Baileychlore, the Zn end member of the trioctahedral chlorite
Transcrição
Baileychlore, the Zn end member of the trioctahedral chlorite
American Mineralogist, Volume 73, pages 135-139, 1988 Baileychlore, the Zn endmember of the trioctahedral chlorite series andGeophysicrjJn".r"ttrt;*[lir,", Deparrmenr of Geology Fn.lNr R-lorp u.s.A. 53706, wisconsin Madison, Austratian Mineral Development Laboratories,Frewville, South Australia, 5063' Australia Ansrnacr Baileychlore occurs as dark green rims on colloform calcite veins within a strongly oxidized collapse karst-breccia containing altered andesite and garnet-vesuvianiteskarn clasts at the Red Dome deposit near Chillagoe, Queensland,Australia. Baileychlore is a new Zn-rich chlorite. The ZnO contents are fairly uniform from 28.2 to 30.5 wto/oat a depth of 89.6 m in the deposit, with a structural formula of (Zn, 'oFeli'Al'.''Mgo 'uMnfrfr'tro36XSi3 45)Or0(OH)tfor the most Zn-rich analysis.The name is for ProfessorSturges 55Alo W. Bailey of the University of Wisconsin and is to be used for any trioctahedral chlorite in which Zn is the dominant divalent octahedral cation. Baileychlore occurs as fine-grainedtransversefibers exhibiting zoned pleochroic colors (greento yellow-green)along their length. Refractive indices areot : I .582 and 1 : 1.614. The measuredand calculateddensitiesare 3. 18(2)and 3. 195g/cm3,respectively.Combined DrA-rcA curves show a major endotherm at 550'C, a small, double-bottomed endotherm in the range 680-750 "C, and an exotherm at 850 "C. The X-ray powder pattern is that of the Ib (B : 97') polytype. The strongestlines (24 given) are ld"b"g.J(hk[)] 14.3(90)(001), I 30),2.450(35)(203,132), 2.660(50X201, 2;tr),3.573@0X004), 4.600(30X0 7.I 4(100X002), a n d 1 . 5 4 2 ( 6 0 X 0 6 0 , 3 3 1U) .n i t - c e l l d i m e n s i o n sa r e a : 5 . 3 4 6 ( 3 ) , b : 9 . 2 5 7 ( 4 ) , c : 14.401(7)A, and P : 97.12(5). The symmetry is probably triclinic Cl or Cl because of semi-random stacking.A one-dimension electron-densityprojection and an asymfor the octahedral metry value of +1.29 suggesta composition (Znrs'Alo,4D035)058sheetwithin the 2: I layer and (Fe?joAl,e.Mgor.Mnfr$r)'03+for the interlayer sheet. the Zn end member of the trioctahedral chlorite series, INrnotucuoN (Zn'AlXSi'Al)Oro(OH)8' or for any trioctahedral ideally Radke et al. (1978) reported chlorite containing 6 to 30 in which Zn is the dominant divalent octahedral chlorite wto/oZnO from a drillhole located near Chilhgl", e"ris analogousto clinochlore' the Mg end The,name cation' rralia. Frondel and Ito (1975) previourt' a"r".iUJi'a and name were approved prior to mineral The ..brunsvigite" "inmember' (chamosite in ;" ;;;cian, manganoan publication,by the IMA commission on New Minerals 1975)containingg.Ailio ferrednomenclatureofBayliss, M.ileTl Names' Holotype material has been deposzno and9.96 wto/oMno from Franklin, Nr* l..r.v, unJ 1{ with the Smithsonian Institution (NMNH 164430)' ited Dunn et al. (19E7) describedthe chlorite lrot'p"-ilu;i.] Australian Museum (no' 13592)' and the Gethe Soulh rpJ.i"r linfurnaceite from the samegeneralarea as u at the Universitv of wisconsin' Madison ""* with up to 24 wto/oZno (primarily tetrahedraD, ii;t; 9t"cv.y5::mr)' (no' ouuu/ MnO, and l0o/oMnrO.. The Australian occurrenceis the only chlorite known to date, however, in which Zn is the OccunnBNcEt MoRPHOLoGY' AND oRIGIN dominant divalent octahedral cation present. The ZnO Baileychlore is known only from one angled drillhole contents range from 22 to 30 wto/ofor