Research Articles 

The only tangible samples of the planet Mars that are available for study in Earth-based laboratories, have up to now, been limited to the so-called SNC (1) meteorites and a single cumulate orthopyroxenite (Allan Hills 84001). The SNCs currently number 110 named stones and have provid-ed a treasure trove for elucidating the geologic history of Mars (2). But because of their unknown field context and geographic origin on Mars, their fairly narrow range of igneous rock types and formation ages (3), it is uncertain to what extent SNC meteorites sample the crustal diversity of Mars. In fact, geochemical data from NASA’s orbiter and lander mis-sions suggest that the SNC meteorites are a mismatch for much of the martian crust exposed at the surface (4). For example, the basalts ana-lyzed by the Mars Exploration Rover Spirit at Gusev Crater (5, 6) are distinctly different from SNC meteorites, and the Odyssey Orbiter gam-ma ray spectrometer (7) (GRS) data show that the average martian crust composition does not closely resemble SNC.

NWA 7034, on deposit at the Institute of Meteoritics, purchased by Jay Piatek from Aziz Habibi, a Moroccan meteorite dealer, in 2011, is a 319.8 g single stone, porphyritic basaltic monomict breccia, with a few euhedral phenocrysts up to several millimeters and many phenocryst fragments of dominant andesine, low-Ca pyroxene, pigeonite, and augite set in a very fine-grained, clastic to plumose, groundmass with abundant magnetite and maghemite; accessory sanidine, anorthoclase, Cl-rich apatite, ilmenite, rutile, chromite, pyrite, a ferric oxide hydroxide phase, and a calcium carbonate identified by electron microprobe analyses on eight different sections at the University of New Mexico (UNM). X-ray diffraction analyses conducted at UNM on a powdered sample and on a polished surface show that plagioclase feldspar is the most abundant phase (38.0 ± 1.2%), followed by low-Ca pyroxene (25.4 ± 8.1%), clinopyroxenes (18.2 ± 4.0%), iron-oxides (9.7 ± 1.3%), alkali feldspars

(4.9 ± 1.3%), and apatite (3.7 ± 2.6%). The x-ray data also indicate a minor amount of iron-sulfide and chromite. The data are also consistent with mag-netite and maghemite making up ~70% and ~30%, respectively, of the iron oxide detected (8).

Numerous clasts and textural varie-ties are present in NWA 7034 that include gabbros, quenched melts, and iron oxide-ilmenite-rich reaction spherules (figs. S1 to S4) (8), however the dominant textural type is a fine-grained basaltic porphyry with feldspar and pyroxene phenocrysts. NWA 7034 is a monomict brecciated porphyritic basalt that is texturally unlike any SNC meteorite. Basaltic breccias are com-mon in Apollo samples, lunar meteor-ites, and HED meteorites, but wholly absent in the world’s collection of SNC meteorites (9). Absence of shocked-produced SNC breccias seems curious at face value, since nearly all of them show evidence of being subjected to high shock pressures, with feldspar commonly converted to maskelynite. Martian volcanic breccias are probably not rare given the observed widespread occurrence of volcanism on Mars. However launch and delivery of such materials to Earth as meteorites has not been observed (9). Although NWA 7034 is texturally heterogeneous both

in hand sample and microscopically (Fig. 1), it can be considered a monomict breccia because it shows a continuous range of feldspar and pyroxene compositions that are consistent with a common petrologic origin (figs. S5 and S6). We find no outlier minerals or compositions that would indicate the existence of multiple lithologies or exotic com-ponents. We also see no evidence for polymict lithologies in either the radiogenic or stable isotope ratios of NWA 7034 solids. However, many clasts and some of the fine-grained groundmass have phases that appear to have been affected by secondary processes to form reaction zones. We observed numerous reaction textures, some with a ferric oxide hydroxide phase, which along with apatite, are the main hosts of the water in NWA 7034 (fig. S2). Impact processes are likely to have affected NWA 7034 by virtue of the fact that this meteorite was launched off of Mars, ex-ceeding the escape velocity – presumably by an impact–although the shock pressures did not produce maskelynite. One large (1-cm) quench melt clast that was found could originate from shock processes (fig. S3). On the other hand, the very fine groundmass with the large phenocrystic feldspars and pyroxenes strongly suggests an eruptive volcanic origin for NWA 7034, thus it is likely that volcanic processes are a source of the brecciation.

Unique Meteorite from Early Amazonian Mars: Water-Rich Basaltic Breccia Northwest Africa 7034 Carl B. Agee,1,2* Nicole V. Wilson,1,2 Francis M. McCubbin,1,2 Karen Ziegler,1 Victor J. Polyak,2 Zachary D. Sharp,2 Yemane Asmerom,2 Morgan H. Nunn,3 Robina Shaheen,3 Mark H. Thiemens,3 Andrew Steele,4 Marilyn L. Fogel,4 Roxane Bowden,4 Mihaela Glamoclija,4 Zhisheng Zhang,3,5 Stephen M. Elardo1,2 1Institute of Meteoritics, University of New Mexico, Albuquerque, NM 87131, USA. 2Department of Earth and Planetary Sciences, University of New Mexico, Albuquerque, NM 87131, USA. 3Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA 92093, USA. 4Geophysical Lab, Carnegie Institution of Washington, Washington, DC 20005, USA. 5School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275, China.

*To whom correspondence should be addressed. E-mail: agee@unm.edu

We report data on the martian meteorite, Northwest Africa (NWA) 7034, which shares some petrologic and geochemical characteristics with known martian (SNC, i.e., Shergottite, Nakhlite, and Chassignite) meteorites, but also possesses some unique characteristics that would exclude it from the current SNC grouping. NWA 7034 is a geochemically enriched crustal rock compositionally similar to basalts and average martian crust measured by recent rover and orbiter missions. It formed 2.089 ± 0.081 Ga, during the early Amazonian epoch in Mars’ geologic history. NWA 7034 has an order of magnitude more indigenous water than most SNC meteorites, with up to 6000 ppm extraterrestrial H2O released during stepped heating. It also has bulk oxygen isotope values of Δ17O = 0.58 ± 0.05‰ and a heat-released water oxygen isotope average value of Δ17O = 0.330 ± 0.011‰ suggesting the existence of multiple oxygen reservoirs on Mars.

