 32.24 -0.12Grand Canyon Red Soil 12h at 25o C 0.05 -16.68 20.98 41.07 -0.21Commercial cement sample 12 h at 25o C 4.99 -19.34 14.38 28.06 -0.09*NWA7034- SO4 3.52 6.74 0.04Overall uncertainty of the procedure is δ13C = 0.1‰, δ17O and δ17O =0.3‰, Δ17O=0.1‰.The precision of the isotopic ratio measurements are +0.03‰. Carbon and oxygen isotopevalues are reported with reference to V-PDB and SMOW.* 1 µmole of sulfate was obtained by dissolving 1g powdered meteorite in Milliporewater and sonicating for 3 hours. The procedure was repeated three times to ensurecomplete removal of water soluble sulfates.Oxygen isotopes (UNM) Oxygen isotope analyses of NWA 7034 were performed by laser fluorination at UNMon acid-washed bulk samples (removal of possible terrestrial weathering products).Pretreated samples (1-2 mg) were pre-fluorinated (BrF5) in the vacuum chamber in orderto clean the stainless steel system and to react residual traces of water or air in thefluorination chamber. Molecular oxygen was released from the samples by the laser-assisted fluorination (25W far-infrared CO2 laser) in a BrF5-atmoshpere, producingmolecular O2 and solid fluorides. Excess BrF5 was then removed from the produced O2by reaction with hot NaCl. The oxygen was purified by freezing to a 13Å molecular sieveat -196°C, followed by elution of the O2 from the first sieve at −131°C to a second 5Åmolecular sieve at −190°C [70]. Measurements of the isotope ratios were then made on aFinnigan DeltaXLPlus dual inlet isotope ratio mass spectrometer, and the oxygen isotoperatios were calibrated against the isotopic composition of San Carlos olivine. Eachsample gas was analyzed multiple times, and each analysis consisted of 20 cycles ofsample-standard comparison. Olivine standards (~1-2 mg) were analyzed daily. Oxygenisotopic ratios were calculated using the following procedure: The δ18O values refer tothe per-mil deviation in a sample (18O/16O) from SMOW, expressed as δ18O =[(18O/16O)sample/(18O/16O)SMOW-1] × 103. The delta-values were converted to linearizedvalues by calculating: δ18/17O’ = ln[(δ 18/17O + 103)/103] × 103 in order to create straight-line mass-fractionation curves. The δ17O’ values were obtained from the linear δ -valuesby the following relationship: δ17O’ = δ17O’ – 0.528 x δ18O’, .Δ17O’ values of zero definethe terrestrial mass-fractionation line, and Δ17O’ values deviating from zero indicatemass-independent isotope fractionation.Hydrogen isotopes (UNM) Hydrogen isotope analyses of NWA 7034 were performd by a thermalcombustion elemental analyzer (Finnigan TC-EA) connected to a gas chromatograph, aHe-dilution system (Finnigan CONFLO II) interface, and a Finnigan DeltaXLPlus dualinlet isotope ratio mass spectrometer with continuous flow abilities for hydrogen. Thetechnique involves reduction of solid hydrous samples by reaction with glassy carbon athigh temperatures. H2 and CO are produced by reaction with the carbon at 1450°C in aHe carrier gas. Product gases are separated in a gas chromatograph and analyzed in amass spectrometer configured to make hydrogen isotope analyses in continuous flow 6
