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Reappraisal of Hydrocarbon Biomarkers in Archean Rocks

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Reappraisal of Hydrocarbon Biomarkers in Archean Rocks Reappraisal of hydrocarbon biomarkers in Archean rocks Katherine L. Frencha,1,2, Christian Hallmannb,c, Janet M. Hoped, Petra L. Schoone, J. Alex Zumbergee, Yosuke Hoshinof, Carl A. Petersf, Simon C. Georgef, Gordon D. Lovee, Jochen J. Brocksd, Roger Buickg, and Roger E. Summonsh aJoint Program in Chemical Oceanography, Massachusetts Institute of Technology and Woods Hole Oceanographic Institution, Cambridge, MA 02139; bMax Planck Institute for Biogeochemistry, 07745 Jena, Germany; cCenter for Marine Environmental Sciences, University of Bremen, 28359 Bremen, Germany; dResearch School of Earth Sciences, The Australian National University, Canberra, ACT 0200, Australia; eDepartment of Earth Sciences, University of California, Riverside, CA 92521; fDepartment of Earth and Planetary Sciences, Macquarie University, Sydney, NSW 2109, Australia; gDepartment of Earth & Space Sciences and Astrobiology Program, University of Washington, Seattle, WA 98195-1310; and hDepartment of Earth, Atmospheric, and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, MA 02139 Edited by Andrew H. Knoll, Harvard University, Cambridge, MA, and approved March 16, 2015 (received for review October 21, 2014) Hopanes and steranes found in Archean rocks have been pre- hydrocarbon biomarkers hosted in Archean rocks would either sented as key evidence supporting the early rise of oxygenic recast or solidify the late Archean framework in which we un- photosynthesis and eukaryotes, but the syngeneity of these derstand one of the most profound biologically mediated trans- hydrocarbon biomarkers is controversial. To resolve this debate, formations of the planet—the Great Oxidation Event [GOE; ∼2.4 we performed a multilaboratory study of new cores from the billion years ago (Ga)] (13). Pilbara Craton, Australia, that were drilled and sampled using unprecedented hydrocarbon-clean protocols. Hopanes and ster- Sample Collection anes in rock extracts and hydropyrolysates from these new cores We present results from three Archean drill cores from the were typically at or below our femtogram detection limit, but Pilbara Craton, Western Australia, that were drilled during the when they were detectable, they had total hopane (<37.9 pg per 2012 Agouron Institute Drilling Program (AIDP) (SI Appendix, < gram of rock) and total sterane ( 32.9 pg per gram of rock) con- Figs. S1 and S2). Core AIDP-1 (21°06’38’’S, 119°06’4’’E) inter- centrations comparable to those measured in blanks and negative sected the volcanic Coucal Formation (3.52 Ga) of the Coon- control samples. In contrast, hopanes and steranes measured in EARTH, ATMOSPHERIC, terunah Subgroup (14). AIDP-2 and AIDP-3 recovered organic- AND PLANETARY SCIENCES the exteriors of conventionally drilled and curated rocks of strati- rich sedimentary rocks from the two zones of lowest regional graphic equivalence reach concentrations of 389.5 pg per gram of metamorphism known in the Pilbara (15). According to previous rock and 1,039 pg per gram of rock, respectively. Polycyclic aro- studies of mineral assemblage and organic matter reflectivity, matic hydrocarbons and diamondoids, which exceed blank concen- these zones are within the prehnite−pumpellyite metamorphic trations, exhibit individual concentrations up to 80 ng per gram of facies and anthracite coal rank, implying maximum burial tempera- rock in rock extracts and up to 1,000 ng per gram of rock in hydro- – < = tures and pressures of 200 300 °C and 7kbar(1bar 100 kPa), EVOLUTION pyrolysates from the ultraclean cores. These results demonstrate – that previously studied Archean samples host mixtures of bio- respectively (15 18). Core AIDP-2 was drilled in the Ripon ’ ” ’ ” marker contaminants and indigenous overmature hydrocarbons. Hills region (21°16 51 S, 120°50 2 E) in the same locality as the Therefore, existing lipid biomarker evidence cannot be invoked RHDH2A core, which was recovered in 1985 using conventional to support the emergence of oxygenic photosynthesis and eukary- otes by ∼2.7 billion years ago. Although suitable Proterozoic rocks Significance exist, no currently known Archean strata lie within the appropri- ate thermal maturity window for syngenetic hydrocarbon bio- The advent of oxygenic photosynthesis set the stage for the marker preservation, so future exploration for Archean biomarkers evolution of complex life on an oxygenated planet, but it is should screen for rocks with milder thermal histories. unknown when this transformative biochemistry emerged. The existing hydrocarbon biomarker record requires that oxygenic oxygenic photosynthesis | eukaryotes | cyanobacteria | Great Oxidation photosynthesis and eukaryotes emerged more than 