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Ashburtonite, a New Bicarbonate-Silicatemineral from Ashburton Downs, Western Australia: Description and Structure Determination

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Ashburtonite, a New Bicarbonate-Silicatemineral from Ashburton Downs, Western Australia: Description and Structure Determination American Mineralogist, Volume 76, pages 1701-1707, 1991 Ashburtonite, a new bicarbonate-silicatemineral from Ashburton Downs, Western Australia: Description and structure determination Jorr, D. Gnrcn Mineral SciencesSection, Canadian Museum of Nature. Ottawa. Ontario KIP 6P4, Canada Enxnsr H. Nrcxnr, Division of Mineral Products, CSIRO, Wembley, Westem Australia 6014, Australia Rorrnr A. Gaur.r Mineral SciencesSection, Canadian Museum of Nature, Ottawa. Ontario KIP 6P4, Canada Ansrnlcr Ashburtonite, ideally HPboCuoSioOrr(HCO3)4(OH)oCl,is a new mineral from Ashburton Downs, Western Australia. It occurs as clustersof clear blue, prismatic crystals up to 0.4 mm long. Associated minerals include diaboleite, duftite, beudantite, caledonite, platt- nerite, cerussite,malachite, and brochantite. The mineral has a vitreous luster and light blue streak. It is brittle with a conchoidal fracture. Ashburtonite is uniaxial positive with ar: 1.786(3)and e : 1.800(4).It is tetragonal,space group l4/m, with a : 14.234(7),c : 6.103(5)A, and Z:2. The strongestX-ray powder-diffractionlines areld(A), I, hk\ 10.2(100,1l0),5.644(70,101), 4.495(100,310), 3.333(100,321), 3.013(90,41l), 2.805(30,202),2.611(50,222), 2.010(30,710,103,631), 1.656(30,642,503). Crystals are elongatedon [001] with forms {ll0}, {100}, {001}, and {301}. The infraredspectrum indicates the presenceof OH and CO, groups.An electron-microprobeanalysis gave PbO 52.2,CuO 18.7,SiO, 14.1,Cl 2.3,HrO(calc.)4.22 and COr(calc.)10.31, -O = Cl: 0.51, total 101.20wto/o; D*,": 4.69 g/cm3.The structurehas beenrefined to R : 3.5 and R* : 2.4o/o.The four-membered, tetrahedral silicate rings are cross linked by ribbons of edge-sharedCu octahedra. The [HCO,] groups are loosely bonded to the sides of larye c axis channels by Cu octahedra and Pb in ninefold coordination. The Pb2* has a stereo- chemically inactive lone pair of electrons, which causesa lowering of symmetry in the atomic structure. INrnooucrroN OccunnnNcr There are many small copper depositsin the Capricorn The Anticline prospect at Ashburton Downs has an Range approximately 1000 km north of Perth, Western assemblageof secondary minerals in a weathered shear Australia. The new mineral, ashburtonite, was found at zone that cuts a seriesof shalesand graywackes.The sec- the Anticline prospect,on Mineral Claim 84, which is on ondary minerals were probably derived from a primary the Ashburton Downs pastoral lease, I 1.2 km west- sulfide assemblageincluding chalcopyrite and galena,but southwest of Ashburton Downs homestead. The speci- they are not available for study. flowever, a few residual mens used in the present description were collected by relic galena crystals can be observed in the secondary Blair Gartrell and brought to E.H.N. Gartrell had noted assemblage.The secondary assemblageconsists essen- several rare speciesand a number of unusual minerals tially ofhydrated carbonates,arsenates and sulfatesofPb that he could not identifu. His astute observations have and Cu, and to a much lesserextent, Zn and Fe. Asso- now resulted in the description of two new mineral spe- ciated with the new mineral ashburtonite are beudantite, cies:gartrellite (Nickel et al., 1989),named in his honor, brochantite, caledonite, cerussite,diaboleite, duftite, and ashburtonite, describedin the present paper. malachite, and plattnerite. Nickel et al. (1989) also report The new mineral and the name were approved by the the presenceof adamite, antlerite, bayldonite, bindheim- Commission on New Minerals and Mineral Names, IMA. ite, carminite, chenevixite, chlorargyrite, chrysocolla, Cotype material is in the Collection of the Canadian Mu- cinnabar, coronadite, cumengite, gartrellite, goethite, seum of Nature under catalogno. CMN 58391 and in the hematite, hemimorphite, hydrozincite, jarosite, laven- Museum of Victoria, Melbourne, under catalog no. dulan, linarite, mimetite, olivenite, paratacamite,and ro- M40712. sasiteat this localitv. 