MEMOIRS OF THE GEOL. SOC. OF JAPAN, No. 11, p.~283-290 (1974)

18. MINERALOGICAL STUDIES ON LEVYNE AND ERIONITE FROM JAPAN

TADATO MIZOTA*, GORO SHIBUYA**,

MrTsuo SHIMAZU* and YOSHIMI TAKESHITA*

Abstract

Levynes and erionite Ii'om three Japanese localities are described to show their compositional variations reflected by their lattice constants and refractive indices. The material from Chojabaru, Iki Island contains 8.41 wt.% Na20 placing it as the sodium dominant analogue ofllevyne, (Na2' Cal AI2Si.012·nH20.

1ll amygdales of a basaltic tuff breccia of Introduction Miocene age with intimate association of Although levyne and erionite are rather some other zeolites including chabazite, rare zeolites, they have been recently found stilbite, phillipsite, natrolite and thomsonite at three localities in Japan, Chojabaru, (SHIMAZU and MrzoTA, 1972). Nagasaki Prefecture, Kawaziri, Yamaguchi The Kawaziri levyne associates intimately Prefecture, and Kuroiwa, Niigata Prefecture. with erionite, chabazite, thomsonite, phil­ Their chemical analyses extend the range of lipsite, heulandite and stilbite in many compositional variation of levyne due to round to subround white amygdales of 1 substitution of Ca by Na2 over the known to 3 cm across contained in a brownish red range presented by FEOKTISTOV et at. (1971) altered basalt lava flow. In the amygdales without any crystallographic break, con­ are also found large amounts of calcite and firming the existence of the isomorphous Na montmorillonite with minor amounts of dominant analogue of levyne, (Na2 , Ca) manganoan calcite, aragonite and halloysite. AI2Si.012 ·6H20. In druses of several to ten cm across found In this paper the mineralogical descriptions in andesite dyke at Kuroiwa, levyne is found of these zeolites are presented with special with diopside, garnet, wollastonite, calcite reference to the variations of chemical com­ and amethyst accompaning some other position, lattice constants and optical zeolites and hydrous calcium silicates such as properties. chabasite, natrolite, apophyllite, epistilbite, heulandite, analcime and gyrolite. Richterite Mode of occurrence is also found in other druses devoid of levyne. Levyne and erionite from Chojabaru occur This uncommon assemblage is considered to be the product of skarnization of calcareous * Department ofGeology and Mineralogy, Faculty xenoliths in the andesite dyke intrucing of Science, Niigata University, Niigata, Japan Miocene calcareous sediments and subsequent ** Mineralogical Laboratory, Faculty of Liberal Arts, Yamaguchi University, Yamaguchi, Japan hydrothermal effects to it.

