MINERALOGICAL NOTL.

S
SralvmrN, L. I. (1955) Ascharite and other borates in magnetite ores of contact-metasomatic deposits. Dokla.dyAhad. Nauh SSS,R, l0l, 937-940 (in I{ussian). (1961) The so called magnioborite. Zopiski Vses. Minerolog. Obshch.90, 754-755 (in Russian). T.trfucur, Y. (1952) The crystal structure of magnesium pyroborate. Acta Cryst. 5, 574-581. 'l'onorov, 'I'he N. A. aNo P. F. KoNovarov (1940) binary system magnesium oxide-boric anhydride. Zltur. ltiz. Kkim.14,1103-1109 (in Russian). War,waln, Taroo (1953) Suanite, a new magnesium borate from Hol Kol, Suan, North Korca. Minerol. Jour. (Japon), L, 54-62; (abs.) Am. M'ineral.40, 941 (1955)

AN MINERALOGIST,

VOL. 48, JULY-AUGUST, 1963

SOMEUNUSUALMINERALSFROM THE "MOTTLED ZONE'' ISRAEL COMPLEX, Y. K. Boxror., Geological Suraey of Israel and.Hebrew (/n'iversity,JerwsalemAND S. Gnoss AND L. I{ellrn, Geological SwraeyoJ Israel. In most parts of Israel a chalky-shaly rock sequence, the Ghareb and Takiye formations is found overlying flint beds of Campanian age. In subsurfacesectionsthis sedimentary rock sequence generally highly is bituminous and may contain 25 per cent or more organic matter. In a number of widely separateareas,however, such as the Hatrurim region and the BeershebaValley in the northern Negev, near Ramleh in the coastalplain and at l{aaleh Adumim in the Jordanian part of the Judean Desert, a peculiar rock complex, the so-called"NIottled Zone," appears instead of this normal sequence. The "NIottled Zone," which reachesa maximum thicknessof 220 m, comprises large number of rock types such a as limestone, chalk, marl, shale as well as gypseous,ferruginous and phosphaticrocks, all distinguishedby a pronouncedbut highly irregular coloration. These various rock types occur without any apparent regularity and passinto each other without distinct boundaries.No bedding can be observed,but a schist-likestructure is fairly common. This rock sequence contains an abundanceof trace elements,among which Ag, V, Ni and Cr are prominent. Chromium, in the form of green chromium silicatesin particular is found in many veins up to 1 m thick and may make up 6 per cent of the vein material. One of the most widespread rock types of the "IIottled Zone" is a very hard, dense,splintery, brown, violet or black rock. I,Iicroscopic examination shows it to be composedmainly of calcite and spurrite,l approxiI Spurrite has also been found in these rocks by E. Sassand tobermorite by C Milton (private communication).

M I N L,RALOGICAL NOT ]':5

925

mately in the ratio 2: 1. Calcite appears as xenomorphic grains, some twinned and up to 0.6 mm in size.The spurrite crystals, which reach up to 0.3 mm, are idiomorphic to hypidiomorphic with pseudohexagonal or prismatic outlines. They show high relief, medium birefringence and are b i a x i a l n e g a t i v e ,w i t h s m a l l 2 V , w e a k d i s p e r s i o n( r ) v ) , x : b , y , \ c : -33", z\a-0o. The crystals exhibit two sets of cleavages, one distinct, the other poor, at an angle ol 79o.Two types of twinning, one simple, the other polysynthetic,are characteristic;the angle betweenthe two planes is 57o.The crystals appear granulated due to intense cracking and generally contain round or elliptical, drop-like inclusions of calcite up to 0.02 mm across. Nl[inorconstituentsof the rock are ch]orite and an as yet unidentified iron sulfide. This composition, derived by microscopicexamination, is compatible with the results of chemicalanalyses,which in addition indicate the presence sometenths per cent of organicmaterial. of The rock is traversed by a criss-cross system of small veinlets, rarely exceeding mm in width. In theseveinletsa number of uncommon min1 erals have been identified, which include vaterite, portlandite, bayerite, minerals of the tobermorite group,l an as yet unknown calcium silicate hydrate related to tobermorite, thaumasite and, very much more abundantly, ettringite. With the exception of portlandite, thaumasite and ettringite these minerals occur in a very fine state of subdivision and frequentiy show a fibrous habit. Bayerite,A1(OH)8,occurs as white fibers with parallel extinction, associated with calcite in one specimenand with calcite and gypsum in another. The mineral was identified by its distinctive r-ray powder pattern. Of the three polymorphic forms of Al(OH) 3 gibbsite is very common, nordstranditehas recently beenreported from two localities,(Wall et al., 1962;Hathaway and Schlanger,1962),but this appearsto be the first recorded natural occurrenceof bayerite, although the material is readily prepared artificially. Vaterite,the third polymorph of CaCO3,has previously been reported from Bailycraighy (nIcConnell, 1960). In the present samplesit was found intimately mixed with calcite and aragonite and in one specimen also with barite. The crystals are too small to be identified under the microscope;they were recognizedby their r-ray powder pattern, which resembles that of the mineral from Baliycraighy. Portlandile,Ca(OH)2,forms tabular crystals which, together with fluorapatite and ettringite, line the walls of the very thin veins in the black spurritic-calciticrocks.They are colorless, transparent,with pearly Iuster and high birefringence, uniaxial negative,c,::1.576I.001. The x-ray pat-

