Redox Freezing and Melting during Peridotite Interaction with Carbonated Metasediments and Metabasics: Experiments at 10 GPa

— The hypothesis of redox freezing is based on the assumption that a Fe–Ni metal phase becomes stable in the peridotite mantle at increasing pressure and can serve as a reducer for carbonate–silicate melts. reduction and formation of elementary C (graphite or diamond) result in an increase in the so...

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Veröffentlicht in:Geochemistry international 2022-07, Vol.60 (7), p.609-625
Hauptverfasser: Girnis, A. V., Woodland, A. B., Bulatov, V. K., Brey, G. P., Höfer, H. E.
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container_end_page 625
container_issue 7
container_start_page 609
container_title Geochemistry international
container_volume 60
creator Girnis, A. V.
Woodland, A. B.
Bulatov, V. K.
Brey, G. P.
Höfer, H. E.
description — The hypothesis of redox freezing is based on the assumption that a Fe–Ni metal phase becomes stable in the peridotite mantle at increasing pressure and can serve as a reducer for carbonate–silicate melts. reduction and formation of elementary C (graphite or diamond) result in an increase in the solidus temperature and melt freezing. Thermodynamic calculations show that equilibrium oxygen fugacity in peridotite with carbon and magnesite is significantly lower than the values buffered by the mineral assemblages of metasediments (garnet–kyanite–SiO 2 –aragonite–elemental carbon) or eclogites (pyroxene–garnet–magnesite–elemental carbon). Hence, redox interaction between carbon-bearing peridotites and metasediments or eclogites may occur in the absence of metal and even in a Fe-free system. To explore this suggestion, we conducted experiments on interaction between forsterite (as a peridotite proxy) with synthetic mixtures simulating carbonatized metasediment (SiO 2 + CaCO 3 + Al 2 O 3 ) and carbonatized eclogite (SiO 2 + MgCO 3 ± Al 2 O 3 ± CaO) at 10 GPa and 1200–1500°C. To reduce the transport of major components, the mixtures were separated by a graphite disc, which also served as a source of C. The interaction resulted in the decarbonation of the carbonate-bearing metasediment or eclogite with diamond formation on the surface of the graphite disc. The graphite disc was dissolved at contact with peridotite, and metasomatic zoning developed. Pyroxene and magnesite with low Ca contents appeared in the distal metasomatic zone. The contents of Ca in the newly formed pyroxene and carbonate increases toward the graphite disc, and high-Ca pyroxene and garnet were observed in the proximal metasomatic zone. The obtained results indicate that coupled redox reactions occur in peridotite and metasediment (or eclogite): Mg 2 SiO 4 + C + O 2 = MgSiO 3 +MgCO 3 and CaCO 3 + 1/3Al 2 S-iO 5 + 2/3SiO 2 = 1/3Ca 3 Al 2 Si 3 O 12 + C + O 2 , respectively. The reactions occur owing to oxygen diffusion along intergranular melt channels. The interaction also involves the transfer of major cations, which resulted in the formation of carbonatized lherzolite and a diamond-bearing eclogite assemblage. Such a process is possible in nature at a contact of carbonated metasediment or eclogite with peridotite. The obtained results indicate that the presence of Fe–Ni metal is not necessary for redox freezing. The processes modeled in the experiments provide a possible explanation for the e
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V. ; Woodland, A. B. ; Bulatov, V. K. ; Brey, G. P. ; Höfer, H. E.</creator><creatorcontrib>Girnis, A. V. ; Woodland, A. B. ; Bulatov, V. K. ; Brey, G. P. ; Höfer, H. E.</creatorcontrib><description>— The hypothesis of redox freezing is based on the assumption that a Fe–Ni metal phase becomes stable in the peridotite mantle at increasing pressure and can serve as a reducer for carbonate–silicate melts. reduction and formation of elementary C (graphite or diamond) result in an increase in the solidus temperature and melt freezing. Thermodynamic calculations show that equilibrium oxygen fugacity in peridotite with carbon and magnesite is significantly lower than the values buffered by the mineral assemblages of metasediments (garnet–kyanite–SiO 2 –aragonite–elemental carbon) or eclogites (pyroxene–garnet–magnesite–elemental carbon). Hence, redox interaction between carbon-bearing peridotites and metasediments or eclogites may occur in the absence of metal and even in a Fe-free system. To explore this suggestion, we conducted