THE AMERICAN MINERAI,OGIST, VOL. 47, MAY JUNE, 1962

CHAMBERSITE, A NEW Russrr-r- M. HoNBe ewp FneNr R. Bncr,l Department oJ Geology and.Mineralogy, Ltniaersityof Colorad.o,Bould,er, Colorailo anil Department.of Geology,Fort Hays Kansas State College, Hays, Kansas.

ABSTRACT is present in brine returns from a gas storage well on Barber's Hill salt dome, Chambers County, . are almost colorless to deep purple, paramorphic isometric with the positive tetrahedron as the dominant form. H 7, G 3.49 (meas.),3.48 (calc.). No , subconchoidalto uneven. Optically biaxial positive, a:t.732, A:1.737,7:I.7M+0.001, 2V:83o*30. Orthorhombic aggregatesmake up para- morphs. Chemical analysis: MnO 41.87, FeO 1.28, MgO 0.05, CaO tr, BzOa49'50, Cl 6.34, remainder-1.39. Total 100.43 minus 0:Cl 1.39, corrected total99.04/e. The formuia is Mnz.goFeo.osMgo.orBzOrrClUnit cell of the low temperature dimorph is orthorhombic, a:8.68, b:8.68, c:12.26it; strongest lines of the r-ray powder pattern are (10) 3.07, (6) 2.74, (6) 2 08, (5) 3.54, (5) 2.17. Differential thermal analysis shows the orthorhombic- isometric inversion at 407" C. and melting at 1065o C.

IwrnopucrroN AND OccunneNcB Chambersitewas first found in 1957in brine returns from a gasstorage well in the Barber's Hill salt dome, Chambers County, Texas. Pre- liminary data from optical examination and #-ray powder diffraction indicated the mineral to be related to but distinctly different from any published descriptions. This conclusion was confirmed by spectrographicdata furnished through the courtesy of C' L. Christ, I. Adler and H. J. Roseof the U. S. GeoiogicalSurvey. These data indicated the mineral to be a manganesechloroborate isostructural with boracite and are substantiatedby other data collectedduring the preseirtstudy. The mineral is analogousto ericaite, the ferrous analogueof boracite (Heide, 1955; Kiihn and Schaacke,1955) and is the second chemical analogueof boraciteto be found in nature. Synthesisof the Mg, Fe, Mn, Zn, Co, and Ni analoguesof boraciteis reportedby Heide et al. (1961). Propertiesreported for the synthetic manganeseanalogue are in good agreementwith thosedetermined in this study for the natural mineral. The only observedoccurrence of chambersiteis from StorageWell No. 1 of the Texas Natural GasolineCorporation on the northwest flank of Barber's Hill salt dome, Mont Belvieu, Chambers County, Texas. The mineral is presentin brine returns from the well, and although accurate information as to the depth of the occurrenceis not available, driller's logsindicate an origin in the main salt massat a depth between2,32O and 2,72OleeL below sealevel. Associatedminerals include ,

I Present address: University of Bahia, Salvador, Brazil.

665 R. M. HONEA AND F. R. BECK

B

Frc. 1. A. Modified paramorphic isometric crystal of chambersite. Forms: o111, -oll7, a007,and d011. B. Penetration twin with twinning axis [111] and twin plane (111). and . A carefulsearch failed to revealother borate mineralsin the accumulated material from evaporation and settling of brines. Geological relationships in the vicinity of the Barber's Hill dome are described by Bevier (1925) and Judson et al. (1932). The salt mass is known from subsurface data to intrude sediments ranging in age from Pleistoceneto Late Cretaceous.The ageof the salt in the intrusion is not definitely known but is at least Late Cretaceousand probably Jurassic. The salt massis cappedby porousrock consistingof limestone,gypsum and anhydrite. Open spacescontain varying amounts of crystalline sulfur, pyrite and calcite. Cap rock and some salt form an overhang relative to the main salt core. Thickness of the cap rock varies from approximately 850 feet over the central part of the dome to only a few feet on the outer edgesof the overhang.

