TY - JOUR
T1 - Dissolution kinetics of strained calcite
AU - Schott, Jacques
AU - Brantley, Susan
AU - Crerar, David
AU - Guy, Christophe
AU - Borcsik, Maria
AU - Willaime, Christian
N1 - Funding Information:
ResearcFhu ndg rant 19455-Gan2d, a Research Corporation grant to Brantley; and NSF grants EAR-82a1n8d7E2 A6R -840765t1o Crerar. Brian Evaancsk nowledgtehse suppoortf NSF grant EAR-8419152D.. A.C. alsgor atefulalyc knowledgseusp port froCm.N .R.S., France, and the Shell Companies Foundation throughout the course of this work. The manusbcerinpet fittefrdo mr eviewbsy J ohn Morse, Eurybiades Busenbaenrdga na nonymourse viewer.
PY - 1989/2
Y1 - 1989/2
N2 - Interaface-limited dissolution of minerals occurs non-uniformly with preferential attack at sites of excess surface energy such as dislocations, edges, point defects, microfractures, etc. Strained crystals are predicted to show higher dissolution rates due to the increased internal energy associated with dislocations and due to enhanced nucleation of dissolution pits at dislocation outcrops on the surface. Using calcite strained to different degrees, we have observed a measurable rate enhancement of two to three times relative to unstrained crystals at temperatures from 3 to 80°C. This rate enhancement is large compared to that predicted from the calculated increase in crystal activity due to strain energy, but small compared to the three orders of magnitude difference in dislocation densities for the crystals tested (106-109 cm-2). Measurements over a range of pH (4.5-8.3) and temperature (3-80°C) showed that the rate enhancement increased with increasing pH and decreasing temperature. Calculations based on the excess free energy of screw dislocations suggest that dissolution rate enhancement should become significant above a critical defect density of roughly 107 cm-2, in apparent agreement with our observations. Crystal dissolution comprises several parallel processes operating in parallel at active sites. The small relative enhancement of dissolution rate with defect density reflects the greater quantity of dissolved material delivered to solution from receding edges and ledges relative to material coming from point defects and dislocations. Our data, coupled with existing information on other minerals, suggest that generally applicable kinetic measurements can be made on low-strain, macroscopic mineral specimens. However, kinetic data on highly strained minerals should include measurement of defect density because of the rate vs. strain correlation. Selective dissolution can be expected to occur in naturally-deformed rocks, where heterogeneity in dislocation distribution could cause solution transfer and deformation.
AB - Interaface-limited dissolution of minerals occurs non-uniformly with preferential attack at sites of excess surface energy such as dislocations, edges, point defects, microfractures, etc. Strained crystals are predicted to show higher dissolution rates due to the increased internal energy associated with dislocations and due to enhanced nucleation of dissolution pits at dislocation outcrops on the surface. Using calcite strained to different degrees, we have observed a measurable rate enhancement of two to three times relative to unstrained crystals at temperatures from 3 to 80°C. This rate enhancement is large compared to that predicted from the calculated increase in crystal activity due to strain energy, but small compared to the three orders of magnitude difference in dislocation densities for the crystals tested (106-109 cm-2). Measurements over a range of pH (4.5-8.3) and temperature (3-80°C) showed that the rate enhancement increased with increasing pH and decreasing temperature. Calculations based on the excess free energy of screw dislocations suggest that dissolution rate enhancement should become significant above a critical defect density of roughly 107 cm-2, in apparent agreement with our observations. Crystal dissolution comprises several parallel processes operating in parallel at active sites. The small relative enhancement of dissolution rate with defect density reflects the greater quantity of dissolved material delivered to solution from receding edges and ledges relative to material coming from point defects and dislocations. Our data, coupled with existing information on other minerals, suggest that generally applicable kinetic measurements can be made on low-strain, macroscopic mineral specimens. However, kinetic data on highly strained minerals should include measurement of defect density because of the rate vs. strain correlation. Selective dissolution can be expected to occur in naturally-deformed rocks, where heterogeneity in dislocation distribution could cause solution transfer and deformation.
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U2 - 10.1016/0016-7037(89)90389-X
DO - 10.1016/0016-7037(89)90389-X
M3 - Article
AN - SCOPUS:0024486522
SN - 0016-7037
VL - 53
SP - 373
EP - 382
JO - Geochimica et Cosmochimica Acta
JF - Geochimica et Cosmochimica Acta
IS - 2
ER -