1

The isotopic composition of volatiles in the unique Bench Crater carbonaceous chondrite 1

impactor found in the Apollo 12 regolith 2

3

K. H. Joy1,2,*, R. Tartèse1, S. Messenger3, M. E. Zolensky2,4, Y. Marrocchi5 , D. R. Frank4,6, 4

and D. A. Kring2. 5

Supplementary Information 6

The Supplementary Information includes: 7

Supplementary note 1: Bench Crater meteorite geological context 8

Supplementary note 2: Methods 9

Supplementary note 3: Light isotope data literature references 10

Figures S-1 to S-10 11

Tables S-1 to S-3 12

Supplementary Information References 13

14

15

16

2

Supplementary Materials 17

18

Supplementary Note S-1: Bench Crater meteorite sample collection additional 19

information 20

Soil sample 12037 (Fig. S-1) with a total mass of 145 g was collected during the second Apollo 21

12 traverse from the rim of Bench crater (Fig. S-3), a 75 m-diameter crater with a characteristic 22

‘bench’ stepped morphology formation in its floor (Fig. S-2). Apollo 12 soils sampled near 23

crater rims have generally acquired ~1% primitive meteorite geochemical signature added from 24

exogenous micrometeorite and IDP influx since the underlying lava flows were deposited at 25

~3.2 Ga (Stöffler et al., 2006), though to date the Bench Crater meteorite is the only projectile 26

debris that has been discovered from this area. 27

28

The 12037 soil may have been mixed in the sample collection bag with a mare basaltic lava 29

sample named 12036, although this is not thought to account for the light isotope compositions 30

of the soil itself (Becker and Clayton, 1978). The soil is compositionally atypical of other 31

Apollo 12 soils; for example, bulk δ15N values range from -80 to -86 ‰, with a high 32

temperature release of N with a δ15N value of -125 ‰ (Becker and Clayton, 1978; Kerridge et 33

al., 1978) (Table 1), making 12037 one of the lunar soil samples with the lowest N isotope ratio 34

(Fig. 8 of the main paper). 35

3

36

Figure S-1. Optical image of grain mount 12037,188. The Bench Crater meteorite is indicated 37

with the arrow. Other small regolith rock fragments in the mount are a collection of impact 38

melt breccias with varying textures. 39

4

40

Figure S-2. Collection context of the 12037 soil sample at the Apollo 12 landing site from the 41

rim of Bench crater. Astronaut traverses and sample selection sites are overlain on LROC 42

Narrow Angle Camera image. Image is courtesy of NASA / Goddard Spaceflight Center / 43

Arizona State University and taken from the LROC website using their Apollo sites viewing 44

webtool and overlay feature function (http://featured-sites.lroc.asu.edu/). 45

46

47

48

49

50

5

51

Figure S-3. Collection site location of soil sample 12037 on the edge of Bench Crater at the 52

Apollo 12 landing site showing astronaut’s shadow. Image is courtesy of NASA (image 53

catalogue AS12-48-7064). 54

55

6

Supplementary Note S-2: Methods and Additional Results 56

2.1 Scanning Electron Microscopy methods and results 57

Scanning electron microscopy (SEM) analyses were carried out on Bench Crater grain mount 58

12037,188 using the NASA JSC JEOL 7600f FEG-SEM, operating with a beam current of 15 59

nA and an accelerating voltage of 25 kV. The system was coupled to a Thermo Scientific 60

energy dispersive x-ray (EDX) detector with NSS (Noran System Six) software to derive <1 61

µm per pixel backscatter electron (BSE) images and spatially resolved element data (~2-3 µm 62

per pixel). Each pixel of data that is collected retains a complete 0-20 KeV energy spectrum 63

and, therefore, we were able to extract maps of C, O, Na, Mg, Al, Si, P, S, K, Ca, Ti, Cr, Fe, 64

and Ni data. Element distribution and concentration maps were then processed using the 65