-283- 284 T. MIZOTA, G. SHlBUYA, M. SHlMAZU and Y. TAKESHITA

Kuroiwa, but the development of polysyn­ Morphology thetic twinning forms deep striations on its Their Levyne from Kuroiwa has a hexagonal prisms, and its interfacial angles could not be by meai tabular habit flattened to c-axis and the measured. (Shimaz largest one reaches 10 mm. across. Most of Levyne from Chojabaru does not show any standard the crystals show interpenetrating twin. They euhedral form and only its basal cleavage is Stanclal are transparent and colourless with vitreous observed. anal< luster. The observed faces are c(OOOl), The crystals of erionite from Chojabaru are r(1012) and s(OlIl). The interfacial angles fibrous with about 1 mm in average length. glass measured by one-circle optical goniometer are Occassionally the columnar aggregates of glass as follows: fibers are found. acluL The e, Haid- obs. calc..mger* Microscopic observations to BENe' c;\r= (0001) ;\ (1012) 43°11' 44°33' 43°58f and optical properties aeceleral 15 KVa c;\s=(OOO1);\ (0111) 61°43' 63°04' 62°37'. The crystals oflevyne have hexagonal shape n1easure tabular to c-axis with about 0.05 mm in width, The calculated figures were obtained from rise to and in many cases penetrating twinning the lattice constants measured by x-ray speclmel relations were observed. Erionite is associated powder diffraction method. The nomen­ that the intimately at Chojabaru and Kawaziri, but clature of c(0001), r(10Il) and s(0221) were tively not found in Kuroiwa. Erionite is epitaxially taken from the work of HAIDINGER *(1828) different intergrown with levyne in general (Fig. 2). and their indices were converted to match rection the unit cell data here employed, because the fixed thl old axial ratio is the half of the present one. The tot< The errors for observation were mainly due three c\ to their dispersed reflection images resulting figures. from the minute twinning, which forms were SlY1> uneven crystal faces. A representative figure with th( of twinned crystals is given in Fig. 1. The of FEOI<' Kuroiwa levyne IS morphologically very this difl similar to that from Antrim, Ireland reported dehydra by STRUNZ (1956). to a hig! The chI Fig. 2. Photomicrograph of levyne and erionite from Kawaziri, one Mico!. erionite i and MI; Levyne is uniaxial negative and shows owing t very low birefringence. The refractive standard indices of three levynes varies to reflect their Erionite Fig. I. Morphology of twinned levyne from compositional variations among which Al-Si Japan, u Kuroiwa. had bee and Ca-(Na2 , K 2 ) substitutions seem to be Levyne from Kawaziri has the same hex­ significant except variations of water content. alumina agonal tabular shape as the material from Erionite from Chojabaru is uniaxial positive 1967), 1, with e = 1.467 and fibers are elongated analyzeCi * Dana's "The System of Mineralogy", 6th Ed. hand K 595 (1914) parallell to c. LEVYNE AND ERIONITE FROM JAPAN 285 f polysyn­ Che:rnical co:rnpositions alumina content of erionite from Maze to be Jns on its 23.48%. Their chemical compositions were surveyed uld not be The final chemical composition of