experiments on interaction between forsterite (as a peridotite proxy) with synthetic mixtures simulating carbonatized metasediment (SiO 2 + CaCO 3 + Al 2 O 3 ) and carbonatized eclogite (SiO 2 + MgCO 3 ± Al 2 O 3 ± CaO) at 10 GPa and 1200–1500°C. To reduce the transport of major components, the mixtures were separated by a graphite disc, which also served as a source of C. The interaction resulted in the decarbonation of the carbonate-bearing metasediment or eclogite with diamond formation on the surface of the graphite disc. The graphite disc was dissolved at contact with peridotite, and metasomatic zoning developed. Pyroxene and magnesite with low Ca contents appeared in the distal metasomatic zone. The contents of Ca in the newly formed pyroxene and carbonate increases toward the graphite disc, and high-Ca pyroxene and garnet were observed in the proximal metasomatic zone. The obtained results indicate that coupled redox reactions occur in peridotite and metasediment (or eclogite): Mg 2 SiO 4 + C + O 2 = MgSiO 3 +MgCO 3 and CaCO 3 + 1/3Al 2 S-iO 5 + 2/3SiO 2 = 1/3Ca 3 Al 2 Si 3 O 12 + C + O 2 , respectively. The reactions occur owing to oxygen diffusion along intergranular melt channels. The interaction also involves the transfer of major cations, which resulted in the formation of carbonatized lherzolite and a diamond-bearing eclogite assemblage. Such a process is possible in nature at a contact of carbonated metasediment or eclogite with peridotite. The obtained results indicate that the presence of Fe–Ni metal is not necessary for redox freezing. The processes modeled in the experiments provide a possible explanation for the existence of diamond-rich eclogites and the scarcity of diamond in peridotite xenoliths.</description><identifier>ISSN: 0016-7029</identifier><identifier>EISSN: 1556-1968</identifier><identifier>DOI: 10.1134/S0016702922070035</identifier><language>eng</language><publisher>Moscow: Pleiades Publishing</publisher><subject>Aluminum oxide ; Aragonite ; Calcite crystals ; Calcium carbonate ; Carbon ; Carbonates ; Carbonation ; Cations ; Decarbonation ; Diamonds ; Earth ; Earth and Environmental Science ; Earth Sciences ; Eclogite ; Experiments ; Forsterite ; Freezing ; Fugacity ; Garnet ; Garnets ; Geochemistry ; Graphite ; Heavy metals ; Inclusions ; Iron ; Kyanite ; Magnesite ; Magnesium carbonate ; Magnesium compounds ; Mantle ; Mineral assemblages ; Mixtures ; Nickel ; Oxidoreductions ; Oxygen ; Peridotite ; Pyroxene ; Pyroxenes ; Redox reactions ; Rocks, Igneous ; Silica ; Silicates ; Silicon dioxide ; Solidus ; Thermodynamic equilibrium ; Thermodynamics</subject><ispartof>Geochemistry international, 2022-07, Vol.60 (7), p.609-625</ispartof><rights>Pleiades Publishing, Ltd. 2022. ISSN 0016-7029, Geochemistry International, 2022, Vol. 60, No. 7, pp. 609–625. © Pleiades Publishing, Ltd., 2022. Russian Text © The Author(s), 2022, published in Geokhimiya, 2022, Vol. 67, No. 7, pp. 603–620.</rights><rights>COPYRIGHT 2022 Springer</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a308t-5b64d2be70059802ccab584a49cfc4f8f84ef65136037a256b1f8f92f98875d93</citedby><cites>FETCH-LOGICAL-a308t-5b64d2be70059802ccab584a49cfc4f8f84ef65136037a256b1f8f92f98875d93</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://link.springer.com/content/pdf/10.1134/S0016702922070035$$EPDF$$P50$$Gspringer$$H</linktopdf><linktohtml>$$Uhttps://link.springer.com/10.1134/S0016702922070035$$EHTML$$P50$$Gspringer$$H</linktohtml><link.rule.ids>314,777,781,27905,27906,41469,42538,51300</link.rule.ids></links><search><creatorcontrib>Girnis, A. V.</creatorcontrib><creatorcontrib>Woodland, A. B.</creatorcontrib><creatorcontrib>Bulatov, V. K.</creatorcontrib><creatorcontrib>Brey, G. P.</creatorcontrib><creatorcontrib>Höfer, H. E.</creatorcontrib><title>Redox Freezing and Melting during Peridotite Interaction with Carbonated Metasediments and Metabasics: Experiments at 10 GPa</title><title>Geochemistry international</title><addtitle>Geochem. Int</addtitle><description>— The hypothesis of redox freezing is based on the assumption that a Fe–Ni metal phase becomes stable in the peridotite mantle at increasing pressure and can serve as a reducer for carbonate–silicate melts. reduction and formation of elementary C (graphite or diamond) result in an increase in the solidus temperature and melt freezing. Thermodynamic calculations show that equilibrium oxygen fugacity in peridotite with carbon and magnesite is significantly lower than the values