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N.Jb.Miner.Mh. Jg.2002 (3) 117–127 Stuttgart, März 2002
Kanonerovite, MnNa3P3O10 · 12H2O, first
triphosphate mineral (Kazennitsa pegmatite,
Middle Urals, Russia)
V. I. Popova, V. A. Popov, Miass, E. V. Sokolova, Moscow, G. Ferraris,
Torino, N. V. Chukanov, Chernogolovka
With 3 figures and 2 tables
Popova, V. I., Popov, V. A., Sokolova, E. V., Ferraris, G. & Chukanov, N. V.
(2002): Kanonerovite, MnNa3P3O10 · 12H2O, first triphosphate mineral (Kazennitsa
pegmatite, Middle Urals, Russia). – N. Jb. Miner. Mh. 2002 (3): 117–127; Stutt-
gart.
Abstract: Kanonerovite, MnNa3P3O10 · 12H2O [a = 14.71(1) Å, b = 9.33(1) Å, c =
15.13(2) Å, b = 89.8(1)0, V = 2075(3) Å3, P21/n, Z = 4], is the first described triphos-
phate mineral. It has been found in the Kazennitsa pegmatite vein, the Alabashka
pegmatite field, Middle Urals, Russia. Associated minerals are quartz, albite, micro-
cline, muscovite, topaz, beryl, cassiterite, milarite. Kanonerovite occurs as tiny,
snow-white radial-platy aggregates on cassiterite, topaz, quartz and microcline. It is
transparent with a white streak and vitreous lustre and does not fluoresce under
long- or short-wave ultraviolet light. In transmitted light kanonerovite is colourless,
transparent, non-pleochroic; biaxial (– ), nearly parallel extinction (aÙc ~ 0–7Ê ); a
= 1.453(2), g = 1.459(2), b and 2V not measured because of the lamellar habit; bi-
refringence is 0.005 –0.006. Kanonerovite is brittle, Mohs hardness of 2.5–3; poor
010 cleavage. Dmeas 1.91(2) g/cm
3, Dcalc 1.90 g/cm
3. Strongest reflections in the
X-ray powder diffraction pattern [d(Å) (I), (hkl)]: 10.50(75)(101), 7.36(100) (200),
6.95(90)(111,–111), 3.316(60)(411,– 411,–123,321,– 321,313), 3.162(50)(214,– 214),
2.889(60)(420,124,032,421). Electron-microprobe analysis gives: Na2O 14.80, K2O
0.05, CaO 0.20, MgO 0.14, MnO 11.20, FeO 0.15, P2O5 35.23, H2O(calc.) 36.46,
sum 98.23 wt.%. Occurrence of the triphosphate group (P3O10) in kanonerovite is
shown by IR-data and the crystal structure of the synthetic equivalent compound.
The mineral is named for Kanonerov Aleksandr Anatol’evich (b. 1955).
Key words: kanonerovite, new mineral, triphosphate, Alabashka, Urals.
DOI: 10.1127/0028-3649/2002/2002-0117 0028-3649/02/2002-0117 $ 2.75
ã 2002 E. Schweizerbart’sche Verlagsbuchhandlung, D-70176 Stuttgart
118 V. I. Popova et al.
Introduction
Kanonerovite, MnNa3P3O10 · 12H2O, is a new mineral approved by the
Commission on New Minerals and Mineral Names (CNMMN) of IMA (In-
ternational Mineralogical Association). The mineral is named for Kanone-
rov Aleksandr Anatol’evich (b. 1955), mining historian (Nizhnii Tagil Mu-
seum of Mining Industry of the Middle Urals), who has been collecting
minerals all his life and who first collected samples of kanonerovite in
1995. In fact, the new mineral was firstly noted (Popov et al. 1996) during
an investigation of samples from Kanonerov’s private collection. Type ma-
terial is deposited at the Mineralogical Museum, Ilmen Natural Reserve,
Miass, Russia.