these latter speci(DDH2) provides paper drilled in 1972 to test beneath the Red Dome a name and additional mens. The present Red Dome deposit is located near Mungana The for species. deposit. data this and structural crystallographic The mineral has been named baileychlore in honor of approximately l5 km west-northwestof Chillagoe,North ProfessorSturgesW.BaileyoftheDepartmentofGeology Queensland,and is being developedas a gold mine by and Geophysics,University of Wisconsin, Madison. Pro- Elders ResourcesLtd. The drillhole extends 180 m and fessorBailey is well known for his researchon the struc- intersectsan assemblageof brecciatedand highly altered tures and polytypism of chlorites, and he was the first to andesitesand garnet-vesuvianiteskarns.Chlorite haspervasively replaced the andesitesand some of the skarns, recognizethe structural type to which these particular Zncalcite has replacedgarnet-rich skarns,and at depths beof rich specimensbelong. Following the nomenclature Bayliss (1975), baileychlore is to be used as the name for low about 120 m, silicification and alteration to iron ox102-{l 35$02.00 0003-004x/88/0 I 35 136 RULE AND RADKE: BAILEYCHLORE Cementing minerals include goethite, hematite, chalcocite, malachite, cuprite, native copper, and calcite. Chlorite occursas matrix material and as a replacement of andesite and skarn clasts. This chlorite is a zincian chamosite. Zir.ciar' chamosite from the collapse karstbrecciais also reportedby Smith (1985).Baileychlore,as distinct from zincian chamosite,has only been identified in dark green, fibrous veinlets up to I mm wide that commonly form on the margins of calcite veins. The primary base- and precious-metal mineralization at Red Dome is associatedwith calcsilicate skarns and includes bornite, sphalerite, and various tellurides, including gold and gold-silvertellurides(Torrey et al., 1986). The zinc chlorites, including baileychlore, have formed by crystallization of remobilized elementsof the primary minerals during weathering by meteoric ground water. Details of this processare discussedby Smith (1985). Crmnarsrnv B photographs Fig. 1. seIr.r (by)rims on colof (A) Baileychlore loformcalcite(cc)veinlets.(B) Transverse fibersofbaileychlore (by)adjacentto calcite(cc)vern. Table 1 presents12 electron-microprobepoint analyses by Radke et al. (1978) for chlorite from four diferent depths.Analyses3 to 8 are for the fibrous baileychloreat a depth of 89.6 m. The ZnO contents of theselatter analysesare fairly uniform from28.2 to 30.5 wt0/0.Allocations of the analysesto the site occupanciesshown in Table I are basedon 14 oxygenatoms, assuming8 OH and all Fe to be ferrous on the basis of qualitative microchemical tests. Analysis 8 for the most Zn-rich specimen gives a formula (Zt2 4BF e2tlA|, rMg - Mnfr.$,Cao, rEorr)(Si3r2Aloos) O'.(OH)8. In samplesof low ZnO content, the deficiency in Zn is compensatedfor by additional Fe2+, and the chlorite is properly termed zincian chamosite. Baileychlore has an appreciable dioctahedral component in that about 0.3 ofthe 6 octahedral sites are vacant. CaO. It is not All of the analysesshow 0.2 to 1.00/o known for certain if this is due to calcite impurities or to Ca in the structure.Ca is not believed to substitute easily into the chlorite structure, although it is present as an essentialcomponent in the hybrid chlorite-mica structure of franklinfurnaceite (Dunn et al., 1987),and there is calcite closely associatedwith the baileychlore. IfCa is excluded from the structure, the formula unit for analysis 8 becomes(Znr roFeljoAl,,,MgoruMn3.6rtr0 36XSi3 s5Aloor)O,.