  16. 16. mode, with the reference hydrogen gas being introduced from the bellows system of thedual inlet [49]. Solid materials (several mg) for bulk analyses were wrapped in silver foiland dropped into the furnace using an autosampler. Using standard correction procedures,results obtained with this method are identical to those obtained conventionally with aprecision for water samples of +/-2‰ (1o). Total time of analysis is less than 2 minutesfor a single hydrogen isotope analysis. For stepwise heating, the sample was placed in aquartz- or ceramic-tube, held in place by quartz wool, and heated by external furnaces.The sample was allowed to dry under He-flow at 50°C prior to gradual increase of thefurnace temperature to the desired temperature. Evolving water was collected in a liquidnitrogen trap. Upon reaching of the required dwell time, the collected water was releasedinto the TC-EA for combustion, and processed as described above. Weight % H2O of thesamples analyzed were calculated by relating the peak-area of the sample to that of theinternational biotite standard NBS-30 (3.5 wt. % H2O). 7
  17. 17. Fig. S1.Backscatter electron image of spherical gabbroic clast composed of fine grained feldspar(dark), pyroxene (light gray), and magnetite and maghemite (white). 8
  18. 18. Fig. S2Backscatter electron image of an apatite-ilmenite-alkali feldspar cluster. White elongatecrystal is ilmenite, light gray crystals are Cl-apatite, medium dark crystals are andesine(Na-Ca plagioclase feldspar), darkest crystals are sanidine (K-feldspar), white finegrained crystals are magnetite or other iron-oxide. 9
  19. 19. <insert page break then Fig S3 here>Fig. S3Backscatter electron image of a portion of a ~1-cm quench melt clast with skeletalpyroxene (dark gray) and olivine (light gray) set in a fine grained to glassy quench crystalmatrix. 10
  20. 20. Fig. S4Backscatter electron image of a magnetite/maghemite-rich “reaction sphere”. White, finegrained phase is magnetite or maghemite, medium and dark phases are very fineintergrowths of pyroxene and feldspar. 11
  21. 21. Or 0 100 10 90 20 80 30 70 40 60 50 50 60 40 70 30 80 20 90 10 100 0Ab 0 10 20 30 40 50 60 70 80 90 100 An All Feldspar NWA 7034Fig. S5Ternary diagram showing the range of feldspar compositions present in NWA 7034 (cyandots, 178 electron microprobe analyses, molar percent). The range in feldsparcompositions displayed by NWA 7034 is much broader than what has been measured inthe shergottites [10], although it matches fairly well with feldspar compositions inChassigny [11]. Ab=albite An=anorthite Or=orthoclase. 12
  22. 22. All Pyroxene NWA 7034 DI HDEN FS 0 20 40 60 80 100Fig. S6Pyroxene quadrilateral showing the range of compositions present in NWA 7034 (cyandots, 410 electron microprobe analyses, molar percent). There are two main clusters ofpyroxenes: 1) a high calcium augitic cluster and 2) a low calcium orthopyroxene clusterthat becomes pigeonitic with increasing ferrosilite. EN=enstatite FS-ferrosiliteDI=diopside HD=hedenbergite. 13
  23. 23. Fig. S7Mg/Si Al/Si diagram modified after McSween et al. [4]. Red dots are analyses fromAlpha-Proton-X-ray Spectrometer (APXS) of rocks and soils from the Spirit Rover atGusev Crater [5-6]. Yellow rectangle is the average martian crust as measured by theGamma Ray Spectrometer (GRS) on the Mars Odyssey Orbiter [7]. The cyan dot is themean value of bulk NWA 7034 as determined by 225 electron microprobe analyses (cyandots) of fine-grained groundmass with error bars giving one standard deviation. 14
  24. 24. Fig. S8Ni versus Mg diagram modified after [71]. Red dots are analyses from Alpha-Proton-X-ray Spectrometer (APXS) of rocks and soils from the Spirit Rover at Gusev Crater [5-6].Yellow rectangle is the average martian crust as measured by the Gamma RaySpectrometer (GRS) on the Mars Odyssey Orbiter [7]. The cyan dot is the mean value ofbulk NWA 7034 as determined by 225 electron microprobe analyses of fine-grainedgroundmass with error bars giving one standard deviation. 15