926

MINERAI,AGICAL NOTES

tern is identical with that of synthetic Ca(OH)2,after correctionfor preferred orientation. Portlandite in nature is very rare; it has previously been found in Scawt Hill (Tilley, 1933), Vesuvius (I{inguzzi, 1937; Carobbi, 1940)and Ettringen (Hentschel,1961). group, predominantly 14 A calcium silicate Minerals oI the lobermorite hydrate but lessfrequently also the 11 A modification were identified in severalsamplesscrapedfrom veins in the reddish-brownrocks. The minerals occur as white fibers with silky luster and form mostly radial aggregates but locaily also lenses to 2 mm in size.Optical data: Negaup tive elongation,biaxial positive, 2Y very small, very Iow birefrigence, B approximately 1.552. X-ray data for the present samples of the 14 A mineral very closelyresemblethose of the type mineral from Crestmore to (Heller and Taylor, 1956).The 11 A modificationprobably corresponds are a lower hydration state of the same material, since the hkO spacings identical for all the 14 and 11 A mineralsexamined. In addition to 11 and 14 A tobermorite another white fibrous material was found which, although it givesrise to a distinctive r-ray pattern, may be a memberof the tobermoritegroup. The fibersshow parallel extinction are elongation.The strongestr-ray spacings at 10.40, and mostly posi^tive 2.92 and 1.806A; the repeat distancein the fiber direction is 7.2 A, with pronouncedpseudohalving.This value is slightly lower than the 7.3 A but pseuspacingusually observedfor fibrous hydrated calcium silicates, of dohalving of the fiber axis is a characteristic the group. The mineral usually occursintergrown with someettringite and tobermorite. Both the unknown material and ettringite exhibit strongly preferred orientation along the fiber axis, but complete randomnessin the perpendiculardirections. Ettringite is oriented with its hexagonalc as fiber axis. The associated tobermorite showsno preferred orientation. Grinding the unknown mineral with water doesnot afiect its r-ray pattern. On heating up to 850oC. the morphology of the fibers remains unchanged. Well oriented wollastonite and partially oriented Iarnite are obtained, with their b axesin the fiber direction. At lower temperatures various oriented but as yet unidentified products were formed;at about 400' C. the material is apparently amorphousto r-rays. products of this mineral and the similarity The thermal decomposition of its r-ray pattern to those of fibrous hydrated calcium silicatessuggest t h a t t h e c h e m i c a lc o m p o s i t i o ni s x C a O , S i O 2 ,y H 2 O , w h e r e 1 1 x 1 2 . Unfortunately it has so far proved impracticable to isolate sufficient quantities of the pure material even for microchemical quantitative analysis. The question whether this mineral representsa distinct speciesor merely a further modification of the tobermorite group must at present remaln oDen,

