THn AMERICAN MINERALOGIST JOURNAL OF TIIE MINERALOGICAL SOCIETY OF AMERICA YoI.47 JANUARY-FEBRUARY, 1962 Nos. 1 and 2 SIGLOITE. A NEW MINERAL FROM TT,NT,T,ECUA, BOLIVIA* ConNnr-rus S. Hunrnur, ln., Harvard, Uniaersity, Cambridge, M assachusetts. RusSBr,r HoNna, Unioersity of Colorad'o,Bouliler, Colorod.o. Ans:rn,qct Sigloite,(Fer+, Fe2+)Al2eOtr(O,OH).8HzO, is a newmineral formed as an oxidation pseudomorphafter paravauxiteat Llallagua,Bolivia. Triclinic; a:5.26, b:1O.52, c:7.06A, a:106"58',g:111"30', t:69"30' a;b:c:0.4990i1:.0.6711;space group PT. Colorstraw yellow. G:2.35 meas.2.36 Calc., H:3. Opticallybiaxial (+), d:1.563' B:1.586,a:1.619,2Y:76o, r(v. Opticalorientation: X-d90" p32o,Y-6-lMo p70", 2-6-46" p66".Analysis gives PzOs 27.47, Al2Or 21.09, FezOe 13.53, FeO 2'76,l^.{nO 0.24, Mgo 0.87,Na2o 0.44, K:o 0.26,sioz 0.11, H2o 33.55, total 100.32, Strongest r-ray powder linesare 9.69 A (10)6.46 (9),4.86 (9). The name is from the Siglo XX mine,Llallagua. OccunnnNcn In 1954 through the courtesy of Senor P. P. Zubrzycki, Chief Ge- ologist, Corporacion Minera de Bolivia, the junior author collected the specimensused in the present study. On the 305-meter level of the Con- tacto vein, Siglo XX Mine, I-lallagua, cavities were found filled with straw yellow intergrowths of crystals; in other cavities similar crystals were perched on wavellite overgrowths on quartz. Although the morpho- logical appearanceof these crystals was similar to paravauxite, the color was sufficiently different to attract attention. Chemical analysis con- firmed the similarity and revealed the causeof the color difference. Most of the ferrous iron of paravauxite had been oxidized to the ferric state. The name, sigloite, taken from the Siglo XX mine, is given to the new mineral, an oxidation pseudomorph after paravauxite. Sigloite is ap- parently the mineral referred to by Bandy (1945, p. 56) as "hydrated paravauxite," a straw yellow alteration of paravauxite assumedto form by hydration. The minerals associated with sigloite, in addition to wavellite and paravauxite, include metavauxite, crandallite, childrenite, and an uni- dentified reddish-brown phosphate. These and other phosphate minerals * Mineralogical Contribution No. 401, Harvard University. 1 C. S. HURLBUT, TR. AND R. HONEA are found in open fractures cutting major cassiteriteveins on all levels of the mine, and were consideredof supergeneorigin by Ahlfeld (1931) and Gordon (1944). Turneaure (1935) indicated that vauxite is supergene but points out the unlikelihood of a supergeneorigin for the large amounts of wavellite. In later publications Bandy (1946) and Ahlfeld and Munoz (1943 and 1955) regard all of the phosphate minerals as belonging to the final phase of hydrothermal mineralization. Sigloite appears to be an ex- ception. Its pseudomorphousnature indicates formation from paravaux- ite during a Iater supergenestage. Pnvsrcer eNt Optrcar- PnoPBnrrns The pale straw yellow to light brown color of sigloite is in marked con- trast to that of paravuxite, which is colorlessto pale green. The two min- erals were observedtogether on only one specimen,and here most crystals were completely either one mineral or the other. However, a few showed a variation in color along their Iength and refractive index changescorre- sponding to the color differences.Although earlier suspected,it was this evidence that led the authors to the conclusion that the sigloite crystals are pseudomorphsafter paravauxite. The perfect {010} cleavageof paravauxite is preserved in sigloite, and in addition there is good {001} cleavage, traces of which are seen on [010]. On the reflectinggoniometer sigloite crystalsshow distorted and curved faces which give continuous signals over a wide angular range. Although one cannot use the measurement for calculations they served to identifythe followingcrystal forms: c{001}, b{010}, a{100} ,mlll}l, M Ill0l, tll2}l, A{011 } , rlltll, hlII2l. Figure 1 showsthe character- istic habit and form development. The hardness of sigloite is 3. The specific gravity measured on the Berman balanceis 2.35; 2.36 calculated. The optical