It has been shown (10) that Fe-Mn systematics of pyroxenes and olivines are an excellent diagnostic for classifying planetary basalts. Fe-Mn of NWA 7034 pyroxenes, as determined by electron microprobe analyses, most resemble the trend of the SNC meteorites from Mars (Fig. 2); other planetary pyroxenes such as in lunar samples and basalts from Earth are poor matches for NWA 7034. Furthermore, feldspar composi-tions (fig. S5) (8) and compositions of other accessory phases in NWA 7034 are consistent with mineralogies commonly found in SNC meteor-ites (11), but not with any other known achondrite group. However, the

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average bulk chemical composition of NWA 7034 does not overlap in major element space with SNC, instead it is remarkably similar to the geochemistry of the rocks and soils at Gusev Crater and the average martian crust composition from the Odyssey Orbiter gamma ray spec-trometer (GRS) (Fig. 3 and figs. S7 and S8). NWA 7034, Gusev rocks, and the GRS average martian crust all have higher concentrations of the alkali elements sodium and potassium in comparison to SNC meteorites. Other major and minor element ratios such as Mg/Si, Al/Si, and Ni/Mg have similarly good matches between NWA 7034 and Gusev Crater rocks (figs. S7 and S8). Although some experimental work has been conducted to link martian meteorites to surface rocks analyzed by the Mars Exploration Rovers (12–14), and aside from the exotic “Bounce Rock” (15) at Meridiani Planum, and hypothesized martian soil compo-nent in Tissint melt pockets (16), there has been no direct link between the bulk chemical compositions of martian meteorites and surface rocks to date.

The rare earth element (REE) abundances of NWA 7034 were de-termined by multi-collector inductively coupled plasma mass spectrome-try (Neptune MC-ICP-MS) at UNM. They are significantly enriched relative to chondritric abundances with a marked negative europium anomaly (Eu/Eu* = 0.67) (fig. S9 and table S2). The REE pattern has a negative slope and light rare earth elements (LREE) are elevated relative to the heavy rare earth elements (HREE) (La/Yb)N = 2.3. Bulk SNC meteorites are much less enriched in REE (17) than NWA 7034 (fig. S10), although LREE enrichment relative to HREE and REE patterns with negative slopes are seen in nakhlites, only magmatic inclusions and mesostasis in nakhlites and estimated nakhlite parent magmas have LREE enrichments comparable to NWA 7034 (17, 18). We observed ubiquitous, relatively large (up to ~100 μm) Cl-rich apatite grains in NWA 7034 which presumably harbor a substantial fraction of the REEs in this meteorite, as merrillite/whitlockite was not identified in any of the investigated thin sections or probe mounts.

A five-point isochron gives an Rb-Sr age for NWA 7034 of 2.089 ± 0.081 Ga (2σ) (MSWD = 6.6), an initial 87Sr/86Sr ratio of 0.71359 ± 54 (Fig. 4), and a calculated source 87Rb/86Sr ratio of 0.405 ± 0.028 (Fig. 5). The Sm-Nd data for the same samples result in an isochron of 2.19 ± 1.4 Ga (2σ). The high uncertainty in the latter is due to minimal separation between the data points generated from analysis of mineral separates. The small error on the Rb-Sr age may come from the abundance and variety of feldspar compositions in NWA 7034 (fig. S5). Furthermore, we are confident that the Rb-Sr isochron and variations in the 87Sr/86Sr values are the result of the time-integrated radiogenic growth from 87Rb and not the results of mixing between end-members with different 87Sr/86Sr values (figs. S11 to S14). The combined REE and isotopic data show that NWA 7034 is an enriched martian crustal rock (Fig. 5). The whole rock has 143Nd/144Nd = 0.511756 and 147Sm/144Nd = 0.1664, giv-ing a calculated initial (source value) 143Nd/144Nd = 0.509467 ± 0.000192 (initial εNd = –9.1 ± 1.7, calculated using the Rb-Sr age) which requires that it be derived from an enriched martian reservoir (19), with an inferred time-integrated 147Sm/144Nd = 0.1680 ± 0.0061, assuming separation from a chondrite-like martian mantle at 4.513 Ga (18). Data for each of our analyses is available in table S3. An age of ~2.1 Ga for NWA 7034 would make it the only dated meteorite sample from the early Amazonian (19) epoch in Mars’ geologic history. NWA 7034 is derived from the most enriched martian source identified to-date; even more enriched than the most enriched shergottites (20–23) (Fig. 5). Based on the REE enrichment, isotopic values, and match to rover ele-mental data, NWA 7034 may better represent the composition of Mars’ crust than other martian meteorites. Although NWA 7034 may not be representative of a magmatic liquid, the negative europium anomaly and absence of merrillite or whitlockite (24) is suggestive that the magma(s) parental to basaltic breccia NWA 7034 either underwent plagioclase fractionation prior to eruption or feldspar was left in the residuum during

partial melting. Due to the instability of plagioclase at high pressure (25), these processes would have necessarily occurred in the crust or upper mantle of Mars. Consequently, the geochemically enriched source that produced NWA 7034 could have originated from the martian crust or mantle, much like the geochemically enriched reservoir(s) that are recorded in the shergottites (26–30).

Confocal Raman imaging spectroscopy (CRIS) conducted at the Ge-ophysical Laboratory, Carnegie Institution, in Washington DC (Carne-gie) identified the presence of macromolecular carbon (MMC) within mineral inclusions in the groundmass minerals of NWA 7034 (8). This MMC is spectrally similar to reduced organic macromolecular carbon that has been identified in several shergottites and a single nakhlite me-teorite (fig. S15) (30), indicating that the production of organic carbon from abiogenic processes in the martian interior may not be unique to SNC-like source regions in Mars. Steele et al. (31) also demonstrated that the formation mechanism of MMC requires reducing magmatic conditions consistent with oxygen fugacities below the fayalite-magnetite-quartz (FMQ) buffer. Consequently, much of the ferric iron in the oxides of NWA 7034, as evidenced by EPMA and XRD analyses, was likely a product of oxidation subsequent to igneous activity as a result of secondary processes.

Bulk carbon and carbon isotopic measurements on NWA 7034 were also carried out at Carnegie using combustion in an elemental analyzer (Carlo Erba NC 2500) interfaced through a ConfloIII to a Delta V Plus isotope ratio mass spectrometer (ThermoFisher) in the same manner as the data reported by (31, 32) (8). These data indicate that at least 22 ± 10 ppm carbon is present within mineral inclusions in NWA 7034, and the δ13C isotopic value of this carbon is –23.4 ± 0.73‰, which is very simi-lar to previous bulk C and δ13C analyses of carbon included in shergottite meteorites analyzed in the same manner (31, 32). These data indicate that multiple geochemical reservoirs in the martian interior may have similarly light δ13C values. The bulk C concentration in the untreat-ed sample performed in these measurements was 2080 ± 80 ppm C, with corresponding δ13C value of –3.0 ± 0.16‰. Scattered carbonate veinlets from desert weathering were observed by BSE imaging and element mapping with the electron microprobe–especially in the near-surface material, but rarer in the deeper interior slices of NWA 7034. Although this carbonate is a minor phase within the meteorite, being below the detection of our XRD-analyses of the bulk sample, we believe this weathering product is sampled in our bulk carbon and carbonate anal-yses (8) (fig. S16).