MINERALOGICALNOTES

927

T h a u m a s i t e ,C a S i O s . C a C O s . C a S O + . 1 4 . 5 H 2h a,s b e e n i d e n t i f i e d i n O two specimens,apparently pure in one and mixed with aragonite, calcite and a modified form of ettringite in the other. It forms very thin prisms with parallelextinction, negativeelongationand fairly high birefringence. The *-ray powder pattern is identical with that of thaumasite from County Down, Ireland (Knill, 1960), of which a specimenwas kindly s u p p l i e db y D r . P . S a b i n e . E t l r i n g i t e ,i d e a l c o m p o s i t i o n6 C a O . A l 2 O 3 . 3 S O r . 3 1 2 O , i s r e l a t i v e l y H widespreadin veins and cavities in "Mottled Zone" rocks both in the

trrc 1. Well-developed prisms of ettringite.

Hatrurim and Ramleh areas. rt is transparent and occurs in three morphologically difierent modifications: as lemon-yellow, hexagonal prisms, as colorlessprisms and as very thin white fibers. The yellow crystals,which show vitreous luster, are only up to ] mm acrossand have no terminal faces,but perfect (1010)cleavage. eualitative microchemical analysis indicates the presence traces of Fe in addition to the major of Ca, Al, SO+ and H2O, which may account for the coloration. The colorlessprisms are exceptionally well developed,up to 3 mm across and terminated by rhombohedral faces (Fig. 1). They are coated with an opaque white powder, which may be a dehydration product. The fibers form radial aggregates or grow perpendicular to the vein walrs. The optical data for the three modificationsare as follows:
yellowprisms white prisms white fibres Ertinction parallel parallei parallel Elongalion e 1.462+.001 + 1 .4.58 . 001 1.4g4+.001
@

+ 1.468 .001 1.462+.001

928

MINERALOGICALNOTDS

It is evident that e of the fibrous modification is considerablyhigher analysisindicatesthe presence than that of the other two. Nlicrochemicai of some Sia+and COr2- in the fibrous, but not in the prismatic variety. With one exception the :r-ray powder photographsof all the samples examined,both fibrous and prismatic, closelyresemblethat of synthetic material. The data correspondto A.S.T.I{. card No. 9-414.The notable with thaumasite mentioned previexceptionis the specimenassociated ously. The powder photograph of this sample can be satisfactorily in-

i
Frc. 2. Intergrowth of ettringite (E) with gypsum (G) (idealized)'

that a:11.23 ft' @t 22.46 A,^c/' Hurlbut and dexed, if it is assumed, B a u m , 1 9 6 0 )a s f o r s y n t h e t i ce t t r i n g i t e ,b u t c : 2 1 . 1 9 A i n s t e a do I 2 I ' 4 4 A. lltre decrease c axis spacing may perhaps be attributed to some in Sia+for Al3+ and/or cor2- for Soa2-substitution. on the other hand no change in cell dimensions was observed for other fibrous specimens which are optically similar and also contain Sia+and COa'-' An interesting phenomenon was observed when several colorless prisms, which at first sight appearedto be singlecrystals, were studied in greater detail. Under the microscopeinclusions were revealed rvith considerablyhigher refractive index than the surroundingareas,positive elongation and optical orientation as indicated in Fig. 2. Single crystai