ImageJ software package to normalise each element to the same brightness scale, assign each 66

element a colour, and recombine the colourised images to make qualitative false-colour 67

element maps as shown in Figure 1 (similar to methods of Joy et al., 2012). Phase proportions 68

in Bench Crater were estimated using pixel counting of components identified in FEG-SEM 69

element maps using Adobe Photoshop. 70

71

Additional BSE images (Fig. 4) and EDX qualitative elemental data were acquired at the 72

University of Manchester (UK) using a FEI Quanta 650 FEG-SEM with the FEI 'Maps' version 73

3.1 and a Bruker Quantax EDX system equipped with an Xflash 6130 30 mm2 detector and 74

running 'ESPRIT' V2.1. 75

76

Major- and minor-element concentrations were obtained using a Cameca SX100 electron probe 77

microanalyser (EPMA) at the University of Manchester. The instrument setup comprised a 15 78

kV accelerating voltage, a 15 nA beam current, dwell times of 20 s on peak for all elements 79

except F (60 s), and spot sizes of 1 μm (focused) and 5 μm (defocused). The instrument was 80

7

calibrated with well characterised mineral and synthetic standards prior to analysis. 81

Uncertainties (1σ standard deviation) associated with our EPMA analyses for silicates were 82

0.9% for Si, 2.4% for Ti, 0.6-1% for Al, 0.6-0.8% for Fe, 0.4-0.7% for Mg, 1% for Ca, 3-5% 83

for Na, 3-6% for K, 6% for P, 5-7% for Cr, 9-12% for Mn, 3-11% for S, and 0.4% for Ca, 0.5% 84

for P, 4-5% for Fe, 6% for Mg, , 4-5% for Na, 9-10% for Mn, 2% for F, and 12-20% for Cl in 85

apatite. 86

87

2.2 Transmission Electron Microscopy methods and results 88

Fine-grained (matrix) material was removed with a needle from a region of matrix adjacent to 89

that removed for NanoSIMS analysis, and was investigated by transmission electron 90

microscopy (TEM). These observations were made using ultramicrotomed sections prepared 91

from grains embedded in EMBED-812 low-viscosity epoxy. We studied the microtomed 92

sections using a JEOL 2000FX STEM at JSC equipped with a LINK EDX analysis system, 93

operated at 200 kV and a take-off angle of 40°, using a similar set up as Tonui et al. (2014). 94

We used natural mineral standards and in-house determined k-factors for reduction of 95

compositional data (normalised to an analytical total of 100%), and a Cliff–Lorimer thin-film 96

correction procedure was employed (Goldstein, 1979). Minerals were identified using a 97

combination of bright-field images and electron diffraction data. 98

99

Results of our new TEM study into Bench Crater particles confirm that both hydrated smectite 100

(saponite) and ‘intermediate phase’ dehydrated phyllosilicates are present throughout the 101

matrix of Bench Crater (Figs. S-4, S-5 and S-6), as reported by Zolensky (1997). 102

8

103

Figure S-4. High-resolution electron micrographs bright field TEM images of particles removed from Bench Crater matrix labelled with identified 104

phases. Field of view (FOV) is ×2500 magnification for the grain on the left (grain 3) and ×5000 magnification for the grain on the right (grain 2). 105

9

106

Figure S-5. Close up bright field TEM image of (a) left Grain 3 and (b) right Grain 2 showing regions with well-developed lattice fringes with d-107

spacings that range from (a) 1.01(3) – 1.15(3) nm, and (b) 1.05(3) – 1.07(3) nm, appearing during dehydration of phyllosilicates under TEM 108

electron beam exposure. 109

10

110

Figure S-6. Ternary diagram with endmember compositions of relative abundances of Fe, Mg 111

and Si + Al, calculated from their weight percentages. The diagram displays the smectite-112

serpentine solid solution lines, and the compositions of matrix phyllosilicates in Bench Crater 113

(TEM and EPMA analyses from this study) and amorphous and intermediate silicate phases 114