their by means of electron probe microanalyser anhydrous part after correction were listed in (Shimazu EMX-2) employing the following show any Table 2 with atomic ratio based on 0=12. standard materials; leavage is Standard materials analysed Elements Table 1. Optical properties for levynes and erionite analcime from Maze Na, Si jabaru are Levyne uniaxial (-) Chojabaru Kuroiwa Kawaziri ge length. glass of anorthite composition Ca, Al 1.481 1.487 1.504 glass of diopside composition Mg :egates of Erionite uniaxial (+) adularia of unknown source K. Chojabaru The correction for E.P.M.A. data was due e 1.467 (e~w) s to BENCE and ALBEE(l968) method. The accelerating voltage of electron beam was Table 2. Partial chemical analyses of levynes and 15 KV and integrating time ofx-ray intensity erionite Jnal shape measurements was for 4 seconds, not to give Levyne 1 in width, Erionite rise to the decomposition of zeolites. The twinning Chojabaru Kawaziri Kuroiwa Chojabaru specimens available were so small in amounts ----- associated wt. % wt. % wt. % wt. % that the water contents were not quantita­ Si0 raziri, but 2 49.7 48.1 51.8 52.1 tively measured but estimated as the Alz0 22.8 24.4- 20.5 20.7 ~pi taxially 3 NazO 8.41 2.07 2.29 7.20 (Fig. 2). difference. In order of its preliminary cor­ K 20 1.27 0.71 0.03 3.34 rection for oxygens, the H 2 0 contents were CaO 3.51 10.6 fixed throughout the calculation procedures. 8.88 1.21 MgO 0.22 0.09 0.09 0.33 The total of metal oxides after corrections of Total 85.91 85.97 83.59 84.88 three cycles were almost same as initial [H2O] (14.09) (14.03) (16.41) (15.12) figures. The water contents, thus estimated, were smaller by 3 to 4 percent in comparison Cations (oxygen = 12 in anhydrous parts) with those of levynes appeared in the paper Si 3.91 3.77 4.10 4.12 of FEOKTISTOV et at. (1971). The reason for Al 2.11 2.25 1.91 1.93 this difference may be due to the partial Na 1.24 0.314 0.315 1.11 K 0.128 0.071 0.003 0.338 dehydration by electron bombardment under Ca 0.296 0.890 0.753 0.103 to a high vaccum condition at least in part. Mg 0.026 0.01 0.01 0.039 The chemical compositions of levyne and d erionite [H2O] (3.70) (3.67) (4.33) (3.99) erionite from Chojabaru reported by SHIMAZU Z 9 9 9 6 and MrzoTA (1972) contained some errors nd shows owing to the compositional ambiguity of Empirical formulae: Chojabaru levyne refractive standard materials employed at that time. ((Naz) O.62CaO.30(Kz)o.06MgO.03)1.01 [Alz.llSi3.91O,Z] • ~flect their Erionite from Maze, Niigata Prefecture, 3.70HzO Kawaziri levyne hich Al-Si Japan, used by them as the standard material (CaO.89(Naz)O.16(K2)O.04Mgo.0l),.10[Alz.z5Si3.770d • em to be had been assumed to be lower content of 3.67HzO Kuroiwa levyne ~r content. alumina (Al 0 = 15.24%, HARADA, et at., z 3 (Cao.75(Na2)O.16(Kz)o.ooMgo.0l)O.9Z[AI,.9,Si4.100,2] • al positive 1967), but it was not the same specimen 4.33HzO elongated analyzed by HARADA et at. On the other Chojabaru erionite ((NaZ)O.56(Kz)O.17CaO.loMgo.04)O.87[AI1.93Si <.l20 12]· hand KAWAHARA et at. (1967) gave the 3.99HzO. 286 T. MIZOTA, G. SHIBUYA, M. SHiMAZU and Y. TAKESHITA

