Rare earth elements and radiogenic strontium isotopes in carbonate minerals reveal diagenetic influence in shales and limestones in the Appalachian Basin

Phan, Thai T.; Hakala, J. Alexandra; Lopano, Christina L.; Sharma, Shikha

doi:10.1016/j.chemgeo.2019.01.018

Title: Rare earth elements and radiogenic strontium isotopes in carbonate minerals reveal diagenetic influence in shales and limestones in the Appalachian Basin

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Abstract

Rare earth element (REE) signatures are often applied to interpret paleoenvironmental conditions in sedimentary basins, however the complicated diagenetic histories in dynamic depositional environments can affect interpretation of measured REE signatures. Prior studies on REE content in shales and limestones indicated that REE in specific mineral phases may provide unique information concerning diagenetic reactions occurring in sedimentary rocks during burial and compaction. Application of sequential extraction techniques to target REE signatures in specific mineral fractions may provide greater insight into the complex processes that occurred during diagenesis and catagenesis. Thus, using this technique, this study provides a detailed account for REE, ⁸⁷Sr/⁸⁶Sr, and δ¹³C in the carbonate fraction of the Marcellus Shale and adjacent formations in the Appalachian Basin. A suite of 49 rock samples collected from two cores recovered from Monongalia County, West Virginia, USA was analyzed. The results showed that the carbonate concretions in calcareous shales and carbonate cements in black shales were very distinct. The REE plus yttrium (REY) were more concentrated in the carbonate concretions than in the carbonate cements. The carbonate concretions displayed REY patterns that are closely similar to modern seawater, while MREE-enrichment was observed in the carbonate cements. Likewise, the ⁸⁷Sr/⁸⁶Sr values inmore »« less

Authors:

^[1]; Hakala, J. Alexandra ^[2]; Lopano, Christina L. ^[2]; Sharma, Shikha ^[3]

National Energy Technology Lab. (NETL), Pittsburgh, PA (United States); Univ. of Pittsburgh, Pittsburgh, PA (United States). Dept. of Geology and Environmental Science; Univ. of Waterloo, Waterloo, ON (Canada). Dept. of Earth and Environmental Sciences
National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)
West Virginia Univ., Morgantown, WV (United States). Dept. of Geology and Geography

Publication Date:: Tue Jan 29 00:00:00 EST 2019

Research Org.:: National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1573909

Alternate Identifier(s):: OSTI ID: 1547819

Report Number(s):: NETL-PUB-21967
Journal ID: ISSN 0009-2541; TRN: US2001126

Grant/Contract Number:: FE0024297

Resource Type:: Accepted Manuscript

Journal Name:: Chemical Geology

Additional Journal Information:: Journal Volume: 509; Journal Issue: C; Journal ID: ISSN 0009-2541

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 58 GEOSCIENCES

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                    Phan, Thai T., Hakala, J. Alexandra, Lopano, Christina L., and Sharma, Shikha. Rare earth elements and radiogenic strontium isotopes in carbonate minerals reveal diagenetic influence in shales and limestones in the Appalachian Basin.  United States: N. p., 2019. 
Web.  doi:10.1016/j.chemgeo.2019.01.018.

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                    Phan, Thai T., Hakala, J. Alexandra, Lopano, Christina L., & Sharma, Shikha. Rare earth elements and radiogenic strontium isotopes in carbonate minerals reveal diagenetic influence in shales and limestones in the Appalachian Basin.  United States.  https://doi.org/10.1016/j.chemgeo.2019.01.018

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                    Phan, Thai T., Hakala, J. Alexandra, Lopano, Christina L., and Sharma, Shikha. Tue .  
"Rare earth elements and radiogenic strontium isotopes in carbonate minerals reveal diagenetic influence in shales and limestones in the Appalachian Basin".  United States.  https://doi.org/10.1016/j.chemgeo.2019.01.018.  https://www.osti.gov/servlets/purl/1573909.

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@article{osti_1573909,

  title        = {Rare earth elements and radiogenic strontium isotopes in carbonate minerals reveal diagenetic influence in shales and limestones in the Appalachian Basin},

  author       = {Phan, Thai T. and Hakala, J. Alexandra and Lopano, Christina L. and Sharma, Shikha},

  abstractNote = {Rare earth element (REE) signatures are often applied to interpret paleoenvironmental conditions in sedimentary basins, however the complicated diagenetic histories in dynamic depositional environments can affect interpretation of measured REE signatures. Prior studies on REE content in shales and limestones indicated that REE in specific mineral phases may provide unique information concerning diagenetic reactions occurring in sedimentary rocks during burial and compaction. Application of sequential extraction techniques to target REE signatures in specific mineral fractions may provide greater insight into the complex processes that occurred during diagenesis and catagenesis. Thus, using this technique, this study provides a detailed account for REE, 87Sr/86Sr, and δ13C in the carbonate fraction of the Marcellus Shale and adjacent formations in the Appalachian Basin. A suite of 49 rock samples collected from two cores recovered from Monongalia County, West Virginia, USA was analyzed. The results showed that the carbonate concretions in calcareous shales and carbonate cements in black shales were very distinct. The REE plus yttrium (REY) were more concentrated in the carbonate concretions than in the carbonate cements. The carbonate concretions displayed REY patterns that are closely similar to modern seawater, while MREE-enrichment was observed in the carbonate cements. Likewise, the 87Sr/86Sr values in the carbonate concretions were similar to those measured for unaltered Middle Devonian carbonates, while the 87Sr/86Sr in the carbonate cements were much more radiogenic. This observation indicates that the carbonate cement could have been inherited radiogenic 87Sr expulsed from clays during illite-smectite transition. Overall, this study demonstrated two distinct processes involved with controlling the carbonate geochemistry within Appalachian Basin shales and limestones: one fraction displaying minimal diagenetic alteration relative to depositional conditions (carbonate concretions in calcareous shales and limestone carbonate in limestones), and another fraction displaying the evidence for extensive chemical alteration during illite-smectite transition and catagenesis (carbonate cements in black shales). Here, in addition, highly variable and significant enrichments of U and Mo demonstrate that the Union Spring member and the Lower Oatka Creek member of the Marcellus Shale in the southwestern Appalachian Basin (MSEEL site) were deposited under mainly anoxic environment whereas intermitted episodes of dysoxic to perhaps oxic conditions occurred during the deposition of the Upper Oatka Creek member.},

  doi          = {10.1016/j.chemgeo.2019.01.018},

  journal      = {Chemical Geology},

  number       = C,

  volume       = 509,

  place        = {United States},

  year         = {Tue Jan 29 00:00:00 EST 2019},

  month        = {Tue Jan 29 00:00:00 EST 2019}

}

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https://doi.org/10.1016/j.chemgeo.2019.01.018

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