SUPPLEMENTARY INFORMATION

SUPPLEMENTARY INFORMATION Extreme oxygen isotope anomaly with a solar origin detected in meteoritic organics Ko Hashizume, Naoto Takahata, Hiroshi Naraoka & Yuji Sano Supplementary Discussions Basic descriptions and preliminary analyses of Yamato-793495 (CR2) Although the studied meteorite, Yamato-793495, is suggested to have experienced a mild thermal metamorphism on the parent body (Wang & Lipschutz, 1998), preliminary N-isotope analyses of the IOM using the stepwise combustion method (Yamamoto et al., 1998) showed d 15 N AIR value as high as +162 (see Supplementary Table 2). The obtained d 15 N AIR value is equivalent to the bulk IOM composition for Renazzo (Alexander et al., 1998), the most representative CR chondrite containing less altered organic matter (Pearson et al., 26), suggesting that the primordial isotope signatures among the organic matter may be well preserved in this Antarctic meteorite. The yield of the insoluble organic matter from this meteorite of.68 wt% (see Methods) is within the range observed among Antarctic CR2 chondrites (.2-.81 wt%; Grady et al., 1991; Alexander et al., 27). Explanations for the enrichment of 17 O relative to 18 O among the anomalous O- isotope grains The small enrichment of 17 O relative to 18 O among the anomalous O-isotope grains is possibly explained by one of the following minor effects associated with the photodissociation of C 17 O and/or C 18 O, which may have occurred in addition to the main effect by the 12 C 16 O self-shielding. Inside a dense gas medium, the self-shielding of C 18 O may become important enough to make a rise in the 17 O/ 18 O ratio in the photodissociated products (Visser et al., 29; Lyons et al., 29). By the first nature geoscience www.nature.com/naturegeoscience 1

explanation, the 17 O-enrichment relative to 18 O observed in this study may pose a lower limit on the column density of CO molecules where the self-shielding was operative. However, the overall effect of the C 18 O self-shielding to alter the 17 O/ 18 O ratio could be partly dismissed (Visser et al., 29) because of the counter-balancing effect anticipated by the partial shielding of C 17 O, whose dissociation lines are quite close to those of C 16 O. Alternatively, the elevation of the 17 O/ 18 O ratio could be due to up to ~4% higher photodissociation rates of C 17 O at several lines, relative to those of C 18 O, suggested by the recent experiments (Chakraborty et al., 28). To resolve this issue, refinements are required in the spectroscopic model involved in the CO photodissociation, integrated in many O-isotope evolution models (Clayton, 22; Yurimoto & Kuramoto, 24; Lyons & Young, 25), where the absorption cross sections for all isotopologues of CO are preliminarily assumed to be the same. Supplementary Methods Note on O isotope calibration Because the BBOT standard sample accidentally charged up at the meteoritic O isotope session, the O isotope composition of the meteoritic IOM was first compared with the terrestrial kerogen sample, then finally calibrated by the formula as follows: d SMOW ={(R sample /R kerogen ) (R kerogen /R BBOT ) (R BBOT /R SMOW )-1} 1 (R= 17,18 O/ 16 O). The two pairs of ratios, (R sample /R kerogen ) and (R kerogen /R BBOT ), were respectively obtained by comparing the isotopic compositions measured by the nanosims during the same sessions, whereas (R BBOT /R SMOW ) was calibrated by traditional mass-spectrometry. Corrections on the isotope data obtained by the nanosims A complete set of H, C, N and O isotope images are obtained after the following corrections: 2 nature geoscience www.nature.com/naturegeoscience

