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Trace Elements in Kyanite, Sillimanite and Andalusite

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Trace Elements in Kyanite, Sillimanite and Andalusite TI{E AMERICAN MINERATOGIST, VOL.45, JULY-AUGUST, 1960 TRACE ELEMENTS IN KYANITE, SILLIMANITE AND ANDALUSITE G. R. PoansoNxaND D. M. Snaw.t Ansrnact 12 Kyanites, 3 sillimanites and 7 andalusites were analysed spectrographically {or various minor and trace-elements. Ga, Cr, Mg, Ti, Li, Cu, Y,Zr and,Mn could be measured in most samples; B, Be and Ba were found in severall Ni, Co, Mo, Sn, Ag, Y, Sc, Sr and Pb were usually below detection limit. No indisputable differences in trace-element contents were found, but andalusite probably contains less Cr, whereas B, Be and Ba may be con- centrated in sillimanite. It is unlikely that trace elements are factors in the polymorphic relations between these minerals. The trace element distribution in aluminum silicates can in general be explained by crystal chemical considerations, but V is rather more abundant than might be expected. Li and B are unexpectedly rich in many samples, suggesting origin under pneumatolytic or greisen conditions: both Li and B could however have come from the parent sediments. One of each of the minerals was analysed chemically. Slight deficiencies oi Al with respect to Si can be explained by substitution of minor and trace-elements for Al. Alkali metals are present in small amounts but Jakob's hypothesis that they are essential con- stituents is untenable. INrnooucrroN The polymorphic minerals kyanite, sillimanite and andalusite present a problem in the interpretation of their stability-fields and the bearing this has on generalquestions of metamorphism.All three have beensyn- thesisedduring the last few years but much remains to be learned of their manner of formation. ft appeared worth while to examine their content of some minor and trace-elements,to enquire whether there might be any systematic differencesof crystal chemical significance. SauprBs The samplesare listed in Table 1: preciselocalities were not available for many. In two cases the specimens were visibly pure gem-quality crystals, but most of the other sampleswere coarse-grainedaggregates, rich in the principal mineral but containing abundant impurities. In sev- eral at leasttwo of the aluminum silicateswere present. Hand-specimens were crushed and sieved, retaining the fraction be- tween 100and 200-meshstainless steel sieves. Magnetic and heavy liquid separation followed. The greatest difficulty was experiencedin separating the aluminum silicatesfrom each other, but repeated fractionation in diluted liquids gave nearly pure concentrates.Purity was checkedcon- tinually by grain mounts in immersion oils, and in the final samples the grains were counted to estimate impurities and contamination. * Present address: Research Council of Alberta, Edmonton, Alberta, Canada. t Department of Geology, McMaster University, Hamilton, Ontario, Canada. 808 809 TRACE ELEMENTS IN RYANITE, SILLIMANITE AND ANDALUSITE Tasrn 1. Smlpr-r Locenrrns, DnsctrprroNs ANDPuRrrv Mineral Impure For€ign Comments on Locality Description ex- grarns grarns mineral extracts tracted % % mica inclusions E1 S. Dakota Pink A with a little white A 4.2 S and mlca. E2 Spain Pink A with veinlets of S A S inclusions and muscovite. S 6.5 A inclusions K and E3 Switzerland Massive A wit}t gray K A 2.5 Limonite stain, and a little muscovite. mica inclusions K Quite clan A. muscovite and D4 Calilornia Pale blue bladed K with K 9.0 muscovite and magnetic qriartz inclusions oxides. and muscovite E5 Germany Blue bladed K in limo- Quartz nitic qmr muscovite ag- lncluslons gregate. Biotite, staurolite in- E7 Wyoming Ftue.gray bladed kyanite ln schEt also contalnlng clusions staurolite and mi@s. nica grains aud in- E9 S. Dakota Coaree pin! A with quutz 53 S, and muscovite. cluslons staio E10 Brazil Blue gem crystal of K K 5.0 Limonite with limonite stain. clan E11 Brazil Green gem crystal of A. Quite Et2 N. Carolina Coarse blue K in two- K 20.0 Mica inclusions mica schist. E13 White RiverJct, Coarseblue K with limo- K 2.0 Limonite stain Vermont nite stain in two-mica garnet gneiss. stain, mica E14 Clarkesville, Large blue-gray crystal of K 80 0.5 Limonite Georgia Iimonite-stained K. inclusions A grains E1s Dillon, Montana Fibrolite with two micas, S 1.7 Limonitic quartz and nicrocline. present inclusions E16 White l\{ts.. Massive A with diaspore 3.8 K and mica Mono Co.. Calif. anC muscovite chlorite grains 817 Salamanca, Coarsepink-green A with 12.0 Mica, Spain muscovite and chlorite and inclusions Muscovite inclusions E18 Broken Hill, Fibrolite-muscovite- s 10.0 NSW. quartz-iron oxide schist. mica, graph- E19 Big Joco River, Kyanite-biotite gleiss. K 14.0 Quartz, 25 miles NW oI rte lnclusrons Mattawa, Ont mica inclu- E,20 Kake Kippawa, Kyanite-biotite gneiss 7.1 Quartz, near Timiska- srons ming, Ont. pyrite inclu- E2l Near E 19 Green K, green nica and K 7.O Mica, pyrite slons L73 1 mile SSE of Coarse blue K in biotite K 9.1 Quartz inclusions North Thetford, gnerss N. H. About 350 sains counted in each ese' * Not detected. -:No information. 