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Chemical characterization of C31 sterols from sponges and Neoproterozoic fossil sterane counterparts.

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Title: Chemical characterization of C31 sterols from sponges and Neoproterozoic fossil sterane counterparts.
Authors: Shawar, Lubna1,2 Lubnas@Caltech.edu, Love, Gordon D.3, Uveges, Benjamin T.1,4, Zumberge, J. Alex5, Cárdenas, Paco6,7, Giner, José-Luis8, Summons, Roger E.1
Source: Proceedings of the National Academy of Sciences of the United States of America. 10/14/2025, Vol. 122 Issue 41, p1-11. 28p.
Subjects: Sponges (Invertebrates), Demospongiae, Analytical chemistry, Sterols, Precambrian, Proterozoic Era, Mass spectrometry, Gas chromatography
Abstract: Putative metazoan body fossils from the Precambrian are curiously lacking morphological characteristics that link them unambiguously to extant animal phyla, including sponges. Chemical fossils such as the rare C30 hydrocarbons 24-iso-propylcholestane (24-ipc) and 26-methylstigmastane (26-mes), however, have been proposed as evidence for the Neoproterozoic emergence of the Demospongiae (Porifera) due to their prevalence in rocks of this age and the occurrence of their sterol precursors in contemporary demosponges. However, there are alternative hypotheses which posit that diagenetic alteration products of algal sterols, or those from Rhizaria or other protists, account for the enigmatic steroid distributions observed in these ancient sedimentary rocks. Here, we report additional support for the Neoproterozoic rise of demosponges through the chemical characterization of two previously unrecognized C31 hydrocarbons--24-n-butylcholestane (24-nbc) and 24-sec-butylcholestane (24-secbc). Precursor C31 sterols from contemporary demosponges, as well as a suite of synthesized C31 sterol standards were reduced to their sterane counterparts. Gas chromatography-tandem mass spectrometry analysis and collisionally activated dissociation mass spectra confirmed the presence of 24-nbc and 24-secbc in well-preserved early Ediacaran rocks, and the coelution of these compounds with synthetic standards enhances the robustness of these findings. Co-occurrence of abundant 24-ipc and 24-secbc was found for numerous Neoproterozoic-Cambrian rock/oil samples, closely mimicking the abundance patterns and high structural selectivity of major C30 and C31 sterols detected in numerous species of modern demosponges. These findings support the hypothesized first emergence of sponges during the Neoproterozoic Era. [ABSTRACT FROM AUTHOR]
Copyright of Proceedings of the National Academy of Sciences of the United States of America is the property of National Academy of Sciences and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Chemical characterization of C<subscript>31</subscript> sterols from sponges and Neoproterozoic fossil sterane counterparts.
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  Data: <searchLink fieldCode="AR" term="%22Shawar%2C+Lubna%22">Shawar, Lubna</searchLink><relatesTo>1,2</relatesTo><i> Lubnas@Caltech.edu</i><br /><searchLink fieldCode="AR" term="%22Love%2C+Gordon+D%2E%22">Love, Gordon D.</searchLink><relatesTo>3</relatesTo><br /><searchLink fieldCode="AR" term="%22Uveges%2C+Benjamin+T%2E%22">Uveges, Benjamin T.</searchLink><relatesTo>1,4</relatesTo><br /><searchLink fieldCode="AR" term="%22Zumberge%2C+J%2E+Alex%22">Zumberge, J. Alex</searchLink><relatesTo>5</relatesTo><br /><searchLink fieldCode="AR" term="%22Cárdenas%2C+Paco%22">Cárdenas, Paco</searchLink><relatesTo>6,7</relatesTo><br /><searchLink fieldCode="AR" term="%22Giner%2C+José-Luis%22">Giner, José-Luis</searchLink><relatesTo>8</relatesTo><br /><searchLink fieldCode="AR" term="%22Summons%2C+Roger+E%2E%22">Summons, Roger E.</searchLink><relatesTo>1</relatesTo>
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  Data: <searchLink fieldCode="JN" term="%22Proceedings+of+the+National+Academy+of+Sciences+of+the+United+States+of+America%22">Proceedings of the National Academy of Sciences of the United States of America</searchLink>. 10/14/2025, Vol. 122 Issue 41, p1-11. 28p.
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  Data: <searchLink fieldCode="DE" term="%22Sponges+%28Invertebrates%29%22">Sponges (Invertebrates)</searchLink><br /><searchLink fieldCode="DE" term="%22Demospongiae%22">Demospongiae</searchLink><br /><searchLink fieldCode="DE" term="%22Analytical+chemistry%22">Analytical chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Sterols%22">Sterols</searchLink><br /><searchLink fieldCode="DE" term="%22Precambrian%22">Precambrian</searchLink><br /><searchLink fieldCode="DE" term="%22Proterozoic+Era%22">Proterozoic Era</searchLink><br /><searchLink fieldCode="DE" term="%22Mass+spectrometry%22">Mass spectrometry</searchLink><br /><searchLink fieldCode="DE" term="%22Gas+chromatography%22">Gas chromatography</searchLink>
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  Label: Abstract
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  Data: Putative metazoan body fossils from the Precambrian are curiously lacking morphological characteristics that link them unambiguously to extant animal phyla, including sponges. Chemical fossils such as the rare C30 hydrocarbons 24-iso-propylcholestane (24-ipc) and 26-methylstigmastane (26-mes), however, have been proposed as evidence for the Neoproterozoic emergence of the Demospongiae (Porifera) due to their prevalence in rocks of this age and the occurrence of their sterol precursors in contemporary demosponges. However, there are alternative hypotheses which posit that diagenetic alteration products of algal sterols, or those from Rhizaria or other protists, account for the enigmatic steroid distributions observed in these ancient sedimentary rocks. Here, we report additional support for the Neoproterozoic rise of demosponges through the chemical characterization of two previously unrecognized C31 hydrocarbons--24-n-butylcholestane (24-nbc) and 24-sec-butylcholestane (24-secbc). Precursor C31 sterols from contemporary demosponges, as well as a suite of synthesized C31 sterol standards were reduced to their sterane counterparts. Gas chromatography-tandem mass spectrometry analysis and collisionally activated dissociation mass spectra confirmed the presence of 24-nbc and 24-secbc in well-preserved early Ediacaran rocks, and the coelution of these compounds with synthetic standards enhances the robustness of these findings. Co-occurrence of abundant 24-ipc and 24-secbc was found for numerous Neoproterozoic-Cambrian rock/oil samples, closely mimicking the abundance patterns and high structural selectivity of major C30 and C31 sterols detected in numerous species of modern demosponges. These findings support the hypothesized first emergence of sponges during the Neoproterozoic Era. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
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  Data: <i>Copyright of Proceedings of the National Academy of Sciences of the United States of America is the property of National Academy of Sciences and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1073/pnas.2503009122
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      – Code: eng
        Text: English
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        PageCount: 28
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    Subjects:
      – SubjectFull: Sponges (Invertebrates)
        Type: general
      – SubjectFull: Demospongiae
        Type: general
      – SubjectFull: Analytical chemistry
        Type: general
      – SubjectFull: Sterols
        Type: general
      – SubjectFull: Precambrian
        Type: general
      – SubjectFull: Proterozoic Era
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      – SubjectFull: Mass spectrometry
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      – SubjectFull: Gas chromatography
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      – TitleFull: Chemical characterization of C31 sterols from sponges and Neoproterozoic fossil sterane counterparts.
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              Text: 10/14/2025
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