(1) The count-loss of secondary ions by the EMs due to the dead-time (44nsec) was corrected. However, the corrections were unimportant for the data with positive oxygen and carbon isotope anomaly, because their ion intensities were not particularly strong (~1 5 and ~1 4 counts/sec for 16 O and 12 C, respectively). (2) Drifts in the position of the rastered area, by several mm, were confirmed to occur during respective analyses, which last for many hours. The drift was corrected by comparing ion images with strong ion counts (e.g., 1 H, 12 C or 16 O) for each cycle, determining the drifted distances to obtain the most focussed images when the ion images were stacked. (3) The slight differences in the rastered field between different analyses of the same area (H, C/CN, O isotopes and OH/O analyses) were corrected in the same scheme with the above correction, by comparing ideally the same ion species obtained by both analyses, or otherwise comparing different ions (e.g., C or CN, and H) potentially emitted from the same host phases. (4) The mass resolution power of the ion-probe was tuned to be high enough to resolve potential interfering ions at adjacent masses from the secondary ions of interest, i.e., H - 2 from 2 H - (M/DM=71); 12 CH - from 13 C - (291); 13 C 14 N - from 12 C 15 N - (427) and 16 OH - from 17 O - (471). Intensities of the interfering species were mostly comparable or weaker than those for the interested ions, except 16 OH -, which was much stronger than 17 O ( 16 OH - / 17 O - ~2) due to the hydrogen-rich nature of the sample. We paid particular attention to the interference of the broad tail of 16 OH - at the peak-top of 17 O -, which occurs typically at a level of (5±2.5) 1-5 times the 16 OH peak-height. The corrected amount on the bulk d 17 O SMOW value for the IOM sample was ~1. However, because the OH/O showed little correlation with the d 17 O values among the IOM samples, the trend between the d 17 O and d 18 O values observed in this study were almost invariable regardless of the correction. nature geoscience www.nature.com/naturegeoscience 3

(5) A monotonic gradation of the isotopic composition within the rastered area was observed commonly among the meteoritic and standard samples, by extents of typically 5 /mm for dd, and <1 /mm for others. This effect in the d value was corrected by multiplying to the isotopic ratio a rate proportional to the relative position from the center of the rastered area, so that the bulk value (d o ) was almost invariable by the correction. The corrections for d 17 O values on respective pixels were fixed to.52 those for the d 18 O values, so that mass-independent fractionations were never created by the correction. (6) The Quasi-Simultaneous-Arrival effect (Slodzian et al., 24) occurs by emission of more than one secondary ions per incident primary ion that cannot be resolved by the detectors. The maximum emission rates of 1 H -, 12 C -, 12 C 14 N - and 16 O - from the BBOT standard sample (C 26 H 26 N 2 O 2 S), whose composition is regarded to be not drastically different from the meteoritic IOM composition, were roughly evaluated to be of the orders of.13,.8,.23 and.3 counts of secondary ions per incident Cs + ion, respectively. We estimated the emission rates of the secondary ions by the imaging of BBOT. We assumed that the maximum counts measured among the rastered area the most closely represent the ideal secondary ion counts determined by the primary ion current, the emission rate of the secondary ion from the target sample, and the transmission of the secondary ion. The transmission was not accurately determined, but the maximum transmission under the given mass resolving power was assumed. According to the formula given by Slodzian et al. (24), we may roughly estimate the maximum amounts of corrections by this effect on the dd, d 13 C, d 15 N and d 17,18 O values to be 6, 4, 12 and 2, respectively, smaller than the ranges of d values observed in this study. However, because it is impossible to estimate the emission rates on respective pixels in our meteoritic sample, no corrections regarding this effect were performed in this study. 4 nature geoscience www.nature.com/naturegeoscience

Supplementary References Alexander, C. M. O'D., Fogel, M., Yabuta, H. & Cody, G. D. The origin and evolution of chondrites recorded in the elemental and isotopic compositions of their macromolecular organic matter. Geochim. Cosmochim. Acta 71, 438-443 (27). Grady, M. M., Wright, I. P. & Pillinger, C. T. Comparisons between Antarctic and non- Antarctic meteorites based on carbon isotope geochemistry. Geochim. Cosmochim. Acta 55, 49-58 (1991). Lyons, J. R. & Young, E. D. CO self-shielding as the origin of oxygen isotope anomalies in the early solar nebula. Nature 435, 317-32 (25). Slodzian, G., Hillion, F., Stadermann, F. J. & Zinner, E. QSA influences on isotopic ratio measurements. App. Surf. Sci. 231-232, 874-877 (24). Wang, M.-S. & Lipschutz, M. E. Thermally metamorphosed carbonaceous chondrites from data for thermally mobile trace elements. Meteorit. Planet. Sci. 33, 1297-132 (1998). Yamamoto, T., Hashizume, K., Matsuda, J. & Kase, T. Distinct indigenous nitrogen isotopic components co-existing in ureilites. Meteorit. Planet. Sci. 33, 857-87 (1998). nature geoscience www.nature.com/naturegeoscience 5