Measurements of oxygen isotopic composition were performed by laser fluorination at UNM on acid- and non-acid-washed bulk sample and at the University of California, San Diego (UCSD) on vacuum pre-heated (1000°C) bulk sample (table S4). The triple oxygen isotope preci-sion on San Carlos olivine standard (δ18O = 5.2‰ vs. SMOW; Δ17O = 0‰) analyzed during sessions at UNM was Δ17O = ±0.03‰, precision at UCSD using NBS-28 quartz standard (δ18O = 9.62‰) was also Δ17O = ±0.03‰. In total, twenty-one analyses of bulk NWA 7034 were carried out (Fig. 6). The mean value obtained at UNM was Δ17O = 0.58 ± 0.05‰ n = 13 for acid washed samples and Δ17O = 0.60 ± 0.02‰ n = 6 for non-acid-washed samples; at UCSD the mean value was Δ17O = 0.50 ± 0.03‰ n = 2 for vacuum pre-heated samples that were dewatered and decarbonated. The combined data give Δ17O = 0.58 ± 0.05‰ n = 21. These interlab values of bulk samples are in good agreement, but are significantly higher than literature values for SNC meteorites (Δ17O range 0.15-0.45‰) (33–36). Figure 6 shows that the δ18O values (5.5 to 7.0‰ vs. SMOW) of NWA 7034 are higher than any determination from the SNC group. The Δ17O values of the non-acid-washed samples meas-ured at UNM are similar to and within error of the acid-washed samples indicating that NWA 7034 has, at most, only minor terrestrial weather-ing products which would drive the non-acid-washed values closer to Δ17O = 0.00. The slope of the best-fit line to the combined UNM acid-

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washed and non-acid-washed data is 0.517 ± 0.025, suggesting that the oxygen isotopic composition of NWA 7034 is the result of mass depend-ent fractionation processes.

There are no other known achondrites or planetary samples with bulk oxygen isotope values similar to NWA 7034. Most achondrite groups have negative Δ17O values or near-zero values as do rocks from the Earth and Moon. The oxygen isotope composition of Venus and Mercury are currently unknown, but NWA 7034 is too oxidized and iron rich to be derived from Mercury (37–39), and it seems to be a poor match for Venus because it experienced low temperature alteration on its parent body and has significant indigenous water, which would not per-sist with the high surface temperatures on Venus (40).

The distinct δ18O and Δ17O values compared to other martian mete-orites can be explained by multiple reservoirs – either within the martian lithosphere or between the lithosphere and a surficial component (41, 42) – or by incorporation of exotic material. The idea of separate long-lived silicate reservoirs is supported by radiogenic isotope studies (21, 23). The distinct Δ17O and δ18O values of the silicate fraction of NWA 7034 compared to all SNC meteorites measured to date further supports the idea of distinct lithospheric reservoirs that have remained unmixed throughout martian history. A near-surface component with high Δ17O values has been proposed on the basis of analysis of low temperature alteration products (41–43), and this may, in part, explain the Δ17O dif-ferences between the bulk and ‘water-derived’ components of NWA 7034. However, the Δ17O value of 0.58‰ for the bulk silicate is different from the Δ17O value of 0.3‰ found in all SNC samples measured to date. If materials with a non 0.3‰ Δ17O value are attributed to a surficial (atmospheric) component, then the bulk of NWA 7034 would have nec-essarily undergone extensive exchange with this reservoir. This is a pos-sibility, given the abundance of low-temperature iron oxides. The ramifications of distinct lithospheric reservoirs are very different from those attributed to a different surficial reservoir. The latter could be ex-plained by photochemical-induced isotope fractionation and/or hydrody-namic escape (44–46), while the former is consistent with a lack of initial planet-wide homogenization and an absence of plate tectonics (41). Isolated lithospheric oxygen isotope reservoirs are inconsistent with a global magma ocean scenario for early Mars, which would have very efficiently homogenized oxygen isotopes in the planet as occurred for the Earth and Moon. Instead, Mars’ differentiation could have been dominated by basin forming impacts that left regional or even hemi-sphere scale magmatic complexes (47, 48) with distinct and varied iso-topic and geochemical characteristics.

Another possibility is that NWA 7034 originally had oxygen isotope values similar to or the same as SNC, but a cometary component with higher δ18O δ17O, and Δ17O was mixed with it through impact processes on Mars, thus producing a Δ17O excess relative to SNC. Until we find clear evidence of such an exotic component in NWA 7034, this scenario seems less likely than the other two.

The oxygen isotope ratio of water released by stepped heating in a vacuum at UCSD (table S5) show that most, if not all, of the water in NWA 7034 is extraterrestrial with Δ17O values well above the terrestrial fractionation line (Fig. 7). NWA 7034 water falls primarily within the range of values for bulk SNC meteorites with a weighted mean value of Δ17O = +0.33 ± 0.01‰, with δ18O and δ17O values giving a slope of 0.52, indicating mass dependent fractionation. Interestingly, the Δ17O value for NWA 7034 water is lower than, and outside the range of, the Δ17O for bulk NWA 7034, offering clear evidence that there are multiple distinct oxygen isotope sources for this sample. The Δ17O value of the water released at the 500-1000°C range (+0.09‰) is approaching terres-trial values, and this could be from decomposition of the terrestrial car-bonate veins in the meteorite and equilibration of the produced CO2 with the released water. Karlsson et al. (41) reported oxygen isotope values of water from several SNC meteorites and also saw that they differed from

the Δ17O of the bulk SNC samples. However, their observed Δ17O-relationship between bulk rock and water is reverse to the one seen in NWA 7034, with waters in general having more positive Δ17O values than their respective host-rock (Nakhla, Chassigny, Lafayette). Only two shergottites (Shergotty, EETA-79001A) have waters with Δ17O values more negative than the host-rock, and Nakhla has water similar to its host-rock. Romanek (43) analyzed iddingsite, an alteration product of olivine and pyroxene, in Lafayette and found the Δ17O value is 1.37‰ for a 90% iddingsite separate, supporting the positive Δ17O shift of Lafa-yette water relative to host-rock. Karlsson (41) argued that this Δ17O difference suggested a lack of equilibrium between water and host rock with the lithosphere and hydrosphere having distinct oxygen isotopic reservoirs. Our data support this conclusion, but suggest that the Δ17O value of the ‘water’ reservoir is not always heavier than the rock reser-voir