(OH)8. The tetrahedral Al content of baileychlore is 0.44 ro 0.49 atoms (Table l), which is near the lower limit for the chlorite structure but is characteristicof the structural form (Ib, P: 97') of baileychlore. The structural formula suggeststhat the octahedral sheetwithin the 2:l layer also has a net negative charge,becauseofthe presence of vacancies,and that the total layer charge is approximately - 1.0.The MnO contentis low, 0.40loor less for all specimensanalyzed,and is in contrast to the high values reported for the zincian chlorites from Franklin, New Jersey(Frondeland Ito, 1975;Dunn et al., 1987). ides are extensive.Below about 50 m the sampleshave a fairly uniform ZnO content between 4 and 6 wto/owith most or all of the ZninZn-bearing chlorites. Most of the results presentedin this paper are from pleochroic, dark green chlorite rims on colloform calcite veins occurring within the breccia at a depth of 89.6 m. This chlorite has the highestZnO content noted (28 to 30 wto/o)and at high magnifications(Fig. l) can be seento form fine transverse fibers about 3-10 pm in diameter. Native copper is generally intergrown with the calciteand fibrous baileychlore. The Red Dome brecciais interpretedby Smith (1985) and Torrey et al. (1986) to be a collapse karst-breccia formed under weatheringconditions by solution of marble by meteoric water. The rock types forming the breccia clasts include skarn, andesite, quartzofeldspathic sandstone,felsic porphyries, and chert; the clastsrangein size Psvsrcal PROPERTTES from a few millimeters to 70 m. The matrix is generally limonitic, goethitic, or chloritic and includes finely lam'It wasnot possibleto obtain completeoptical properties inated sandstonesdeposited by meteoric ground water. becauseof the fine grain size and fibrous character of t37 RULE AND RADKE: BAILEYCHLORE analysisof chlorites(wt%) TneLe1. Electron-microprobe DePth Sample: sio, Tio, At,o3 FeOMnO MgO CaO ZnO Total 24.4 0.6 17.9 29I 0.1 6.4 O2 6.0 85.4 27.3 0.6 19.6 22.5 0.4 4.7 0.5 10.7 85.8 32.1 n.d 12.5 14.5 0.15 4.7 0.9 28.2 93.1 31.8 n.d. 12.6 14.1 0.13 4.7 0.9 28.8 93.0 32.4 n.d. 12.4 13.7 0.16 4.5 1.0 29j 93.3 32.0 n.d. 12.9 12.5 0.13 4.4 1. 0 30 4 93.3 32j n.d. 12.5 13.5 0.14 4.6 0.9 29.4 93.1 32.0 n.d. 12.4 12.9 0.15 4.6 1.0 30.5 93.5 si Al 2 838 1.162 3.087 0.913 J CZb Al Zn Fe Mg Mn Ca Ti Total 1.283 0.517 2.893 1.100 0.012 0 028 0.054 5.89 1.695 0.897 2.126 0.785 0.037 0.062 0.005 5.61 1.143 2.293 1.331 o.775 0.014 0110 Number of cations on the basis of Olo(OH)s Tetrahedralcations (> : 4) 3.524 3.517 3.528 3.558 3.5't2 0.476 0.483 0.472 0.442 0.488 octahedral cations 1.127 1.193 1.154 1.160 1.146 2.478 2.468 2.389 2.361 2.343 1.187 1.145 1.245 1.261 1.300 0.751 0.714 0.748 0.731 0.767 0.014 0 . 0 12 0.013 0 . 0 12 0 . 0 15 0.118 0.114 0j12 0.105 0.114 5.67 5.67 0.472 5.64 97.6m (320ft) 96.7 m (317ft) 89.6 m (294 ft) 5 1 . 5m ( 1 6 9f t ) 5.66 5.65 5.68 25.6 0.6 15.8 26.7 0.15 6.4 0.4 14.2 89.8 25.3 0.4 18.3 22.9 0.16 6.2 0.3 14.4 88.0 11 12 26.2 0.14 16.0 17.6 0.1 5.1 0.5 22.6 88.2 27.4 0.2 16.8 25.4 0.15 5.3 0.45 14.5 90.2 2.919 1.081 2.876 1.'124 3.046 0.954 3.067 0.933 1.043 1.192 2.543 1.082 0.01 5 0.049 1.333 1.208 2.184 1.058 0.01 6 0.034 0.033 5.87 1.235 1.940 1.707 0.883 0.010 0.061 0.012 5.85 1.275 1.196 2.375 0.883 0.014 0.035 0.017 5.82 5.97 others are of zincianchamosite; Note..Analvstwas p. K. Schultz.Modifiedfrom Radke et al. (1978).Analyses3 to I are of