(from this study see Table S-1 and also Zolensky, 1997), compared with the composition of 115

matrix phases of CM, CR, CI chondrites and the Bells meteorite (see Figure 5 of van Kooten 116

et al., 2018 and references therein). Bench Crater matrix compositions are magnesian, and are 117

most similar to CI-types. 118

11

Supplementary Table S-1. Normalised element compositions of matrix material and minerals in Bench Crater as (a) reported in Zolensky (1997) 119

and (b) measured in hydrated phases by TEM from grains 2 and 3 shown in Figures S-4 and S-5. Water was not determined in the TEM EDX 120

analysis, and all totals are normalised to 100%. Abbreviations are I: Intermediate, FM: Ferro-magnesian clast, M: Matrix, S: Saponite. 121

Zolensky (1997) This study

Grain 2 Grain 3

grain2b grain2d grain2e grain2f grain2j #1 grain2j #2 grain3a grain3b grain3d grain3h grain3i grain3l

Method TEM TEM EPMA EPMA TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM TEM

Phase S I FM M I I I I I S S I I I S I/mixed

Element wt%

Si 27.39 21.41 22.50 20.13 25.22 19.08 23.38 25.57 24.79 30.21 31.52 21.83 20.29 25 29.03 21.27 Ti 0.03 0.03 Al 2.70 1.43 1.83 1.77 2.32 1.57 2.42 2.21 2.53 2.4 2.32 1.63 1.99 2 2.58 1.87 Cr 0.41 0.75 0.58 0.45 0.59 0.61 0.59 0.52 0.32 0.59 0.55 0.48 0.65 0.44 Fe 4.90 8.78 7.98 9.40 7.23 13.88 8.37 8.57 7.76 8.66 8.13 7.57 10.59 8.56 7.20 11.52

Mn 0.02 0.01 Mg 17.73 23.40 19.25 17.40 18.76 22.92 19.35 18.41 17.57 12.5 14.61 20.21 22.57 17.81 14.72 14.91 Ca 0.07 0.14 0.88 0.65 0.32 0.29 0.05 0.33 0.30 Na 0.30 0.50 K 0.10 0.14 P 0.01 0.35

Ni 0.16 0.98 0.16 0.6 0.08 0.1 0.13 1.89 S 0.05 2.07 0.19 0.26 1.19 0.17 3.51 O 46.87 44.00 42.71 40.17 45.22 41.62 45.88 44.72 47.16 45.19 41 48.13 44.56 46.06 45.21 44.28

Total 100 100 95.51 94.29 100 100 100 100 100 100 100 100 100 100 100 100

122

12

Supplementary Table S-2. Normalised modal mineral proportions established from pixel 123

analysis of composite phase maps. All black pixels in the image (i.e, epoxy / cracks) were 124

discarded from the analysis. 125

Phase # of pixels % section area

Sulphides 354687 5.3 Carbonates 159971 2.4 Magnetite 836180 12.4 Ti-oxide 18923 0.3 Apatite 158172 2.3 Aqueously altered chondrule 649920 9.6 Matrix 4564001 67.7 Total 6741854 100

126

13

Supplementary Table S-3. EPMA phase chemistry. n.r. = not reported. b.d. = below detection limits. 127

Agglutinitic crust Bulk 12037 soil Apollo 12 soils #1 #2 #3 #4 #5 Average 2 SD Average 2 SD SiO2 44.96 45.75 43.77 44.87 44.37 44.74 ±1.47 44.8 46.16 ±1.76 TiO2 2.19 2.14 2.11 2.32 2.06 2.16 ±0.19 3.5 3.11 ±1.06 Al2O3 12.73 12.89 12.73 12.90 12.83 12.82 ±0.16 15.1 13.92 ±2.3 Cr2O3 0.38 0.36 0.33 0.34 0.32 0.35 ±0.05 0.36 0.34 ±0.3 FeO 16.04 15.77 16.55 16.28 17.34 16.40 ±1.20 14.9 15.37 ±2.66 MnO 0.18 0.18 0.16 0.18 0.19 0.18 ±0.02 0.25 0.21 ±0.05 MgO 10.99 10.69 10.52 10.87 11.30 10.87 ±0.59 10.2 9.76 ±1.18 CaO 9.20 9.25 9.15 9.25 8.68 9.11 ±0.49 10.5 10.63 ±0.22 Na2O 0.75 0.60 0.46 0.68 1.01 0.70 ±0.40 0.65 0.51 ±0.28 K2O 0.29 0.31 0.32 0.32 0.30 0.31 ±0.02 0.38 0.29 ±0.18 P2O5 0.45 0.42 0.39 0.36 0.41 0.41 ±0.07 n.r. 0.35 ±0.14 S 0.20 0.19 0.21 0.20 0.33 0.23 ±0.11 n.r. n.r. Total 98.36 98.57 96.71 98.58 99.14 98.27 100.64 100.65 Mg # 55.0 54.7 53.1 54.3 53.7 54.2 55.0 53.1 An # 84.4 86.3 88.3 85.2 79.9 84.8 86.6 89.3 FeO/MnO 89.0 88.9 101.7 92.4 90.5 92.3 59.6 72.5 Aqueously altered chondrule

