TY - JOUR

T1 - C-and N-bearing species in reduced fluids in the simplified C–O–H–N system and in natural pelite at upper mantle P–T conditions

AU - Sokol, Ivan

AU - Sokol, Alexander

AU - Bul’bak, Taras

AU - Nefyodov, Andrey

AU - Zaikin, Pavel

AU - Tomilenko, Anatoly

PY - 2019/11/1

Y1 - 2019/11/1

N2 - C-and N-bearing species in reduced fluids weree studied experimentally in C–O–H–N and muscovite–C–O–H–N systems and in natural carbonate-bearing samples at mantle P–T parameters. The experiments reproduced three types of reactions leading to formation of hydrocarbons (HCs) at 3.8–7.8 GPa and 800–1400◦ C and at hydrogen fugacity (f H2) buffered by the Fe–FeO (IW) + H2 O or Mo–MoO2 (MMO) + H2 O equilibria: (i) Thermal destruction of organic matter during its subduction into the mantle (with an example of docosane), (ii) hydrogenation of graphite upon interaction with H2-enriched fluids, and (iii) hydrogenation of carbonates and products of their reduction in metamorphic clayey rocks. The obtained quenched fluids analyzed after the runs by gas chromatography-mass spectrometry (GC–MS) and electronic ionization mass-spectrometry (HR–MS) contain CH4 and C2 H6 as main carbon species. The concentrations of C2-C4 alkanes in the fluids increase as the pressure and temperature increase from 3.8 to 7.8 GPa and from 800 to 1400◦ C, respectively. The fluid equilibrated with the muscovite–garnet–omphacite–kyanite–rutile ± coesite assemblage consists of 50–80 rel.% H2 O and 15–40 rel.% alkanes (C1 > C2 > C3 > C4). Main N-bearing species are ammonia (NH3) in the C–O–H–N and muscovite–C–O–H–N systems or methanimine (CH3 N) in the fluid derived from the samples of natural pelitic rocks. Nitrogen comes either from air or melamine (C3 H6 N6) in model systems or from NH4 + in the runs with natural samples. The formula CH3 N in the quenched fluid of the C–O–H–N system is confirmed by HR–MS. The impossibility of CH3 N incorporation into K-bearing silicates because of a big CH3 NH+ cation may limit the solubility of N in silicates at low f O2 and hence may substantially influence the mantle cycle of nitrogen. Thus, subduction of slabs containing carbonates, organic matter, and N-bearing minerals into strongly reduced mantle may induce the formation of fluids enriched in H2 O, light alkanes, NH3, and CH3 N. The presence of these species must be critical for the deep cycles of carbon, nitrogen, and hydrogen.

AB - C-and N-bearing species in reduced fluids weree studied experimentally in C–O–H–N and muscovite–C–O–H–N systems and in natural carbonate-bearing samples at mantle P–T parameters. The experiments reproduced three types of reactions leading to formation of hydrocarbons (HCs) at 3.8–7.8 GPa and 800–1400◦ C and at hydrogen fugacity (f H2) buffered by the Fe–FeO (IW) + H2 O or Mo–MoO2 (MMO) + H2 O equilibria: (i) Thermal destruction of organic matter during its subduction into the mantle (with an example of docosane), (ii) hydrogenation of graphite upon interaction with H2-enriched fluids, and (iii) hydrogenation of carbonates and products of their reduction in metamorphic clayey rocks. The obtained quenched fluids analyzed after the runs by gas chromatography-mass spectrometry (GC–MS) and electronic ionization mass-spectrometry (HR–MS) contain CH4 and C2 H6 as main carbon species. The concentrations of C2-C4 alkanes in the fluids increase as the pressure and temperature increase from 3.8 to 7.8 GPa and from 800 to 1400◦ C, respectively. The fluid equilibrated with the muscovite–garnet–omphacite–kyanite–rutile ± coesite assemblage consists of 50–80 rel.% H2 O and 15–40 rel.% alkanes (C1 > C2 > C3 > C4). Main N-bearing species are ammonia (NH3) in the C–O–H–N and muscovite–C–O–H–N systems or methanimine (CH3 N) in the fluid derived from the samples of natural pelitic rocks. Nitrogen comes either from air or melamine (C3 H6 N6) in model systems or from NH4 + in the runs with natural samples. The formula CH3 N in the quenched fluid of the C–O–H–N system is confirmed by HR–MS. The impossibility of CH3 N incorporation into K-bearing silicates because of a big CH3 NH+ cation may limit the solubility of N in silicates at low f O2 and hence may substantially influence the mantle cycle of nitrogen. Thus, subduction of slabs containing carbonates, organic matter, and N-bearing minerals into strongly reduced mantle may induce the formation of fluids enriched in H2 O, light alkanes, NH3, and CH3 N. The presence of these species must be critical for the deep cycles of carbon, nitrogen, and hydrogen.

KW - Deep carbon cycle

KW - Deep nitrogen cycle

KW - Fluid

KW - Hydrocarbons

KW - Mantle

KW - Methanimine

KW - Pelite

KW - Subduction

KW - pelite

KW - HYDROCARBONS

KW - EARTHS MANTLE

KW - mantle

KW - fluid

KW - deep carbon cycle

KW - deep nitrogen cycle

KW - methanimine

KW - CARBON

KW - HYDROGENATION

KW - hydrocarbons

KW - NITROGEN SPECIATION

KW - SUBDUCTION ZONES

KW - OXIDATION-STATE

KW - HIGH-PRESSURES

KW - 5.5-7.8 GPA

KW - subduction

KW - DIAMOND CRYSTAL-GROWTH

UR - http://www.scopus.com/inward/record.url?scp=85075504397&partnerID=8YFLogxK

U2 - 10.3390/min9110712

DO - 10.3390/min9110712

M3 - Article

AN - SCOPUS:85075504397

VL - 9

JO - Minerals

JF - Minerals

SN - 2075-163X

IS - 11

M1 - 712

ER -