TY - JOUR

T1 - Fe-oxide fracture fillings as a palæo-redox indicator

T2 - structure, crystal form and Fe isotope composition

AU - Dideriksen, Knud

AU - Christiansen, Bo C.

AU - Baker, J.A.

AU - Frandsen, C.

AU - Balic Zunic, Tonci

AU - Tullborg, E.

AU - Mørup, S.

AU - Stipp, Susan Louise Svane

PY - 2007

Y1 - 2007

N2 - Penetration of oxygenated waters to the deeper sub-surface may occur in association with deglaciation events and significantlychange the geochemical processes acting at depth. Such a scenario may compromise long-term storage of radioactive waste in underground repositories where copper canisters would corrode in the presence of oxygen. In this study, Fe-oxides from fractures in granite drill-cores and from drilling debris were investigated and a method developed to trace the low-temperature, oxidising conditions whichmay have been caused by prior deglaciations.X-ray diffraction andMössbauer spectroscopy showed that all the examined fracture fillings contained Fe-oxides. Based on their structure and form, three genetic types of Fe-oxides were identified: (I) coarse-grained (~ 100 nm) hydrothermal hematite; (II) very fine-grained (~ 10 nm) amorphous Fe-oxides that precipitated during drilling; (III) Intermediate grain-size crystalline Fe-oxides, that are interpreted to have formed naturally at low-temperatures (~ 10 °C). Fe isotope composition of the Fe-oxides was determined by multiple-collector inductively coupled plasma mass spectrometry using a 58Fe-54Fe double-spike. d56Fe of the Fe-oxides ranges from -0.8 to +0.8‰ (relative to the IRMM-14 standard). Hydrothermal samples have intermediate d56Fe (-0.3 to 0.0‰), whereas natural low-temperature samples may be isotopically lighter (-0.8 to 0.0‰), and samples precipitated from drilling activity are isotopically heavier (-0.2 to 0.8‰). Within the three genetic suites, d56Fe correlates with the relative proportion of Fe(III). For the hydrothermal samples, Fe isotope composition likely reflects input of partially dissolved chlorite. The Fe isotope composition and Fe redox state of the low-temperature and drillinduced samples is consistent with a conceptual model where Fe isotope fractionation occurs during dissolution and oxidation. In our study, the deepest sample showing evidence of natural low-temperature oxidation, putatively as a result of penetration of oxidising surface waters during deglaciation, is from a depth of ~ 100 m.

AB - Penetration of oxygenated waters to the deeper sub-surface may occur in association with deglaciation events and significantlychange the geochemical processes acting at depth. Such a scenario may compromise long-term storage of radioactive waste in underground repositories where copper canisters would corrode in the presence of oxygen. In this study, Fe-oxides from fractures in granite drill-cores and from drilling debris were investigated and a method developed to trace the low-temperature, oxidising conditions whichmay have been caused by prior deglaciations.X-ray diffraction andMössbauer spectroscopy showed that all the examined fracture fillings contained Fe-oxides. Based on their structure and form, three genetic types of Fe-oxides were identified: (I) coarse-grained (~ 100 nm) hydrothermal hematite; (II) very fine-grained (~ 10 nm) amorphous Fe-oxides that precipitated during drilling; (III) Intermediate grain-size crystalline Fe-oxides, that are interpreted to have formed naturally at low-temperatures (~ 10 °C). Fe isotope composition of the Fe-oxides was determined by multiple-collector inductively coupled plasma mass spectrometry using a 58Fe-54Fe double-spike. d56Fe of the Fe-oxides ranges from -0.8 to +0.8‰ (relative to the IRMM-14 standard). Hydrothermal samples have intermediate d56Fe (-0.3 to 0.0‰), whereas natural low-temperature samples may be isotopically lighter (-0.8 to 0.0‰), and samples precipitated from drilling activity are isotopically heavier (-0.2 to 0.8‰). Within the three genetic suites, d56Fe correlates with the relative proportion of Fe(III). For the hydrothermal samples, Fe isotope composition likely reflects input of partially dissolved chlorite. The Fe isotope composition and Fe redox state of the low-temperature and drillinduced samples is consistent with a conceptual model where Fe isotope fractionation occurs during dissolution and oxidation. In our study, the deepest sample showing evidence of natural low-temperature oxidation, putatively as a result of penetration of oxidising surface waters during deglaciation, is from a depth of ~ 100 m.

KW - Faculty of Science

KW - Radioactive waste repository

KW - Fe isotope

KW - Granite

KW - Fractures

KW - Fe-oxide

KW - Oxidation

M3 - Journal article

VL - 244

SP - 330

EP - 343

JO - Chemical Geology

JF - Chemical Geology

SN - 0009-2541

ER -