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Mineralogical Studies of the Nitrate Deposits of Chile: YII

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Mineralogical Studies of the Nitrate Deposits of Chile: YII American Mineralogist, Volume 79, pages 1003-1008, 1994 Mineralogical studies of the nitrate deposits of Chile: YII. Two new saline minerals with the composition&(Na,K)oNa.Mgro(XO4)rrGO t)'r'l2HrOz Fuenzalidaite (X : S) and carlosruizite (X : Se) Juorrn A. Kor.rNnnr,Howlno T. EvaNs,Jn., Jnvrns J. McGrp, Gnoncr E. Enrcxsm U.S. Geological Survey, National Center 959, Reston, Virginia 22092,U.5.A. ArsrnLcr Two new isostructural saline minerals from the nitrate deposits of northern Chile have the composition IQ(Na,K)oNa.Mg,o(XOo),r(IOr),r. l2HrO: fuenzalidaite(FNZ, X : S) and carlosruizite (CLR, X : Se,S,Cr).They are trigonal, P3cl; for FNZ c : 9.4643(4), c : 27.336(6)A; for CLR a: 9.5901(8),c:27.56(2) A. The crystalsform thin hexagonal plateson {0001} up to 0.2 mm across,beveled at the edgesby {1012}. The crystalsare transparent and pale yellow; optics are uniaxial negative with <^r: 1.622(5),e : 1.615(5) (FNZ), and co: 1.655(3),e : 1.642(l) (CLR). The crystalstructure (R* : 0.043 for FNZ, 0.053 for CLR) consistsof two complex slabsnormal to the c axis, each having a double layer of iodate groups (IOr), bounded at the top and bottom by layers of SOo or SeOn g.roups.The strongestX-ray powder lines [d, (1, hkl)l for FNZ are 13.67 (50,002), 7.05 (40,102),3.927 (100,202),3.023 (41,212,117),2.681 (33,302); for CLR, 13.75(30,002), 7.10 (20,102),3.56t (100,204),3.082 (32,206), 3.058 (39,2t2,tt7),2.715 (39,302). Ixrnooucrrox OCCTTNNTI\ICE AND ASSOC:IA'TED MINERAI^S The two new minerals, fuenzalidaite (fwen-zaJeed'-a- Small amounts (a few tens of milligrams each)of fuen- ite) and carlosruizite (kar-los-ru-eez'-ite),are members of zalidaite and carlosruizite were found in nitrate ore from a solid solution series,IQ(Na,K)oNauMg'o(XO4)', (IO3)',' two localities in the Chilean nitrate fields. Fuenzalidaite l2HrO, for which the end-membershave X : S for the occurs as blebs and flattened aggregatesofbright yellow former and X : Se for the latter. With the exception of micaceousmaterial in veins and veinlets of white nitrate Se,the componentsof theseminerals are widespreadcon- ore, called caliche blanco, in a former nitrate mine about stituents of the Chilean nitrate ores. Se was not known to I km south of the former plant site of Oficina Santa Luisa. occur in these ores until it was discovered as a major Carlosruizite was found as -200 pm platy crystals in component in carlosruizite by X-ray spectroscopyin the samplesof iquiqueite, Na.KrMg(CrOo)BroOrr(OH)'l2H2O scanningelectron microscope (SEM). Subsequentanaly- (Ericksen et al., 1986), obtained by leaching caliche sesofseveral specimensofnitrate ore from scatteredlo- amarillo (yellow nitrate ore) from samplesin the Iquique calities in the Chilean nitrate fields showed them all to office of the former Servicio de Minas del Estadoof Chile, contain Se in amounts ranging from a few parts per mil- now the Servicio Nacional de Geologia y Mineria. The lion to nearly 50 ppm. field locality of these samplesis not precisely known but The new minerals are named for Humberto Fuenzalida probably is in the vicinity of Z,apiga,where caliche ama- P. (1904-1966)and