  25. 25. 100S ample/C hondrite 50 NWA-7034 Whole Rock 25 NWA-7034 Leachate 10 La Ce Pr Nd S m E u Gd Tb Dy Ho Er Tm Yb Lu Fig. S9 Chondrite-normalized REE pattern of NWA 7034 whole rock and leachate. The pattern, with strong LREE/HREE enrichment (La/Yb)N=2.3 and pronounced Eu anomaly (Eu/Eu*=0.67) appears to be from an evolved terrestrial planet crust. Some of the LREE/HREE enrichment is likely to have been inherited from the source. In addition the sample has high 232Th/238U (K-value) of 5.2 (Table S1), which also likely represents source enrichment. 16
  26. 26. 100 50 NWA 7034 (WR)S ample/C hondrite 25 Shergotty (WR) 10 Nakhla (WR) Tissint (WR) 1 La Ce Pr Nd S m E u Gd Tb Dy Ho Er Tm Yb Lu Fig. S10 Chondrite-normalized REE pattern of NWA 7034 whole rock compared with some SNC meteorites. Shergotty [40] is a so-called enriched shergottite, Tissint [16] is a so-called depleted shergottite, and Nakhla [40] shows LREE enrichment relative to HREE, with negative slope, seen in most nakhlites. 17
  27. 27. 0.780 0.760 LGT& 87Sr& 86Sr& 0.740 DRK$2& WR& 0.720 DRK$3& DRK$1& 0.700 0.79 0.80 0.81 0.82 0.83 0.84 0.85 0.86 0.87 1& (&&&&&&)&x100& Sr&Fig. S11The inverse Sr concentration plotted against the 87Sr/86Sr ratio of the whole rock andmineral separates. On such a diagram samples that are related by two-component mixingwould define a parabola. In this case there is no clear pattern, which is inconsistent withthe isotopic data being the result of two component mixing. 18
  28. 28. 0.780 ! 0.780 ! Model& Measured& LGT& 0.760 ! 0.760 ! 87Sr& 0.740 ! 0.740 ! 86Sr& WR& DRK.2& LGT& 0.720 ! 0.720 ! DRK.3& DRK.1& 0.700 ! 0.700 ! -0.25! 0.00! 0.25! 0.50! 0.75! 1.00!Fig. S12Results of two component mixing calculation based on the Sr concentration end members(whole rock and the mineral fraction DRK-2). The red circles are model results, whileblue circles are measured values. Note the large divergence between the calculated andmeasured values of the light mineral fraction (LGT). 19
  29. 29. 0.7700% LGT# 0.7500% 87Sr# 86Sr# 0.7300% DRK+1# WR# DRK+2# R²#=#0.99994# DRK+3# 0.7100% 0% 20% 40% 60% 80% Rb#(ppm)#Fig. S13The Rb concentration plotted against the 87Sr/86Sr ratio of the whole rock and mineralseparates. The near perfect relationship between the two values (R2 ~ 1) is a goodindication that variations in the 87Sr/86Sr values are the result of the time-integratedradiogenic growth from 87Rb and not the results of mixing between end-members withdifferent 87Sr/86Sr values. 20
  30. 30. Age = 1957 ± 320 Ma MSWD = 5.0 0.727 wr 0.725 87Sr/86Sr 0.723 The three dark fraction 0.721 separates. 0.719 0.15 0.25 0.35 0.45 87Rb/86SrFig. S14Rb-Sr isochron constructed from the whole rock and dark mineral fractions, giving anage, within error of the isochron that includes that light fraction. These data show that theage is not simply controlled by the high 87Rb/86Sr light fraction. 21
  31. 31. Fig. S15Light microscopy and CRIS images of a feldspar grain in NWA 7034 hosting mineralinclusions A) light microscopy image of inclusions several microns below the surface ofa Feldspar grain. B-F) Confocal Raman Imaging Spectroscopy images of individualphases identified in the field of view B) Feldspar, C) apatite, D) magnetite, E) pyroxeneF) reduced macromolecular carbon. All of the Raman peak positions used to generate theRaman spectroscopic images B-F are the same as those described in [31, 67-68]. Theassociation of MMC with magnetite. The association of MMC with magnetite andpyroxene with or without the presence of apatite has been seen in previous studies [30]. 22