Matrix Amorphous phase Ferro-magnesian phase SiO2 47.63 49.94 49.63 47.72 47.46 48.18 47.50 47.60 46.55 47.27 48.23 47.96 48.07 48.24 47.76 38.47 44.48 TiO2 0.08 b.d. 0.07 b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. 0.20 0.00 Al2O3 2.99 3.71 4.15 3.79 3.66 3.08 2.99 3.44 2.94 3.10 2.93 3.60 3.41 3.09 2.95 2.75 3.18 Cr2O3 1.13 1.01 1.78 1.68 0.48 0.48 0.53 0.48 0.39 0.35 0.52 0.42 0.61 0.45 0.59 0.55 0.67 FeO 14.74 11.11 10.23 10.44 8.98 10.00 10.02 8.56 11.72 9.04 9.33 7.28 9.22 9.49 9.89 15.93 12.05 MnO 0.29 0.20 0.13 0.09 0.10 0.08 b.d. b.d. b.d. b.d. b.d. b.d. 0.08 b.d. 0.09 0.17 0.00 MgO 27.22 25.26 30.66 29.73 30.56 33.71 32.56 31.68 33.21 32.17 28.94 32.86 32.79 33.50 32.36 22.38 29.15 CaO 0.12 0.37 0.14 0.15 0.14 0.11 0.21 0.18 0.22 0.23 0.13 0.23 0.08 0.07 0.10 0.06 0.04 NiO b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. 3.60 1.06 Na2O 0.40 0.09 0.25 0.47 0.59 0.37 0.69 0.55 0.48 0.59 0.26 0.49 0.41 0.49 0.52 0.71 0.87 K2O 0.07 0.06 0.11 0.18 0.11 0.10 0.15 0.31 0.09 0.14 0.12 0.15 0.09 0.09 0.10 0.12 0.20 P2O5 b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. S 0.10 0.20 0.04 0.02 0.02 0.06 0.06 0.10 0.60 0.01 0.34 0.02 0.03 0.08 0.14 6.23 1.80 Total 94.77 91.95 97.18 94.29 92.09 96.17 94.71 92.91 96.20 92.90 90.80 93.02 94.78 95.51 94.50 91.16 93.49 Mg # 76.7 80.2 84.2 83.5 85.8 85.7 85.3 86.8 83.5 86.4 84.7 88.9 86.4 86.3 85.4 71.5 81.2 An # 12.8 61.3 19.9 12.5 10.8 12.0 12.8 11.4 18.5 15.6 17.2 18.0 8.8 6.9 8.9 4.3 2.4 Aqueously altered chondrule Apatite1 Apatite2 Apatite3 F 0.77 0.79 1.13 Cl 0.06 0.03 0.05 MgO 0.20 0.19 0.21 SiO2 0.14 0.07 0.24 CaO 55.76 56.45 56.37 MnO 0.20 0.23 0.19 FeO 0.72 0.44 0.73 Na2O 0.40 0.54 0.47 P2O5 43.19 44.05 43.37 Total 101.44 102.78 102.76 F2 = -O 0.32 0.33 0.47 Cl2 = -O 0.01 0.01 0.01 Corrected Total 101.11 102.44 102.27

128

14

2.3 Oxygen isotope methods 129

The oxygen isotope compositions of silicates, magnetite and carbonate was measured in situ in 130

the Bench Crater meteorite 12037,188 thin section using a CAMECA IMS 1270 E7 at CRPG-131