buffered by the mineral assemblages of metasediments (garnet–kyanite–SiO 2 –aragonite–elemental carbon) or eclogites (pyroxene–garnet–magnesite–elemental carbon). Hence, redox interaction between carbon-bearing peridotites and metasediments or eclogites may occur in the absence of metal and even in a Fe-free system. To explore this suggestion, we conducted experiments on interaction between forsterite (as a peridotite proxy) with synthetic mixtures simulating carbonatized metasediment (SiO 2 + CaCO 3 + Al 2 O 3 ) and carbonatized eclogite (SiO 2 + MgCO 3 ± Al 2 O 3 ± CaO) at 10 GPa and 1200–1500°C. To reduce the transport of major components, the mixtures were separated by a graphite disc, which also served as a source of C. The interaction resulted in the decarbonation of the carbonate-bearing metasediment or eclogite with diamond formation on the surface of the graphite disc. The graphite disc was dissolved at contact with peridotite, and metasomatic zoning developed. Pyroxene and magnesite with low Ca contents appeared in the distal metasomatic zone. The contents of Ca in the newly formed pyroxene and carbonate increases toward the graphite disc, and high-Ca pyroxene and garnet were observed in the proximal metasomatic zone. The obtained results indicate that coupled redox reactions occur in peridotite and metasediment (or eclogite): Mg 2 SiO 4 + C + O 2 = MgSiO 3 +MgCO 3 and CaCO 3 + 1/3Al 2 S-iO 5 + 2/3SiO 2 = 1/3Ca 3 Al 2 Si 3 O 12 + C + O 2 , respectively. The reactions occur owing to oxygen diffusion along intergranular melt channels. The interaction also involves the transfer of major cations, which resulted in the formation of carbonatized lherzolite and a diamond-bearing eclogite assemblage. Such a process is possible in nature at a contact of carbonated metasediment or eclogite with peridotite. The obtained results indicate that the presence of Fe–Ni metal is not necessary for redox freezing. The processes modeled in the experiments provide a possible explanation for the existence of diamond-rich eclogites and the scarcity of diamond in peridotite xenoliths.</description><subject>Aluminum oxide</subject><subject>Aragonite</subject><subject>Calcite crystals</subject><subject>Calcium carbonate</subject><subject>Carbon</subject><subject>Carbonates</subject><subject>Carbonation</subject><subject>Cations</subject><subject>Decarbonation</subject><subject>Diamonds</subject><subject>Earth</subject><subject>Earth and Environmental Science</subject><subject>Earth Sciences</subject><subject>Eclogite</subject><subject>Experiments</subject><subject>Forsterite</subject><subject>Freezing</subject><subject>Fugacity</subject><subject>Garnet</subject><subject>Garnets</subject><subject>Geochemistry</subject><subject>Graphite</subject><subject>Heavy metals</subject><subject>Inclusions</subject><subject>Iron</subject><subject>Kyanite</subject><subject>Magnesite</subject><subject>Magnesium carbonate</subject><subject>Magnesium compounds</subject><subject>Mantle</subject><subject>Mineral assemblages</subject><subject>Mixtures</subject><subject>Nickel</subject><subject>Oxidoreductions</subject><subject>Oxygen</subject><subject>Peridotite</subject><subject>Pyroxene</subject><subject>Pyroxenes</subject><subject>Redox reactions</subject><subject>Rocks, Igneous</subject><subject>Silica</subject><subject>Silicates</subject><subject>Silicon dioxide</subject><subject>Solidus</subject><subject>Thermodynamic equilibrium</subject><subject>Thermodynamics</subject><issn>0016-7029</issn><issn>1556-1968</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNp1kV1LBCEUhiUK2j5-QHdC11PqqKPdxVJbUBR9XA_OzLGMTTd16YN-fA670EWEF0fOe55XzzkIHVByRGnNj-8JobIhTDNGGkJqsYEmVAhZUS3VJpqMcjXq22gnpRdCOK91M0HfdzCED3weAb6cf8LGD_ga5nm8D8s4hluIbgjZZcCXPkM0fXbB43eXn_HUxC54k2GkskkwuFfwOa19sulMcn06wWcfi2Kz1jKmBM9uzR7asmaeYH8dd9Hj-dnD9KK6upldTk-vKlMTlSvRST6wDkpfQivC-t50QnHDdW97bpVVHKwUtJakbgwTsqMlqZnVSjVi0PUuOlz5LmJ4W0LK7UtYRl-ebJlUXChN2Vh1tKp6MnNonbchl17LGeDV9cGDdSV_2pAyY1lLVQC6AvoYUopg20Vp0cTPlpJ23Er7ZyuFYSsmLcbhQvz9yv_QD9Vqji8</recordid><startdate>20220701</startdate><enddate>20220701</enddate><creator>Girnis, A. 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V.</creatorcontrib><creatorcontrib>Woodland, A. B.</creatorcontrib><creatorcontrib>Bulatov, V. K.</creatorcontrib><creatorcontrib>Brey, G. P.</creatorcontrib><creatorcontrib>Höfer, H. E.