Supplementary Figure Legends Supplementary Fig. 1. Images of the isotope and elemental (secondary ion) compositions at Area #1 in the acid insoluble organic matter extracted from Yamato-793495 (CR2). The figures in black and white describe the stacked ionintensity images obtained at three different sessions, O isotope sessions ( 16 O and 13 C), C and N isotope sessions ( 12 C, 12 C 14 N) and H isotope sessions (H). The d values represent permil deviations of the isotopic ratios for respective pixels normalized by the bulk ratios calculated from the total ion counts obtained from the entire rastered area of 5 5mm 2. The s values represent the significance of the isotope anomalies, i.e., the d values divided by the counting statistic errors put on them. Isotopic anomalies are better recognized by the s images, where domains with significant d anomalies are clearly discriminated from those with less ion counts which exhibit noisy d values actually reflecting their large counting statistic errors. The ion-compound ratios (C - /O -, CN - /C - and OH - /O - ) are likewise normalized by the bulk ratio for the rastered area. The size of the pixels for the images is 78 78nm 2. The white bars shown at the bottom of respective panels denote 3mm scale bar. Supplementary Fig. 2. a,b. The d 18 O and d 13 C isotope images for the 17,18 O- rich domain in Yamato-793495 (CR2) IOM Area #1, where pixels with s 18 O < 5 are masked. Counterparts (domains with s 18 O < 5) are shown in c,d. In the (b) carbon isotope image for the 17,18 O-rich domain, significantly positive d 13 C values are confirmed among the majority of pixels. Supplementary Fig. 3. The d 18 O versus d 13 C diagram for Yamato-793495 (CR2) IOM Area #1. Data for pixels with O or C ion counts less than 1/25 the average counts are plotted in gray color. The inserted figure describes the s 18 O versus s 13 C relationship. Though it is difficult to confirm the correlation by the 6 nature geoscience www.nature.com/naturegeoscience

d 18 O versus d 13 C diagram, a broad positive correlation is observed among bulk of the data points in the s 18 O versus s 13 C diagram. Besides the main stream data exhibiting the correlation, with the highest d 13 C PDB values of 288±45 (d 18 O SMOW =134±22 ) (pixel#339 in Supplementary Data 1) or 285±46 (226±12 ) (pixel#287), a couple of exceptional data (848±44 (9±38 ) (pixel#3247); 457±41 (24±8 ) (pixel#2838)) are observed with large d 13 C (s 13 C) values but with little oxygen isotope anomaly, confirming the previous study (Floss & Stadermann, 29) on the IOM samples from CR3 chondrites that reports anomalous C isotope spots not particularly associated with isotope anomalies in O or N. Supplementary Fig. 4. The oxygen three-isotope diagram plotted for Yamato- 793495 (CR2) IOM Area #1. The isotopic ratios are expressed in the forms of Ln(R/R SMOW ) 1 (R= 17,18 O/ 16 O), instead of the forms in traditional d expression, plotted in Fig. 2 of the main paper. In this diagram, isotope fractionation trends are expressed by straight lines. The slope-1 (d 17 O=d 18 O) line is shown for comparison. The inserted figure describes the s 17 O versus s 18 O relationship. Data for pixels with ion counts less than 1/25 the average counts are plotted in gray color. The solid line in this figure corresponds to the slope-1 line. Supplementary Fig. 5. Mean compositions (d 17 O, d 13 C, d 15 N, d D, C/O, OH/O and CN/C) plotted against the mean d 18 O values of the pixels sorted by their s 18 O values for Yamato-793495 (CR2) IOM Area #1. Note that d values are plotted here instead of the d values calibrated by the reference standards. The d value represents the isotopic anomalies normalized by the bulk composition for the rastered area. Each data point is calculated from the total counts of respective ions from pixels that fit within the range of n s 18 O<n+2 (n: even nature geoscience www.nature.com/naturegeoscience 7

