『Abstract
We dissolved Boulder Creek Granodiorite in a plug flow reactor
for 5794 h at pH = 1 and T = 25℃. The primary purpose of the experiment
was to identify controls on dissolved δ44/40Ca, δ44/42Ca,
and δ26/24Mg values during granite weathering. Herein,
we also examine the origin of Ca and Mg isotopic variability among
minerals composing the Boulder Creek Granodiorite, and we constrain
fundamental characteristics of granite weathering important for
quantifying the elemental and isotopic geochemistry of the reactor
output. Nine Ca-bearing minerals display an 8.80‰ range of δ44/40Ca
values and a 0.51‰ range of δ44/42Ca values. Three
Mg-bearing minerals display a 1.53‰ range of δ26/24Mg
values. These ranges expressed at the mineralogical scale are
higher than the ranges thus far reported for bulk igneous rocks.
Most of the δ44/40Ca variability reflects 40Ca
enrichment in K-feldspar, and to a lesser extent, biotite, due
to the radioactive decay of 40K over the 1.7 Ga age
of the rock, whereas the entire range of δ44/42Ca values
reflects mass-dependent isotope fractionation during igneous differentiation
and crystallization. The range of δ26/24Mg values may
represent either fractionation during the chloritization of biotite
or interaction of the Boulder Creek Granodiorite with Mg-rich
metamorphic fluids having low δ26/24Mg values.
The elemental and isotopic composition of the reactor output
varied substantially during the experiment. We synthesize the
mineralogical and fluid data using coupled mass-conservation equations
solved at non-steady-state. Model calculations reveal an intricate
balance between increasing specific surface area and decreasing
mineral concentrations. While surface area normalized dissolution
rate constants were time-invariant, specific surface area increased
as a power-law function of time through positive feedbacks between
mechanical disaggregation, chemical dissolution, and mineral depletion.
Variations in dissolved δ44/40Ca, δ44/42Ca,
and δ26/24Mg values reflect conservative mixing rather
than fractionation. Apatite and calcite initially control δ44/40Ca
and δ44/42Ca values, followed by biotite, titanite,
epidote, hornblende, and plagioclase. The release of radiogenic
40Ca clearly defines the period where biotite dissolution
dominates. The brucite layer of chlorite initially controls δ26/24Mg
values, followed by biotite, the TOT layer of chlorite, and hornblende.
Through direct isotopic tracking, these results demonstrate that
trace minerals, such as apatite and calcite in the case of Ca
and brucite in the case of Mg, dominate elemental release during
the incipient stages of granite weathering. The results further
show that biotite dissolution dominates the middle stages of granite
weathering and that plagioclase dissolution only becomes important
during relatively late stages. The Ca and Mg isotope variations
associated with these stages are distinct and potentially resolvable
in soil mineral weathering studies.』
1. Introduction
2. Minerals and methods
2.1. Characterization and preparation of the granite and
its minerals
2.2. Plug flow reactor experiment
2.3. Chemical and isotopic analyses
3. Results and discussion
3.1. Mineralogy and petrology of the Boulder Creek Granodiorite
3.2. General geochemistry of the output solutions
3.3. Magnesium isotope geochemistry of the rock, minerals, and
output solutions
3.4. Calcium isotope geochemistry of the rock, minerals, and
output solutions
3.5. Description of numerical model for mineral dissolution
3.5.1. Coupled conservation equations for the solid and fluid
3.5.2. Specific surface area: A power-law function of time
3.6. Solution of numerical model for mineral dissolution
3.6.1. The dissolution of Mg-bearing minerals
3.6.2. The dissolution of Ca-bearing minerals
3.6.3. The dissolution of K-feldspar and concentrations profiles
for Al and Si
3.7. Feedbacks between mechanical and chemical weathering
4. Conclusions and implications
Acknowledgements
Appendix A. Supplementary data
References