CNRS (Nancy, France). The secondary ions 16O-, 17O-, and 18O- produced by a ~1 nA Cs+ 132

primary ion beam with a diameter of ~15 µm were measured in multi-collection mode with 133

two off-axis Faraday cups (FC) for 16,18O- and the axial electron multiplier (EM) for 17O-. To 134

avoid 16OH- interference on the 17O- peak, the entrance and exit slits of the central EM were 135

adjusted to obtain a mass resolving power (MRP) of ~7000 for 17O-. The multicollection FCs 136

were set on slit 1 (MRP = 2500). The total measurement times were 360 seconds (240 s 137

measurement + 120 s pre-sputtering). We used five terrestrial standard materials (San Carlos 138

olivine, magnetite, diopside, dolomite and calcite) to define the instrumental mass fractionation 139

line for the three oxygen isotopes. The instrumental mass fractionation (IMF) due to the matrix 140

effect was corrected for magnetite, calcite and dolomite by using standards with similar 141

chemical composition. The IMF for intermediate phase analyses was corrected by using San 142

Carlos olivine due to the lack of appropriate standards. This may induce small inaccuracies of 143

up to a few ‰ for δ18O values, as suggested by a recent investigation of O isotope analysis in 144

serpentine-group minerals by SIMS (Scicchitano et al., 2018) that shows that matrix bias for 145

antigorite-olivine was up to 3 ‰ on δ18O (with ca. 3-4 wt% Al2O3, the amorphous and 146

intermediate phases in Bench Crater would have a composition roughly comparable to that of 147

the antigorite reference sample analysed by Scicchitano et al. (2018), the reference antigorite 148

having lower FeO [~4 wt.%] and higher MgO [~37.5 wt.%]). The Mg# seems to be of the key 149

parameter controlling matrix effect for O isotope analysis of mafic minerals by SIMS (e.g., 150

Eiler et al., 1997; Isa et al., 2017). Fortunately, amorphous and intermediate phases of Bench 151

Crater altered chondrules and San Carlos olivine have similar Mg# at ca. 85 for Bench Crater 152

aqueously altered chondrule phases (Supplementary Table S3) and ca. 90 for San Carlos 153

15

olivine (Fournelle, 2011). Finally, it is important to note that matrix effects due to standard-154

sample mismatch would not affect ∆17O values. Typical count rates obtained were 6.5 × 108 155

cps for 16O, 2.5 × 105 cps for 17O, and 1.4× 106 cps for 18O on the calcite, dolomite and 156

magnetite standards, and 5.0 × 108 cps for 16O, 1.9 × 105 cps for 17O, and 1.0 × 106 cps for 18O 157

on the olivine standard. Typical measurement errors (2σ), which took into account the errors 158

in each measurement as well as the external reproducibility of the standards, were estimated to 159

be ca. 0.8 ‰ for δ18O, 0.5 ‰ for δ17O, and 0.8 ‰ for ∆17O (where ∆17O represents the deviation 160

from the TFL, with ∆17O = δ17O - 0.52 × δ18O). After analyses, we checked the SIMS spot 161

locations to identify specific phase components within the analysed area (see Figs. S-7 and S-162

8). 163

164

16

165

Figure S-7. Location of the ~ 15 µm SIMS spots within (a) silicate phases in the largest aqueously altered chondrule, and (b) within magnetite 166

phases. 167

168

17

169

Figure S-8. Location of the ~ 15 µm SIMS spots locations in (a) dolomite and (b) predominantly calcite with minor dolomite phase. 170

18

2.4 NanoSIMS methods 171

NanoSIMS analyses were carried out on uncoated samples. Two 15 × 15 µm areas (Area 1: see 172

Fig. 6, and Area 2) of Bench Crater fragments pressed into gold foil were spatially mapped for 173