810 G, R. PEARSON AND D. M. SHAW Tnnr,n 2. DnrnnurNerroNs or. Cr sy DrT,rnnnNrMnuroos Analysts Sample Shaw E3 6 ppm 12ppm E2A 17ppm E4 27 35 E15 83 43 E5 39 46 E18 140 95 F7 180 210 E10 50 67 E1 10 Et2 11 t9 E2B 11 llJ 33 43 E3A 14 E14 98 E9 7 E19 105 E11 62 820 11 2l E16 1n E2l 170 200 817 11 L7s 35 72 AN,q,rvrrcar Mnrnoos The following elementswere determined,using quantitative spectro- graphic methods: B, Be, Ga, Cr, Ti, Li, Mg, V, Cu,Zr, Mn, Ba, Sr. In addition the following were sought but were usually absent: Ge, y, pb, Mo, Ag, Ni, Co, Sc,Sn. The methods have already been described (Pearson, 1955; Shaw, 1959).The latter referencedescribes a generalmethod for silicates,which was modifiedin this instanceby using standardsmade from a pure silica- alumina matrix. Precision was from 5-157a of amount present for most elements.Some elements(Ga, Cr, Ti, V, Cu, Zr, Mn) were determined several years apart by difierent analysts using difierent methods: the agreementwas generallysatisfactory, as may be seenfrom the example in Table 2, which gives the two sets of analysesfor Cr (averagesof trip- Iicate determinations).The two sets of data were averagedin eachcase to give the valuesin Table 3. The resultson Be, Mg and ri wereobtained by averaging the results on two difierent spectral lines. Drscussror.r The significanceof contaminationmust first be discussed.The data in Table 1 showedthat most of the sampleswere free of foreign grains,but usually contained intergrowths. rn no case did the admixed mineral, whether an inclusionor alteration, constitutemore than r/20 of the host grain, as estimatedunder the microscope:the volume of the contamina- tion would thus be about (l/20)3/2 or about t/oJ Il 10/6 oI all grains in- 1 This assumes a spherical particle embedded in a larger sphere. TRACE ELEMENTS IN KVANITE, SILLIMANITE AND ANDALUSITE 811 clude such intergrowths the total impurity amounts to about 0.1/6 by volume or 0.24.3/6 by weight. Thus the total contribution of the im- purity to the analysis of the host mineral would be 2000-3000 ppm, in- cluding both major and minor elements. One might therefore expect that the Iesspure samples,as counted with the microscope,should in fact show no clear evidence of contamination, when compared with the apparently quite clean samples.This is seen to be the case,if specimensE 38 and E 11, both of which appearedquite pure, are comparedwith E 12 and E 17, which contain respectively20 and 12/6 of intergrowths. The trace-elementsuite of the latter pair show no marked differencesfrom the previous pair, even for Mg, Ti and Li, which might be expected from mica contamination. It may perhaps be concluded that contamination is not as seriousas first inspection of Table 1 would suggest,but it must neverthelessbe borne in mind throughout the following discussion. The averagetrace-element contents of the three minerals are presented in Table 4, which includes abundancesin the crust and in pelitic rocks (the latter from Shaw, 1954,1956). The distribution of someelements in individual mineral groups is rather erratic (e.g. Ti in kyanite, Table 3), and the significance of the averagesis therefore uncertain. In addition Tesrn 3. Tnncn-Er,rul'ltrA-xer,vsns or 12KvaNrrns. 3 Srr,r,r- MANTTESeNo 7 ANoer,osrres Sample Number 2 5 Ga (,r E38 55 9 250 94 6.2 36 tr. 20 E4 54 31 280 190 23 85 6 E5 43 OJ 43 1.0 40 7 8 E7 190 1,600 100 20 29 E10 28 59 70 38 .2 83 7 Et2 29 38 60 tr. .1 25 92 49 E13 34 15 63 120 It 93 tr. 6 E14 29 9 43 110 8.4 JI lr. 6 E19 24 105 41 54 tr. 11 F 20 66 16 45 .2 5 26 5 821 61 r80 t70 100 22 4 L73 L2 46 t.-) 90 tr. 20 E2A 100 .tl 7.9 110 tr. 1,900 280 90 11 E18 35 830 2.9 150 180 E1 t< 2r0 130 280 250 4.5 8 tr, 11 tr E28 16 58 150 81 220 1.9 45 tr 12 tr. E3A 61 160 190 56 tr 30 E9 62 170 86 96 2.5 36 tr 5 E11 160 140 tr, 3.0 46 8 5 tr. E16 tr 45 tr. 3,200 8.3 51 280 10 5 817 10 69 300 110 580 2.9 35 E. 34 33 Triplicate amlyses, expressedin ppm * Below detection limit.
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