TY - JOUR
T1 - Hydrogen and deuterium diffusion in non-stoichiometric spinel
AU - Bromiley, Geoffrey D.
AU - Brooke, Jennifer
AU - Kohn, Simon C.
PY - 2017/7
Y1 - 2017/7
N2 - High pressure/temperature annealing experiments are used to determine diffusivities of H+ and D+ in non-stoichiometric spinel, a low-pressure analogue for nominally anhydrous minerals in Earth’s mantle. Data are fitted to the following Arrhenius law: Diffusivity (m2/s) = 4 ± 1 × 10−12 exp(−54 ± 2 kJ mol−1/RT). At low temperatures, H+ and D+ diffusion in non-stoichiometric spinel is charge balanced by flux of O vacancies, with infrared data consistent with protonation of both octahedral and tetrahedral O–O edges in non-stoichiometric spinel, and additional fine structure due to Mg–Al mixing and/or coupling of structurally incorporated H+ with cation vacancies. Absence of changes in the fine structure of O–H absorption bands indicates that H+ can become locally coupled and uncoupled to other defects during bulk diffusion. As such, proton conductivity in spinel group minerals, arising from faster flux of uncoupled H+, can only be calculated from H+ mobility data if the extent of defect coupling is constrained.
AB - High pressure/temperature annealing experiments are used to determine diffusivities of H+ and D+ in non-stoichiometric spinel, a low-pressure analogue for nominally anhydrous minerals in Earth’s mantle. Data are fitted to the following Arrhenius law: Diffusivity (m2/s) = 4 ± 1 × 10−12 exp(−54 ± 2 kJ mol−1/RT). At low temperatures, H+ and D+ diffusion in non-stoichiometric spinel is charge balanced by flux of O vacancies, with infrared data consistent with protonation of both octahedral and tetrahedral O–O edges in non-stoichiometric spinel, and additional fine structure due to Mg–Al mixing and/or coupling of structurally incorporated H+ with cation vacancies. Absence of changes in the fine structure of O–H absorption bands indicates that H+ can become locally coupled and uncoupled to other defects during bulk diffusion. As such, proton conductivity in spinel group minerals, arising from faster flux of uncoupled H+, can only be calculated from H+ mobility data if the extent of defect coupling is constrained.
KW - deuterium
KW - diffusion
KW - hydrogen
KW - mantle
KW - Spinel
UR - http://www.scopus.com/inward/record.url?scp=85023782034&partnerID=8YFLogxK
U2 - 10.1080/08957959.2017.1353091
DO - 10.1080/08957959.2017.1353091
M3 - Article (Academic Journal)
AN - SCOPUS:85023782034
SN - 0895-7959
VL - 37
SP - 360
EP - 376
JO - High Pressure Research
JF - High Pressure Research
IS - 3
ER -