Carlos Ruiz F. O. l9l6);both played ril/o is especiallyabundant. major roles in the 20th century development of geology Among the 25 speciesof saline minerals that have been in Chile. Ruiz planned and directed the first national geo- identified in the Chilean nitrate ores (Ericksen, 1993), I I logical institution (inauguratedin 1957), the Instituto de are known to be associatedwith the two new minerals InvestigacionesGeol6gicas, now the Servicio Nacional de reported here. Veins and veinlets containing fuenzalidaite Geologia y Mineria, which beganthe first systematicgeo- consist chiefly of a fine-grained mixture of nitratine logic mapping and study of mineral deposits in Chile. (NaNOr) and halite; tiny blebs of fibrous probertite Similarly, Fuenzalida planned and directed the first school [NaCaBrOr(OH)o. 3HrO] and platy darapskite[Nar(NOr)- of geology in Chile (inauguratedin 1958) at the Univer- (SO").HrO)l occur in cavities. The fractured bedrock in sity of Chile. The two new mineral speciesand names which these veins occur also contains abundant veinlets have been approved by the Commission on New Min- of anhydrite (CaSO"). The dense caliche amarillo con- erals and Mineral Names of the IMA. taining carlosruiziteconsists chiefly of a fine-grainedmix- 0003404x/94109I 0-l 003s02.00 1003 1004 KONNERT ET AL.: zuENZALIDAITE AND CARLOSRUIZITE Tlau 1. Crystallographicdata for fuenzalidaiteand carlosruizite Fuenzalidaite Carlosruizite Formula GMlNa6Mglo(XO1I2(lO3),r. 12HrO Cations M (Kr rNarr) (K14Na26) x (So*Seo*) (Seo sso $Cro,o) Formula weight 4225.8 4520.1 D* g/cmg 3.2U 3.400 Optical properties Color transparent,pale yellow Character uniaxial(-) uniaxial(-) Refractiveindices @ 1.622(5) 1.655(3) e 1.615(s) 1.6420) Crystallography Spacegroup PJcl P3,c1 Unitcell data a (A) 9.4643(4) 9.5901(8) c(A) 27.3it6(6) 27.s612) v(4.) 2120.s(41 2195.0) z 1 1 cla 2.888 2.877 Morphology thin, hexagonal plates {0001} bounded by {10T2} Structure analysis Diffractometer modified Picker automatic Radiation Nb-filteredMoKa (0.7107 A) Absorption coeff. tt (cm-1) 52 76 Crystd dim. (mm) 0.12x0.12x0.020 0.24x0.12x0.013 Range of 2d (") 4-40 4-50 ReflectionsMeasured 2078 3864 Independent 704 1325 For refinem. 520 691 Reliabilitytactors R 0.0&t 0.087 R* (1/o na) 0.043 0.053 Goodness of fit 1.76 1.86 ture of nitratine, halite, and darapskite. The residuesof Cnysr.qlr.ocRAprry AND srRUcruRE ANALysts leaching this material in cold water contain dietzeite Although the crystal morphology of both fuenzalidaite (IO,), (CrOo)], briiggenire . [Ca, [Ca(IO3), H,O], tarapa- and carlosruizite is rhombohedral, single-crystal X-ray caite (KrCrOo), lopezite (KrCrrOr), ulexite [NaCa- precessionphotography shows a primitive trigonal lat- B506(OH)6.5HrOl, probertite, and gypsum (CaSOo. tice. The two crystals are isomorphous, with the same 2H,O). flat, hexagonal habit (Fig. l) and very similar crystallo- graphic properties. The precessionpatterns show sym- pRopERTTES Prrysrclr- AND oprrcAr, metry and extinctions of the spacegroups P3cl or P3c; Fuenzalidaite and carlosruizite occur as thin, colorless the former centrosymmetric group (no. 165) was fully to pale yellow, transparent, euhedral, platy crystals with confirmed by the subsequent structure determination. hexagonal outline, generally <200 p,m in diameter and Unit-cell parameters (Table