Puvsrc,lr Pnoppnrrrs Chambersite occurs in subhedral to euhedral crystals ranging from less than 1 mm to I.2 cm on an edge.Crystals are paramorphicisometric, and are composedof aggregatesof the low temperature orthorhombic modifi- cation of the mineral. The dominant form is the positive tetrahedron (111),which is commonlymodified by facesof (001),(110), and (111). Figure 1 illustrates a typical modified crystal, although all combinations of the modifying forms were observed.A single morphologically twinned crystal was foundl it consistsof interpenetrating tetrahedronswith the twinning axis (111) and twin plane parallelto an octahedralface. Similar twins have been describedfor tetrahedrite.Inversion of the isometric to the orthorhombicdimorph is accompaniedby microscopicallyobservable twinning. Paramorphsare seenon optical examination to consistof an aggregateof crystals with irregular contacts. Both optical and r-ray work indicate analogy to boracite dimorphism in which the high temperature CHAMBERSITE 667

Tesle 1. Oprrc,r.rPnoprnrms or Crl,LMsnpsrrrCoupenro Wrtr Bonacrrp eNo Enrcerrn

Chambersite Boracite Ericaite q | .732+0.001 1.658 1.737+0.001 t.662 co. 1.75 7 1.744+0.001 1.668

Biaxial (*) Biaxial (*) ? 2V 83"+ 3" 82r" ? 0.012 0.010 ?

1. Chambersite-present study. 2. Boracite-Guppy, 1944. 3. Ericaite-Kiihn and Schaacke, 1955. form is isometric hextetrahedral whereas the low temperature modifica- tion is orthorhombic pyramidal (Ito et al. I95t). The mineral has no cleavageand breaks with a subconchoidal to un- even fracture. The hardnessis 7. Crystals vary from almost colorlessto deep purple, the intensity of coloration apparently varying with very slight oxidation of manganese,for the color is deepenedby continued ex- posure to sunlight. Synthetic manganeseboracite is colorless(Heide et al. 1961). Specificgravity, as determined for nine sampleswith the Berman balance,is 3.49*0.02 (3.48 calculatedfor pure chambersite).A specific gravity of 3.484 is reported for the synthetic manganese analogue of boracite(Heide et al.,l96t). In transmitted light the orthorhombic dimorph has optical properties as listed in Table 1. As shown in the table, indices of refraction are close to the approximate value determined for the ferrous analogue-ericaite, and considerably higher than for boracite.

Cnpurcar Couposrrrow Chambersite is a manganesechloroborate-MngBzOraCl. Quantitative analysis (Table 2) indicates Iimited substitutional solid solution of Fe2+ and Mg2+ to give the formula (Mnz.soFeo.osMgo.or)BzOraCl.The mineral is thus the manganeseanalogue of boracite (MgaBzOraCl)and of ericaite (essentiallyFeaBzOrrCl). Manganese is reportedin ericaitein amountsup toMnO-2.327o (Kuhn and Schaacke,1955), but has not previously been reported in natural material as the principal cation. Heide el al. (1961) report completesolid solution betweenthe synthetic Mg-, Fe-, and Mn- boracite products, and list resulting changesin density and cell-edge. 668 R. M. HONL,A AND F. R. BECK

Tesr,n 2. Cqrurcar- Couposr:rroNor CrraMeEnsrrp

MnO 13 97 4r.87 .5903 FeO 1.28 .0178 3.00 Mgo 0.05 .0012 CaO tr BzO: 50.36 49.50 .7108 3.50 CI 7.32 6.3+ .1788 088 Remainder 1?O

Total 101.65 100.43 Less O:Cl 165 1.39

100.00 99.O+

A. Theoretical weight percentagesfor MnsBzOuCl. B. Chambersite, Mont Belvieu, Barber's llill salt dome, Chambers County, Texas. Remainder includes SiOz 0.32, TiO2-t'race,AlrO3 0.12, NarO 0.05, KrO 0.03, HrO 0.87. Analyst: M Chiba, Japan Analytical Chemistry Research Institute. C. Molecular amounts calculated from B. D Nlolecuiar proportions calculated from B.