numbers). The compositions of various compounds and isotopes are examined among the pixels with significantly anomalous d 18 O values. a. The histogram obtained by the sorting, and the mean d 18 O values for the pixels that belong to respective bins are plotted. b. The mean d 17 O and d 13 C values are plotted against the d 18 O values. c. The mean d 15 N and d D values are plotted against the d 18 O values. d. The C - /O -, OH - /O - and CN - /C - ratios normalized by the bulk ratios are plotted against the d 18 O values. Supplementary Fig. 6. Mean compositions (d 18 O, d 13 C, d 15 N, C/O, OH/O and CN/C) plotted against the mean d D values of the pixels sorted by their sd values for Yamato-793495 (CR2) IOM Area #1. Refer to the caption of Supplementary Fig. 5 for other notes. Supplementary Fig. 7. Mean compositions (d 18 O, d 15 N, d D, C/O, OH/O and CN/C) plotted against the mean d 13 C values of the pixels sorted by their s 13 C values for Yamato-793495 (CR2) IOM Area #1. Refer to the caption of Supplementary Fig. 5 for other notes. Supplementary Fig. 8. Mean compositions (d 18 O, d 13 C, d D, C/O, OH/O and CN/C) plotted against the mean d 15 N values of the pixels sorted by their s 15 N values for Yamato-793495 (CR2) IOM Area #1. Refer to the caption of Supplementary Fig. 5 for other notes. Supplementary Fig. 9. Scanning electron microprobe (SEM) backscattered electron image of Yamato-793495 (CR2) IOM Area #1 obtained after the SIMS analyses. The domains enclosed by the yellow lines represent those where their average elemental compositions, analysed by the energy dispersion spectroscopy (EDS) attached to the SEM, are shown in Supplementary Fig. 1. 8 nature geoscience www.nature.com/naturegeoscience

The domains (b) to (e) are those which show characteristic O isotope composition, (b) normal, (c,d) 17,18 O-rich, or (e) 16 O-rich. Supplementary Fig. 1. The SEM-EDS spectra for several areas of Yamato- 793495 (CR2) IOM Area #1 obtained after the SIMS analyses. The 4 domains (b-d), which are the subset of the whole area (a), are discriminated by their typical O isotopic compositions. Measurement has been performed by (EDS) JEOL JED-23 attached to (SEM) JEOL JSM-551LV, scanned by a 2 KeV electron beam working at a low vacuum mode. The vertical scales of respective panels are adjusted so that the heights of Cs La peaks at 4.286 KeV, which originate from the primary beam of the nanosims, are roughly the same among the panels. Large amounts of fluorides seem to be present, produced during the chemical extraction procedure of the IOM. The entity of F peaks and important parts of Mg, Al and Si peaks likely come from the fluorides. We assign the peak at.68 KeV primarily to F Ka (.677 KeV), although some contribution from Fe La (.75 KeV) is anticipated. Peaks of Fe, Ni, Mn and most of the Cr likely originate from the stainless steel sample holder. Au comes from the gold-film applied before the SIMS analyses. Important parts of C, O and S peaks may originate from the organic sample. We acknowledge no particular difference in the overall spectra between the (c,d) 17,18 O-rich domains and (a) the whole area or (b) the normal O isotope domain, suggesting that the bulk chemical composition of the 17,18 O-rich O carrier is not largely different from the bulk organic sample, which is consistent with the observation by the nanosims. We also note that the heights of Si peaks in (c,d) are close to the background level, suggesting that quartz, which was the carrier for the 17,18 O-rich oxygen observed by Aléon et al. (25), is not the host phase for the 17,18 O-rich oxygen found in this study. The heights of O, Mg and Al peaks are distinguishably high nature geoscience www.nature.com/naturegeoscience 9

in the (e) 16 O-rich domain compared to the other spectra. We infer that the 16 O- rich oxygen is hosted in refractory oxide minerals enriched in Mg and Al. Supplementary Fig. 11. The d 18 O values of respective pixels of Yamato- 793495 (CR2) IOM Area #1, plotted against the a. C/O ratios normalized by the bulk ratio, b. 16 O counts and c. 13 C counts. Data for pixels with O ion counts less than 1/25 the average counts are plotted in gray color. The extremely high d 18 O values occur in (a) at a broad range around the typical C/O ratio, i.e., C/O ~ C/O bulk, which likely represents the typical composition of the IOM. We infer that the carrier of the 17,18 O-rich oxygen is the organic matter with a composition not largely different from the bulk composition. In (b) and (c), the positive d 18 O values appear at broad ranges around the moderate counts of 16 O or 13 C. We may explain this by geometry effects in the measurement. The variations in the secondary ion counts per pixel measured by the ion-microprobe not only reflect the abundance and the emissivity of the elements from respective areas, but also, particularly in the case measuring the non-polished and irregularly-shaped samples, local geometric conditions of the samples, such as the shape, inclination or the roughness (Hashizume and Chaussidon, 29). The significantly positive d 18 O values observed at moderate 16 O counts, i.e., at not too low and not too high counts, suggest that the isotope anomaly is unrelated to the analytical artefacts related to the background noise of the detector or counting statistics, nor to the problems that may occur when measuring high ion intensities, such as the uncertainties in the dead-time correction for the electron multiplier or the QSA effect (Slodzian et al., 24). Significantly negative d 18 O values ( to -5 ) are observed at a C/O range as low as (1-1 to 1-2 ) x C/O bulk in (a), or at the highest counts of 16 O in (b). We infer that the 16 O-rich oxygen is hosted by oxide minerals possibly dispersed among the IOM (see 1 nature geoscience www.nature.com/naturegeoscience

