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Unleashing the Potential of Glendonite: a Mineral Archive for Biogeochemical Processes and Paleoenvironmental Conditions

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Unleashing the Potential of Glendonite: a Mineral Archive for Biogeochemical Processes and Paleoenvironmental Conditions RESEARCH FOCUS: RESEARCH FOCUS Unleashing the potential of glendonite: A mineral archive for biogeochemical processes and paleoenvironmental conditions Jörn Peckmann Institut für Geologie, Universität Hamburg, 20146 Hamburg, Germany Ikaite (CaCO3 × 6H2O) is a calcium carbonate mineral that forms at low Temperature may not be the only trigger for the disintegration of temperatures close to the freezing point of water and is metastable under ikaite. Disintegration has been suggested to be favored by (1) a decrease surface conditions in natural environments. It occurs as an early diagenetic in alkalinity and concentration of dissolved phosphate (Bischoff et al., mineral in marine sediments, where it grows close to the sediment-water 1993), or (2) changing pore-water chemistries reflecting the transition interface, typically forming centimeter-sized single euhedral crystals to from an environment shaped by organoclastic sulfate reduction to an stellate crystal aggregates (Zabel and Schulz, 2001). Its precipitation is environment shaped by anaerobic oxidation of methane (Greinert and favored by elevated carbonate alkalinity, high pH, and high concentrations Derkachev, 2004). Upon destabilization, ikaite transforms into a mush of dissolved phosphate (Bischoff et al., 1993; Hu et al., 2015; Zhou et al., of water and small crystals of calcite and sometimes vaterite, another 2015). Ikaite readily transforms into calcite upon an increase of temperature polymorph of calcium carbonate (Suess et al., 1982; Selleck et al., 2007). or a change of pore-water chemistry (Pauly, 1963; Swainson and Ham- The secondary phase formed first is represented by carbonate bundles mond, 2001); the external shape of crystals and crystal aggregates is com- referred to as ‘replacive calcite’ (Teichert and Luppold, 2013). The extent monly maintained and the product is referred to as glendonite. Glendonite to which carbonate ions are exchanged in this process may be variable, is consequently not a mineral but a pseudomorph of calcite after ikaite. likely depending on the actual driving force of the transformation. Inter- Both ikaite and glendonite have been known for a long time, but the deriva- estingly, experiments with ikaite and newly formed calcite resulting from tion of glendonite from ikaite was only confirmed after crystal aggregates heating treatment revealed no change of stable isotope patterns under of ikaite resembling glendonite were found in organic-rich sediments of laboratory conditions (Greinert and Derkachev, 2004). Knowledge of the Bransfield Strait off the Antarctic Peninsula (Suess et al., 1982). The the extent of potential exchange of carbonate ions in the transformation relatively narrow temperature limits under which ikaite can form make this process is essential for the interpretation of the factors governing ikaite mineral an indicator of glaciomarine and cold deepwater settings (Selleck precipitation and the subsequent transformation to other calcium car- et al., 2007). The occurrence of glendonite is consequently of paleoclimatic bonate minerals. The initial transformation of ikaite is accompanied by significance and has been used as evidence for cold-water depositional a decrease of volume of approximately one-third, generating pore space environments in the rock record (James et al., 2005; Wang et al., 2017). (Selleck et al., 2007). Most of this pore space tends to be filled by a vari- In addition to low temperatures, formation of ikaite in marine sedi- ety of carbonate cements including deeper burial cements, but silica and ments requires a local biogeochemical process that increases alkalin- other minerals may occur (Qu et al., 2017). As glendonite is made up of ity. The two processes that have been proposed that may be capable of a complex paragenetic sequence of secondary minerals, it is of limited inducing ikaite formation are organoclastic sulfate reduction (Suess et al., use as a paleoenvironmental archive. Studies looking into glendonite 1982) and sulfate-driven anaerobic oxidation of methane (Schubert et al. formation would ideally focus on replacive calcite, but the small size of 1997); both are biogeochemical processes in which organic compounds its crystals and interfingering with later carbonate cements commonly are oxidized at the expense of sulfate. Authigenic minerals resulting from preclude phase-specific sampling for stable isotope analysis. the remineralization of organic compounds are typified by lowδ 13C values To test if anaerobic oxidation of methane was responsible for the for- (Irwin et al., 1977). Because methane is more 13C depleted than organic