\ I -j Levy

Na2 0 showin,l

(Al 2Si/

.. . (1120] Beca, prepan and po'

'1< of levYl (1)

Minerab

Levyne

Erionite

The one en( the syst to Ca-l\ of diffr the sal R3m, i crystall, extincti satisfies erionite

(3) a b ~c* Fig. 3. X-ray precession photographs of levynes. FEOK a: hkO plane, ,11=30°, CoKa. (I): single crystal of Kuroiwa levyne formula (2): Kawaziri with weak diffraction spots of erionite included USSR" (3): Chojabaru with relatively strong erionite spots b: upper layer of Ilkl reciprocal plane, "=0.078, ,11=30°, CoKa. NaO•711 (I): single crystal pattern of Kuroiwa levyne H 20, ( (2): and (3): twinned levyne and erionite diffraction pattern from Kawaziri and Chojabaru, respectively. 2.046 Si, LEVYNE AND ERIONITE FROM JAPAN 287

Levyne from Chojabaru has the highest Table 3. X-ray powder data for levynes Na 0 content of those hitherto reported, 2 Chojabaru Kuroiwa Kawaziri showing it to have the composition (Na , Ca) h k z d(obs). d(obs.) d(obs.) I d (coale.) (Al Si 0 ) '6H O with Na Ca. z 4 1z z z> A .__--=.-A ._---._-_....A A- I 0 I 10.32 23 10.35 10 10.35 16 10.32 X-ray studies 012 8.13 53 8.12 30 8.17 60 8.15 003 7.53 46* 7.51 5 7.68 14 7.68 Because of the extreme difficulties to 110 6.65 100* 6.69 12 6.68 17 6.67 prepare pure materials, a part of x-ray single 2 0 2 5.18 30 5.16 25 5.17 445.16 and powder studies was made on the mixture o I 5 4.225 70 4.227 25 4.276 61 4.278 of levyne and erionite as given below: 122 4.098 100 4.080 100 4.080 100 4.080 3 0 0 3.859 30* 3.856 15 3.851 36 3.848 006 3.777 43* 3.782 3 3.839 Methods of X-ray studies Minerals Localities 205 3.576 20* 3.567 12 3.601 7 3.601 X-ray single X-ray (precessiol1L powder 2 I 4 3.474 30 3.461 12 3.477 25 3.478 303 3.451 10 Chojabaru mixture mixture 3.441 10 3.440 (Figs. 3a-3, 3b-3) (Table 3) 220 3.335 25* 3.340 15 3.333 20 3.333 twinned. 107 3.122 53* 3.123 15 3.163 15 3.164 Spots splitting 3 I 2 3.103 20 3.089 12 3.086 27 3.085 Kuroiwa "pure" Levyne pure 401 2.880 50* 2.867 5 2.861 21 2.864 (Figs. 3a-l, 3b-l) (Table 3) 1 3 4 2.815 94* 2.800 60 2.799 100 2.798 I(awazil'i 111ixture "pure" (Figs. 3a-2, 3b-2) Cfable 3) 3 0 6 2.699 30* 2.696 3 2.716 10 2.718 twinned. 2 I 7 2.605 37 2.600 13 2.627 34 2.627 Spots splitting 232 2.581 5 2.581 410 2.534 23* 2.522 II 2.519 17 2.519 Erionite baru Cfable 0+5 2 .446 3 2 .446 I 4 3 2.403 20 2.394 6 2 .397 II b 2.394 The lattice constants of three levynes and 051 2.278 2 2.278 2 2.295 9 2.297 one erionite are tabulated in Table 4 to show 330 2.230 10 2.225 6 2.222 14 2.222 the systematic variations of a and c according 2 4· I 2.202 12* 2.171 3 2.173 2b 2.172 to Ca-Naz substitution. Since the appearances 3 3 3 2.1'14 10 2.113 4 2.130 12 2.134 of diffraction spectra of these levynes obey I 46 2 . 109 4 2 . 106 the same extinction rule corresponding to 505 2.064 6 2.064 R3m, it is highly plausible that there is no 244 2.040 3 2.040 crystallographic break among them. The * Intensities may be affected by contaminating extinction rule of erionite from Chojabaru erionite. CujNi radiation. Diffractometer method. satisfies that of P63/mmc hitherto assigned to Calibrated by silicon as internal standard. erionite. specifying it to be richest in Na20 content than hitherto reported. But the appearance Discussion and conclusion ~c* of levyne from Chojabaru shows the pos­ FEOKTISTOV et al. (1971) gave the chemical sibility that the range of substitution of Ca formula of levyne from Tolstomysovsk Sill, by Naz m this mineral reaches to the Na USSR as: analogue Na2[AlzSi401z]·nHzO. K content

NaD.711 CaD.701 FeD.D49 AI l •997 Si3.939 0 12 4.62 of the Chojabaru specimen is relatively high d H 20, or ((NaZ)D.356 CaD.701 )I.D57 (FeD.D49 AI l . 997 ) (KzO = 1.27 wt. %) suggesting that the con­ Z.D46 Si3.939 0IZ 4.62 HzO, siderable amount of K+ can also replace 288 T. MIZOTA, G. SHIBUYA, M. SHIMAZU and Y. TAKESHITA

Table 4. Unit cell constants of levypes and erionites from by x­ Powder diffractometer Mineral Locality Precession camera o axis ( aA cA aA cA erion Chojabaru 13.380(5) 22.684(9) 13.39(3) 22.64(4) (1972 Levyne Kuroiwa 13.350(5) 22.759(9) 13.35(3) 22.74(4) Kawaziri 13.330(5) 23.033(9) 13.33(3) 22.98(4)