H, C, and N isotope analyses using the NASA JSC NanoSIMS 50L ion microprobe following 174

established protocols (e.g., Nakamura-Messenger et al., 2006). Two 10 × 10 µm areas (Area 3 175

and 4) were spatially mapped for further H isotope analysis in a separate session using standard 176

protocols for NanoSIMS D/H measurements (e.g., Nakamura-Messenger et al., 2006). A ~30 177

pA, 16 kV Cs+ primary ion beam was rastered over 10 × 10 µm areas and negative secondary 178

ions of 1H-, 2H-, 12C-, and 18O- were measured simultaneously with electron multipliers. For 179

each measurement between 20 and 40 successive image planes were acquired from the same 180

field of view. These measurements were performed in low mass resolution, taking advantage 181

of the very low negative ion yield of H2- relative to 2H-. A nuclear magnetic resonance probe 182

was used to maintain a stable magnetic field during the ~ 2-hour course of each measurement. 183

An electron flood gun was used for charge compensation. Instrumental mass fractionation for 184

H, C, and N isotope ratios was corrected based on analysis of the terrestrial KG-17 kerogen 185

(δDVSMOW = -108‰, δ13CPDB = -24.1‰ and δ15NAir = 3.2‰; Schimmelmann et al., 2001), the 186

NIST NBS 30 biotite (δDVSMOW = -65.7‰; Grőning, 2004), and a 1-hydroxybenzotriazole 187

hydrate (δDVSMOW = -8.1‰, δ13CPDB = -29.9‰ and δ15NAir = -6.1‰; Ito et al., 2014). 188

189

Isotopic images were processed using in house software written by S. Messenger. This software 190

was used to align successive image planes, define regions of interest (ROIs), correct for EM 191

deadtime and quasi-simultaneous arrival (QSA) effects, and obtain isotopic and elemental 192

ratios. The bulk meteorite composition is taken as the average. Reported errors in isotopic ratios 193

take into account counting statistical errors, uncertainties on calculated isotopic ratios for 194

reference materials, and isotopic variations during the course of analyses. ROIs were defined 195

19

by the 18O and/or 12C images that were used to show the location of the sample/standard and to 196

exclude contributions from the adjacent substrate. Images have been smoothed by a moving n 197

× n average where n = 9 pixels for isotope ratio maps, corresponding to ~700 nm resolution. 198

NanoSIMS images shown in Figures 6, S-9, and S-10 were created using the l’Image software 199

package (L. Nittler, Carnegie Institution of Washington). 200

201

Isotope ratios are reported using the conventional delta notation in per mil (‰), where δ15N = 202

[((15N/14N)measured/(15N/14Nstandard)-1) × 1000], δ13C (‰) = [((13C/12C)measured/(13C/12C)standard) -1) 203

× 1000] and δD = [((D/H)measured/(D/H)standard) -1) × 1000]. The standards are Air for N isotopes 204

(15N/14N = 3.6765 × 10-3), VPDB for C isotopes (13C/12C = 1.1237 × 10-2) and the Vienna 205

Standard Mean Ocean Water (VSMOW) with a D/H of 1.5576 × 10-4 (e.g., Hoefs, 2009). No 206

spallogenic isotope corrections were applied to the isotopic data as the 12037 parent soil has a 207

low 10-20 My cosmogenic exposure history (Arrhenius et al., 1971; Becker et al.,1978) (see 208

also Supplementary Materials Note S-1). 209

210

To ensure that the H isotope analyses are accurate we also analysed a small sample of the CM2 211

chondrite Murchison using the same approach as for Bench Crater (Table 1 and Figs. S-9 and 212

S-10). This also allows us to compare the spatial H isotopic variability within and between the 213

samples. Murchison is a highly heterogeneous and complex volatile-rich carbonaceous 214

chondrite, which may have undergone various shock pressures on its parent body both before 215

(of 22 to > 30 GPa) and after (<10 GPa) aqueous alteration (Lindgren et al., 2016). The bulk 216

sample δD of -117 ± 98 ‰ (2σ) we determined for Murchison is well within the two sigma 217

range of that reported by bulk analysis techniques (e.g., -62 ± 6 ‰ in Alexander et al., 2012). 218

NanoSIMS imaging also revealed that the Murchison sample displays µm-sized D-rich 219