We determined the deuterium to hydrogen isotope ratio (δD value vs. SMOW) and the water content of whole-rock NWA 7034 at UNM by both bulk combustion and stepped heating in a continuous flow, helium stream with high-T carbon reduction (49) (Fig. 8 and table S6). Six whole-rock combustion measurements yielded a bulk water content of 6190 ± 620 ppm. The mean δD value for the bulk combustion analyses was +46.3 ± 8.6‰. The maximum δD values in two separate stepwise heating experiments were +319‰ and +327‰, reached at 804°C and 1014°C respectively (table S6), similar to values seen in the nakhlites (50). Figure 8 shows that most of the water in NWA 7034 is released between approximately 150-500°C, and that there are two plateaus of δD values, one around –100‰ at 50-200°C and a second around +300‰ at 300-1000°C. This suggests that there are two distinct δD components in NWA 7034, a low temperature negative value component and a high temperature positive value component. One possibility is that the low temperature negative values are from terrestrial water contamination, although the Δ17O values in water released at even the lowest tempera-ture step of 50°C has a 0.3‰ anomaly (Fig. 7). It is also possible that protium-rich water is released at the lowest steps of dehydration, alt-hough such fractionation is not observed on terrestrial samples. Alterna-tively, the hydrogen, but not oxygen isotope ratios could have been affected by terrestrial alteration. Finally, it is possible that nearly all the released water from NWA 7034 is in fact martian and not terrestrial. In this case, the hydrogen isotope ratios have fractionated as a function of temperature, or there are two distinct hydrogen isotope reservoirs.

Our data show that NWA 7034 has more than an order of magnitude more indigenous water than most SNC meteorites. The amount of water released at high temperature (>320°C) is 3280 ± 720 ppm. Leshin et al. (50) measured an average of 249 ± 129 ppm H2O released above 300-350°C in seven bulk SNC meteorites, with exception of the anomalous Lafayette nakhlite which released 1300 ppm H2O above 300°C. They (50) argued that some of the water released at temperatures as low as 250°C could in fact be from martian alteration products. Given our oxy-gen water analyses this could also be the case for NWA 7034 at tempera-tures as low as 50°C. Hence the total amount of martian water in NWA 7034 could be in the vicinity of 6000 ppm, possibly supporting hypothe-ses that aqueous alteration of near surface materials on Mars occurred during the early Amazonian Epoch 2.1 billion years ago either by magmatically derived or meteoric aqueous fluids (51–53).

The young 2.1 Ga crystallization age of NWA 7034 requires that it is planetary in origin. Its major, minor, trace, and isotopic chemistry is inconsistent with originating from Earth, Moon, Venus, or Mercury, and it is most similar to rocks from Mars. Yet still, NWA 7034 is unique from any other martian meteorites, as it is the most geochemically en-riched rock from Mars that has been found to date. Moreover, the bulk chemistry of NWA 7034 is strikingly similar to recently collected orbital and lander data collected at the martian surface, allowing for a direct link between a martian meteorite and orbital and lander spacecraft data from

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Mars. NWA 7034 is also distinct from the SNC meteorites because it has higher bulk δ18O and Δ17O, suggesting the existence of multiple oxygen isotopic reservoirs within the lithologic portion of Mars.

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Acknowledgments: We acknowledge Jay Piatek, MD for acquiring the NWA 7034 specimen and for his generous donation to the UNM Meteorite Museum, which has enabled this research and sample allocations for future research on NWA 7034. We also acknowledge M. Spilde, V. Atudorei, and J. Connolly at the University of New Mexico for assistance with data collection. CA, NW, and FM acknowledge support from NASA’s Cosmochemistry Program (NNX11AH16G to CA and NNX11AG76G to FM). SE acknowledges support from the New Mexico Space Grant Consortium, NASA Earth and Space Science Fellowship NNX12AO15H, and NASA Cosmochemistry grant NNX10AI77G to Charles K. Shearer. MT and RS acknowledge NSF award (ATM0960594) that allowed the development of analytical technique to measure oxygen triple isotopic composition of small (< 1 micro mole) sulfate samples.

Supplementary Materials www.sciencemag.org/cgi/content/full/science.1228858/DC1 Materials and Methods Figs. S1 to S16 Tables S1 to S6 References (57–71)

15 August 2012; accepted 14 December 2012

Published online 3 January 2013 10.1126/science.1228858

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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.

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).

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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 87Rb/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 87Sr/86Sr data and 2% errors for the 87Rb/86Sr data were used for age calculation. Larger errors were assigned to the 87Rb/86Sr 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.

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.

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Fig. 7. Δ17O versus temperature diagram showing the values for NWA 7034 water released by stepped heating. Vertical error bars are given for each data point, horizontal line segments show the temperature range for each step, and the thickness of the line segment indicates the relative proportion of water released at each step. Dashed line is the mean value of Δ17O for NWA 7034 water. Also shown are ranges of Δ17O for bulk NWA 7034 analyses and for bulk SNC values from the literature. TFL = terrestrial fractionation line.

Fig. 6. Oxygen isotope plot showing the values of NWA 7034 from this study, units are per mil. Cyan dots, 13 analyses of bulk acid-washed and 6 analyses of bulk non-acid-washed (UNM), cyan squares, 2 analyses of dry, de-carbonated bulk, preheated to 1000°C (UCSD). Red dots are SNC meteorites from the literature (33–36, 41). TFL = terrestrial fractionation line, slope 0.528.

Fig. 5. (A) Plot of bulk rock La/Yb ratio vs. εNd calculated at 175 Ma for NWA 7034 and basaltic Shergottites. Solid line represents two-component mixing line between NWA 7034 and QUE 94201. (B) Plot of calculated parent/daughter source ratios for NWA 7034, basaltic Shergottites, Nakhlites and Chassigny (Nak/Chas), and lunar mantle sources. Solid line represents two-component mixing line between depleted lunar mafic cumulates and lunar KREEP. Depleted lunar mafic cumulates are estimated by (54–56). Lunar KREEP is estimated by (56). Data for basaltic Shergottites, Nakhlites and Chassigny are from (22, 23) and references therein.

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Fig. 8. δD versus temperature diagrams showing the data for 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.

