Etch pits quartz

Gratz, A. J., S. Manne, and P. K. Hansma (1991), "Atomic Force Microscopy of Atomic-Scale Ledges and Etch Pits Formed During Dissolution of Quartz", Science 251,1343-46. 

For C crit t 161"6 ls a double root to the maximization equation, and there is an inflection point in the AG function (curve D on Figure 1). Since there is no activation barrier to opening up the etch pit, any pit nucleated at a dislocation should open up into a macroscopic etch pit. Similarly, for C < Ccr t, there are no real solutions and no maxima and minima in the A G function, and nucleated pits open up into etch pits. At 300°C, the calculated Ccr t for quartz equals 0.6CQ. 

A very accurate measurement of Ccrjt would allow back-calculation of the surface energy for a given crystal. Because Ccrjt is dependent on the square of Y, such a measurement could be a very sensitive method of measuring interfacial energy at dislocation outcrops. The calculated interfacial energy from our experiments is 280+ 90 mJm- for the rhombohedral face of quartz at 300°C. Parks (10) estimated 25°C value of 360 + 30 mJm is well within the experimental error of our measurement. The best way to determine the value of Ccrjt would be to measure etch pit nucleation rate on... 

Figure 2. The effect of dissolved Si concentration on etch pit density on quartz surfaces etched a) in sealed autoclaves for 6.5 hours, b) in a flow reactor for 6.5 hours (R5), 31.5 hours (R5SK), and 25-28 hours (R9). Reproduced with permission from Ref. 16. Copyright 1986 Pergamon Press.

Low temperature etching. Our data suggests that, under hydrothermal conditions the rate of pit formation is dramatically reduced, although perhaps not completely stopped, at C = Ccrjt. Etch pits on a natural, hydrothermally-etched quartz surface therefore indicate extended dissolution times, but not necessarily etching at C < Ccrit This is because the rate of etch pit formation even above Ccr t can be significant at elevated temperatures (as shown by crystal R9). However, at low temperatures, formation of etch pits when C > C would be less likely, and natural surfaces etched at low temperature should record the saturation state of the etching fluid. 

Based on predicted weathering and erosion rates of the region, we estimate the profile to be several million years old. Because the soil has developed in situ, the topmost grains have reacted with water for the greatest extent of time. With depth, the total "lifetime" of the particles as soil decreases. This implies that the topmost quartz surfaces should be "reactively mature" (all fines removed, deep grown-together etch pits) and the bottom-most quartz surfaces should be "reactively young" (plentiful fines, fresh surfaces). ... 

In general, the shape and character of etch pits may reveal information about the impurity content of the crystal. "Beaked pits (pits with curved apexes, see 12) can indicate impurity haloes. Some forms of the arcuate etching we observed in quartz (16) may be examples of beaking. Very shallow pits can form at aged dislocations while very deep pits form at new dislocations. "Aging" may be related to impurity diffusion in the crystal lattice. 

Several refinements of our experiments could test these theories further. By measuring etch pit densities as well as pit dimensions on sequentially-etched crystals, nucleation rate data and pit growth data could be collected, yielding information about the rate-limiting steps and mechanisms of dissolution. In addition, since the critical concentration is extremely dependent on surface energy of the crystal-water interface (Equation 4), careful measurement of Ccrit yields a precise measurement of Y. Our data indicates an interfacial energy of 280 + 90 mjm- for Arkansas quartz at 300°C, which compares well with Parks value of 360 mJm for 25°C (10). Similar experiments on other minerals could provide essential surface energy data. 

Brantley S. L., Crane S. R., Crerar D., Hellmann R., and Stallard R. (1986) Dissolution at dislocation etch pits in quartz. Geochim. Cosmochim. Acta 50, 2349-2361. 

Fig. 7-10. Graphical results of a Monte Carlo simulation of progressive dissolution and etch pit formation around a screw dislocation in quartz. Etch profiles illustrate the removal of high energy material adjacent to the dislocation with time (reprinted wilh permission from Blum and Lasaga, 1987 Copyright 1987, John Wiley Sons.)...

These findings, together with the observation that etch pits are developed in a similar manner on both deformed and undeformed samples of feldspar and calcite (e.g., see Murphy, 1989), indicate that etch pits may only be weakly related to dislocations. Probably, the dense etch pitting observed in natural samples of quartz and silicates must reflect their aqueous chemical environment (i.e., the presence of ligands, which considerably enhance dissolution) and the presence in these solids of localized chemical impurities such as aluminium, which favor the specific adsorption of F and organic ligands as oxalate, silicilate, and similar. This specific adsorption on chemical impurities may result in localized enhancements of dissolution as illustrated by Figure 17. 

Figure 3. SEM/EDX images of (a) ferric hydroxide coating on a feldspar grain, (b) EDX spectra of ferric hydroxide on a quartz grain, (c) chemical weathering of biotite platelets, and (d) etch pits on a plagioclase mineral grain. All grains were taken from surface sediments of Lake Cristallina, Switzerland. Photographs are courtesy of Professor Rudolf Giovanoli, Laboratory of Electron Microscopy, University of Bern.

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