Chojabaru 13.311 (5) 15.143(6) 13.31(3) 15.18(3) Erionite Kawaziri 13.33(3) 15.16(3) TARD Ca++(ot Na+). The highest KzO content advic Table 5. X-ray powder data for erionite from was KzO= 1.61 wt. % in the specimen from Chojabaru and Iceland (FEOKTISTOV et at., ditto). The FLEIS d (obs.) A I d (calc.) A h k Ca(Na K ) substitution is almost maintained 21 z D. C 11.52 1 0 0 within the range of reliability of chemical 11.57 100 Must 9.21 15 9.17 1 0 1 analysis on the three specimens of the present Than 7.62 13 7.57 002 work. SHEPPARD and GUDE (1969) reported 6.66 90 6.66 1 1 0 Univ that erionite IS generally alkali-rich III the 6.36 4 6.33 1 0 2 Th substitution between Ca and (Naz, K ) and 5.77 13 5.76 200 z Cent, 3 5.40 5 5.39 2 0 1 has a Sif(AI+Fe+ ) ratio of2.92 to 3.78. They the I 4.64b 9 4.62 1 0 3 also mentioned that erionite occurred gener­ 4.36 80 4·.36 210 d-vaJ ally in such a silicic rock as rhyolitic welded 4.192 5 4.187 2 I I 3.843 45 3.843 3 0 0 tuff at Durkee, Oregon, except for the 3.783 67 3.786 004 erionite in altered basalt at Maze, Niigata, 3.609 26 3.597 1 0 4· Japan. Erionites from Chojabaru and BENel 3.328 32 3.328 2 2 0 Kawaziri, Japan, are found in altered basaltic con 3.304s 5 3.298 213 of s 3.199 19 3.197 310 tuff breccia and III altered basalt lava, 3.173s 5 3.164 204 respectively, that is, at all of the three 3.128 3 I 1 3.130 20 localities III Japan erionites are found III 2.945 11 2.945 3 I 2 basic rock. 2.880 69 2.882 400 2.865s 20 2.858 2 I 4 Erionite from Chojabaru has a SijAl ratio 2.831 58 2.831 4 0 I of 2.14 which IS considerably small with 2.694 14 2.693 402 respect to the figures given by SHEPPARD 2.514 22 2.516 4 1 0 and GUDE (1969). But the data in Table 2 2.498s 10 2.499 2 2 4 2.219 15 2.219 3 3 0 show the deficiency of the total of alkalis and 2.129 18 2.129 3 3 2 alkali-earths, because the (Ca, Mg)-(Naz, 2.097 4 2.094 5 0 3 Kz) substitution is not maintained over the I. 900 4 1.899 406 reliability of analysis which may be caused 1.881 2 1.880 4 3 1 1.8456 9 1.8459 5 2 0 by the error of analysis. "i'iJiK-= I. 7840 12 1.7842 433 The space groups of levyne and erionites C. i~i 1.6637 19 1.6639 440 do not change throughout composition ranges ;fiii, 1.5942 7 here presented and are R3m and P63 jmmc, J:. l) {j: b: broad peak, s: shoulder peale CujNi radiation. respectively. G/M, Diffractometer method. Calibrated by silicon as internal standard. The orientation relations between them v t:'iVi LEVYNE AND ERIONITE FROM JAPAN 289

from Chojabaru and Kawaziri are determined 403. by x-ray single crystal method. The a and c FEOKTISTOV, D. G., USHCHAPOVSKAYA, Z. F. and era axis of levyne are parallel to a and c axis of KASHAEV, A. A. (1971), On finding of levyne in the traps of Siberian Platform. Zapiski Vses. cA erionite as described by SHIMAZU and MIZOTA lvIiner. Obshch., vol. 100, p. 745-748. (in .64(4) (1972). Russian) .74(4) HARADA. K., IWAMOTO, S. and KIHARA, K. (1967), .98(4) Acknowledgetnents Erionite, phillipsite and gonnardite in the .18(3) The authors wish to express their gratitude amygdale of altered basalt from Maze, Niigata . 16(3) Prefecture, Japan. Amer. Mineral., vol. 52, p . to Dr. E. PASSAGLIA and Prof. Dr. G. GOT­ 1785-1794. TARDI, University of Modena, for valuable ) content KAWAHARA, A. TAKANO, Y., TAKABATAKE, M. and advice about chemical compositions of levyne men from URATANI, Y. (1967), The composition and and erionite. They also thank Dr. M. crystal structure of erionite from Maze, Niigata 0). The FLEISCHER of Geological Survay Washington, prefecture, Japan. Sci. PalJers Call. Ceneral mintained D. C. and Dr. A. KATO of National Science Education, Vniv. Tokyo, vol. 17, p. 237-248. chemical Museum, Tokyo, for their kind advices. SHEPPARD, R. A. and GUDE, A. J. 3d (1969), he present Chemical composition and physical properties Thanks are due to Dr. M. KOMATSU, Niigata I reported of the related zeolite offretite and erionite. Amer. University, for electron probe analysis. ch in the Mineral., vol. 54, p. 875-886. The HITAC 8350 computer of Computer SHIMAZU, M. and MIZOTA, T. (1972), levyne and K ) and 2 Center of Niigata University was used for .78. They erionite from Chojabaru, Iki Island, Nagasaki the calculation of unit cell constants and Prefecture, Japan. Jour. JaiJan. Assoc. Min. Pet. :ed gener­ d-values of levyne and erionite. Econ. Ceol., vol. 67, p. 418-4·24. :ic welded STRUNZ, H. (1956), Die Zeolithe Gme1init, for the References Chabasit, Levync (Phakolith, Herschelit, , Niigata, Offretit). Neues Jahrb. lVIineral., Monatshafle, mru and BENCE, A. E. and ALBEE, A. L. (1968), Empirical Nr. 11, p. 250-259. ~d basaltic correction factors for the electron microanalysis (Received Jan. 15, 1974-) of silicates and oxides. j. Ceol., vol. 76, p. 382- salt lava, the three found in