mation of glendonite enclosed in Paleogene strata of western Washington matter used in organoclastic sulfate reduction (Whiticar, 1999), meth- State (USA), Qu et al. (2017) extracted lipid biomarkers (organic mol- ane-derived carbonates are characterized by particularly low δ13C values ecules that can be traced back to their source) from large crystal aggre- (Peckmann and Thiel, 2004). Both biogeochemical processes typically gates of glendonite that occur in the periphery of methane-seep deposits. increase pore-water alkalinity, adding to the pool of dissolved inorganic Although the seep deposits formed by anaerobic oxidation of methane carbon in pore water, and resulting in authigenic carbonate minerals that and biomarkers of the prokaryotes driving this process are abundant in reflect mixing of different carbon sources (Peckmann and Thiel, 2004). the seep limestones, the glendonite with δ13C values as low as −21‰ Based on average stable carbon isotope compositions of terrestrial organic yielded no such biomarkers. Instead, glendonite was found to contain matter (~−30‰), marine organic matter (~−20‰), and methane (−30 to biomarkers of organoclastic sulfate reduction. This finding was surpris- −110‰), only ikaite with δ13C values lower than approximately −30‰ can ing based on the ample evidence for anaerobic oxidation of methane in be confidently interpreted to result from anaerobic oxidation of methane the form of seep deposits occurring in the same strata that bear abundant (e.g., Teichert and Luppold, 2013). However, many ikaite and glendonite glendonite. In order to constrain the relative importance of different bio- specimens reveal δ13C values between −10‰ and −25‰, impeding iden- geochemical processes in glendonite formation, it is necessary to iden- 13 tification of the biogeochemical process that induced mineral formation. tify additional criteria in cases when δ Ccarbonate values do not allow for Due to the circumstance that stable carbon isotope signatures are often discrimination between organoclastic sulfate reduction and anaerobic ambiguous, other proxies are required to decide if mineral formation oxidation of methane. was induced by organoclastic sulfate reduction or anaerobic oxidation In this issue of Geology, Morales et al. (2017) document the link of methane. Unfortunately, such reconstruction is further compromised between periods of pronounced methane seepage and glendonite by the uncertainty regarding the factors that govern the transformation formation, studying an extensive set of glendonites that are widely dis- of ikaite to glendonite. tributed in Early Jurassic to Early Cretaceous strata of Siberia (Russia). It GEOLOGY, June 2017; v. 45; no. 6; p. 575–576 | doi:10.1130/focus062017.1 ©GEOLOGY 2017 Geological | Volume Society 45 | ofNumber America. 6 For| www.gsapubs.org permission to copy, contact [email protected]. 575 Downloaded from http://pubs.geoscienceworld.org/gsa/geology/article-pdf/45/6/575/999555/575.pdf by guest on 29 September 2021 is a strength of this study that the factors that govern ikaite precipitation Greinert, J., and Derkachev, A., 2004, Glendonites and methane-derived Mg-cal- and its transformation to glendonite are not confused. Emphasizing the cites in the Sea of Okhotsk, Eastern Siberia: Implications of a venting-related ikaite/glendonite formation: Marine Geology, v. 204, p. 129–144, doi:10 .1016 actual transformation process, the authors coin the phrase ‘ikaite fossil- /S0025 -3227 (03)00354 -2. ization.’ They find evidence in support of the hypothesis that anaerobic Heindel, K., Birgel, D., Brunner, N., Thiel, V., Westphal, H., Gischler, E., Ziegenbalg, oxidation of methane is instrumental for the preservation of ikaite. Ana- S.B., Gabioch, G., Sjövall, P., and Peckmann, J., 2012, Post-glacial microbialite lyzing the composition of gas inclusions and the stable carbon isotopic formation in coral reefs of the Pacific, Atlantic, and Indian Oceans: Chemi- composition of gases, Morales et al. document a deep origin of short-chain cal Geology, v. 304–305, p. 117–130, doi: 10 .1016 /j .chemgeo .2012 .02 .009. Hu, Y.-B., Wolthers, M., Wolf-Gladrow, D., and Nehrke, G., 2015, Effect of pH hydrocarbons. With this sophisticated approach, evidence for (1) a rapid and phosphate on calcium carbonate polymorphs precipitated at near-freezing transformation of ikaite to glendonite and (2) a deep reservoir of ther- temperature: Crystal Growth & Design, v. 15, p. 1596–1601, doi: 10 .1021 mogenic methane is found. The latter observation agrees with seepage of /cg500829p. hydrocarbons, and is in accord with low δ13C values and the presence Irwin, H., Curtis, C., and Coleman, M., 1977, Isotopic evidence for source of dia- carbonate genetic carbonates formed during burial of organic-rich sediments: Nature, of carbonate mineral phases reminiscent of seep carbonates. Although the v. 269, p. 209–213, doi: 10 .1038 /269209a0.
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