Quantitative spectrographicanalysis of a separatesample by H. J. Rose of the U. S. GeologicalSurvey (pers. comm. from C. L. Christ, 1958)gave:

Mn Fe Mg Ca Sr Ba BSi 15 1.7 0.20 0.2 0.0 0.0 10 0.050

Looked for but not found: Cu, Ag, Au, Hg, Pd, Pt, Mo, W, Re, Ge, Sn, Pb, As, Sb, Bi, Zn, Cd, Tl, In, Co, Ni, Cr, V, Ga, Sc, Y, Yb, La, Ce, Nd, Zr, Th, Nb, P. Results are reported to have an overall accuracy of +15/6 except near the limits of detection where one dieit is reported. X-Rev Sruov X-ray unit cell data determinedby indexing of the powder diffraction pattern are given in Table 3. Indexing is basedon analogy of the powder patterns of chambersiteand boraciteand on the unit cell data presented in the structure analysisof boraciteby Ito et al. (1951).The paramorphic isometriccrystals availablein this study are composedof crystal aggre- gatesof the orthorhombic modification,and singlecrystal data could not be obtained.Figure 2 showsthe correspondenceof the powder patterns of boracite and the manganeseanalogue. Indexed powder diffraction spacingsare given in Table 4 with calcu- lated valuesof d from the unit cell constantscited above.It is worthy of note that the pseudotetragonalnature of the unit cell, combined with a CHAMBERSITE 669

Frc. 2. Photograph comparing r-ray powder difiraction patterns of (A) chambersite and (B) boracite from Luneburg, Germany. Fe radiation, Mn filter. Contact print. close approximation of theaxial ratio cf a of 1/2, allows indexing of the powder pattern for a pseudoisometric cell with the dimension a\/2 :12.27A. An o of 12.248+0.005Ais reported for synthetic manganese boracite(Heide et al.,196l).

Trtnnuar- BBgevlon Differential thermal analysis curves were prepared, using a Deltatherm DTA unit, of chambersite ground to minus 100 mesh. The curves have a sharpendothermic reactionat 407oC. and the beginningof a broad endo- thermic trough at 1065oC. The low temperaturereaction results from in- version of the low temperatureorthorhombic dimorph to the high tem- perature isometric modification and indicates a higher temperature for

T,q.sr-n3. Unn Cor,r,Cor.rsraNrs ron CuansnnsrrrCouparun Wrrn Tnoso<.r1. Bonncrlrr. Splcn Gnoup Basro oN Arlr,ocy ro Low Bon,rctrl' aNo Nor DBTtnMrlrso rN PnnseN:r Sruov

Chambersite Boracite 8.68+0.01A' 8 54A 8.68+0.01A 8.54 12.26+0.01ll^ t2.07 Pca Pca 4(MnrBzOrCl) 4(MgsBzOraCl)

1. Determined in present study. 2. lto et al. (1951). 670 R. M. HONEA AND F. R, BECK

Tasr,B 4. X-Rlv Pomnn Dil'lnlctroN PertrnN oF CHAMBERSTTElRoM B.a.nsnn's Hrr,r, Sllr f6w, MoNr Bnr-vrnu, CreMerns CouNrv, Tnxes. Sp,q,cBGnoup Pca.; o:8.684, b:8.68, e:12.26; Fe Raora.troN,Mn Frr.rnn,Wlvpr.nrctr l.9373A. Connocreo lon Frr-n Srrnrxxecn

.l..T .l I hht hht :. I Itkl' , 1 (meas., rc.L.l( meas. ) (calc.J (meas./ (carc..l