properties of sigloite are given in Table 1 with those of paravauxite for comparison. It will be noted that ihe oxidation of the iron has produced an appreciablerise in refractive indices and increasein the birefringence. Figure 2 shows diagramatically the optical orientation of sigloite. A comparison of the stereogramsof Fig. 3 and 4 shows the marked differencein the optical orientation of paravauxite and sigloite. CnE,rurcarCouposrrtoN A chemical analysis of sigloite, made on the same material used for optical and x-ray study, is given in Table 2 with an analysis of paravaux- ite. The analyses correspond closely except for the state of oxidation of the iron. In sigloite, to balance the excesspositive charge of Fe"', there is assumedto be a concomitant substitution of oxygen for hydroxyl giv- SIGI,AITE, A NEW MINERAL M _-)----t- Frc. 1. Sigloite. pseudomorph after paravauxite. ing the formula (Fe3+Fez+){I, (por, (O,OH)r.gH2O. There is one for_ mula weight per unit cell. Difierential thermal analysis curves of sigloite and paravauxite are given in Fig. 5. The differencesin the marked endothermic peaks, be_ tween 100oand 300" c, resulting from the loss of water, indicale a difier- ence in the role of water in the two minerals. After heating to 1000o c, both sigloite and paravauxite yield a red powder. An r-ray powder photo- Tnnr,n 1 Oprrcar, propr-rrns ol Srcr,orrr .luo pnnavauxrre Orientation Indices (Na) E p x 900 32" a:1.563 opt. * y -lM Sigloite 70 €:1.586+0.001 2Y:76" -46 z 66 t:1.619 r<v strong x6l 56" a:1.552 opt.t Paravauxite Y 180 55 F:1.559+0.001 2Y:72" -61 <A z t:1.572 r<v C, S, ITURLBUT, JR. AND R. HONEA Frc. 2. Optical orientation of sigloite' Fro. 3, Sigloite. Frc. 4. Paravauxite. Stereograms showing optical orientation. Tl's]-E 2, Cunurcar, Arqelvsrs or Srcr-orrE 1. Sigloite 2. Paravauxite PrOu 27.47 27.64 AlzOa 2r.o9 2t.00 FezOs 13.53 1.52 FeO 2.76 13.60 MnO o.24 CaO 0.28 Mgo 0.87 0.22 NurO 0.M KzO o.26 SiOs 0.11 t.20 HzO JJ.JJ 35.05 t00.32 100.51 1. Jun Ito, analyst. 2. E. V. Shannonanalyst, in Gordon (19114). PARAVAUXITE SIGLOITE Fro. 5. Difierential thermal analysis curves of paravauxite and sigloite. Tasln 3. UNrr Cnrr. Drlmwsroxs oF Sror,orrE AND IsosrRUcruRAL MTNERAT-s Sigloite Paravauxite Gordonite Laueite a s.26A s.23A s.24A s.2sA o 10.52 ro.52 10.49 10.66 c 7.06 6.96 6.96 7.r4 d 106"58' r07"17, 107"25', 107'55' 11130 ttl 24 11104 11059 .Y 69 30 72 29 72 22 7r 07 aibic 0.4990i110.67110.497ltl;0.6671 0 .4990:1 :0 . 6635 0.4953:1:0.6698 G 2.35 2.36 2.23 2.4+-2.49 Ref. Dana System Dana System Strunz 1951 1951 t954 C. S. HURLBUT, JR. AND R. EONEA Tesrn 4. Ironxso x-Rlv Powonn PerrenN Or Srcr-Orrn.Fe Reotlrrow, Mn FII,rnn. r:1.9373 A d(meas.) d(calc.) | d(meas.) I hkl d(calc.) 9.6eA 10 010 9.70 2.0eA T51 2.lO 6.46 9 001 6.45 z42 2.lo 5.83 2 011 5.90 032 2.O9 4.86 9 II1 4.85 t22 2.08 020 4.85 2.04 2rl 2.03 4.79 J 110 4.78 20r 2.O3 4.68 4br 100 4.70 113 2.03 3 .91 , 120 3.96 t.952 212 1.959 3 .83 3 110 3.84 051 1.9s8 3.6r J 111 3.57 T40 1.946 3.33 T12 3.35 1.917 220 r.9r9 3.2s 3 012 3.25 21r 1.916 3.23 030 3.23 1.898 r32 1.903 o02 3.23 203 1.889 3.16 3 031 3.13 1.868 23t 1.870 3.09 + 130 3.08 252 1.870 111 3.08 1.806 tI T23 1.808 2.99 3 120 2.99 1.76r I 051 1.765 2.89 2 012 2.90 22t r.76r 121 2.89 T24 r.76t 2.82 I32 2.81 113 t.756 T2r 2.79 1.750 151 1.752 031 2.79 161 r.751 2.72 3 1r2 2.70 IT4 1.7s0 2.62 1 12r 2.64 2s0 r.747 zn 2.61 1.732 32r 1.738 2.58 22r 2.59 n2 r.736 T4r 2.59 2r3 |.733 2.56 5 032 2.54 t.669 2.39 2b 212 2.40 1.626 220 2.39 1.615 77a 2.38 1.570 2.34 200 2.35 t.524 II3 2.33 1.498 2.27 3 T22 2.28 t.464 2.12 J oE3 2.t2 r.n7 1.358 r.292 * b:broad. SIGI.OITE. A NEW MINERAL Tesrr 5. Srcrortn d-Sp,tcrriTosColm.q'n.ro wrrs Isosrnucrunel MrNrrer,s. 1 ar.ro4-Fe R.aola.rroN,Mn Fu,rnn; 2 nr.lo3-Cu RenrerroN, Ni Frr.rnn 1. Sigloite 2. Paravauxite 3. Gordonite 4. Laueite d I d I d I dI 9.6eA 10 e.82A 10 e.78A 10 9.91A 10 6.46 9 6.38 9 6.32 6.57 7 5.83 2 5.92 1 4.86 6.17 2 4.86 9 4.9r 4 4.76 4.95 8 4.79 ? 4.20 9 4.50 1 4.27 | I 468 4bf 4.15 2 4.15 1 4.15 | 3.9r 4 3.91 3.94 J 4.O2 5 n 3.83 J 3.61 J .55 z 3.93 5 3.61 J 3.25 7 3.61 2 3.70 2 333 2 J.