Kanonerovite is the first described example of a triphosphate mineral
and, after the pyrophosphates canaphite CaNa2P2O7 · 4H2O (Peacor et al.
1985, Rouse et al. 1988) and wooldridgeite Na2CaCu2+22(P2O7)2(H2O)10
(Hawthorne et al. 1999, Cooper & Hawthorne 1999), is the third occur-
rence of condensed phosphates as minerals.
Occurrence
Kanonerovite is of hydrothermal origin and occurs in the Kazennitsa peg-
matite vein, the Alabashka pegmatite field, Middle Urals, Russia (57Ê 47¢ N
and 61Ê 03¢ E). Associated minerals are quartz, albite, microcline, muscovite,
topaz, beryl, cassiterite and milarite.
The Kazennitsa pegmatite vein is confined to the central part of the Ala-
bashka pegmatite field, Middle Urals, on the right bank of the Alabashka
river, a small tributary of the Neiva river (Fig. 1a). On the whole, 44 peg-
matite veins are known for the Alabashka pegmatite field. Mining at the
Kazennitsa vein was set up at the end of the XVIII century mainly for beryl
and aquamarine. Even if not constantly continued, in 1938 the exploration
of the vein reached a depth of 10–14 m. In 1991–1993, a new exploration of
the vein proceeded to a depth of 30 m. In spite of its more than 200-year
history, the mineralogy of the Kazennitsa vein had never been described in
well known publications on the Urals mineralogy, e.g. Vertushkov (1954),
till recently (Rozhkov et al. 1991, Popov et al. 1996).
The Kazennitsa vein is about 150 m in length with thickness from 0.5 to
3m (Fig. 1b). It is a granite pegmatite of muscovite –albite–microcline type
and is localised in biotite granite–gneisses and porphyry granites. The vein
Kanonerovite 119
Fig. 1. The Kazennitsa vein (K): geographic position (a); schematic plan at a depth
of 20 m (b); cross-section of the southern part (c) showing the pegmatite zones 1, 2
and 3 (see text).
has three main zones (Fig. 1 c): an outer zone 0.3–0.6 m thick contains a
two-feldspar pegmatite with potassic feldspar, biotite and oligoclase; an in-
termediate zone 0.2 –0.7 m thick is built by a two-feldspar pegmatite with
microline, albite–oligoclase and biotite; a central pegmatoid blocky zone
120 V. I. Popova et al.
with big crystals of microcline, albite–oligoclase, quartz and muscovite.
The central zone of the vein contains more than 200 cavities ranging from
few centimetres up to 2–3 meters. In these cavities the following minerals
have been reported: muscovite, quartz, elbaite, topaz, milarite, calcite, cha-
bazite, stilbite – stellerite, rutile, fluorite, pyrrhotite, sphalerite, pyrite, and
kanonerovite, the only P-bearing mineral.
Appearance and physical properties
Kanonerovite occurs as thin white crust on quartz, topaz, and cassiterite
crystals. The crust consists of radial-lamellar cotton-like aggregates (0.1–
1.2 mm) composed by apparent individual monoclinic prismatic crystals
which are [001] elongated and 100 platy with dimensions of few tenths of
mm. Somewhere kanonerovite is covered by secondary fine-flake yellow-
ish-white muscovite and rare crystals of stellerite. Kanonerovite is transpar-
ent, colourless with a white streak and vitreous lustre, brittle; it shows Mohs
hardness 2.5 –3; poor 010 cleavage, no parting, uneven fracture; fluoresce
absent under long- or short-wave ultraviolet light. Dmeas 1.91(2)g/cm
3 was de-
termined by floatation in Clerici liquid, Dcalc 1.90 g/cm
3. It has been possible
to determine the morphology on a unique crystal (Fig. 2) which later went
lost: 100 , 001 , 010 , 023 , 423 and 210 forms were observed.
