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Download the Scanned American Mineralogist, Volume 67, pages 3E5-393, 1982 Campigliaite, CuaMn(SO4)2(OH)6.4Id2O, a new mineral from Campiglia Marittima, Tuscany, Itaty I. Occurrenceand description Srrvro MeNcnerrr aNo Cesare Seseru cNR cento di studio'v;':';"0;,y'7,',3:;,r;i,';!Iy::";;ii per la Mineralogia e la Geochimica dei sedimenti Abstract Campigliaite, a new copper and manganesesulfate mineral, occurs as tufts of light blue crystals in the sulfide ore bodies of Temperino mine, campiglia Marittima, Tuscany, Italy. It is monoclinic,space group C2,with a : 21.707,0: 6.09g;c = I.245A,p : tOO.j..ftre tiny crystals, elongated[010] and flattened {100},are always twinned (100)-The calculated densityis3.06gcm-3.Opticallyitisbiaxiat(-)witho: i.589,p= 1.645,y= l.659.The strongest lines in the X-ray powder partern are 10.6g(100)(200),5.34 (60x400), 3.56 (,14X600),2.673(5)(022 and 800). The structure was solved using 689 independentreflections and refined to an R value of 0.124.The dominant structural feature is the arrangementof copper-oxygenpolyhedra into dense sheets, parallel to (100). The sulfate groups are linked Uy a to both sides of sheets. The Mn atom coordinates four water molecules and two oxygen"o*i. atoms of sulfate groups belongingto the sameCu-O-S layer. Subsequentlayers are connectedto each other by hydrogen bonds. The relationship between the structuies of campigliaite and devillite and serpierite is discussed. Introduction geology and ore deposits of the area is given in the In previous a paper (Conticini et al., l9g0) dealing above quoted paper, specially devoted to secondary with the alteration minerals from Campiglia Marit- minerals. The main tunnel of the third level of the tima (Tuscany, Italy) we briefly described a miner- "Miniera del Temperino" which goesfrom ,,pozzo al, a hydrated basic sulfate of copper and manga- Earle" to "Pozzo Gowet" crosses through sulfide nese, which appeared to be different from any ore bodies (chalcopyrite, pyrite, sphalerite, galena, known sulfate. Further study revealed the mineral pyrrhotite, e/c.). Starting from the point where the in question to be a new species. tunnel leaves the marbles and goes into the skarn, The mineral, CuaMn(SO4)2(OH)6.4H2O,is named many copper oxysalts appear in the order: mala- campigliaite for the locality. Both the mineral and chite, brochantite, antlerite, chalcanthite. This se- the name have been approved by the Commission quence is related to the increasing acidity of solu- on New Minerals and Mineral Names, IMA. A type tions and the increasing concentration of SOa. specimen is deposited in the mineralogicalMuseum Serpierite also is common and widespread in the of Florence University (regional collection #Zl4lI). tunnel. However the most common and widespread On the basis of the ideal formula, cell parameters secondary mineral is gypsum which occurs both as and crystal structure, campigliaite is related to the transparent crystals and as incrustations on other serpierite-devillite series"and,if one extra molecule minerals. It is interesting to note that when two or of H2O is neglected, it can be considered the more copper sulfates are present together, one can manganese analogueof devillite. observe antlerite often grown on brochantite and chalcanthite grown on antlerite Occurrence and paragenesis Campigliaite was found only on the vugs of an geographic The location of Campiglia Marittima ilvaite-rich skarn, collected in a side-tunnel (..gal- is depicted in Figure l. A brief account of the leria del fornello") of the main tunnel. It occurs as 0003-m4)v82t0304-03E5$02. 00 385 386 MENCHETTI AND SABELLI: CAMPIGLIAITE LiYorno o si.n" I Campiglia M. Grosseto Fig. 2. Scanningelectron photomicrographof tufts of campigliaite.Crystals are about0.2 mm long. Mns.ee(Cu3.ez, Zno sg)(SO4) r.78(OH)0.+a' 6. 55HzO on Fig. l. Location map of the Campiglia Marittiina mine, the basis of total metal : 5. Tuscany, Italy. A wet chemical analysis, attempted on a small amount of purified material (less than 1 mg) con- tufted aggregatesof tiny lath-like crystals (Fig. 2) of firmed the previous results for Mn, Cu and Zn a pale blue color, associated with gypsum and (atomic absorption spectrometry). Unfortunately us sometimes with small amounts of brochantite and the scarceness of available material did not allow antlerite. Often campigliaite and gypsum are closely to obtain reliable results for the SO4 content. A mixed; however campigliaite appears grown on TGA analysis, performed in order to obtain the HzO gypsum crystals (Fig. 3). The genesisof campig- content. was also unsuccessful. liaite is probably related to the sulfate solutions formed by the oxidation of pyrite and other sulfide minerals. The presence