fibrousbaileychlore; n d. : not determined. - Total Fe as FeO. baileychlore. The mean refractive index is about 1.59. Values of a : 1.582 and t : 1.614 were measuredfor baileychlore from the 89.6-m depth. The chlorite fibers exhibit a zoned pleochroic color with the zoning parallel to the chlorite veins (zoned along the length ofthe fibers) to produce a colloform-type banding. The zoning is in shadesof greenand yellow-green.The pleochroismis weak with the strongestcolors in the darker bands. The measured density of baileychlore from the 89.6-m depth is 3.18(2),which comparesfavorably with a calculateddensity of 3.195 g/cm3for the most Zn-ich material of analysis 8 (Table 1). Simultaneousore and TGAruns were carried out using a Rigaku Denki model M8076 instrument. A 50-mg sample of hand-picked and finely gound baileychlore was used, with an equal amount of calcined alumina as reference.The heating rate was 10 "C/min in a static atmosphereofair. The principal thermal effects(Fig. 2) and their interpretations are as follows: (l) Ambient to 120 'C: A small broad endotherm accompaniedby a loss of moisture (-30lo wt loss). (2) 150-200 'C: A very small ora endotherm and weight lossattributed to loosely combinedwater. (3) 280-330 oC:A very small ore endotherm and weight loss probably due to a trace ofgoethite contaminant. (4) 400-600 "C: A major prn endotherm and weight loss due to dehydroxylation ofthe interlayer sheet of chlorite. (5) 680-750 oC:A very small, broad, doublebottomed endotherm and correspondingweight loss due to dehydroxylation of the 2:l layer of chlorite. (6) 780880'C: A broad exothermic ore peak with no weight loss. This is attributed to formation of a high-temperaturealuminosilicate phasefrom the decomposedchlorite at about .C: The DrA curye showsan in850 'C. (7) 1000-1200 creasingendothermic band with significant weight loss. This is probably due to sintering of the sample, which exhibited pronounced shrinkage. The major feature of the pre curve is the dehydroxylation of the interlayer sheet at 550 "C. The dehydroxylation ofthe 2:l layer is lesswell defined in the range680750 'C, and it is likely that some of its dehydration is included in the 550 oC endotherm. The endotherms in general are not as sharp as those from well-crystallized trioctahedral chlorites and occur at lower temperatures, presumably because of poorer crystallinity and consequent releaseof water more readily and over a largerange of temperature.The presenceof octahedral vacanciesin baileychlore (Table 1) also may afect the curve. Mii{ler ( 1963) noted a large endotherm at 544 "C and two small endothermsat 680 and 725'C for dioctahedralchlorite. Srnucrumr- DATA poorly crystalline and gives X-ray powis Baileychlore der patternsin which the ftkl peaksarebroad. Both DebyeScherrerand difractometer patterns (Table 2) taken with graphite-monochromatedFeKa and CuKo X-radiation are recognizableas being characteristicofthe ID (P :97) polytype as defined by Bailey and Brown (1962). In this polytype the interlayer sheet is oriented so that its slant is in the same direction as that of the octahedral sheet within the 2:l layer. The interlayer is positioned asym- 138 RULE AND RADKE: BAILEYCHLORE ob+TET. Fig. 2. Combined DrA-rcA curves for baileychlore metrically for hydrogenbonding so that is has a b position relative to the 2:l layer on one side but an a position relative to the layer on the other side. The presenceofthe Fig. 3. One-dimensional projectionusing electron-density Ib (P : 97") polytype is consistentwith