In transmitted light kanonerovite is colourless, transparent, non-pleo-
chroic. It is biaxial negative with nearly parallel extinction (aÙc ~ 0–7Ê ); a
= 1.453(2), g = 1.459(2); b and 2V were not measured because of the very
thin lamellar habit; birefringence is 0.005 –0.006; dispersion not observed.
Chemical data
Chemical analysis of kanonerovite was done by EMPA (JXA-733 electron
microprobe; Table 1). Eighteen points, six on each of three different grains,
were analysed. Standards were as follows: scapolite (Ca, Na, Mg), osumi-
lite (K), ilmenite (Mn, Fe), apatite (P). Kanonerovite is not soluble in water;
after dissolution in HNO3 it reacts with (NH4)2MoO4 giving evidence of
phosphorus. H2O has been detected by infrared spectroscopy (see ranges
3300 –3600 cm–1 and 1590–1700 cm–1 in Fig. 3); the scarcity of material did
not allow a direct measurement of the water content and its amount was
taken as 36.46 wt.% on comparison with the synthetic analogue (Rakoto-
mahanina et al. 1972, Lightfoot & Cheetham 1987). On the basis of 22
Kanonerovite 121
Fig. 2. Morphology of kanonerovite.
oxygen atoms per formula units (apfu) the following empirical chemical
formula for kanonerovite was obtained:
(Mn0.95Mg0.02Fe0.01)S 0.98(Na2.86Ca0.02K0.01)S 2.89P2.98O9.87 · 12.13H2O. The
ideal formula MnNa3P3O10 · 12H2O requires Na2O 15.68, MnO 11.96, P2O5
35.90 and H2O 36.46. The low analysed content of Na can be due to the vol-
atility of this element but also to the instability of the sample under the elec-
tron beam because of an easy loosing of water.
Infrared data
The infrared (IR) spectrum (Fig. 3) for kanonerovite was obtained by a Per-
kin Elmer Fourier spectrometer on a KBr pellet containing about 0.001 mg
of kanonerovite. The positions (cm–1) of the main absorption bands are as
122 V. I. Popova et al.
Table 1. Chemical composition of kanonerovite.
Oxide Wt.% Range Atom Apfu
Na2O 14.80 11.49 –16.33 Na 2.86
K2O 0.05 0.04 – 0.08 K 0.01
CaO 0.20 0.02 – 0.34 Ca 0.02
MgO 0.14 0.08 – 0.23 Mg 0.02
MnO 11.20 10.09 –11.60 Mn2+ 0.95
FeO 0.15 0.00 – 0.32 Fe2+ 0.01
P2O5 35.23 33.23 –36.37 P 2.98
H2Ocalc.* 36.46 H 24.26
Total 98.23 96.72 –99.74
* H2O calculated by comparison with the synthetic phosphate MnNa3P3O10·12H2O
(Rakotomahanina et al. 1972, Lightfoot & Cheetham 1987).
follows: 447.9, 519.7, 558.5, 668.0, 875.6, 908.5, 992.3, 1034.2, 1117.9,
1153.8, 1327.3, 1590.6, 1650.4, 3311.1, 3394.9, 3586.3.
The band corresponding to the P–O asymmetrical stretching vibrations
has its maximum at 1117.9 cm–1 and indicates condensation of P-tetrahedra
(Mel’nikova et al. 1985); for orthophosphates this maximum is usually lo-
calised in the 1020–1080 cm–1 range. The large splitting of the band corre-
sponding to the bending O–P–O-vibrations (558.5–668.0 cm–1) is also
characteristic for condensed (but not ortho-) phosphates. Furthermore, the
908 cm–1 band of symmetric stretching vibrations of PO4-tetrahedra is char-
acteristic for the condensed phosphates, while in orthophosphates this band
is shifted towards higher frequencies (~940 –960 cm–1).