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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.1228858

This PDF file includes:

Materials and Methods

Figs. S1 to S16

Tables S1 to S6

References

2

Methods Electron microprobe (UNM)

Electron microprobe analyses and back-scattered electron images were performed using a JEOL 8200 Electron Probe Microanalyzer, equipped with five wavelength dispersive spectrometers. Quantitative analyses were carried out on two thin sections and three probe mounts of NWA 7034 taken from different locations in the stone. Analyses were made using a tungsten filament electron gun at 15 kV accelerating voltage and 20nA beam current. Most analyses were collected with 1µm-diameter beam, but feldspar analyses were collected using a 10-20µm-diameter beam, and plumose groundmass (bulk composition) 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 by X-ray diffraction (XRD) in the XRD Laboratory in the Department of Earth and Planetary Sciences at the University of New Mexico, using a Rigaku SmartLab diffractometer system with the SmartLab Guidance system control software for system automation and data collection. Cu-K-alpha radiation (40 kV, 40 mA) was used with a D/teX Ultra High Speed Silicon Strip Linear (1D) detector. The powdered sample was prepared in a thick deep powder mount and analyzed at 40 kV and 25 mA using a continuous scanning procedure with a n effective step size of 0.02 degrees at a scan rate of °2θ/min over the range 5–90 °2θ with incident slits set to 0.5 deg, and both receiving slits set to the maximum (20 mm). JADE® (MDI, Pleasanton, CA) analysis software was used to determine modal abundances of the major minerals present. Peak intensity variations were in general accord with qualitative estimates of modal abundance by petrography, so we attempted to quantify the modal abundances of minerals in NWA 7034 using the Rietveld refinement tool in the JADE® (MDI, Pleasanton, CA) analysis software. The variation in mineral mode between the two XRD analyses is likely a result of 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 on the Thermo X-Series II inductively coupled plasma mass spectrometer (ICPMS). A whole rock powder was leached with 1M acetic acid for 10 minutes, and then dissolved in an acid consisting of 20% concentrated nitric acid and 80% HF in Teflon bombs at 120°C for 48 hours. The solution was transferred to a Teflon beaker and dried down. It was 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 solution was analyzed against standard BHVO-2. Results are listed in Table S2 relative to values reported for BHVO-2 [57-58].

Subsamples of NWA-7034 were separated using a magnet. The fine-grained nature of the sample and the high concentration of magnetite made separation of minerals difficult. The subsample powders were leached with 1M acetic acid for 10 minutes, and then dissolved in an acid consisting of 20% concentrated nitric acid and 80% HF in Teflon bombs at 120°C for 48 hours. The leachates were collected. The five separates consisted of the whole-rock aliquot, a light mineral fraction that could consist of feldspars

3

and Cl-apatite, and three dark Fe-rich mineral fractions. The subsample powders were leached with 1M acetic acid for 10 minutes, and then dissolved in an acid consisting of 20% concentrated nitric acid and 80% HF in Teflon bombs at 120°C for 48 hours. Each dissolved subsample was transferred to Teflon beakers and spiked with a mixed 84Sr-87Rb spike and a 146Nd-149Sm spike, and 2 drops of perchloric acid were added. Samples were fluxed and then lightly dried down and redissolved in 6M HCl with 10 drops of boric acid. After another light dry down, the subsamples were dissolved in 2M HCl and dried softly, and redissolved in 1M nitric acid for column chemistry. Subsamples were passed through Tru-spec resin to collect the REE fraction, and then through Sr-spec resin to collect the Sr fraction. The waste included the Rb fraction and was collected for Rb column chemistry. The Sr fraction was passed through the Sr-spec resin again. Two column chemistry procedures were modified for Rb separation. The methods used are after [59-60]. [59] processed microsamples and used AG50 WX8 (50-100 mesh) cation resin to separate Rb. [60] passed the Rb fraction through AG50W-X12 (200-400 mesh) to separate the Rb. Both methods produced the same results. The REE fraction was passed through Ln-spec cation resin to separate both Nd and Sm after the methods of [61]. Two subsamples of basalt standard BHVO-2 were processed through the Sr-Rb column chemistry with the NWA-7034 subsamples.

Subsample Rb, Sr, Nd, and Sm separates were analyzed on a Thermo Neptune multi-collector inductively coupled plasma mass spectrometer (MC-ICPMS), and these included three leachates. Results are listed in Tables S1 and S2. Concentrations of Rb and 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 standard as 9.8±1 and 389±23 ug/g, respectively [57]. Our 87Sr/86Sr value for BHVO-2 is 0.70347, which is identical to that reported by [62], and relative to a 87Sr/86Sr value of 0.71025 for NBS 987. We measured the 87Rb/85Rb for a SPEX brand ICP standard to be 0.38567 normalized to 91Zr/90Zr [after 59], a value within error of the reported terrestrial value 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 values based on normalization to a Sr double-spike are higher than those normalized to 92Zr/90Zr or 91Zr/90Zr by about 0.2% (0.386353 ± 0.000004; [64]). These value differences are insignificant with respect to the errors on our Rb-Sr isochron age. Rb and Sr results from the three leachates that were passed through the columns fall on the isochron. Isochron ages were constructed with ISOPLOT [65].

Elemental and isotopic analysis of carbon (Carnegie)

The chemical (ppm C) and isotopic composition (δ13C relative to V-SMOW) of carbon 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 mass spectrometer (ThermoFisher). Carbon concentrations were calculated using a calibration derived from measuring a homogenous sediment sample (Peru Mud, Penn State University) containing 6.67% C (by weight). For this study, 10-100 mg of this standard was 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 into 4x6mm Ag capsules that were pre-combusted at 599°C in air for 2 to 4 h to remove organic carbon contamination. Blanks from capsules were 0.2±0.07 mg (n=72). Details

4

for this were published in [29, 66]. This same protocol was followed for the NWA 7034 sample presented in this study. In general, 5-10 mg of powdered meteorite matrix was weighed for concentration and isotopic measurements. This meteorite contained measurable nitrogen concentrations, which is unusual for other Martian meteorite samples measured [31]. Therefore, in this study, we report values for NWA 7034 that were prepared in pre-combusted Ag boats. Samples were acidified within the boats and soluble 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 presented without blank correction for isotopic composition, because blanks were below normal detection limits with the Carlo Erba-Delta V system. The bulk C concentration in the untreated sample was 2080 ± 80 ppm C, with corresponding δ13C value of -3.0 ± 0.16‰. Subsequent to acid washing, the bulk C concentration 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 by optical microscopy and back scattered electron microscopy at UNM, and by isotopic analyses of inorganic carbonate at UCSD . The acid-washed and muffled sample yielded 22 ± 10 ppm C, with an isotopic value of -23.4 ± 0.73‰, which is very similar to previous bulk C and δ13C analyses of shergottite meteorites after acid-washing and muffling [31-32]. Raman analysis (Carnegie)

