MINERALOGICAL MAGAZINE, DECEMBER 1986, VOL. 50, PP. 687-91 Metavivianite and kerchenite" a review K. A. RODGERS Department of Geology, University of Auckland, Private Bag, Auckland, New Zealand ABSTRACT. Metavivianite has been shown to be not Sluys, 1971). Poullen interpreted his results as dimorphous with vivianite. Assuming the homogeneity showing that oxidation of monoclinic vivianite and uniformity of the original type samples, it is a triclinic resulted in a reduction of symmetry through pro- hydrated ferri-ferrous hydroxy phosphate whose formula duction of a ferri-ferrous hydroxy phosphate may be given as Fe~+xFe3+(po4)2(OH)x(8--x)H20 hydrate of the type where x > 1.4. The precise oxidation limits between which the triclinic lattice is stable are not known but the Fe23 + xVe3 + (POg)z(OH)x(8 - x)HzO structure persists close to total oxidation of all iron. The structure of metavivianite was established using a frag- assuming that compensation of the kind proposed ment of kerchenite whose formula as originally given is by Moore (1971) applied (and cf. Gamidov and covered by the general metavivianite formula. Assuming Mamedov, 1960). The X-ray diffraction signature of the homogeneity of the original (1907) samples,kerchenite this alteration product was that given by Ritz et al. and metavivianite appear to be identical. (1974) for metavivianite. Poullen (1979) noted, in KEYWORDS: metavivianite, vivianite, kerchenite. passing, that a similar alteration may occur in parasymplesite with partial oxidation producing a METAVIVIANITE is a triclinic iron phosphate mixed diffraction pattern containing prominent hydrate. It was first described by Ritz et al. (1974) reflections of triclinic symplesite. from the Big Chief pegmatite, South Dakota, In a series of papers, Chevalier et al. (1980), occurring as green crystals intimately intergrown Dormann and Poullen (1980), Fejdi et al. (1980), with kryzhanovskite in cavities in triphylite. These and Dormann et al. (1982) presented extensive authors adjudged the mineral to be dimorphous structural and chemical data in support of Poullen's with vivianite (Fe3(PO4)2 8H20) and isostructural conclusions. Many of these data were derived from with symplesite (Fe3(AsO4)2'8H20). These con- vivianite-metavivianite admixtures produced by clusions were reached on the basis of similarities in both artificial and natural oxidation of vivianite the X-ray diffraction patterns of metavivianite and and synthetic F%(POa)2 "8H20. While this in- symplesite and from direct electron microprobe formation is useful in defining the nature and limits comparison of the composition of metavivianite of the structural and compositional relationship with an unlocalized vivianite: 'metavivianite and that exists between vivianite and the redefined the vivianite are nearly identical in composition for metavivianite, it is data concerned with two meta- all elements with Z < 10 [sic] and therefore by vivianite samples identified as being mono- analogy with vivianite the formula of metavivianite mineralic that help characterize the ferri-ferrous is (Fe,Mn)3(PO4)2 8H20' (pp. 897-8). Regrettably, nature of the mineral. no separate analyses were reported for either The first of these was a specimen identified by Fe z +/Fe 3+ or water. Recent work has shown that Dormann and Poullen (1980, p. 634) as metavivian- the above conclusions are not correct and that ite from the Yukon, Canada, and containing MnO metavivianite is neither a ferrous phosphate nor an 2.83 ~, MgO 2.98 ~o, and CaO 0.72 ~. The M6ss- octahydrate and so cannot be dimorphous with bauer spectrum of this sample was interpreted as vivianite (e.g. Dormann et al., 1982; Rodgers and indicating a percentage occupancy of iron sites in Johnston, 1985). the lattice of Felz+ = 1~o, Fe 3+ = 32~o, Fei] += Crystal chemistry. For some years X-ray diffrac- 2~, Fed+= 65~, (Fe3+ = 49~, Fe3ff = 16~o), tion data for vivianites have been reported which where sites I and II are similar to and derived from include prominent reflections of metavivianite (e.g. those specified by Mori and Ito (1950) for their Poullen, 1979; Henderson et al., 1984; Sameshima model of the vivianite structure, and where Fel3+ et al., 1985) although such reflections may not have and Fei3+ are identified as distinct types of Fell + been recognized as coming from metavivianite (e.g. sites within metavivianite(cf. Dormann et al., 1982); Minato et al., 1956; Zwann and Kortenburg van der the hyperfine spectral parameters of Fei3i+ are Copyright the Mineralogical Society 688 K. A. RODGERS close to those ofFer While no formula was given by TABLE I, Chemical and structural data For metavivianite and Dormann and Poullen (1980) their data were kerchenite calculated by Rodgers and Johnston (1985) as Fe2+ Fe~.