Supplementary Figs. 9 and 1), possibly showing O isotopic compositions similar to the anhydrous minerals contained in primitive chondrites. Supplementary Fig. 12. Images of the isotopic ratios obtained from Yamato- 793495 (CR2) IOM Area #2. Refer to the caption for Fig. 1 for other notes. The anomalous isotopic compositions for O, C, N and H observed in Area #1 are reproduced in a different area of the same sample. Supplementary Fig. 13. Images of the isotope and elemental (secondary ion) compositions of Yamato-793495 (CR2) IOM Area #2. Refer to the caption of Supplementary Fig. 1 for other notes. Supplementary Fig. 14. The oxygen three-isotope diagram plotted for Yamato- 793495 (CR2) IOM Area #2. Refer to Fig. 2 for other notes. The 17,18 O-rich oxygen isotope anomaly observed in Area #1, plotted close to the slope-1 line, was reproduced in Area #2. The record (d 17 O SMOW, d 18 O SMOW ) values obtained in Area #2 are (+212±41, +171±18 ) (pixel#743 in Supplementary Data 2) or (+249±3, +162±13 ) (pixel#1743). Supplementary Fig. 15. Correlations between the d 18 O or dd anomalies and other isotope anomalies observed in Yamato-793495 (CR2) IOM Area #2. a,c. The average d 17 O, d 13 C, dd and d 15 N values plotted against the d 18 O values. Pixels are sorted by the significance of the d 18 O anomalies. b,d. The same with (a,c) but the pixels are sorted instead by the d D anomalies. The correlations observed in Area #1 between d 18 O and d 13 C values, and between dd and d 15 N values, were reproduced in Area #2. Supplementary Fig. 16. The oxygen three-isotope diagram plotted for terrestrial kerogen extracted from a Permian sedimentary rock. The shown data (Kerogen #1) are obtained just before the O isotope analysis for Yamato- nature geoscience www.nature.com/naturegeoscience 11

793495 (CR2) IOM Area #1, and are used for calibration of the meteoritic data. The measurement was performed by the imaging mode, in the same protocol for the oxygen isotope measurement applied to the meteoritic IOM. Each data point represent ion counts obtained from an area of 3125 3125nm 2, or 32 32 raw-pixels, a 16 larger area than the plots for the meteoritic IOM, to compare the performance of the isotopic analyses between data points for the meteoritic and standard samples with almost equivalent counting statistic errors. This is because the duration of the analysis for the terrestrial standard sample was much shorter (1/32) than for the meteoritic IOM analyses. Number of the data points is 225. Data for pixels with ion counts less than 1/25 the average counts are plotted in gray color. The inserted figure describes the s 17 O versus s 18 O relationship. Supplementary Fig. 17. Histograms of the significances in the d 18 O or D 17 O values among pixels obtained by the imaging of the terrestrial kerogen. The datasets are the same with those for Supplementary Fig. 16. The D 17 O value is defined by d 17 O.52xd 18 O, representing the deviation from the massdependent fractionation line. The curves shown in both panels represent the frequency expected by the Gaussian distribution, i.e., the proportion of pixels expected to fit in the section between s-.5 and s+.5. The distribution of the d 18 O values is broader than the Gaussian distribution, whereas the distribution of the D 17 O is totally explained by the counting statistics. We may conclude that there may exist some instrumental mass-fractionations locally within the imaging area, however, the fractionation, if exist, is a mass-dependent one. The standard mean deviation of the d 18 O values (2 ), weighed by the error bars, is larger than the standard size of their counting statistic errors (Ö{S(w err 2 )/Sw}) (14 ). This can be explained by existence of a local instrumental massfractionation in the 18 O/ 16 O ratio with a typical size of 14 that occur 12 nature geoscience www.nature.com/naturegeoscience

independently to the counting statistic deviation. The standard mean deviation of the D 17 O values is identical to the standard size of their counting statistic error bars (34 ). Supplementary Fig. 18. The bulk O isotopic compositions of the BBOT standard sample, compared among values measured at different spots. The deviations of respective d values from the average values among the nine measurements are shown here. All measurements fit within 2.2s deviation from the average value, which is reasonably explained by the counting statistics combined with a small uncertainty in the instrumental mass-fractionation ( 4 in d 18 O), which may occur locally as observed in the case of imaging analysis of terrestrial kerogen. nature geoscience www.nature.com/naturegeoscience 13