0003{04x/91/0910-1701$02.00 r70r 1702 GRICE ET AL.: ASHBURTONITE DESCRIPTION AND STRUCTURE Fig. l. Scanningelectron microscope photomicrograph showingashburtonite crystals elongated on [001].Scale bar is Fig.2. Crystaldrawing of ashburtonite,clinogaphic projec- 10pm. tron. Prrvsrcll,, oprrcAl,, AND cHEMTcAL pRopERTrEs is no discernible fluorescencein either long- or short- Ashburtonite occurs as very small crystals, distinctly wave ultraviolet light. in HCI blue with no greenishtint, up to 400 pm long and 30 pm Ashburtonite decomposesrapidly concentrated concentrated wide clustered in aggregatesup to 20 mm in diameter and slowly in0.2 M HCl, l:l HNOr, and (Fig. l). Ashburtonite crystals are prismatic, elongated HrSOo. parallel to [001] with a dominant prism { I l0} and sbme- Crrnprrclr, coMProsrrroN times a minor prism { 100}, and terminated by a pinacoid {001} or a combinationof a pinacoidand pyramid {301} Chemical analysis was performed on a JEOL 733 Su- faces(Fig. 2). A dipyramidal development was noted on perprobe using Tracor-Northern 5600 automation. The some crystals. wavelength-dispersive mode was used; data reduction was Ashburtonite is transparent,with a vitreous luster and done with the Tracor-Northern Task seriesof programs pale blue streak. Crystals are very brittle, breaking with using a conventional ZAF correction routine. The oper- a conchoidal fracture and no apparentcleavage. Hardness ating voltage was l5 kV, and the beam culrent was 0.020 could not be determined becauseof the small grain size, pA. The electron beam was defocusedto 20 pm and three and the density could not be measuredaccurately; how- spectrometerswere used simultaneously to minimize de- ever, grains sink in Clerici solution (i.e., the density is composition of the sample under the electron beam. A greater than 4.07 ilcm').The calculated density is 4.69 100-s energy-dispersivescan indicated that no elements g/cm3.Ashburtonite is uniaxial *, <,r: 1.786(3)and e : with Z > 9 other than those reported here were present. 1.800(4),as determined in Na light. The lower refractive Standards used were cuprite (CuKa), mimetite (CLKa), index was determined by the oil immersion method, but sanbornite (SiKa), and crocoite (PbMa). The presenceof the immersion oils above n: 1.785 react with ashbur- COI- and OH- ions was established by infrared spec- tonite forming an opaque residue; thus a Berek compen- troscopy and by crystal-structure analysis. The result of sator was used to determine birefringence,from which e averaginganalyses from four separatecrystals is given in was calculated. A Gladstone-Dale calculation using the Table l. The empirical formula based on 12 cations calculateddensity gives a compatibility index of -0.010, (Pb2*,cu2*,sia*)is HPbr.recuoo,sio ooo,r.03(HCo3)o(oH)4- which is regardedas superior (Mandarino, l98l). There Cl,,o. The ideal formula is HPboCuoSioO,r(HCOJ.(OH)4C1. GRICE ET AL.: ASHBURTONITE DESCRIPTION AND STRUCTURE I 703 TABLe1. Chemical composition of ashburtonite Theoretical composition z (wt%) of F Atomic HPboCuoSioO,, Oxide Wto/" proportions' (HCO3)1(OH)1Cl z Pbo 52.17 Pb 3.99 51.44 CuO 18.66 Cu 4.01 18.33 N sio, 14.O7 si 4.00 13.84 cl 2.28 cl 1.10 2.O4 CO,.. 10.31 HCO3 4.00 10.15 H.o't 4.22 OH 4.00 4.66 JE00.0 2800.o 1900.0 1400.0, 900,00 400.00 $/AVENUMBERS(CM-r ) 101.71 o 27.45 100.46 o: cl -0.51 -0.46 Fig. 3. Infraredspectrum ofashburtonite. 101.20 100 X-uv cRysrAlr,ocRApHy Ar\rD cRysrAL 'On basisot Pb+ Cu+ Si: 12. " Calculatedfrom stoichiometryand crystal-structureanalysis. Other STRUCTURE DETERMINATION componentsdetermined by electronmicroprobe analysis. Precessioncamera photographs show ashburtonite to be tetragonal with possible spacegroup choicesI4/m, 14 and 14.As crystals of this mineral tend to be needlelike, parallel photograph The four analysesgave totals rangingfrom I 00.5 to I 0 1.8 elongate to [001], c axis exposures wto/o. were necessarilyvery long, 5G-70 h, using Mo radiation at 1.5 kW of power. X-ray powder-diffraction data, ob- tained with a Debeye-Schenercamera having a diameter INrnnnrn ANALysrs of I14.6 mm and CuKa radiation, are given in Table 2. High-resolution infrared spectrawere recorded for the TABLE2. X-raypowder diffraction data for ashburtonite wavenumber region 400-3800 cm-' using a Nicolet 5DX Fourier transfom infrared spectrometerwith a diamond ilt" anvil cell microsampling device. Two samplesof ashbur- 110 10.065 10.2 100 tonite approximately I mg in sizewere studied with iden- 200 7.117 7.14 20 101 5.609 5.644 70 tical results; one of the spectrais shown in Figure 3. The 220 5.033 5.039 10 recorded portion between 1900 and 2400 cm-t has been 310 4.501 4.495 100 removed becauseit contains diamond spectra. 400 3.558 3.583 20 321 3.315 3.333 100 The spectrum has a large number of absorbancepeaks 420 3.183 3.192 20 resulting from the complex atomic structure of ashbur- 411 3.005 3.013 90 202 2.804 2.805 30 tonite. We cannot interpret the spectrum in detail, but 222 2.609 2.611 50 five bands give useful information on the grossaspects of 3't2 2.526 I z.szz 20 the ashburtonite structure. The complete absenceof a 440 2.516 l 530 2.441 2.439 20 band near 1600 cm-' indicates a lack of HrO in the struc- 332 2.257 2.259 20 ture. The weak peak 422 2.203 that seemsto exist in that region can 2.194 20 be attributed to adsorbed HrO. In contrast there is a broad, 611 2.',t85 ', 541 2.089 2.090 20 intense band from 2900 to 3700 cm characteristic of 512 2.060 2.058 10 the stretchingfrequency range of the OH- ion. The broad- 710 2.015 probably 103 2.014 2.010 30 ness results from contributions of OH in the 631 2.004 '1.974 bicarbonate (HCO, ) ion in addition to regular OH-.
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