  32. 32. Fig. S16Oxygen three isotope plot of CO2 obtained during step wise acid dissolution of Martianmeteorite NWA7034. Step1, 2 and 3 at 25o C indicate Ca rich phases of CO3 and step 4 at150o C indicates Fe-Mn-Mg rich CO3 phase. For comparison oxygen triple isotopiccomposition of CO2 obtained from Ca rich phase of CO3 of terrestrial soils from desertsand carbonates from ALH84001 and Nakhlite martian meteorites are included. Oxygentriple isotopic composition of water soluble sulfate in NWA 7034 is also shown. 23
  33. 33. Bulk%Compositon%NWA%7034 225#microprobe#analyses#of#plumose#groundmass 20#micron#beam Average StdDev ###SiO2## 47.55 1.81 ###Al2O3# 11.21 1.56 ###TiO2## 0.98 0.22 ###Cr2O3# 0.18 0.09 ###MgO### 7.81 1.68 ###MnO### 0.28 0.05 ###CaO### 8.93 1.27 ###FeO### 13.00 2.47 ###NiO### 0.05 0.02 ###Na2O## 3.74 0.52 ###K2O### 0.34 0.06 ###P2O5## 0.76 0.21 ###Cl#### 0.22 0.06 ###SO3### 0.10 0.21 ##Total#(wt%)# 95.11 1.37 Na+K 4.09 0.53 Ca/Si 0.29 0.04 Mg/Si 0.21 0.05 Al/Si 0.27 0.03 Mg# 0.52 0.05 Fe/Mn#(molar) 47 9Table S1. 24
  34. 34. NWA-7034-WR BHVO-2 BHVO-2 BHVO-2 Element (this study) (this study) (Wilson (Wanke et al.) Sc 12.28 ± 0.087 32.29 ± 0.924 ) 32 ± 1 31.8 Y 40.68 ± 0.096 25 ± 0.414 26 ± 2 25.5 La 13.66 ± 0.375 15.65 ± 0.287 15 ± 1 15.2 Ce 34.63 ± 0.573 39.36 ± 0.621 38 ± 2 38 Pr 4.823 ± 0.106 5.488 ± 0.194 5.3 Nd 22.7 ± 0.420 26.22 ± 0.379 25 ± 1.8 25 Sm 6.433 ± 0.064 6.507 ± 0.029 6.2 ± 0.4 6.2 Eu 1.585 ± 0.016 2.253 ± 0.043 2.06 Gd 7.454 ± 0.038 6.799 ± 0.166 6.3 ± 0.2 6.3 Tb 1.425 ± 0.007 1.088 ± 0.030 0.9 0.93 Dy 8.432 ± 0.301 5.798 ± 0.148 5.25 Ho 1.751 ± 0.029 1.096 ± 0.008 1.04 ± 0.04 0.99 Er 4.954 ± 0.113 2.873 ± 0.016 2.5 Tm 0.7493 ± 0.024 0.4108 ± 0.008 0.34 Yb 4.306 ± 0.065 2.204 ± 0.035 2.00 ± 0.2 2 Lu 0.6861 ± 0.019 0.3658 ± 0.004 0.28 Th 2.635 ± 0.063 1.252 ± 0.035 1.20 ± 0.3 1.2 U 0.5124 ± 0.024 0.3682 ± 0.007 0.41Table S2.All results are in ppm. Errors from this study are reported as analytical absolute standarderrors. Wilson = [57], which are certified values for BHVO-2 powder standard. Wankeet al. = Values measured for BHVO-2 by [58]. 25
  35. 35. Rb-Sr and Sm-Nd isotopic and concentration data for NWA 7034 and BHVO rock standard 87 wt. (mg) Rb/86Sr Error 87 Sr/86Sr abs error Rb (ppm) Sr (ppm) WR 34.69 0.4275 0.009 0.726229 0.00001 17.06 115.49 LGT-1 24.43 1.8251 0.037 0.768746 0.00001 75.62 119.88 DRK-1 43.09 0.2715 0.005 0.721567 0.00001 11.32 120.62 DRK-2 37.64 0.2206 0.004 0.720430 0.00001 9.57 125.55 DRK-3 43.93 0.2209 0.004 0.720396 0.00001 9.50 124.47 BHVO-2-1 61.55 0.0706 0.000 0.703471 0.00001 9.72 398.16 BHVO-2-2 112.15 0.0714 0.000 0.703467 0.00001 9.82 397.94 147 144 143 144 Wt. (mg) Sm/ Nd error Nd/ Nd error Sm (ppm) Nd (ppm) WR 34.69 0.16642 0.00017 0.51176 0.00010 5.16 18.73!Table S3.Sr isotopic ratios were normalized to 86Sr/88Sr ratio of 0.1194, while Nd isotopic ratioswere normalized to 144Nd/146Nd ratio of 0.7219. Errors are 2-σ of the mean. 26
  36. 36. NWA 7034 Laser Fluorination DataUNMBulk solids acid-washed δ17O δ18O Δ 17O 4.13 6.59 0.65 3.93 6.40 0.55 3.78 5.97 0.63 3.54 5.81 0.47 4.30 7.19 0.51 3.90 6.31 0.56 3.84 6.16 0.59 3.76 6.06 0.56 3.93 6.28 0.61 3.81 6.10 0.59 4.54 7.52 0.64 3.73 5.92 0.61 3.88 6.24 0.59Average 3.93 6.35 0.58Stdev 0.26 0.50 0.05Bulk solids non-acid-washed δ17O δ18O Δ 17O 4.01 6.46 0.60 3.98 6.33 0.63 3.96 6.32 0.62 4.15 6.75 0.58 3.84 6.19 0.57 3.86 6.21 0.58Average 3.96 6.38 0.60Stdev 0.11 0.21 0.02UCSDBulk solids dry and decarbonated to 1000C δ17O δ18O Δ 17O 3.43 5.59 0.48 4.03 6.64 0.53Average 3.73 6.12 0.50Stdev 0.43 0.75 0.03Table S4.Oxygen isotope data (relative to V-SMOW; precision of Δ17O’ values is 0.03‰). 27
