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

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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

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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

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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

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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

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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

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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).

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

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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.

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<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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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).

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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.

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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.

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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].

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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.

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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.

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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)

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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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