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HEMIHEDRITE, a NEW MINERAL from ARIZONA Srnwby A

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HEMIHEDRITE, a NEW MINERAL from ARIZONA Srnwby A THE AMERICAN MINERAIOGIST, VOL. 55,JULY-AUGUST, I9?O HEMIHEDRITE, A NEW MINERAL FROM ARIZONA SrnwBy A. Wrrlraus, WesternErploration, Ofice, Phelps DodgeCorporation, Douglas, Arizona 85607; JouN W. ANtttoNv, Department oJ Geology,Unilersity o.f Arizona, Tucson. Arizona 85721. AssrRacr Hemihedrite is a new species discovered at the Florence Lead-Silver mine in Pinal County, Arizona. A second locality is the Rat Tail claim near Wickenburg, Maricopa County, Arizona. Hemihedrite is named in allusion to its morphology. Crystals exhibit tdcliidc hemi 'Ihree hedral slrnmetry with a:120"01', B:91o49', T:55o55', a:b:c:0.8345:l:0.9360. twin laws have been found. The refringence is a:2.105, F:2.32, t:2.65(25'C); optically (*) with 2V(calc.) :88'. Dispersion is strong and unsymmetric. Crystals are orange to almost black and have a safiron yellow streak. Hardness on the Mohs scale is 3. Unit-cell data at 22"C are as follows: PI; a:9.497+.001A, 6:11.443+.002 A, c: 10.841+.002 A; a:120o30', A:92"06', z:55o50'. The Delaunay cell is a': 9.954 A, b':10.841 i:', c':9.497 L; at:92006', 9:107o58', tt:123"16'. The most intense X-ray Iinesare:4.872 (90) (t20).4364 (80) (220),3.301(100) (r22),3146 (80) (320),3.102(80) (103, 102), 2.924 (55) (253), 2.849 (45) (%:2).2.182 (45b) (411, 340). t':123o16'. Trans- formation (morphology to Delaunay cell) is T10/001/100. Chemical analyses combined with structural information lead to the composition ZnFz[Pbs(CrOr)sSiOa]:(with Z:l), although chemical compositional variation is indicated. Specific gravity is 6.42 (meas. at24.2oC) and the density (calc.) is 6.50 g/cm3. Hemihedrite forms in the oxide zone of lead-bearing veins. Associated minerals may include the following: cerussite, phoenicochroite, vauquelinite, willemite, and wulfenite. INrnooucrroN Specimensof the new mineral were first collected and submitted to us by R. W. Thomssen.The specimenswere found at the FlorenceLead- Silver mine in the Tortilla mountains, Pinal County, Lrizona. Subse- quent trips to the locality yielded ample material for this investigation. During the study a secondlocality was discoveredon the Rat Tail claim (formerly the Pack Rat claim) near Wickenburg, Maricopa County, Arizona. Material from the type locality in Pinal County was used as a basis for this investigation. At both localities the speciesis rather abun- dant. The speciesis named in allusion to its distinctive morphology.r GBor-ocv At the Florence Lead-Silver mine an adit has been driven along a strong fault zone striking N 70' E and dipping 70" to 77" to the southeast. r The mineral and name have been approved by the Commission of New Minerals and Mineral Names, IMA. 1088 IIEMIIIEDRITE 1089 Lead minerals including hemihedrite and wulfenite are concentrated in a shoot of small horizontal dimensions localized within the sheared and mineralized rubble and gougein the hanging wall of the fault. Where the Iead minerals occur, a crosscut has been driven exposing the fault zone and hanging wall rocks. The zone consistsof nine feet of calcite and as- sociated iron oxides cementing partly altered and replaced fragments of quartzite, limestone, and latite porphl'ry. Remnant galena occurs as replacementsof siliceousfragments adjacent to the fault plane near the footwall side of the zone. Supergenealteration of the calcite and galenahas been most intense on the north side of the fault zone in a narrow selvagewhich consists of a loose aggregate of finely crushed and highly altered rock fragments and iron oxides.Secondary lead minerals occur as oxidation products in cavi- tites left by the leaching of galena, on fractures traversing the fault-zone rubble, and in the aforementioned highly'altered selvage. Strongly brecciated Mississippian Escabrosa Limestone, intruded by altered latite porphyry, comprisesthe south wall of the mineralized zone. Large displacement on the northeast fault has brought these hanging wall .rocks against a footwall section composed of vertically-dipping Precambrian Troy Quartzite and underlying units of the Mescal Lime- stone. A dike of altered diabase separates the Troy Quartzite and the uppermost chertstone unit of the Mescal Limestone on the surface over the adit. Underground the diabase has been displaced by a small fault and is not visible. OccunneNce Hemihedrite occurs in an oxide assemblageindicative of alkaline solu- tions of relatively low Eh (Williams, 1966).Primary minerals from which the oxide assemblageis derived consisted of galena, sphalerite, pyrite, and minor tennantite. Chalcopyrite occursvery sparingly as blebs in the sphalerite. Chromates occur where the oxide ores are near an altered diabase dike; one sample of this dike showed a CrOs content of 0.14 weight percent by X-ray fluorescenceanalysis. Oxidation