Cited by 312Paleontology and Stratigraphy of FossilsOrigins and Evolution of LifeGeological and Geochemical Analysis

The DOI matches its Crossref record; 43 of the 43 references it cites were found in a registry or an index; 2 of the 91 sources its claims cite were checked for support.

Reappraisal of hydrocarbon biomarkers in Archean rocks

Open access

Abstract

Significance: The advent of oxygenic photosynthesis set the stage for the evolution of complex life on an oxygenated planet, but it is unknown when this transformative biochemistry emerged. The existing hydrocarbon biomarker record requires that oxygenic photosynthesis and eukaryotes emerged more than 300 million years before the Great Oxidation Event [∼2.4 billion years ago (Ga)]. We report that hopane and sterane concentrations measured in new ultraclean Archean drill cores from Australia are comparable to blank concentrations, yet their concentrations in the exteriors of conventionally collected cores of stratigraphic equivalence exceed blank concentrations by more than an order of magnitude due to surficial contamination. Consequently, previous hydrocarbon biomarker reports no longer provide valid evidence for the advent of oxygenic photosynthesis and eukaryotes by ∼2.7 Ga.

Overview

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TL;DR

New ultraclean Archean drill cores from the Pilbara Craton contain hopanes and steranes at or below blank/femtogram levels, whereas exteriors of conventionally drilled equivalent rocks are contaminated by these biomarkers. The authors conclude that previously reported Archean hydrocarbon biomarkers cannot be used as evidence for oxygenic photosynthesis and eukaryotes by ∼2.7 Ga.

Key findings

  • In AIDP-2 and AIDP-3 rock extracts, hopanes and steranes were typically at or below femtogram detection limits; when detectable, total hopane was <37.9 pg per gram of rock and total sterane was <32.9 pg per gram of rock, comparable to blanks and negative controls. In hydropyrolysates, neither total hopane nor total sterane exceeded cumulative blank concentrations (<20 pg per gram of rock).
  • In contrast, exteriors of conventionally drilled and curated RHDH2A rocks of stratigraphic equivalence reached 389.5 pg per gram of rock total hopane and 1,039 pg per gram of rock total sterane in the abstract; Table 1 lists RHDH2A sawed surfaces at 250 and 259 pg per gram hopane and 1,092 and 509 pg per gram sterane.
  • PAHs and diamondoids exceeded blank concentrations, with individual concentrations up to 80 ng per gram of rock in rock extracts and up to 1,000 ng per gram of rock in hydropyrolysates from the ultraclean cores; the results text reports hydropyrolysate individual PAH concentrations up to 1,039 ng per gram of rock.
  • The authors conclude that previously studied Archean samples host mixtures of biomarker contaminants and indigenous overmature hydrocarbons, so existing lipid biomarker evidence cannot support the emergence of oxygenic photosynthesis and eukaryotes by ∼2.7 Ga; no currently known Archean strata lie within the appropriate thermal maturity window for syngenetic hydrocarbon biomarker preservation.

Methods

  • Multilaboratory study of new Archean drill cores from the Pilbara Craton, Western Australia, drilled during the 2012 Agouron Institute Drilling Program using hydrocarbon-clean protocols; AIDP-1 provided negative control samples, while AIDP-2 and AIDP-3 recovered organic-rich sedimentary rocks.
  • Rock extracts and hydropyrolysates were analyzed by gas chromatography–mass spectrometry in full scan and metastable reaction monitoring modes, with compound-specific carbon isotopic analyses and PAH/diamondoid measurements; interiors and exteriors of 10 biomarker target samples from AIDP-2 and 2 from AIDP-3 were analyzed for extractable hydrocarbons, and hydropyrolysates were analyzed from eight samples.
  • Approximately 10–40 g of rock powder were extracted per sample; results were compared with blanks, negative controls, and a conventionally drilled RHDH2A core to assess contamination versus syngeneity.