</creatorcontrib><collection>CrossRef</collection><collection>Aqualine</collection><collection>Water Resources Abstracts</collection><collection>Environmental Sciences and Pollution Management</collection><collection>ASFA: Aquatic Sciences and Fisheries Abstracts</collection><collection>Aquatic Science &amp; Fisheries Abstracts (ASFA) 2: Ocean Technology, Policy &amp; Non-Living Resources</collection><collection>Aquatic Science &amp; Fisheries Abstracts (ASFA) Professional</collection><jtitle>Geochemistry international</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Girnis, A. V.</au><au>Woodland, A. B.</au><au>Bulatov, V. K.</au><au>Brey, G. P.</au><au>Höfer, H. E.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Redox Freezing and Melting during Peridotite Interaction with Carbonated Metasediments and Metabasics: Experiments at 10 GPa</atitle><jtitle>Geochemistry international</jtitle><stitle>Geochem. Int</stitle><date>2022-07-01</date><risdate>2022</risdate><volume>60</volume><issue>7</issue><spage>609</spage><epage>625</epage><pages>609-625</pages><issn>0016-7029</issn><eissn>1556-1968</eissn><abstract>— The hypothesis of redox freezing is based on the assumption that a Fe–Ni metal phase becomes stable in the peridotite mantle at increasing pressure and can serve as a reducer for carbonate–silicate melts. reduction and formation of elementary C (graphite or diamond) result in an increase in the solidus temperature and melt freezing. Thermodynamic calculations show that equilibrium oxygen fugacity in peridotite with carbon and magnesite is significantly lower than the values buffered by the mineral assemblages of metasediments (garnet–kyanite–SiO 2 –aragonite–elemental carbon) or eclogites (pyroxene–garnet–magnesite–elemental carbon). Hence, redox interaction between carbon-bearing peridotites and metasediments or eclogites may occur in the absence of metal and even in a Fe-free system. To explore this suggestion, we conducted experiments on interaction between forsterite (as a peridotite proxy) with synthetic mixtures simulating carbonatized metasediment (SiO 2 + CaCO 3 + Al 2 O 3 ) and carbonatized eclogite (SiO 2 + MgCO 3 ± Al 2 O 3 ± CaO) at 10 GPa and 1200–1500°C. To reduce the transport of major components, the mixtures were separated by a graphite disc, which also served as a source of C. The interaction resulted in the decarbonation of the carbonate-bearing metasediment or eclogite with diamond formation on the surface of the graphite disc. The graphite disc was dissolved at contact with peridotite, and metasomatic zoning developed. Pyroxene and magnesite with low Ca contents appeared in the distal metasomatic zone. The contents of Ca in the newly formed pyroxene and carbonate increases toward the graphite disc, and high-Ca pyroxene and garnet were observed in the proximal metasomatic zone. The obtained results indicate that coupled redox reactions occur in peridotite and metasediment (or eclogite): Mg 2 SiO 4 + C + O 2 = MgSiO 3 +MgCO 3 and CaCO 3 + 1/3Al 2 S-iO 5 + 2/3SiO 2 = 1/3Ca 3 Al 2 Si 3 O 12 + C + O 2 , respectively. The reactions occur owing to oxygen diffusion along intergranular melt channels. The interaction also involves the transfer of major cations, which resulted in the formation of carbonatized lherzolite and a diamond-bearing eclogite assemblage. Such a process is possible in nature at a contact of carbonated metasediment or eclogite with peridotite. The obtained results indicate that the presence of Fe–Ni metal is not necessary for redox freezing. The processes modeled in the experiments provide a possible explanation for the existence of diamond-rich eclogites and the scarcity of diamond in peridotite xenoliths.</abstract><cop>Moscow</cop><pub>Pleiades Publishing</pub><doi>10.1134/S0016702922070035</doi><tpages>17</tpages></addata></record>
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subjects Aluminum oxide
Aragonite
Calcite crystals
Calcium carbonate
Carbon
Carbonates
Carbonation
Cations
Decarbonation
Diamonds
Earth
Earth and Environmental Science
Earth Sciences
Eclogite
Experiments
Forsterite
Freezing
Fugacity
Garnet
Garnets
Geochemistry
Graphite
Heavy metals
Inclusions
Iron
Kyanite
Magnesite
Magnesium carbonate
Magnesium compounds
Mantle
Mineral assemblages
Mixtures
Nickel
Oxidoreductions
Oxygen
Peridotite
Pyroxene
Pyroxenes
Redox reactions
Rocks, Igneous
Silica
Silicates
Silicon dioxide
Solidus
Thermodynamic equilibrium
Thermodynamics
title Redox Freezing and Melting during Peridotite Interaction with Carbonated Metasediments and Metabasics: Experiments at 10 GPa
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