MINERALOGICALNOTES

929

oscillation and rotation photographsshowedeach individual to be composed of two well-definedcrystals, gypsum and ettringite, in perfectly parallel orientation. with the crystal mounted along the direction of elongation,the layer Iines are strictly parallel. The hexagonalc axis of the ettringite is paraliel to the morphological c axis of the gypsum crystal (the [101] direction on Bragg's notation). The optical data are compatible. It seemsplausible to assumethat, when a supply of Al3+-containing solutions becameavailable under highly specificphysico-chemical conditions, ettringite grew directly upon existing gypsum crystals. A close structural relationship between gypsum and ettringite may, therefore, be inferred, but remains to be investigated. No satisfactory explanation of the genesisof this unusual mineral assemblage can at present be given. The rock sequence question is in doubtlessly of sedimentary origin, as shown by the, admittedly very rare, occurrenceof badly preservedfossils.rt is most unlikely that the rocks of the "Mottled Zone" have been affected even by distant magmatic activity. There is no evidenceof contemporaneous later magor matic activity in or around any of the occurrences this rock complex; of more important, in all four localities mentioned the ,,Mottled Zone,, rocks occupy the same stratigraphic position. In the Hatrurim area severalhundred meters of the underlying strata, mainly limestonesand dolomites of l{iddle to Upper Cretaceous age, are exposed, but no signs of contact metamorphism or hydrothermal alteration can be found in theseunderlying rocks. It has been assumed(Bentor and Vroman, 1960)that the rocks of the "I{ottled Zorte" were originally similar in compositionto the bituminous sedimentsof the Ghareb and Takiye Formations. At some time after burial of thesestrata by marine sedimentsof Eoceneage, ground water rich in oxygen gained accessto the sedimentsand causedoxidation of the sulphide minerals and of organic matter. Owing to low thermal conductivity of the overlying sedimentsthe temperature of the ground water rose through the heat of oxidation and its geochemicalactivity was thereby enhanced.The result was a generalredistribution of major and minor elementsand the crystallization of new minerals. For processesof this kind the term sed.imentary hyd.rothermal act'ivity has been proposed.The minerals describedin this paper probably developedin the final stagesof this processthrough reactionsbetweenhot circulating groundwaterand the rock. None of thesemineralsseemsto_have formed at a temperature higher than 100o C., but it is doubtful whether the abundant formation of spurrite, a mineral typical of high-temperature contact metamorphosedlimestones,can be explained by this mecha-

930

MINERALOGICALNOTES

nism. The presenceof minerals such as portlandite and ettringite indiof cates an extremely high alkalinity, in excess pH:11, which also rehigh alkalinity is most unusual, but mains unexplained.Water of such has been observed, although not explained, in at least one case: the spring of Aqua de Ney, California. (Feth et al,.196l). The data presentedhere are the result of a preliminary study of this are interesting rock sequence.Further unusual mineral assemblages under investigation. AcrNowrnoGMENT We are grateful to Dr. NI. Fleischerfor drawing our attention to some iisted below. of the references
RrlonaNcrs map of Israel.sheet16: Mt' Sdom' Y. BENroR, K. eNoA. VnouaN, (1960)The geological 5841. Geol. Surtey I srael', Bull. Volcan.7,25 Cnnosrr,G. (1940) Acto,22, Cosmochim' aNo C. E. RoennrsoN,(1961)Geochem' Fnrn, J. H., S. M. RocERS 75-86. Nature,196,265. H-rrxrwr.v, J. C. aNo O. S. Scnr-nxcrn,(1962) ' Si'Ii'cates Datafor the Cal'ci'um Hnr.Ion, L. auo H. F. W. Tlvr-on, (1956)Crystallographic H.M.S.O.London,33. HrNrscnnr.,G. (1961)Fortscl*.Mineral.39, 345' Am. Mi'neral.45,1137. Hunrrur, C. S. nNoM. L. Bnuu (1960) D. KNrr-r-, C. (1960)Mineral. Mog.32,416. Mag.32,535. Mineral'. McCorwolr,, M. D. C. (7960) Mi'neral.8,5. MrNcuzzr,C. (1937)PerioiJico Minerol.Moy.23,419. C. Trr-r,nv, E. (1933) E. War,r., R. D., E. B. Wor-rnNonN, H. Bn.tno axr T. DBexs (1962)Nature,L96,264' J.

THE AMERICAN

MINERALOGIST,

VOL. 48, JULY-AUGUST'

1963

CHEMICAL FORMULAOF AKSAITE, THE PROBABLE A NEW HYDRATED MAGNESIUMBORATEI Suruey, ANDRrcHARoC. Enl, U' S' Geological Joen R. Cr,anr< Washington 25, D. C. and.Menlo Park, Colifornia. Aksaite, a new hydrated magnesium borate' has recently been described by Blazko et at. (1962). Crystallographic,optical and chemical data were given, but theseauthors stated that the chemicaicomposition of aksaite remains in doubt. The two chemical formulas suggestedby a t h e m a s m o s t p r o b a b l ea r e : 2 M g O ' S B z O a ' 8 H z O n d 3 M g O ' 7 B 2 O a .1oHrO.
1 Publication authorized by the Director, U. S. Gological Survey.