Raman spectra and images were collected using a Witec α-Scanning Near-Field Optical Microscope that has been customized to incorporate confocal Raman spectroscopic imaging. The excitation source is a frequency-doubled solid-state YAG laser (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 a x100 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 a f/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 x100 LWD objective, with a focal plane depth of ~800nm. This instrument is capable of operating in several modes. Typically 2D imaging and single spectra modes were used during this study. Single spectra mode allows the acquisition of a spectrum from a single spot on the target. Average spectra are produced typically using integration times of 30 seconds per accumulation and 10 accumulations to allow verification of weak spectral features. Further details on the Raman instrument used can be found in [31, 67-68]. We used both transmitted and reflected light microscopy to locate the field of interest. Target areas were identified on the thin section in transmitted light. The microscope was then switched to reflected light and refocused to the surface. At which point X, Y and Z piezos of the stage were reset. Switching back to transmitted light then allows an accurate measurement of the depth of the feature of interest. The height and width of the field of interest within the light microscopy image were then measured and divided by the lateral resolution of the lens being used, to give the number of pixels per line. The instrument then takes a Raman spectrum (0-3600 cm-1

using the 600 lines mm-1 grating) at each pixel

using an integration time of between 1 and 6 s per pixel. A cosmic ray reduction routine was used to reduce the effects of stray radiation on Raman images, as was image

5

thresholding to reject isolated bright pixels. Fluorescence effects were inhibited by the use of specific peak fitting in place of spectral area sums and by the confocal optics used in this instrument. The effects of interfering peaks were removed by phase masking routines based on multiple peak fits as compared to standardized mineral spectra. This produces 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 RRUFF project (www.rruff.info).

Isotopic analysis of inorganic carbonates and sulfates (UCSD) These analyses were performed by acid extraction, gas chromatography, fluorination and isotope 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 upon acid 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 to isolate terrestrial contamination from the Martian meteorite. C and O-triple isotopic composition of carbonates was measured following the method developed by Shaheen et al. [69]. Inorganic sulfate was extracted by dissolving 1 g of NWA7034 in 2 mL of Millipore water, sonicated for 3hours and supernatant collected in a vial. The step was repeated twice to ensure complete removal of water soluble ions. Organic impurities were removed from the supernatant by treating with 30% H2O2 (1.0 mL) and further passing through polyvinyl pyrolydine (PVP), C18 (Alltech) resins. SO4 was separated from other anions using liquid chromatography, converted to silver sulfate and pyrolyzed at 1050 oC for oxygen isotope analysis.

The carbonate and sulfate weathering products that were sampled in oxygen triple isotope analyses of carbonate and sulfate done by step-wise acid dissolution at UCSD yielded values of Δ17O=-0.04±0.04‰ n=4 and Δ17O=+0.04‰ n=1, respectively, with a bulk 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 desert dust samples (δ17O = 15-21‰ δ18O = 29-41‰). However, NWA7034 carbonates and desert soil samples possess Δ17O~0. Oxygen triple isotope analysis of water soluble sulfate (δ17O = 3.7‰ δ18O= 6.7‰) showed mass dependently fractionated oxygen reservoirs. The Δ17O ~ 0 of secondary minerals (carbonates and sulfates) indicates their precipitation from a water reservoir with no oxygen isotope anomaly suggesting either terrestrial origin or subaerial martian water reservoir not in contact with the martian atmosphere and decoupled from the other oxygen carrying reservoirs. The Carnegie measurements show that there is significant organic carbon from both indigenous and exogenous terrestrial sources. Both Carnegie and UCSD detected terrestrial carbonate component in their bulk samples although they have significantly different values in the total measured carbon and the bulk value of δ13C. We attribute these differences to heterogeneous distribution of carbonate in NWA 7034, with a heterogeneous input of organic 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 0.013 NWA7034 2nd h at 25o C 0.06 0.75 23.62 45.89 -0.05 NWA7034 12 h at 25o C 0.2 0.56 23.72 46.09 -0.05

6

NWA7034 3 h at 150o C 0.07 0.17 19.23 37.43 -0.07 Arizona Test Dust 12 h at 25o C 4.96 -8.97 15.10 29.48 -0.10 Owen Lake Dust 12 h at 25o C 5.08 -3.64 18.21 35.60 -0.15 Black Rock Desert Dust, Nevada

12 h at 25o C 7.03 -6.069 18.04 35.25 -0.15

YaDan GanSu dust, China 12 h at 25o C 7.38 -13.52 16.51 32.24 -0.12 Grand Canyon Red Soil 12h at 25o C 0.05 -16.68 20.98 41.07 -0.21 Commercial cement sample 12 h at 25o C 4.99 -19.34 14.38 28.06 -0.09 *NWA7034- SO4 3.52 6.74 0.04

Overall 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 isotope values are reported with reference to V-PDB and SMOW. * 1 µmole of sulfate was obtained by dissolving 1g powdered meteorite in Millipore water and sonicating for 3 hours. The procedure was repeated three times to ensure complete removal of water soluble sulfates. Oxygen isotopes (UNM)

Oxygen isotope analyses of NWA 7034 were performed by laser fluorination at UNM on acid-washed bulk samples (removal of possible terrestrial weathering products). Pretreated samples (1-2 mg) were pre-fluorinated (BrF5) in the vacuum chamber in order to clean the stainless steel system and to react residual traces of water or air in the fluorination chamber. Molecular oxygen was released from the samples by the laser-assisted fluorination (25W far-infrared CO2 laser) in a BrF5-atmoshpere, producing molecular O2 and solid fluorides. Excess BrF5 was then removed from the produced O2 by reaction with hot NaCl. The oxygen was purified by freezing to a 13Å molecular sieve at -196°C, followed by elution of the O2 from the first sieve at −131°C to a second 5Å molecular sieve at −190°C [70]. Measurements of the isotope ratios were then made on a Finnigan DeltaXLPlus dual inlet isotope ratio mass spectrometer, and the oxygen isotope ratios were calibrated against the isotopic composition of San Carlos olivine. Each sample gas was analyzed multiple times, and each analysis consisted of 20 cycles of sample-standard comparison. Olivine standards (~1-2 mg) were analyzed daily. Oxygen isotopic ratios were calculated using the following procedure: The δ18O values refer to the 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 linearized values 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 -values by the following relationship: δ17O’ = δ17O’ – 0.528 x δ18O’, .Δ17O’ values of zero define the terrestrial mass-fractionation line, and Δ17O’ values deviating from zero indicate mass-independent isotope fractionation. Hydrogen isotopes (UNM)