6.15 110 6.15 2.17 224 2.r7 | 641 152 1.642 002 6.12 400 2.17 512 r.&2 5.46 1 111 5.49 040 2.t7 r36 t-&l 433 L tt2 4.34 2.08 125 2.08 316 1.641 200 4.32 215 2.08 2M 1.640 o20 4.32 t4r 2.08 424 1.640 1 4.08 t 20r 4.09 4tl 2.08 1598 1 127 1.599 3.91 I 120 3.89 233 2.08 217 1.599 2to 3.89 323 2.08 t4s 1.598 354 202 3.54 402 2.06 415 .598 o22 3.54 042 2.06 r.57r .572 3.40 I 113 3.+r 006 2.05 513 .572 3.07 10 0(X 307 134 2.05 1.534 40 .534 220 3.O7 314 2.05 008 .533 2.98 221 2.97 330 2.05 1.488 118 .488 203 2.97 016 1 992 350 1.488 n 1A tt4 n 1A r42 1.989 s30 1.488 130 2.74 ila 1.989 406 1 488 310 2.74 1.941 1 lt6 |.941 o46 1.488 222 2.74 r.916 i 225 1.918 r.477 + lJ/ 1.478 2.67 | 131 2.68 tAl |.917 317 t.478 311 268 A)1 1.917 1.446 1 208 r.M7 2.50 3 201 2.51 403 1.917 028 1.447 024 2.5t 1.851 206 1.851 600 l.M6 132 251 026 1 851 060 I.M6 312 2.5r I 830 135 1.830 t.+17 zJl |.417 2.39 124 241 315 1.830 327 1.417 214 2.41 1.77r 404 r.772 161 r.4r7 230 230 2.41 o44 r.772 611 | -417 320 2.41 1.753 243 r.7541.410 246 1.408 2.28 1 115 2.28 +23 r.754 426 1.408 133 2.28 226 .698 1.398 155 1.391 313 2.28 I r17 .686 515 1.39r 151 686 t.372 2 2ffi 1.372 .)rt .686 620 r.372 the orthorhombic-isometricinversion than for either boracite(265' C.) or ericaite (310-315' C.). The endothermic trough starting at 1065' C. marks the beginningof melting. The observedinversion temperatureof 407' C. correspondsprecisely to that reported for synthetic manganese boracite by Heide et al. (1961). CHAMBERSITE 671

Cooling curves have a broader exothermic reaction at approximately 400' C. with slight maxima at 405oC. and 395' C. separatedby a shallow trough. The significanceof doubling of the low temperature maximum on coolinghas not beeninvestigated, but probably resultsfrom better resolu- tion during the slowercooling process showing both the breakdownof the isometric modification and crystallization of the orthorhombic form. A rapid inversion is indicated by the closecorrespondence of temperatures on both heating and cooling curves.

NauB The name is in allusionto the locality in ChambersCounty, Texas.

AcrNowI,BIGMENTS

We wish to expressour appreciation to B. F. Dyer, Jr. who 6.rst noted the mineral, and to N. E. Van Fossan of the Texas Natural Gasoline Corporation who furnished data concerning the occurrenceand gave per- missionto collect additional material. Thanks are also due C. L. Christ and his associatesI. Adler, H. J. Rose,H. T. Evans, Jr., Mary E. Mrose, and Joan R. Clark of the U. S. GeologicalSurvey for their assistancein furnishing data in the early stages of the investigation. One of the co- authors,F. R. Beck, completedthe early work under the tenure of a Na- tional Science Foundation Science Faculty Fellowship. Funds for the quantitative analysis were furnished by the George and Anna Garrey Fund. Rplnnoxcrs Bnvrnn, G. M. (1925), The Barber's Hill oil field, Chambers County, Texas. Bull,. Am. A ssoc.P etrol. GeoL,9, 958-973. Gurev, E. M. (1944), Boracite from a boring at Aislaby, Yorkshire. Mineral. Mag.,27, 51-53. Hnroo, F. (1955), Uber bemerkenswerte Borazitvorkommen in den Kalilagern des Siid- harzbezirkes. Chemie d.erF.rde, 17r 2ll-216. Hrror, F., G. Warron, eNn R. Unr,a,u (7961),Zur Kristallchemie desBotazits. Natur- uis sensckaf ten, 48, 97 -98. Iro, T., N. Monnroro, eNn R. Saoanace (1951), The olboracite Acta Cryst., 4, 310-316. JuosoN, S. A., P. C. Mutrnv, auo R. A. Sraurv (1932), Overhanging cap rock and salt at Barbers Hili, Chambers County, Texas. BIJL. Am. Assoe. Petrol,. Geol. 161 469482. KUrrN, R. aNl I Scneecre (1955), Vorkommen und Analyse der Boracit- und Ericait- krystalle aus dem Salzhorst von Wathlingen-Hanigsen. Kotri, u.nd.Steinsotrz,llr 3342.

Monuscript receiaed,Nolember 6, 1961.