  37. 37. Oxygen isotopes Time heating (hrs) wt% H2O St.Dev.Temperature (°C) Water Yield (µmol) values 50 1.5 16.2 0.024 δ18O= -21.780 0.045 δ17O= -11.047 0.065 17 Δ O= 0.453 18 150 3 76.0 0.111 δ O= -3.883 0.027 δ17O= -1.794 0.039 Δ17O= 0.256 18 320 1 91.0 0.133 δ O= -4.729 0.030 17 δ O= -2.135 0.024 Δ17O= 0.362 500 1 39.2 0.057 δ18O= -1.634 0.021 17 δ O= -0.481 0.031 17 Δ O= 0.382 1000 1 5.56 0.008 δ18O= 11.019 0.037 δ17O= 5.909 0.064 Δ17O= 0.0910 17 Total 228 0.333 Δ O= 0.330 0.011!Table S5.Oxygen Isotopic Composition of Water Extracted from NWA 7034 by Stepwise Heating(relative to V-SMOW; precision of Δ17O’ values is 0.03‰) 28
  38. 38. NWA 7034 D/H bulk analyses (whole rock) Bulk analyses (combustion) δD‰ wt.% H 2 O 50 0.63 59 0.60 41 0.65 35 0.68 50 0.64 42 0.50 Step-wise heating (continuous flow): 3 runsT range °C δD‰ time @ T (min) wt.% H 2 O % of total H 2 O50-100 -142 38 0.10 17.89100-150 -114 38 0.05 9.79150-325 -88 38 0.22 40.12325-493 143 38 0.15 27.82493-804 327 38 0.02 4.3950 -103 155 0.01 2.2650-105 -125 38 0.02 4.98105-150 -126 38 0.05 10.25150-321 -91 38 0.19 39.72321-505 220 38 0.19 40.17505-804 274 120 0.01 1.59804-1014 319 120 0.00 0.52 Hydrogen isotope values of bulk samples and of stepwise heated increments (‰ relative to V-SMOW).Weight % H2O calculated relating the peak-area of the sample to that ofthe international standard NBS-30 ( 3.5 wt. % H2O)Table S6. 29
  39. 39. References1. A. H. Treiman, J. D. Gleason, D. D. Bogard, The SNC meteorites are from Mars. Planet. Space Sci. 48, 1213 (2000). doi:10.1016/S0032-0633(00)00105-72. H. Y. McSween, T. L. Grove, J. Wyatt, Constraints on the composition and petrogenesis of the Martian crust. J. Geophys. Res. Planets 108, 5135 (2003). doi:10.1029/2003JE0021753. L. E. Nyquist et al., in Chronology and Evolution of Mars, R. Kallenbach, J. Geiss, W. K. Hartmann, Eds. (Springer, New York, 2001), p. 105.4. H. Y. McSween Jr., G. J. Taylor, M. B. Wyatt, Elemental composition of the Martian crust. Science 324, 736 (2009). doi:10.1126/science.1165871 Medline5. R. Gellert et al., Alpha Particle X-Ray Spectrometer (APXS): Results from Gusev crater and calibration report. J. Geophys. Res. Planets 111, E02S05 (2006). doi:10.1029/2005JE0025556. D. W. Ming et al., Geochemical properties of rocks and soils in Gusev Crater, Mars: Results of the Alpha Particle X-Ray Spectrometer from Cumberland Ridge to Home Plate. J. Geophys. Res. Planets 113, E12S39 (2008). doi:10.1029/2008JE0031957. W. V. Boynton et al., Concentration of H, Si, Cl, K, Fe, and Th in the low- and mid-latitude regions of Mars. J. Geophys. Res. Planets 112, E12S99 (2007). doi:10.1029/2007JE0028878. See supplementary materials on Science Online.9. S. P. Wright, P. R. Christensen, T. G. Sharp, Laboratory thermal emission spectroscopy of shocked basalt from Lonar Crater, India, and implications for Mars orbital and sample data. J. Geophys. Res. Planets 116, E09006 (2011). doi:10.1029/2010JE00378510. J. J. Papike, J. M. Karner, C. K. Shearer, P. V. Burger, Silicate mineralogy of martian meteorites. Geochim. Cosmochim. Acta 73, 7443 (2009). doi:10.1016/j.gca.2009.09.00811. F. M. McCubbin, H. Nekvasil, Maskelynite-hosted apatite in the Chassigny meteorite: Insights into late-stage magmatic volatile evolution in martian magmas. Am. Mineral. 93, 676 (2008). doi:10.2138/am.2008.2558