Limitations

  • Stated: only a single compound-specific isotopic measurement was possible for the 116.09 m sample, so analytical uncertainty and reproducibility are not well constrained; future studies are required to test the possible mixing observation; the biomolecular precursors of the PAHs and diamondoids are unknown; and duration of heating and organic matter type complicate direct conversions between vitrinite reflectance, H/C ratio, and burial temperature.
  • Stated: no currently known Archean strata lie within the appropriate thermal maturity window for syngenetic hydrocarbon biomarker preservation, so future exploration should screen for rocks with milder thermal histories.
  • Evident from the text: the study focuses on the Pilbara Craton and specific AIDP/RHDH2A cores, so the absence of detectable syngenetic hopanes and steranes in these samples does not by itself rule out their preservation in all Archean rocks; the authors acknowledge this by calling for future exploration of less mature archives.

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Integrity signals

Registry

Crossref · 10.1073/pnas.1419563112

Cites

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  • It may state two separate claims as one. 26
  • Probably not a substantial claim. 11
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  • The paper relies on this without support.

    Laboratory blanks and negative controls capture all hydrocarbon contamination relevant to the AIDP samples.

    “Hopanes and steranes in the rock extracts from AIDP-2 and AIDP-3 were typically at or below femtogram detection limits, but if they were detectable, the total sterane and total hopane concentrations were comparable to blank and negative control concentrations”
    “Instead, contamination is the only explanation for the reproducibility of the detectable surficial hopanes and steranes in conventionally drilled and curated Archean samples (3,6,7,11) and the undetectable or blank level-equivalent hopane and sterane concentrations in samples from the ultraclean AIDP drill cores.”
  • The paper relies on this without support.

    Hydropyrolysis releases kerogen-bound organic matter without significant carbon isotopic fractionation.

    “The isotopic match between the AIDP bulk organic matter and the hydropyrolysate PAHs supports a syngenetic origin for the hydropyrolysate PAHs generated by thermochemical cleavage of covalent bonds within the host kerogens.”
  • The paper relies on this without support.

    The carbon isotopic anomaly at 2.6–2.7 Ga is a reliable stratigraphic marker for comparing AIDP bulk organic δ13C.

    “In contrast, the δ 13 C values of extractable PAHs do not covary with the AIDP bulk organic δ 13 C through the carbon isotopic anomaly at 2.6-2.7 Ga”
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Metadata

Authors
French, K. L., Hallmann, C., Hope, J. M., Schoon, P. L., Zumberge, J. A., Hoshino, Y., Peters, C. A., George, S. C., Love, G. D., Brocks, J. J., Buick, R., & Summons, R. E.
Affiliations
  • Massachusetts Institute of Technology (US)
  • Max Planck Society (DE)
  • Australian National University (AU)
  • University of California, Riverside (US)
  • Macquarie University (AU)
  • University of Washington (US)
Venue
Proceedings of the National Academy of Sciences
Published
2015-04-27
Volume
112
Issue
19
Pages
5915-5920
ISSN
  • 0027-8424 (ISSN-L)
  • 1091-6490
OpenAlex
W1970132751
Cited by
307
References
43
Citations by year
2026: 13 · 2025: 23 · 2024: 21 · 2023: 14 · 2022: 38 · 2021: 26 · 2020: 27 · 2019: 41 · 2018: 41 · 2017: 25 · 2016: 26 · 2015: 11
FWCI
25.95
Type
journal article
Language
en
Open access
Locations
  • Proceedings of the National Academy of Sciences (publishedVersion)
  • Europe PMC (PubMed Central) (publishedVersion)
  • PubMed Central (publishedVersion)
  • PubMed (publishedVersion)
  • eScholarship (California Digital Library) (submittedVersion)
  • eSpace (Curtin University) (submittedVersion)
  • ANU Open Research (Australian National University) (submittedVersion)
Funders
  • Agouron Institute (private foundation, no grant number)
  • NSF FESD (1338810)
  • NSF GRFP (DGE-1122374)
Topics
  • Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
  • Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
  • Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geological and Geochemical Analysis
Keywords
Archean rocks, hopanes, steranes, hydrocarbon biomarkers, polycyclic aromatic hydrocarbons, diamondoids, eukaryotic origin, Pilbara Craton, thermal maturity
MeSH terms
Cyanobacteria, Archaea, Australia, Fossils, Hydrocarbons, Oxygen, Paleontology, Photosynthesis, Polycyclic Aromatic Hydrocarbons, Solvents, Temperature, Biomarkers, Geologic Sediments

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