Supplementary Table 1. Bulk isotopic composition of Yamato-793495 (CR2) IOM obtained by NanoSIMS imaging, and the calibration with the running standard samples. Oxygen isotope calibration 17 O/ 16 O 18 O/ 16 O 13 C/ 16 O 16 OH/ 16 O Y793495 IOM Area #1 *1,*2.395.2368.1389.8114 (1s error bar, ) 5.2.19.7.3 Terrestrial Kerogen (#1).3914.2388.3342.14878 (1s error bar, ) 9.7.96.24 2.6 Y793495 IOM Area #2 *1,*2.3799.19629.1172.754 (1s error bar, ) 4.7.22.9.4 Terrestrial Kerogen (#2).3762.19738.4148.13576 (1s error bar, ) 9.7 1.52.34 4.4 d 17 O SMOW d 18 O SMOW D 17 O SMOW (*3) Y793495 IOM Area #1 d o values ( ) 21.8 23.4 9.7 (1s error bar, ) 4.9 1.7 5. Y793495 IOM Area #2 d o values ( ) 22.6 18.7 12.9 (1s error bar, ) 5.6 2.1 5.7 *1: Secular decay of 16 O sensitivity (.12 permil/cycle) corrected *2: Tail of 16 OH interfered to 17 O peaktop ( 16 OH x (5 ± 2.5) x 1-5 ) corrected. *3: D 17 O º d 17 O -.52 d 18 O Carbon & nitrogen isotope calibration 13 C/ 12 C 15 N/ 14 N CN/C Y793495 IOM Area #1.159.439 1.4784 Statistic Error ( ).6.8.1 Y793495 IOM Area #2.1514.429 1.1821 Statistic Error ( ).5.8.1 BBOT (1st).1157.368 1.845 Statistic Error ( ) 2.2 2.9.3 BBOT (2nd).1199.3587 1.785 Statistic Error ( ) 2.3 2.9.3 BBOT (3rd).136.3552 1.3731 Statistic Error ( ) 3.1 4.5.4 BBOT (average).1521.367 1.6542 Standard Deviation ( ) 44 18 147 14 nature geoscience www.nature.com/naturegeoscience

Carbon & nitrogen isotope calibration (continued) d 13 C PDB d 15 N AIR Y793495 IOM Area #1 d o values ( ) -19 9 (1s error bar, ) 44 18 Y793495 IOM Area #2 d o values ( ) -26 87 (1s error bar, ) 44 18 Hydrogen isotope calibration 2 H/ 1 H Y793495 IOM Area #1.22256 Statistic Error ( ) 5.6 Y793495 IOM Area #2.24554 Statistic Error ( ) 4.7 BBOT.9413 Statistic Error ( ) 8.9 dd SMOW Y793495 IOM Area #1 d o value ( ) 1168 (1s error bar, ) 11 Y793495 IOM Area #2 d o value ( ) 1392 (1s error bar, ) 1 Isotopic compositions of the standard samples d 18 O SMOW dd SMOW d 13 C PDB d 15 N AIR BBOT d values ( ) 21.4-83 -25-27 BBOT : C 26 H 26 N 2 O 2 S (2,5-Bis(5'-tert-butyl-2-benzoxazolyl)thiophene) BBOT values were calibrated using the traditional mass spectrometry. 18 O - / 16 O - 17 O - / 16 O - OH - /O - C - /O - Terrestrial Kerogen values 1.29 1.16 1.22.22 (1s error bar, ) 1.4 14 x( 18 O - / 16 O - ) BBOT x( 17 O - / 16 O - ) BBOT x(oh - /O - ) BBOT x(c - /O - ) BBOT Terrestrial Kerogen : Natural kerogen extracted from Permian sedimentary rock Ratios for BBOT and Kerogen obtained by the NanoSIMS under the same conditions are compared. nature geoscience www.nature.com/naturegeoscience 15

Supplementary Table 2. Nitrogen isotope data of Yamato-793495 (CR2) IOM obtained by the stepwise combustion analysis. Y793495 IOM (.25 mg) Temperature ( o C) C (ppm) N (ppm) d 15 N AIR ( ) (1s error) 3 32388 18 16.1 ±.9 4 78535 28 162.4 ± 1. 5 119733 622 14.6 ±.8 6 3769 194 11.6 ±.8 7 1471 46 115. ± 2. 8 13 58.7 ± 2. 1 751 13 25.4 ± 3.1 Total 27488 1274 117.7 ±.5 See Yamamoto et al. (1998) for the analytical method 16 nature geoscience www.nature.com/naturegeoscience