;i/Al ratio nall with S*~V~~~CIU~/~~W~~$~~~ SHEPPARD 1. Table 2 Mffi~A, ~~li~, ~~~~, tr~~~ clkalis and (~ i§')

Mg)-(Na2 , over the B*~ftm~lli~nk~~~Et, I~~Y~~K~ Na20 8.41, K 20 1.27 wt.% t, c.n::t~fIH'f~~1,LV' be caused V'L, "C n G(l)1t"F*JJ.!$(;, t:il-TYE~, )[l:jJj'~l(l)rdJ(I) OOf* .:5~l::'igBE(I)r:jJ~, 'b-:Jt'bTJvtJ~t<::lll/v~v'6. ~ ~tj\\':@!<::X'1 ~K ~v'LEJfjE:-a::;Jo c. tJ, -:J t::.. l::'i9ll LL Ca-Na(K) il!Ul:-a::;;x.6 t, :Bt l erionites c.nG(I)~~~~~, ~M~mlli~m~~~o ~~~ 1¥f@:m(l)'b(l)~, ~::t~~lli~nk'b(l)(I)r:jJ~~~~ ion ranges ~ti, B*~ii, 1972'¥:!itIIi~~~I~iIh:Bt"tf@:!J' G,@I;i$K :5TK'b -:J t 'bili:v'*JJ.~:-a:: 'b -:J LV' 6 c. t t<:: tJ, 6. }JUft.(I)~l::'i9B~ti, ;;l-YiiJIlEtWj~K# P63 /mmc, J:. ~ti tlbL§E~~nt::.. "C(I)fik, 1973,¥,1IDt!fl:}I!1JL!J' :Bt1¥f@:, I I) G~:§!Ji, !/fr i,lg !JfU~ '6J:. ~ i"rT !Ji~ 1':1:',[...1::.. c. n G(I) ~lL;Jo~, ~l::"i~ILt:i(l) (991) OO1:t<::, druK{$:!itL een them ~ l::'i9B~ (l)1t "F *JJ. gj(:-a:: .ttM-t 6 t, :!it 1¥f @: m(l) 'b (I)!Ji t::'I I) ~Yiijil:t:ltJi'iji'jj[KW~Ln'6. LtJ'L~'6m(l) 290 T. MIZOTA, G. SHIBUYA, M. SHIMAZU and Y. TAKESHITA

ve'ilj!lEli, .:r.Lt/ilj/~Ec~l£LLv'tJv'. '1t.::, )11 *:;ItTiE~, }ffi JJTl¥ (J) {iiliJi , 1~"Fk:lJ.gX; c- JE (J) ffi ~ I,,'H* m;Jo J: lJ":Bi:~ JW: ilt v t."ilj/~ Eli, A t.0;j', JV5\lZ IIT':L\ (J) c j!~h 'tt-:Jc75';tGil,Z,. i ~:'i"iilt GO°@jiJ!z;5\lZ,'ffi'tO/VI,f'/vl,c< l)iJ';tLn'i.SiJ , ±i!! :g, v~~E~, 5\lZ~~ft.~~~<, *~~(J)x.~.~ Chojabaru fr(~JW: mGhi.S~~t~i.S. ~:'i"i~v~~E~, ft.~~~~ Kawaziri )11 IJi'. (J)~~~.fi~~$(J)E~.~M~(J)~J0~~~.L Kuroiwa Ll£ t:;t.::~ tJJV /@!t~'tc t tJ '5 &"yj"G U'ilttJ\'t:if;L LV'i.S.