the composition seven00/ reflections. The unlabeledpeakat z : 0.35 is a difand mode of origin of this chlorite. Bailey and Brown fractionripple. (1962)consideredthe Ib (0 :97") polyrypero be the least stable of the four chlorite structuresknown at that time, dimensional bands and thus of semirandom stacking of to form at the lowesttemperature,and to have the smallest adjacent layers and interlayers. This is true also for all substitution oftetrahedral Al for Si. single crystalsstudied to date of both lb (B : 97) and Ib Cell dimensions derived by least-squaresrefinement of (B : 90) chlorite from other localities. Bailey and Brown the X-ray powderdata area: 5.346(3),b : 9.257(4),c : ( I 962) consideredthe symmetry of all chlorites with semi14.401('7)A, and P : 97.12(5)'. Although single crysrals random stackingto be triclinic, Cl or Cl. are not available, the shapesof the powder-diffraction It did not prove possibleto make an oriented-clayslide peaksat d : 4.600 and 1.745 A are suggestiveof two- by settling from a liquid suspensionor by suction through ceramic tile, even for every dilute suspensionafter disaggregationby ultrasonic treatment. This is probably due TABLE 2. Baileychlore X-raypowderdata to the fibrous nature of baileychlore. The integrated intensities of seven nonoverlapped basal reflections were 4," (A) 4". (A) measuredfrom an unoriented slide using a Philips X-ray 001 90 14.3 14.290 002 100 7.14 7.145 difractometer with graphite-monochromated CuKa ra003 5 4.76 4.763 diation and a sequenceof %' to l' vertical divergenceslits. 4.628 02;1130 4.600 The intensities were corrected for the Lp factor for ran4.602 004 40 3.s73 3.572 domly oriented crystallites, converted to -F values, and 005 10 2.860 2.858 used to construct a l-dimensional electron-densitypro2.668 5U 2.660 jection (Fig. 3). Becausethe two octahedral sheetsin the 2.667 2.594 chlorite structureare separatedby c/2, all octahedralcatJ 2.59 2.593 B ions diffract in phasewith one another for even orders of 2.450 35 2.450 2.449 00/ regardlessof the distribution of cations between the B 2.27 2.268 two sheets.Comparison of the sum of these observed.F zvc 2.078 I 15 2.080 ^E values with a similar sum calculated for the octahedral 134 2.076 | 007 2 2.040 2.041 composition of baileychloreyields a scalingfactor to place 206,135 2 B 1.89 1.892 the observedvalues on an absolute scale. 15:'24:3120 1.745 1.748 D The peak for the octahedralcations within the 2: I layer 1.737 207,136 10 1.722 1.724 at z : t/zin Figure 3 has greaterelectron density that that 060,33i 60 1.542 1.543 for the octahedralcations ofthe interlayer sheetat z: 0. 062,333,331 za 1.508 1,508 'l.443 209,138 10 1.44 Integration of the areas of these two peaks and scaling 00.10 3 1.428 1.429 relative to a content of 27 electrons for the resolved in<E 064,335,333 1. 4 1 5 1. 4 1 6 ,l terlayer OH plane gives a total of 116 electrons, which 065,336,334 136 1.358 261 1.336 may be compared with 125 electrons for the octahedral 20 1.335 402,260 1.334 cation total of analysis 8 of Table I (assuming500/oion't.297 404 20 1.295 262 ization).The excessofelectron densityin the 2:l layer is 1.296 2 0 .0 1 : 13 .i i 1. 1 9 8 1. 