X-ray crystallography
No single crystals of kanonerovite suitable for X-ray diffraction were avail-
able from the described cotton-like aggregates of very brittle material; as
mentioned above, a presumably unique crystal used for morphology deter-
mination went lost. An X-ray diffraction powder pattern (Table 2) has been
obtained by a 114.6 mm Debye-Scherrer camera (FeKa, l 1.9374 Å). Index-
ing was done by taking into account the diffraction intensities calculated
(SHELXL, Sheldrick 1981) by using the structural data of Lightfoot &
Kanonerovite 123
Table 2. X-ray diffraction powder pattern of kanonerovite [a 14.71(1), b 9.33(1), c
15.13(2)Å, b 89.8(1)Ê ] (I) and of synthetic phosphate MnNa3P3O10 · 12H2O (JCPDS
27-0753) (II); calculated data (III) are from the structure published by Lightfoot
& Cheetham (1987) [a 14.763(2), b 9.325(4), c 15.140(4)Å, b 89.87(2)Ê ].
I II III
Imeas. dmeas. dcalc. Imeas. Dmeas. Icalc. dcalc. h k l
75 10.50* 10.56 100 10.6 78 10.58 1 0 1
10.53 61 10.56 – 1 0 1
35 7.88* 7.94 5 7.93 29 7.94 0 1 1
100 7.36 7.35 45 7.37 79 7.38 2 0 0
90 6.95* 6.99 35 6.98 100 6.99 1 1 1
6.98 – 1 1 1
20 5.87 5.88 16 5.87 46 5.88 0 1 2
5 5.46 13 5.46 1 1 2
15 5.40 5.39 5 5.39 11 5.40 – 2 1 1
35 4.80* 4.78 20 4.77 10 4.78 1 0 3
4.77 17 4.77 – 1 0 3
10 4.65 4.66 7 4.67 13 4.66 0 2 0
6 4.59 9 4.60 2 1 2
9 4.59 – 2 1 2
10 4.44 4.44 11 4.43 27 4.45 1 2 0
4.44 9 4.44 0 1 3
4 4.17 9 4.18 – 3 1 1
25 3.97 3.97 11 3.97 41 3.97 0 2 2
3 3.81 6 3.83 – 1 2 2
5 3.82 2 2 1
20 3.76 3.77 10 3.77 16 3.78 3 1 2
6 3.77 – 3 1 2
45 3.50 3.52 50 3.52 13 3.53 – 3 0 3
3.51 29 3.52 – 3 0 3
3.50 11 3.50 2 2 2
20 3.42 3.42 20 3.43 0 2 3
3.41 11 3.42 1 1 4
60 3.316 3.338 25 3.34 11 3.348 4 1 1
3.334 47 3.345 – 4 1 1
3.333 20 3.335 – 1 2 3
3.299 20 3.30 17 3.304 3 2 1
3.296 10 3.302 – 3 2 1
3.294 12 3.299 3 1 3
124 V. I. Popova et al.
Table 2. Continued.
I II III
Imeas. dmeas. dcalc. Imeas. Dmeas. Icalc. dcalc. h k l
50 3.162 3.168 15 3.17 20 3.170 2 1 4
3.161 14 3.165 – 2 1 4
10 3.124 3.120 11 3.12 13 3.128 4 1 2
3.114 13 3.123 – 4 1 2
60 2.889 2.887 24 2.894 4 2 0
2.882 7 2.883 1 2 4
2.875 14 2.875 0 3 2
18 2.843 4 2 1
20 2.679 2.695 10 2.702 – 4 2 2
2.683 10 2.685 2 1 5
2,679 12 2.681 – 2 1 5
15 2.581 2.586 17 2.589 – 3 3 1
10 2.532 2.541 8 2.545 4 1 4
2.534 6 2.540 – 4 1 4
2.522 3 2.525 3 2 4
5 2.523 0 0 6
15 2.479 2.479 12 2.483 – 3 1 5
4 2.461 6 0 0
48 2.391 2.398 5 2.400 – 2 2 5
2.388 16 2.389 2 0 6
2.383 11 2.386 – 2 0 6
10 2.150 2.149 5 2.152 4 3 3
2.146 7 2.150 – 4 3 3
20 1.845 1.838 13 1.845 8 0 0
10 1.736 1.732 5 1.733 3 5 1
1.730 6 1 6
10 1.647 1.647 5 1.650 6 2 6
1.647 2 1.648 – 3 5 3
1.643 3 1.646 – 6 2 6
10 1.515 1.514 3 1.514 – 1 6 2
1.514 3 1.514 0. 0. 10
1.513 2 1.513 2 6 1
* Reflections not included in the refinement of cell parameters
Kanonerovite 125
Fig. 3. IR-spectrum of kanonerovite; ordinate and abscissa show transmittance and
wavenumbers (cm–1) respectively.