~(PO4)z(OH)2.95.1 H20. 1 2 3 4 5 The second sample came from Kamysch-Burun Fe2+/Fe3+ 0.613 0.034 0.176 0.321 0.319 (USSR) and was used by Dormann et al. (1982) to FeO 23.85 9.50 9.49 Fe 03 13.55 32.89 32.965 determine the precise nature of the metavivianite Ni~ D.13 MnO 4.Z 1.83 1.99 1.84 structure. 'Le cristal utilis6 pour l'6tude structurale MgO 2.98 1,54 1.56 est un fragment de clivage pr61ev6 sur un 6chantil- CaO 0,5 0,72 0.49 0.46 P 0 28.4 28.19 28.21 Ion... est conserve sous le nom de "kerchenite ~" H~O 5 25,04 24.91 mais se compose en r~alit6 de deux phases Total 99.64 99.435 min6rales, l'une monoclinique et l'autre triclinique' a~ 7,81 7.84 9.08 9.11 (p. 148). In their earlier study, Dormann and 4.65 4.67 s ~ 94.77 95.04 Poullen (1980) had been able to distinguish and 6 ~ 97.15 96.94 separate vivianite and metavivianite in similar yO 107.37 107.72 samples using a binocular microscope: 'Cette i. Type metavivlanite, Big Chief, South Dakota. Ritz et al (1974), operation fut relativement ais6e, les limites des Rodgers and Johnston (1985). 2. Metavivianite, Yukon. Darmann and Poullen (1980). domaines monocliniques et tricliniques &ant 3. Metavivianite, Bamysch-Burun. Dormannetel (1982). toujours tr6s nettement marqu6es' (p. 634). 4,5. Kerchenite, Ketch. Popoff (1907). Presumably, the same technique was used to select the fragment of metavivianite in the 1982 study. The M6ssbauer spectrum of this fragment showed the structure of vivianite as being maintained in the 85 % of the total iron was Fe 3+ which must yield a oxidation sequence until 40 % of the total iron had formula (as above) Fe0.asF%.~5(PO4)/(OH)2.ss2 + 3 + been oxidized, corresponding to a formula 5.4H10 (but cf. Dormann et al. (1982, p. 154) Fe~.~Fe3+(po4)z(OH)I.26.8HBO. although the formula given by them does not use a simple Fe z + ~ Fe 3 + + OH- compensation as its They stress that in the triclinic lattice the Fe~ site is basis of calculation and, further, there should be completely oxidized while 'Le taux d'oxydation du 3 Fe atoms with a valency of + 2.66 and not 1 as site II varie de 20 % environ, valeur inf6rieure fi celle they indicate). des vivianites monocliniques les plus oxyd6es Subsequently, Rodgers and Johnston (1985) re- jusqu'& pratiquement 100% (m&avivianite de investigated type metavivianite from Big Chief by Yukon). L'esp~ce triclinique admet donc des M6ssbauer spectroscopy. They obtained a formula teneurs en Fe 3 +allant de 50 % ~ 100 % du fer total, of FeH4FeLs6(PO4)z(OH)l.866.1HBO2+ 3+ in which (p. 637). Further, M6ssbauer spectral studies were 62% of the iron was Fe 3+, a considerably lower unable to distinguish triclinic phase, Fe3§ proportion than in either the Kamysch-Burun or specimens from disordered X-ray amorphous Yukon specimens. Composition and structural material. parameters of the above samples are summarized in Dormann et al. (1982) appeared to have qualified Table I. the above on the basis of combined M6ssbauer, Compositional ran#e. Both Dormann and Poullen structural and thermal studies. They summarized (1980) and Dormann et al. (1982) were primarily their findings for natural crystals as: concerned with examining the oxidation sequence (i) limits of oxidation of monoclinic lattice of vivianite. Structural changes occurring in the 0~<Fe 3 + <50%, 0~<Fe~ + ~<40%, sequence monoclinic vivianite~triclinic meta- 0 ~< Fet3ot+ ~< 47 %, vivianite ~ X-ray amorphous iron phosphate enabled them to attempt to define the composi- all iron being in the monoclinic phase only; tional limits within which the triclinic phase was the (ii) lower limits of oxidation for the triclinic preferred stable entity. Unfortunately, the results lattice to be stable obtained by artificially oxidized synthetic and Fe~]+ /> 20 25%, Fe 3+ = 100%, natural vivianites and naturally oxidized natural Fe3ot+ ~> 47-50%, vivianites are not in complete agreement. These difficulties have led to inconsistencies in inter- all iron being in the triclinic phase only. The preting oxidation data in earlier studies, e.g. percentages are for each lattice site or for the total Vochten et el. (1979), McCammon and Burns sites. The only observation these workers make (1980), Henderson et el. (1984), (and cf. Same- concerning the upper limit of oxidation is that the shima et al., 1985). disordered phase is not formed until all the iron has Dormann and Poullen (1980, p. 636) regarded been oxidized. METAVIVIANITE AND KERCHENITE 689 Rodgers and Johnston (1985) found that 8 ~o of Palache et al. (1951) placed the name under a iron in Fe I was unoxidized while, despite their 'Variety' heading within their section on vivianite assertion to the contrary, Dormann and Poullen and equated it with 'Oxidized Vivianite', noting (1980) reported that 3 ~o of iron in Fel was ferrous.