793495 IOM Area #1 δ 18 O 16 O >6 s 18 O >25 2 3 15 1 5 13 C 3mm δ 17 O <-3 >6 s 17 O -5 <-1 >15 3 1 5 <-3 <-5 12 C δ 13 C >6 s 13 C >8 3 4 12 C 14 N δ 15 N <-3 >6 s 15 N <-4 >15 3 1 5 <-3 <-5 1 H δ D >4 sd >15 3 1 2 1 5 Max- Count C/O CN/C <-1 OH/O <-5 1 n xbulk >1 x1-1.5 x1-2 -.5 <x1-3 <-1 Supplementary Fig. 1 Hashizume, Takahata, Naraoka & Sano, 211 nature geoscience www.nature.com/naturegeoscience 17

1 2 3 4 5 6 7 793495 IOM Area #1 min = -1 ; max = +4 min = -1 ; max = +2 d 18 O SMOW (s 18 O³5) d 13 C PDB (s 18 O³5) >max 8 1 2 3 4 5 6 7 d 18 O SMOW (s 18 O<5) d 13 C PDB (s 18 O<5) 8 <min A B C D E F G H A B C D E F G H Supplementary Fig. 2 Hashizume, Takahata, Naraoka & Sano, 211 18 nature geoscience www.nature.com/naturegeoscience

793495 IOM Area #1 15 1-1 s 13 C 1 s 18 O 2 5 d 13 C PDB ( ) d 18 O SMOW ( ) Supplementary Fig. 3 Hashizume, Takahata, Naraoka & Sano, 211 nature geoscience www.nature.com/naturegeoscience 19

793495 IOM Area #1 Slope 1 Ln( 17 O/ 16 O/( 17 O/ 16 O) SMOW ) x1 ( ) s 17 O 1 s 18 O 1 2 Ln( 18 O/ 16 O/( 18 O/ 16 O) SMOW ) x1 ( ) Supplementary Fig. 4 Hashizume, Takahata, Naraoka & Sano, 211 2 nature geoscience www.nature.com/naturegeoscience

2 1 Frequency (% of pixels ) 5 1 15 2 25 3 a s 18 O -1 3 2 d 17 O ( ) d 13 C ( ) d d 18 O ( ) Frequency 1 R/R bulk -1 2 1-1 -2-3 2 1.5 1 b c R = C/O R = OH/O R = CN/C d 15 N ( ) d D( ).5 d -1-5 5 1 15 2 25 d 18 O ( ) Supplementary Fig. 5 Hashizume, Takahata, Naraoka & Sano, 211 nature geoscience www.nature.com/naturegeoscience 21

sd 2 16 12 8 4-4 3 2 Frequency (% of pixels ) 1 2 3 4 5 6 d D dd ( ) Frequency d 18 O ( ) d 13 C ( ) a 1 R/R bulk -1 3 2 1-1 2 1.5 1 b c d 15 N ( ) R = C/O R = OH/O R = CN/C.5 d -1 1 2 3 4 d D ( ) Supplementary Fig. 6 Hashizume, Takahata, Naraoka & Sano, 211 22 nature geoscience www.nature.com/naturegeoscience

Frequency (% of pixels ) 1 2 3 4 5 6 s 13 C 2 16 12 8 4-4 3 2 d 13 C ( ) d 18 O ( ) d 13 C ( ) Frequency a 1-1 2 15 1 5 b d 15 N ( ) d D ( ) R/R bulk -5 2 1.5 1 c R = C/O R = OH/O R = CN/C.5 d -2 2 4 6 8 1 d 13 C ( ) Supplementary Fig. 7 Hashizume, Takahata, Naraoka & Sano, 211 nature geoscience www.nature.com/naturegeoscience 23

Frequency (% of pixels ) 1 2 3 4 5 6 s 15 N 2 16 12 8 4-4 3 2 d 15 N ( ) d 15 N ( ) Frequency d 18 O ( ) d 13 C ( ) a 1-1 2 15 1 5 b d D ( ) R/R bulk -5 4 3 2 c R = C/O R = OH/O R = CN/C 1 d -3-2 -1 1 2 3 4 5 d 15 N ( ) Supplementary Fig. 8 Hashizume, Takahata, Naraoka & Sano, 211 24 nature geoscience www.nature.com/naturegeoscience