Hydrogen isotope analyses of NWA 7034 were performd by a thermal combustion elemental analyzer (Finnigan TC-EA) connected to a gas chromatograph, a He-dilution system (Finnigan CONFLO II) interface, and a Finnigan DeltaXLPlus dual inlet isotope ratio mass spectrometer with continuous flow abilities for hydrogen. The technique involves reduction of solid hydrous samples by reaction with glassy carbon at high temperatures. H2 and CO are produced by reaction with the carbon at 1450°C in a He carrier gas. Product gases are separated in a gas chromatograph and analyzed in a mass spectrometer configured to make hydrogen isotope analyses in continuous flow

7

mode, with the reference hydrogen gas being introduced from the bellows system of the dual inlet [49]. Solid materials (several mg) for bulk analyses were wrapped in silver foil and dropped into the furnace using an autosampler. Using standard correction procedures, results obtained with this method are identical to those obtained conventionally with a precision for water samples of +/-2‰ (1o). Total time of analysis is less than 2 minutes for a single hydrogen isotope analysis. For stepwise heating, the sample was placed in a quartz- 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 the furnace temperature to the desired temperature. Evolving water was collected in a liquid nitrogen trap. Upon reaching of the required dwell time, the collected water was released into the TC-EA for combustion, and processed as described above. Weight % H2O of the samples analyzed were calculated by relating the peak-area of the sample to that of the international biotite standard NBS-30 (3.5 wt. % H2O).

8

Fig. S1. Backscatter electron image of spherical gabbroic clast composed of fine grained feldspar (dark), pyroxene (light gray), and magnetite and maghemite (white).

9

Fig. S2 Backscatter electron image of an apatite-ilmenite-alkali feldspar cluster. White elongate crystal is ilmenite, light gray crystals are Cl-apatite, medium dark crystals are andesine (Na-Ca plagioclase feldspar), darkest crystals are sanidine (K-feldspar), white fine grained crystals are magnetite or other iron-oxide.

10

<insert page break then Fig S3 here>

Fig. S3 Backscatter electron image of a portion of a ~1-cm quench melt clast with skeletal pyroxene (dark gray) and olivine (light gray) set in a fine grained to glassy quench crystal matrix.

11

Fig. S4 Backscatter electron image of a magnetite/maghemite-rich “reaction sphere”. White, fine grained phase is magnetite or maghemite, medium and dark phases are very fine intergrowths of pyroxene and feldspar.

12

An0 10 20 30 40 50 60 70 80 90 100

Or

0

10

20

30

40

50

60

70

80

90

100

Ab

0

10

20

30

40

50

60

70

80

90

100

All Feldspar NWA 7034

Fig. S5 Ternary diagram showing the range of feldspar compositions present in NWA 7034 (cyan dots, 178 electron microprobe analyses, molar percent). The range in feldspar compositions displayed by NWA 7034 is much broader than what has been measured in the shergottites [10], although it matches fairly well with feldspar compositions in Chassigny [11]. Ab=albite An=anorthite Or=orthoclase.

13

FS0 20 40 60 80 100

EN

All Pyroxene NWA 7034

HDDI

Fig. S6 Pyroxene quadrilateral showing the range of compositions present in NWA 7034 (cyan dots, 410 electron microprobe analyses, molar percent). There are two main clusters of pyroxenes: 1) a high calcium augitic cluster and 2) a low calcium orthopyroxene cluster that becomes pigeonitic with increasing ferrosilite. EN=enstatite FS-ferrosilite DI=diopside HD=hedenbergite.

14

Fig. S7 Mg/Si Al/Si diagram 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 cyan dot is the mean value of bulk NWA 7034 as determined by 225 electron microprobe analyses (cyan dots) of fine-grained groundmass with error bars giving one standard deviation.

15

Fig. S8 Ni 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 Ray Spectrometer (GRS) on the Mars Odyssey Orbiter [7]. 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.

16

NWA-7034 Whole Rock

La Ce P r Nd Sm E u Gd Tb Dy Ho E r Tm Yb Lu

Sam

ple/Cho

ndrite

10

25

50

100

NWA-7034 Leachate

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.

17

NWA 7034 (WR)

La Ce P r Nd Sm E u Gd Tb Dy Ho E r Tm Yb Lu

Sam

ple/Cho

ndrite

1

10

25

50

100

Nakhla (WR)

Shergotty (WR)

Tissint (WR)

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.

18

0.700

0.720

0.740

0.760

0.780

0.79 0.80 0.81 0.82 0.83 0.84 0.85 0.86 0.87

DRK$2&

DRK$3& DRK$1&

LGT&

WR&

1&Sr&(&&&&&&)&x100&

87Sr&86Sr&

Fig. S11 The inverse Sr concentration plotted against the 87Sr/86Sr ratio of the whole rock and mineral separates. On such a diagram samples that are related by two-component mixing would define a parabola. In this case there is no clear pattern, which is inconsistent with the isotopic data being the result of two component mixing.

19

0.700 !

0.720 !

0.740 !

0.760 !

0.780 !

-0.25! 0.00! 0.25! 0.50! 0.75! 1.00!0.700 !

0.720 !

0.740 !

0.760 !

0.780 !Model&Measured&

DRK.2&

WR&

LGT&

DRK.3& DRK.1&

LGT&

87Sr&86Sr&

Fig. S12 Results 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, while blue circles are measured values. Note the large divergence between the calculated and measured values of the light mineral fraction (LGT).

20

R²#=#0.99994#0.7100%

0.7300%

0.7500%

0.7700%

0% 20% 40% 60% 80%

DRK+2#DRK+3#

DRK+1# WR#

LGT#

Rb#(ppm)#

87Sr#86Sr#

Fig. S13 The Rb concentration plotted against the 87Sr/86Sr ratio of the whole rock and mineral separates. The near perfect relationship between the two values (R2 ~ 1) is a good indication that variations in the 87Sr/86Sr values are the result of the time-integrated radiogenic growth from 87Rb and not the results of mixing between end-members with different 87Sr/86Sr values.