of the sulfide ores has been almost complete so that only minor amounts of galena remain in an oxide assemblageconsisting largely of hemihedrite, wulfenite, willemite, and cerussite. Other speciesnoted are vauquelinite, minium, and mimetite. The paragenesisin the oxide asemblageis as follows: cerussite (first) followed by hemihedrite and wulfenite, with wulfenite continuing to crystallize after hemihedrite, and vauquelinite (last). Willemite is evi- dently earlier and mimetite is later than most wulfenite. Wulfenite con- temporaneous with hemihedrite is orange and chrome-free. Wulfenite 1090 S. A. WILLIAMS, AND J. W. ANTHONY which has replaced hemihedrite is brilliant red and contains, in one ana- lyzed specimen,0.83 weight percent CrOa. Continued crystallization of Iater wulfenite was marked by continuously decreasingchrome contentl Iate wulfenite is yellow and chrome-free. At the Rat Tail claim hemihedrite occursin a similar assemblagewhich consists largely of hemihedrite, willemite, cerussite, and phoenico- chroite, with minor amounts of mimetite and vauquelinite. These minerals have formed by oxidation of galena, sphalerite, and pyrite in quarlz veins which cut an andesite agglomerate. Pnvsrcer. PnopBnrrrs Crystals of hemihedrite range in color from bright orange to henna brown to almost black. Crystals vary in length from 0.2 to 10 mm, and average 0.5 mm. The streak is saffron yellow (Munsell 5Y 8/10). Hard- nesson the Mohs scaleis 3. The specificgravity measuredon the Berman density balance is6.42 (24.2"C). CnBlrtcar- Couposrrrou The initial qualitative spectrographic examination of hemihedrite showedmajorPb, Cr, and Zn;traces of Ca, Si, Mg, Cu, Ni, Ag, andAl; and failed to show F. Several quantitative analyseswere made by differ- ent methods for Pb, Cr, and Zn. One of theseanalyses showed significant Ca and a second showed significant Si. The infrared spectrum failed to reveal either water or hydroxyl, but did confirm chromate ion. A thermo- gravimetric balance tracing showed no weight loss to 313oC, then a gradual loss amounting to 10.7 percent of the initial weight between 313oCand 967"C.The crystal-structureanalysis (McLean and Anthony, 1970) indicated two sites that would be most logically filled by Si in the one instance and F in the other, based on scattering power, charge, and atom size. Subsequent chemical work verified their presence.Electron- microprobe examination of hemihedrite established that the silicon is uniformly distributed throughout the mineral and not present in a sepa- rate phase. Table 1 presents the analytical results. The empirical composition derived from the average analysis (column 14, Table 1) by assuming six CrOgper unit cell as indicated by the struc- ture and the consistencyof the Cr analysesis: Znr.rTFs.2rlpb 1.36(CrO.r) 3(SiOq) o.ar]r. The ideal formula deducedfrom the crvstal structure is: znF,[Pb6(cron) rsio,l,. The excessZn and defrciency of Pb in the analysesare presumably due HEMIHEDRITE 1091 ?\q.: N oO\Oi or e b\ r HO\C4 ro\oN iF O'GJd \od\or o. *r NC)4N sNc)N ao oo'd; E :>. Ni9N $N 90 NOo14 4N r) o rN vt o :N Ni n !r ltl fl I FE: ^o:: E =N6 r ii<'idLN ,i aeh a N Fl z N q (.) <ir = q U N N tsl a F N rN q':\9 NiNC) NN s a aq N r No. O\ NO a 1q q No rN r .. k ! -. >i>>J2d !s cd d tr- ^--/{ 6' 55853," F TO92 S. A. WILLIAMS AND T. W. ANTHONY to substitution of Zn for Pb in some samples. Fluorine in the amount indicated by the colorimetric analyses is inconsistent with the evidence from the structure and with the charge requirements of the remainder of the compound. The addition of both SiOzand F in the amounts indicated by the analysesmade subsequent to the analyses 2-4 ol Table 1 would result in totals consistently greater than 100 percent (average 103.6)' while addition of fluorine in the amount indicated by the structure analysis would give totals much closer to 100 percent (average 101.2) in all cases.Therefore, we believe the fluorine analysesto be too high. The results of the refined X-ray structure analysis (R:4 percent) (Mcl-ean and Anthony, 1970) lead us to the ideal composition ZnFz[Pbr(CrOa)3SiOa]2,but the variability in the analysesindicates that some compositional variation does exist. There is, however, insufficient chemical evidence to justify proposing a specificformula to expressthe compositional variation for the species. Reactions of hemihedrite to certain reagents are as follows: in 1:1 HNOa, white powdery Pb(NOe)zis formed; in 1:1HCI, a coating of PbClz slowly develops. Hemihedrite is slowly decomposedin 20 percent KOH, but is unaffected by 20 percent NHTOH. Monpnolocv Hemihed.rite crystals of great perfection and ideal size for goniometry were easily obtained. About 40 crystals were measured on a Stoe two- circle goniometer. Many of these were doubly terminated. About a dozen twins were also examined. The morphological study shows that the crystals are triclinic hemihedral.
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