793495 IOM Area #1 a b c d e 1 mm Supplementary Fig. 9 Hashizume, Takahata, Naraoka & Sano, 211 nature geoscience www.nature.com/naturegeoscience 25

(a) Y793495 Area #1, Whole Cr Ka C Ka Ni La Al Ka Si Ka Au Ma S Ka O Ka Mg Ka Cs La Cs Lb & Fe Kesc Mn Ka & Cr Kb Fe Kb F Ka & Fe La Fe Ka Ni Ka (b) Normal O Isotope Domain (c) 17,18 O-rich Domain, Part 1 (d) 17,18 O-rich Domain, Part 2 (e) 16 O-rich Domain.8 1.6 2.4 3.2 4. 4.8 5.6 6.4 7.2 8 Energy (kev) Supplementary Fig. 1 Hashizume, Takahata, Naraoka & Sano, 211 26 nature geoscience www.nature.com/naturegeoscience

13 C counts 16 O counts C/O/(C/O)bulk 793495 IOM Area #1 a b c d 18 O SMOW ( ) Supplementary Fig. 11 Hashizume, Takahata, Naraoka & Sano, 211 nature geoscience www.nature.com/naturegeoscience 27

793495 IOM Area #2 1 min = -12 ; max = +24 min = -12 ; max = +24 d 18 O SMOW d 13 C PDB 2 3 4 max 5 6 7 8 1 2 d 15 N AIR dd SMOW 3 4 5 6 7 8 min = -15 ; max = +75 min = -1 ; max = +8 A B C D E F G H A B C D E F G H min Supplementary Fig. 12 Hashizume, Takahata, Naraoka & Sano, 211 28 nature geoscience www.nature.com/naturegeoscience

793495 IOM Area #2 16 O 3mm δ 18 O >3 s 18 O >16 2 8 1 13 C δ 17 O <-1 >3 s 17 O <-8 >8 2 4 1 <-1 <-4 12 C δ 13 C >2 s 13 C >8 1 4 12 C 14 N δ 15 N <-1 >8 s 15 N <-4 >15 6 1 4 2 5 <-2 <-5 1 H δ D >9 sd >12 7 8 5 3 4 1 Max- Count C/O CN/C CN/C <-1 OH/O <-4 1 n xbulk >1 x1-1.5 x1-2 -.5 <x1-3 <-1 Supplementary Fig. 13 Hashizume, Takahata, Naraoka & Sano, 211 nature geoscience www.nature.com/naturegeoscience 29

793495 IOM Area #2 Slope 1 d 17 O SMOW ( ) s 17 O s 18 O 1 5 d 18 O SMOW ( ) Supplementary Fig. 14 Hashizume, Takahata, Naraoka & Sano, 211 3 nature geoscience www.nature.com/naturegeoscience

15 793495 IOM Area #2 a d 17 O SMOW d 13 C PDB b 1 5-5 -1 3 c d 15 N AIR dd SMOW /1 d 2 1-4 4 8 12 5 1152 d 18 O SMOW ( ) dd SMOW ( ) Supplementary Fig. 15 Hashizume, Takahata, Naraoka & Sano, 211 nature geoscience www.nature.com/naturegeoscience 31

Terrestrial Kerogen (Imaging) d 17 O ( ) s 18 O 2 s 17 O -2-4 -2 2 4 d 18 O ( ) Supplementary Fig. 16 Hashizume, Takahata, Naraoka & Sano, 211 32 nature geoscience www.nature.com/naturegeoscience

Frequency (%) 4 35 3 25 2 15 1 5 35 3 25 2 15 1 5 a. D 17 O b. d 18 O Terrestrial Kerogen (Imaging) -3-2 -1 1 2 3 4 5 s value º (D 17 O or d 18 O)/(Counting statistic errors) Supplementary Fig. 17 Hashizume, Takahata, Naraoka & Sano, 211 nature geoscience www.nature.com/naturegeoscience 33

d 17 O - d 17 O average 3 2 1-1 -2 BBOT Spot-to-Spot s 17 O 2 1-1 - 1 1 2 s 18 O -3-3 -2-1 1 2 3 d 18 O - d 18 O average Supplementary Fig. 18 Hashizume, Takahata, Naraoka & Sano, 211 34 nature geoscience www.nature.com/naturegeoscience