1 9 8 27 electrons(9 electronsper cation). Theseelectron-denA/ote.MonochromaticFeKa radiation.Cameradiameter114.6 mm. lnsity values should not be consideredaccuratebecauseof tensitiesestimatedvisually.B : broad peak. the availability ofonly seven00/ reflectionsand the con. Two-dimensional band. sequentpresenceofFourier termination effects.The data /G I* t- l' 139 RULE AND RADKE: BAILEYCHLORE areinternally consistent,however,becausethe heavy-atom asymmetrycalculatedfrom the 00/ intensitiesis +1.29. This meansthat there are 1.29more heavy atoms of Zn + Fe in the 2:l layer than in the interlayer. For this calculation the method of Petruk (1964)was modified by construction ofa graphappropriatefor an averageheavy atom of ZnourFeo ,r. It is not possiblewith thesedata to give an unequivocal distribution ofthe octahedral cations over the two octahedral sheets.However. if the vacanciesare in the trans M(l) sitesof the 2:1 layer, as in most layer silicates,it is more likely that the heavier Zn (Z : 30 vs. Z - 26 for Fe) would also be in the 2:l layer. There is no evidence for tetrahedralZnfrom Figure 3, in contrast to the Si'Zn, tetrahedral composition found in franklinfurnaceite by Dunn et al. (1987). A reasonablecation distribution for the composition of analysis 8 that satisfiesboth the ob' served asymmetry and the electron-density values is (ZnrroAlo,oEorr)0"-for the octahedralsheetof the 2: I for the interlayer layer and (Fe?joMnES,Al,orMgoru)'03+ sheet.This gives an asymm€try of +1.29 for the heavy atoms with 23 more electronsin the octahedraof the 2: I layer. The net negative chargeof0.45 on the tetrahedral sheetsis augmentedby a negative charge of 0.58 on the octahedralsheetfor this distribution to give a net charge of -1.03 for the 2:l layer as a whole. However, it must be emphasizedthat other cation distributions are possible and that resolution of the problem requiresa larger number of 00/ intensities. by Petroleum ResearchFund Grant 17966'AC2'C, administered by the American Chemical Society.The ssr.aphotog,raphswere kindly provided by E. D. Glover. RrrnnnNcns Bailey,S.W.,and Brown, B.E.(1962)Chloritepolvtypism:I. Regularand semi-random oneJayer structures.American Mineralogist, 47, 819850 Bayliss,Peter. (1975) Nomenclature ofthe trioctahedral chlorites' Canadian Mineralogist,13, 178-180. Dunn, P J., Peacor,D.R., Ramik, R.A., Su, S,C.,and Rouse,R.C. (1987) Franklinfurnaceite,a Ca-Fe3'-Mnr+-Mn2+ zincosilicateisotypic with chlorite from Franklin, New Jersey.American Mineralogist, 72' 81281 6 . Frondel, Clifford, and lto, Jun. (1975) Zinc-rich chlorites from Franklin, New Jersey.NeuesJahrbuchfilr Mineralogie Abhandlungen,123' lllll5 Miiller, German. (l 963) Zur Kenntnis di-oktaedrischerVierschicht-Phyllosilikate (Sudoit-Reiheder Sudoit-Chlorit-Gruppe). Proceedings,IntemationalClay Conference1963,Stockholm'I, l2l-130. Petruk, william. (1964)Determination of the heavy atom content in chlorite by meansof the X-ray diffractometer.American Mineralogist' 49, ol-fl. Radke, Frank, Schultz,P.K, and Brown, R.N. 1978)Contributionsto Australasianmineralogy,9, Zinc-rich chlorite from Chillagoe'Queensland. Australian Mineral Development Laboratories Bulletin 23, 2528. Smith, J.T. (1985) A mineralized solution collapsebreccia, Red Dome, Mungana,North Queensland.B.Sc.thesis,JamesCook University, North Queensland,Townsville. Torrey, C.D., Karjalainen,H., Joyce,P.J., Erceg,M., and Stevens,M' ( I 986) Geotogyand mineralisation of the Red Dome (Mungana) gold skam deposit, North Queensland,Australia' EGRU Contribution No' 21, Geology Department, JamesCook University, North Queensland, Townsville. AcrNowr,rncMENTs This researchwas supported in part by the Australian Mineral Development Laboratories,in part by NSF Grant EAR-8614868, and in part Mencn 30, 19E7 Meruscnu'r RBcETvED SEPrer"lnnn23, 1987 ACCEPTED M,c,NUSCRIPT