300 million Event | Pilbara years before the Great Oxidation Event [∼2.4 billion years ago (Ga)]. We report that hopane and sterane concentrations lucidating the timing of the advent of oxygenic photosyn- measured in new ultraclean Archean drill cores from Australia Ethesis relative to the rise of atmospheric oxygen represents a are comparable to blank concentrations, yet their concentra- key challenge in geobiology. The detection of hopane and ster- tions in the exteriors of conventionally collected cores of strati- ane hydrocarbons in Archean sedimentary rocks has provided an graphic equivalence exceed blank concentrations by more than avenue for examining the evolution of biological oxygen cycling (1–7). an order of magnitude due to surficial contamination. Conse- These results, in addition to inorganic evidence (e.g., refs. quently, previous hydrocarbon biomarker reports no longer 8 and 9), suggest that atmospheric oxygen accumulation provide valid evidence for the advent of oxygenic photosyn- was suppressed for hundreds of millions of years following thesis and eukaryotes by ∼2.7 Ga. the emergence of oxygenic photosynthesis. However, the interpretation of the Archean biomarker record has become Author contributions: K.L.F., C.H., S.C.G., G.D.L., J.J.B., R.B., and R.E.S. designed research; K.L.F., C.H., J.M.H., P.L.S., J.A.Z., Y.H., C.A.P., and R.B. performed research; K.L.F., C.H., controversial, with recent arguments for a nonsyngenetic origin Y.H., S.C.G., G.D.L., J.J.B., and R.E.S. analyzed data; and K.L.F., C.H., Y.H., S.C.G., G.D.L., J.J.B., of these hydrocarbons (10, 11). Furthermore, the discovery of R.B., and R.E.S. wrote the paper. hopanes and steranes in metamorphosed Archean rocks requires The authors declare no conflict of interest. that, if these carbon skeletons are syngenetic, then they have This article is a PNAS Direct Submission. persisted despite experiencing prolonged burial temperatures well 1Present address: Department of Marine Chemistry and Geochemistry, Woods Hole above the end of the oil window (∼150 °C), which is the temper- Oceanographic Institution, Woods Hole, MA 02543. ature range over which conventional oil is generated from a 2To whom correspondence should be addressed. Email: [email protected]. source rock (12). In addition to clarifying the upper limits for This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10. hydrocarbon biomarker preservation, resolving the origin of the 1073/pnas.1419563112/-/DCSupplemental. www.pnas.org/cgi/doi/10.1073/pnas.1419563112 PNAS Early Edition | 1of6 Downloaded by guest on September 28, 2021 drilling methods (19) and reportedly contains syngenetic Archean core material from drying out. After purging with high purity Ar, biomarkers (3, 4). Spatially separated by less than 1 km, AIDP-2 the sample bags were sealed and frozen at –20 °C in the dark and RHDH2A both intersect the Carawine Dolomite (<2.63 Ga) of until the whole cores were sawed. In total, the whole-core sam- the Hamersley Group and the Jeerinah Formation (2.63–2.67 Ga) ples were packaged, purged, and frozen in less than 20 min after of the Fortescue Group (20), so they sample the same stra- recovery from depth. tigraphy and have experienced the same regional metamorphic effects (Fig. 1). AIDP-3 (21°46’32’’S, 117°34’11’’E), which in- Methods tersected the Marra Mamba Iron Formation and the Jeerinah Systematic blank analyses using solvent rinses and sawed pieces of a com- Formation, was drilled as a time-equivalent core in deeper busted brick demonstrated that the diamond-rimmed blade used with the water facies than AIDP-2. It is stratigraphically equivalent newly purchased, water-cooled saw constructed entirely of stainless steel and to WRL-1, which was the subject of the first report, to our aluminum was a significant vector for hydrocarbon biomarker contamina- knowledge, of Archean biomarkers for cyanobacteria and tion. After exhausting other methods (see SI Appendix), the saw blade was heated to 300 °C for 1 h and was sonicated in solvent, after which solvent eukaryotes (1). rinses and combusted brick blanks verified that sawing no longer contrib- The AIDP cores were drilled and sampled using protocols uted detectable hydrocarbon contaminants. Subsequently, the frozen chosen to minimize hydrocarbon contamination. At the begin- whole-core samples were sawed into book-matched halves at the Australian ning of the AIDP campaign, all core barrels were cleaned with National University (ANU), which were distributed to multiple laboratories soap and water, and, subsequently, only new drill bits were used. for independent analyses. The extractable biomarker methods and data Water without added lubricants was used as the sole drilling fluid described below are specific to the ANU/Massachusetts Institute of Tech- for the entirety of the program.
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