Ti-rich potassium-richterite samples were synthesized at 900°C and 1 kbar PH20 and characterized by Fourier-transform infrared spectroscopy (FTIR) and Rietveld structure refinement. The infrared spectrum of end-member Ti-free potassium-richterite shows a main band at 3734 cm-I assigned to an OH anion bonded to three octahedral Mg cations and directed toward K at the A site facing a tetrahedral ring of composition Si6. When Ti is introduced into the structure, two new overlapping components appear in the infrared spectrum. Using a symmetric Gaussian model, they can be resolved into two single bands at 3711 and 3698 cm-I. These two bands are assigned to OH groups facing rings of tetrahedra with compositions SisTi and Si4Ti2, respectively. Their intensities are linearly related to the Rietveld-refined Ti content at T2 up to 0.8 apfu (atoms per formula unit). The analysis of relative band intensities indicates short-range disorder of Si and Ti over the T2 sites. tensities and to derive the short-range order associated with Si-Ti substitution at the T2 sites in the structure. This work required development of an accurate and physically consistent model for depicting the absorption band shape and for the spectrum-fitting procedure. The situation in the present study is almost ideal: Because the samples were previously characterized by a variety of techniques, and both the location and amount ofTi present in the phase are known, the spectrum-fitting procedure can be optimized. INTRODUCTION In the OH-stretching region of OH-bearing minerals, the measured infrared absorptions are not usually single bands but consist of overlapping components that must be resolved for use in quantitative interpretation. In the past, there has been much infrared spectroscopy done on natural amphiboles (Strens 1966; Burns and Strens 1966; Burns and Greaves 1971), but the method fell into disuse owing to the difficulties involved. Specifically, most natural amphiboles are chemically complex, which introduces too many sources of uncertainty into the spectrum-resolution procedure. However, IR analysis of well characEXPERIMENTAL METHODS terized, compositionally simple, synthetic solid-solutions The amphiboles studied here are those synthesized at is more tractable and provides an ideal situation for ex900°C and 1 kbar PH20by Della Ventura et al. (1991). amining the behavior of OH absorption bands in terms Description of the synthesis conditions and characterizaof multiplicity, position, shape, and intensity. tion methods may be found in Mottana et al. (1990), In the last few years, we have devoted much effort to Della Ventura et al. (1991), and Paris et al. (1993). Along this approach. By experimentally producing selected catthe join between potassium-richterite and the Ti endion substitutions at single structural sites in amphiboles, member of potassium-richterite, a single-phase amphibands can be associated with specific substitutions at parbole was obtained for compositions up to 0.6 apfu of Ti ticular crystallographic sites. These efforts have allowed in the system; for higher Ti contents, minor amounts of us to make progress in understanding some crystal-chemadditional Ti-bearing phases were observed (Della Venical aspects of the clino-amphibole structure (Robert et tura et al. 1991). Only the single-phase experimental al. 1989; Della Ventura and Robert 1990; Della Ventura products (i.e., those with a nominal content up to 0.6 Ti et al. 1991, 1993a; Hawthorne et al. 1993). The evolution apfu in the amphibole) were used for structure refinement ofIR spectra in the OH-stretching region along the Si-Ti by the Rietveld method, with final RB<a88 values in the join for potassium-richterite has been briefly considered range 4-6%. Full details of the XRD data collection and in previous works (Della Ventura and Robert 1988; Della refinement procedures may be found in Della Ventura et Ventura et al. 1991, 1993a). Here we propose a model to al. (1993a, 1993b). Detailed discussion of the Rietveld quantify the Si-Ti substitution from measured band inresults is beyond the scope of the present paper. We merely 0003-004X/96/0 102-0056$05.00 56 DELLA VENTURA ET AL.: Si AND Ti DISORDER IN RICHTERlTE note that, for all samples, the refined tetrahedral site occupancies are coincident (within 20-)with the nominal values. For the FTIR data collection, samples were prepared as KBr pellets using the procedure of Robert et al. (1989). Spectra in the range 4000-3000 cm-I were recorded on a Perkin-Elmer model1760 spectrometer equipped with a DTGS detector and a KBr beam splitter and operating at a nominal resolution of I cm-I. Low-temperature spectra were collected on a Bruker IFSl13V spectrophotometer equipped with a nitrogen-cooled cryostat.
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