of manganesein campig- liaite is related to ilvaite. According to Rodolico (1931)ilvaite from Campigliahas 9.5% MnO which is a very high content for this mineral. ChemistrY Preliminary qualitative analyses of campigliaite, made with an oRTEcX-ray microanalyzer, revealed the presenceof Cu, Mn,Zn, S and no other element with atomic number greaterthan 11. Many quantita- tive analyses were carried out by means of an enr snuQ electron microprobe using chalcopyrite, sphalerite and hortonolite as standards.It is impor- tant to note that these analyses were done under unfavorable conditions, since campigliaite crystals are very tiny and decompose under the electron beam. The average values of the three best analy- ses, MnO 9.95, CuO 40.60,ZnO 4.47, SO320.15, Fig. 3 Scanning electron photomicrograph of crystals of HzO 24.83Vo (by difference), correspond to campigliaite grown on gypsum. Crystals are about 0.2 mm long. MENCHETTI AND SABELLI: CAMPIGLIAITE 387 The structural analysis yielded the formula Table 1. X-ray powder pattern of campigliaite Mn2*Cu*1SO4)2(OH)6.4H2O, where Cu : (Cu, Zn). This formula, which is somewhatdifferent from the hkl d (calc) d (obs) I/Io previous one, is supportedby the density calculated '10.678 from the Gladstone-Dale relationship. This ideal 200 10.68 100 formula requires 400 ].JJY 5.34 60 MnO I 0.50, CuO47 . I l, SO3 23 .7 l, -402 4.239 4.26 1 H2O 18.68Vo. -1 12 4.126 4.13 1 600 3.559 3.56 44 Campigliaite is slowly soluble in acetic acid with- out evident effervescence, -602 3.272 3.28 1 suggestingthe absence 004 2.766 2.768 of CO3. o22 2.670_ 800 z-ot.t 5 204 2.568 X-ray crystallography 2.570 -422 2.475 2.478 1 X-ray single crystal study (Weissenbergcamera 404 2.294 2.295 1 10 0 0 2.136 2.137 and single-crystal ditrractometer) 't.781 revealed all crys- 12 0 0 1.780 2 tals tested to be twinned with (100) as the twin -226 1 qo" 1.595 1 plane. Campigliaite is monoclinic with l_:auesym- 026 1.578 1.578 1 14 0 0 metry 2/m. Space groups consistent 4 E' A with the ob_ 040 i.;;i, served systematic extinctions are C2lm, Cm and C2, the latter being the one favored by the structur- al analysis. The X-ray powder diffraction pattern, given in mined by meansof a least-squarescalculation from Table 1, philips was obtained by meansof a diffrac- powder data are: a : 21.707(l),b : 6.098(2),g : tometer, with CoKa radiation, NaF as internal 11.245(r)4,F : 100.3(1)". standard, ll4" 20 per minute. Indexing was per- formed on the basis of lattice parameters deter- Physicalproperties and morphology mined on the single-crystal diffractometer and tak- Crystals of campigliaite are transparent and light ing into account the intensities of reflections blue in color with vitreous luster. The perfect collected for the structural study. In this powder cleavage {100} is fully explained by the structure. pattern only three reflections have relative intensi- The measured density, determined by the heavy- ties greater than 5. Moreover all three of these liquid method,reaches 3.0 g cm-3, but unfortunate- reflections belong to the /r00 series. This depends ly this is an uncertain datum; becauseof the small- on the crystal structure and on a strong enhance- ness of crystals, it was very difficult to determine ment of intensities due to a preferred orientation when the mineral was suspended in the liquid. caused by the {100} cleavage.Keeping this in mind Calculated figures for the density are 3.063 g cm-3 there is a similarity evident between the powder (normalized empirical formula with 7 HzO in total) patterns of campigliaite and serpierite and devillite and 3.060g cm-3 (Ghdstone-Dale law on the same (Faraoneet al.,1967). In the serpieriteand devillite formula using the data of Mandarino, 1976).If l0 patterns are many lines which are not present in the H2O are assumed, as directly derived from the campigliaite pattern; however the three stronger analysis, the value of "Gladstone-Dale" density lines (1100series) are closely related. A slight simi- drops to 2.93e cm-3. The densityvalues of serpiei- larity is also found with the pattern quoted by rcros ite and devillite are very close to that of campigliaite for the mineral woodwardite from Carnarvonshire. (Table 2) and thus support the chemical formula of Wales (card no. I7-l3Z). No other similarities can campigliaite derived from the structural analvsis. be found; actually the chemical formula of wood- Under the microscopel the mineral appeais in a wardite, which is a hydrated sulfate of Cu and Al, is pale greenish-blue color and without evident ple- uncertain, while lattice parameters, space group ochroism. It is biaxial negative with refractive indi- and crystal structure are unknown. According to cesc: 1.589,B: 1.645,y:1.659.
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