20

hotspots with δD values up to 4800 ± 400 ‰ (Fig. S-9), comparable to D-rich hotspots values 220

reported by Busemann et al. (2006) and Remusat et al. (2010, 2016). 221

222

Figure S-9. NanoSIMS images showing the H, C, O elemental and D/H isotopic distribution 223

in the Murchison CM2 meteorite. Intensities are in counts per second, δD values are given in 224

permil normalised to VSMOW. Images have been smoothed by a moving n × n average, where 225

n = 3 and 9 pixels for intensity and δD maps, respectively, corresponding to ~235 and 705 nm 226

spatial resolution. The Murchison sample displays µm-sized D-rich hotspots (δD of 2300 ± 340 227

‰ and 4800 ± 400 ‰ (2σ) and a bulk matrix δD of -117 ± 98 ‰ (2σ). 228

229

21

230

Figure S-10. Comparison of the D/H distribution in Murchison (a) and Bench Crater (b). 231

Murchison is characterised by a bulk matrix δD value of -117 ± 98 ‰ (2σ) with D-rich hotspots 232

ranging from δD = 2300 ± 340 ‰ to 4800 ± 800 ‰ (2σ), which is consistent with organic 233

globules observed previously in the matrix of other primitive carbonaceous chondrites (e.g., 234

Busemann et al., 2006; Nakamura-Messenger et al., 2006; Remusat et al., 2010, 2016). On the 235

other hand, Bench Crater matrix (Area 1 – see also Figure 6 of the main paper) does not display 236

these D-rich hotspots that are common among the most primitive chondrites and IDPs. 237

238

22

Supplementary Note S-3: Light isotope data literature references. 239

The data displayed in Figure 8 of the main paper are compared with different planetary 240

materials where the H and N isotope compositions from other sources include present-day 241

solar-wind (Marty et al., 2011, 2012; Huss et al., 2012), the proto Sun (Robert et al., 2000), 242

TiN component in a CAI indicative of solar N nebula (Meibom et al., 2007), gas giant planets, 243

Enceladus and Titan (Hartogh et al., 2011 and references therein; Fouchet et al., 2000; Owen 244

et al., 2001; Niemann et al., 2005; Flechter et al., 2014), Earth (McKeegan and Leshin, 2001, 245

and references therein; Mortimer et al., 2015 and references therein), comets and their 246

constituent phases (Meier and Owen, 1999; Hartogh et al., 2011; Altwegg et al., 2015; Füri 247

and Marty, 2015), meteorites and their components (Kerridge, 1985; Pearson et al., 2006; 248

Alexander et al., 2012), Tagish lake meteorite (crosses are nanoglobule hotspots from 249

Nakumura-Messenger et al., 2006; circles are bulk compositions from Pearson et al., 2006; 250

Alexander et al., 2012), Adelaide meteorite (Kerridge, 1985), interplanetary dust particles 251

(Messenger, 2000), martian reservoirs (atmosphere, water reserves and postulated mantle 252

composition; Usui et al., 2015 and references therein, Wong et al., 2013), lunar apatite 253

(Greenwood et al., 2011; Barnes et al., 2013; Tartèse et al., 2013, 2014), lunar regolith 254

(Kerridge et al., 1978; Liu et al., 2012; Füri et al., 2012; Stephant and Robert, 2014), lunar 255

volcanic glasses (Saal et al., 2013), lunar breccias (Füri et al., 2012), lunar mare basalt 256

(Mortimer et al., 2015) and Apollo 12 soil 12037 (Becker and Clayton, 1978; Kerridge et al., 257

1978). 258

259

260

23

Supplementary Materials Reference List 261

Alexander, C. M. O'D., Bowden, R., Fogel, M. L., Howard, K. T., Herd, C. D. K., Nittler, L. 262

R., 2012. The Provenances of Asteroids, and Their Contributions to the Volatile Inventories 263

of the Terrestrial Planets. Science 337, 721-723. 264

Altwegg K., et al. 2015. 67P/Churyumov-Gerasimenko, a Jupiter family comet with a high 265

D/H ratio. Science 347, 1261952. 266

Arrhenius, G., Liang, S., MacDougall, D., Wilkening, L., Bhandari, N., Bhat, S., Lal, D., 267

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