l) were refined from X-ray 20 pm thick. The crystals have a pseudorhombohedral powder data obtained with the Guinier-Hiigg focusing habit, flattenedon {0001} with bevelededges {10T2} (Fig. camera (Table 2). l). They are slowly soluble in HrO. Scanning electron Single-crystalintensity data for both crystals were col- micrographs(Fig. l) show that some crystalshave regular lected with a Krisel-modified Picker automated diffrac- fractures parallel to { I 1201that may mark cleavageplanes. tometer. After application of the usual corrections for Surfacesof some crystals show abundant round or elon- Lorentz-polarization and absorption (by Gaussianquad- gate cavities (Fig. lB), which probably were formerly filled rature) and normalization to ,E values, the -F data for with saline fluids. The crystalsare brittle and break easily carlosruizite were used for a structure analysis. At the into multiple fragments. Hardness could not be mea- outset, the chemical formula was unknown, but an X-ray sured, but to judge from the easeofbreaking, it is on the spectroscopictest in the SEM showed the presenceof I, order of 2-3. The luster is vitreous. S, K, Mg, Na, Cr, and even Se. Both minerals are uniaxial negative. Their refractive Starting with the Se-rich carlosruizite crystal, the first indices, measured with Na light by immersion on the E map derived from a Multan analysis at once revealed spindle stage,are given in Table l. Determined on the the position of the I atom. Subsequently,each of the con- basis of the structural formulas defined in Table I and stituent atoms (identified from electron density and co- the molar refractivities listed by Mandarino (1976), the ordination considerations),K, N4 Mg, and finally O, ap- Gladstone-Dale compatibility for fuenzalidaite is good, pearedin turn, in structure-factorelectron-density cycles, and for carlosruizite, fair (Mandarino, l98l). until the whole structure was clearly revealed.This pro- KONNERT ET AL.: FUENZALIDAITEAND CARLOSRUIZITE 1005 TABLE2. X-ray powder data for fuenzalidaiteand carlosruizite Fuenzalidaite Carlosruizite d*" (A) d*" (A) ilh d* (A) 4* (A) ah 002 13.67 13.67 50 13.79 13.75 30 102 7.03 7.05 40 7.11 7.10 20 104 5.249 5.254 4 s.303 111 4.663 4.665 13 4.724 113 4.200 4.200 3 4.251 200 4.098 4.099 I 4.153 202 3.926 3.927 100 3.976 3.974 16 204 3.515 3.515 24 3.557 3.561 100 210 3.098 3.099 16 3.139 211 3.078 3.078 I 3.119 3.112 3 206 3.047 3.048 I 3.080 3.082 32 212 3.021 l 3.023 41 sos' 39 117 3.012 | 3:3fl1) 214 2.822 2.822 4 2.857 2.860 2 2.756 0,0,10 2.734 ) 2.731 1 300 2.732 | 2.768 302 2.679 2.68',1 33 2.714 2.717 39 208 2.624 2.624 2 2.651 304 2.537 2.537 10 2.569 2.570 12 217 2.4270 2.4269 <1 2.454 220 2.3661 2.3665 2 2.398 222 2.3314 2.3273 21 2.362 2.361 14 223 2.2901 2.2905 6 2.320 2.323 4 311 2.2654 2.2654 9 2.2955 2.2948 5 312 2.2424 2.2434 2 2.2719 2.2713 4 224 2.2359 2.2348 <1 2.264'l 313 2.2056 2.2060 <1 2.2343 2.2378 2 219 2.1688 2.1691 <1 2.1919 314 2.1570 2.1575 I 2.1254 2.1256 2 308 2.1339 2.1329 1 2.1579 315 2.0990 2.0993 2 2.1254 2.1256 2 2,1,10 2.0497 2.0490 <1 2.O710 402 2.0264 2.0261 <1 2.0531 2.0543 4 2,0,'t2 1.9911 1.9957 1 2.OO97 404 1.9628 1.9634 2 1.9884 1.9879 4 320 1.8804 1.8802 3 1.9054 1.0925 1 406 1.8688 1.8692 2 1.8920 322 1.8628 1.8624 12 1.8869 1.8875 12 Fig.
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