Cheetham (1987). The results presented in Table 2 clearly show that kano-
nerovite is the natural equivalent of synthetic MnNa3P3O10 · 12H2O. The re-
fined cell parameters are a 14.71(1) Å, b 9.33(1) Å, c 15.13(2) Å, b 89.8(1)0,
V 2075(3) Å3; a : b : c = 1.5766 :1:1.6217 to be compared with 1.571:1:1.620
obtained from morphological data; space group P21/n, Z 4. These values
well agree with those published by Rakotomahanina et al. (1972) (a and c
interchanged).
Conclusions
Availability of structural data published for synthetic MnNa3P3O10 · 12H2O
contributed to identify the first natural triphosphate approved by the
CNMMN with the name kanonerovite. The presence of condensed phos-
phate anions in kanonerovite is proved also by the IR spectrum. Rakoto-
mahanina et al. (1972) obtained several triphospates M2+Na3P3O10 · 12H2O
126 V. I. Popova et al.
(M = Ni, Co, Mn, Mg, Zn, Cd), at room temperature, by addition of a salt
of the cation M2+ to a solution of sodium triphosphate. This could indicate
that kanonerovite formed in the Kazennitsa vein under favourable chemical
conditions without particular pressure and temperature requirements.
Acknowledgements
Grateful thanks to the colleagues of the Ilmen Natural Reserve and Mineralogical
Institute, L. A. Pautov, P. V. Khvorov, E. I. Churin and N. I. Kashigina for their
help during this work; to A. A. Kanonerov, who provided a sample of kanonerov-
ite, to V. P. Demochkin, for useful information on the history of exploration of the
Kazennitsa vein. V.I.P. and V.A.P. benefited of grant 98-05-64565 from Russian
Fund for Basic Research and E.V.S. of a NATO Guest Fellowships grant by CNR
(Rome). G.F. acknowledge funds granted by MURST (40% projects) and CNR.
References
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Kanonerovite 127
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Received: July 24, 2001.
Author’s addresses:
V. I. Popova, V. A. Popov, Institute of Mineralogy, Ural Branch of Russian Acad-
emy of Sciences, Miass, Chelyabinsk Region, 456301 Russia.
e-mail: poppv@ilmeny.ac.ru.
E. V. Sokolova, Department of Crystallography and Crystal Chemistry, Faculty of
Geology, Moscow State University, Vorob’evy Gory, 199899 Moscow, Russia.
e-mail: sokolova@ms.umanitoba.ca.
G. Ferraris, (corresponding author): Dipartimento di Scienze Mineralogiche e Pe-
trologiche, Università di Torino, Via Valperga Caluso 35, 10125 Torino, Italy.
e-mail: ferraris@dsmp.unito.it.
N. V. Chukanov, Institute of Chemical Physics Problems, Russian Academy of
Sciences, Chernogolovka, Moscow Region 142432 Russia.
e-mail: chukanov@icp.ac.ru.


Kanonerovite, MnNa3P3O10.12H2O, first triphosphate mineral (Kazennitsa pegmatite, Middle Urals, Russia)

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Kanonerovite, MnNa3P3O10.12H2O, first triphosphate mineral (Kazennitsa pegmatite, Middle Urals, Russia)

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