21

0.719

0.721

0.723

0.725

0.727

0.15 0.25 0.35 0.45

87Sr

/86Sr

87Rb/86Sr

Age = 1957 ± 320 Ma MSWD = 5.0

wr

The three dark fraction separates.

Fig. S14 Rb-Sr isochron constructed from the whole rock and dark mineral fractions, giving an age, within error of the isochron that includes that light fraction. These data show that the age is not simply controlled by the high 87Rb/86Sr light fraction.

22

Fig. S15 Light microscopy and CRIS images of a feldspar grain in NWA 7034 hosting mineral inclusions A) light microscopy image of inclusions several microns below the surface of a Feldspar grain. B-F) Confocal Raman Imaging Spectroscopy images of individual phases identified in the field of view B) Feldspar, C) apatite, D) magnetite, E) pyroxene F) reduced macromolecular carbon. All of the Raman peak positions used to generate the Raman spectroscopic images B-F are the same as those described in [31, 67-68]. The association of MMC with magnetite. The association of MMC with magnetite and pyroxene with or without the presence of apatite has been seen in previous studies [30].

23

Fig. S16 Oxygen three isotope plot of CO2 obtained during step wise acid dissolution of Martian meteorite NWA7034. Step1, 2 and 3 at 25o C indicate Ca rich phases of CO3 and step 4 at 150o C indicates Fe-Mn-Mg rich CO3 phase. For comparison oxygen triple isotopic composition of CO2 obtained from Ca rich phase of CO3 of terrestrial soils from deserts and carbonates from ALH84001 and Nakhlite martian meteorites are included. Oxygen triple isotopic composition of water soluble sulfate in NWA 7034 is also shown.

24

Bulk%Compositon%NWA%7034225#microprobe#analyses#of#plumose#groundmass20#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 0.53Ca/Si 0.29 0.04Mg/Si 0.21 0.05Al/Si 0.27 0.03Mg# 0.52 0.05Fe/Mn#(molar) 47 9

Table S1.

25

Table S2. All results are in ppm. Errors from this study are reported as analytical absolute standard errors. Wilson = [57], which are certified values for BHVO-2 powder standard. Wanke et al. = Values measured for BHVO-2 by [58].

Element BHVO-2

(this study) BHVO-2 (Wilson)

BHVO-2 (Wanke et al.)

Sc 12.28 ± 0.087 32.29 ± 0.924 32 ± 1 31.8Y 40.68 ± 0.096 25 ± 0.414 26 ± 2 25.5La 13.66 ± 0.375 15.65 ± 0.287 15 ± 1 15.2Ce 34.63 ± 0.573 39.36 ± 0.621 38 ± 2 38Pr 4.823 ± 0.106 5.488 ± 0.194 5.3Nd 22.7 ± 0.420 26.22 ± 0.379 25 ± 1.8 25Sm 6.433 ± 0.064 6.507 ± 0.029 6.2 ± 0.4 6.2Eu 1.585 ± 0.016 2.253 ± 0.043 2.06Gd 7.454 ± 0.038 6.799 ± 0.166 6.3 ± 0.2 6.3Tb 1.425 ± 0.007 1.088 ± 0.030 0.9 0.93Dy 8.432 ± 0.301 5.798 ± 0.148 5.25Ho 1.751 ± 0.029 1.096 ± 0.008 1.04 ± 0.04 0.99Er 4.954 ± 0.113 2.873 ± 0.016 2.5Tm 0.7493 ± 0.024 0.4108 ± 0.008 0.34Yb 4.306 ± 0.065 2.204 ± 0.035 2.00 ± 0.2 2Lu 0.6861 ± 0.019 0.3658 ± 0.004 0.28Th 2.635 ± 0.063 1.252 ± 0.035 1.20 ± 0.3 1.2U 0.5124 ± 0.024 0.3682 ± 0.007 0.41

NWA-7034-WR (this study)

26

Rb-Sr and Sm-Nd isotopic and concentration data for NWA 7034 and BHVO rock standard

wt. (mg) 87Rb/86Sr Error 87Sr/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

Wt. (mg) 147Sm/144Nd error 143Nd/144Nd 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 ratios were normalized to 144Nd/146Nd ratio of 0.7219. Errors are 2-σ of the mean.

27

NWA 7034 Laser Fluorination Data

UNMBulk solids acid-washed

δ17O' δ18O' Δ17O'4.13 6.59 0.653.93 6.40 0.553.78 5.97 0.633.54 5.81 0.474.30 7.19 0.513.90 6.31 0.563.84 6.16 0.593.76 6.06 0.563.93 6.28 0.613.81 6.10 0.594.54 7.52 0.643.73 5.92 0.613.88 6.24 0.59

Average 3.93 6.35 0.58Stdev 0.26 0.50 0.05

Bulk solids non-acid-washed

δ17O' δ18O' Δ17O'4.01 6.46 0.603.98 6.33 0.633.96 6.32 0.624.15 6.75 0.583.84 6.19 0.573.86 6.21 0.58

Average 3.96 6.38 0.60Stdev 0.11 0.21 0.02

UCSDBulk solids dry and decarbonated to 1000C

δ17O' δ18O' Δ17O'3.43 5.59 0.484.03 6.64 0.53

Average 3.73 6.12 0.50Stdev 0.43 0.75 0.03

Table S4. Oxygen isotope data (relative to V-SMOW; precision of Δ17O’ values is 0.03‰).

28

Temperature (°C) Time heating (hrs)

Water Yield (µmol) wt% H2O Oxygen isotopes

values St.Dev.

50 1.5 16.2 0.024 δ18O= -21.780 0.045

δ17O= -11.047 0.065

Δ17O= 0.453

150 3 76.0 0.111 δ18O= -3.883 0.027

δ17O= -1.794 0.039

Δ17O= 0.256

320 1 91.0 0.133 δ18O= -4.729 0.030

δ17O= -2.135 0.024

Δ17O= 0.362

500 1 39.2 0.057 δ18O= -1.634 0.021

δ17O= -0.481 0.031

Δ17O= 0.382

1000 1 5.56 0.008 δ18O= 11.019 0.037

δ17O= 5.909 0.064

Δ17O= 0.0910

Total

228 0.333 Δ17O= 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‰)

29

δD‰ wt.% H2O50 0.6359 0.6041 0.6535 0.6850 0.6442 0.50

T range °C δD‰ time @ T (min) wt.% H2O % of total H2O50-100 -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 of the international standard NBS-30 ( 3.5 wt. % H2O)

Bulk analyses (combustion)

Step-wise heating (continuous flow): 3 runs

NWA 7034 D/H bulk analyses (whole rock)

Table S6.

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