Ion microprobe analysis of graphite from ca. 3.8 Ga metasediments, Isua supracrustal belt, West Greenland: Relationship between metamorphism and carbon isotopic composition

In-situ ion microprobe measurements of carbon isotopic compositions of graphite were made in seven metasediments and two carbonate rocks from the ca. 3.8 Ga Isua supracrustal belt, West Greenland. The δ¹³C values of micron-scale graphite globules in the metasediments and the carbonate rocks vary from -18 to +2‰ and from -7 to -3‰, respectively. The maximum δ¹³C value of graphite globules in the metasediment rises from -14 to -5‰, as the metamorphic grade increases from epidote-amphibolite to upper amphibolite facies. In a single hand specimen, the δ¹³C values of graphite inclusions in garnet are ~7‰ lower on average than those outside garnet. Similarly, graphite armored by quartz apparently shows a few permil lower δ¹3C values than those on grain boundaries between noncarbonate minerals. The fact that early crystallized minerals include relatively ¹³C-depleted graphite indicates that the regional metamorphism increased the δ¹3C values of the Isua graphite. This is consistent with the regional trend of ¹³C-enrichment accompanied by the increase of metamorphic grade. The minimum fractionation between graphite and carbonate is consistent with the equilibrium fractionation at about 400 to 550 °C. These observations indicate that isotopic exchange with isotopically heavy carbonate caused ¹³C-enrichment of Isua graphite. The δ¹³C values of graphite reported here (δ¹³C > -18‰) were produced either as a metamorphic modification of organic carbon with initially much lower δ¹³C values, or as an abiological reaction such as decomposition of carbonate. If the isotopic exchange between carbonate and graphite during the regional metamorphism controlled the ¹3C-enrichment of Isua graphite, previously reported large ¹³C-depletion of graphite, especially armored by apatite (Mojzsis et al., 1996) was probably premetamorphic in origin. This supports the existence of life at Isua time (ca. 3.8 Ga).