A possible new mineral species ferrogate
720
A POSSIBLE NEW MINERAL SPECIES, “FERROGATEHOUSEITE”
(Fe,Mg)5(PO4)2(OH)4 FROM CONTU PEGMATITE, ROMÂNIA
1906
IGR
1
2
2
1
1
2
N. CALIN , A-M. FRANSOLET , M. BAIJOT , S. MARINCEA , D-G. DUMITRAS , F. HATERT ,
1
1
M.A. ANASON , A.M. IANCU
1. Department INI, Geological Institute of Romania, 1 Caransebes Str. , RO-012271, Bucharest, Romania,
nicolae_cln@yahoo.com
2. Université de Liège, Laboratoire de Minéralogie, B18, Sart Tilman, 4000, Belgique.
phosphate
Gatehouseite, Mn5(PO4)2(OH)4, is a rare Mn-bearing
phosphate, since this mineral is only reported in a
sedimentary iron ore deposit in Australia (Pring and
Birch, 1993). Like in many Mn-bearing phosphates
structures, Fe may replace Mn and a complete solid
solution often exists between the Mn- and Fe-bearing
end-members. One more time, our work leads us to
consider the existence of an hypothetic new species,
“ferrogatehouseite”, which would be the iron
dominant equivalent species of gatehouseite.
quartz
phosphate
muscovite
muscovite
albite
feldspar
albite
quartz
feldspar
muscovite
quartz
muscovite
phosphate
phosphate
Hand specimens of pegmatites from Contu
During the research on the Li-bearing pegmatites from
Contu (Cibin Mountains, South Carpathians, Romania) a
rich phosphate association, including heterosite –
purpurite, lithiophilite – triphylite, sicklerite –
ferrisicklerite, fluorapatite, vivianite, monazite, wolfeite
was identified. Other associated minerals include
spodumene, quartz, muscovite, K-feldspar, plagioclase,
beryl, cassiterite, columbite group minerals, lepidolite,
rutile, scarce schorl, uraninite, topaz, spessartine,
sillimanite, titanite. Pegmatites from Contu are hosted
by micaschists and gneisses related to the Sebes - Lotru
Series.
0
50
1 = schists and muscovite-bearing gneisses;
2 = kyanite schists; 3 = staurolit schists;
4 = garnet-bearing schists;
5 = amphibolites, gneisses and schists;
6 = pegmatites quartzo-feldspathic;
7 = albite and spodumene-bearing pegmatites;
8 = graphic pegmatites.
100Km
Geological map of Romania
Table 5. Unit-cell parameter for heterosite
Sample
N 113
N 107 b
29 B
N 109
N 114 A
N 128
Ci_1d
Ce. 1C
Ce. 2D
N 129
N 122
N 120
Mean
Table 1. Unit-cell parameters for triphylite
Sample
a(Å)
b(Å)
c(Å)
23C1
4,719(1)
10,368(6)
6,035(5)
65CI
4,718(4)
10,366(3)
6,031(2)
9E
4,712(4)
10,379(6) 6,039(10)
29B
4,718(1)
10,378(3)
6,033(4)
Ci 1D
4,712(8)
10,375(7)
6,047(6)
Ci 1D1
4,713(7)
10,380(6)
6,038(7)
Mean
4,715(4)
10,374(5)
6,037(6)
Sabau et.al. (1990)
4,698(4)
10,365(5)
6,034(9)
Anderson et al. (2000) 4.6908(2) 10.3290(3) 6.0065(2)
Losey et al. (2004)
4,7138(6) 10,3826(1) 6,0499(5)
To achive this the goals of this work, a series of analytical
methods were used as follows:(1)optical study with Leica and
Jenapol-U polarizing microscopes; (2) X-ray powder diffraction
using a Bruker D8 Advance diffractometer (Ni-filtred Cu Ka
radiation, = 1.54060Å, accelerating voltage 40 Kv, beam
current 40 mA); (3) electron-microprobe analyses, using
CAMECA SX 50 device in wavelength-dispersive mode.
P2O5
FeO
MnO
MgO
CaO
Li2O
Total 1
Total 2
Triphylite
Phosphates belonging to the triphylite - lithiophilite series
generally occur as nests in the spodumene and feldspar
masses. They from granular masses of greenish gray
color that turns locally into dark or black, due to the
weathering. Both optical and scanning electron microscope
studies show that triphylite abundantly contains inclusions
of wolfeite and of a gatehouseite - like phase, the later
occurring on the (001) perfect cleavage plane of triphylite.
P2O5
FeO
MnO
MgO
CaO
Li2O
Total 1
Total 2
Triphylite
X-ray powder data were obtained on a representative sample
and indexed according to ICDD file 01-070-0516, belonging
to gatehouseite. These data allow the refinement of the
unit-cell parameters, in the space group P212121(19). The
refined parameters are: a = 9.103(3) Å, b = 18.019(6) Å and
c = 5.685(9) Å. The a and b parameters are slightly larger
while c is slightly smaller compared to those of gatehouseite,
given by Pring and Birch (1993), i.e., a = 9.097(2) Å,
b = 18.002(3) Å and c = 5.693(2) Å.
P
Fe2+
Mn
Mg
Ca
Li
Triphylite
P
Fe2+
Mn
Mg
Ca
Li
Sample
N 103
Ce 59
23C1
N 112
Mean
ICDD 00-033-0802
a(Å)
b(Å)
c(Å)
5,945(6)
5,941(7)
5,943(9)
5,945(4)
5,944(7)
5,946
10,076(8)
10,061(5)
10,056(8)
10,061(9)
10,064(8)
10,063
4,793(1)
4,791(8)
4,796(2)
4,797(7)
4,794(5)
4,793
Ferrisicklerite
9/c2
10/c2
11/c2
19/c4
20/c4 39/c12 40/c12
%
%
%
%
%
%
%
45.94
45.98
45.79
45.93
46.51
46.26
46.18
30.73
30.9
30.46
30.23
30.8
29.64
29.45
15.04
15.14
15.23
15.21
15.1
15.65
16
0.3
0.28
0.29
0.24
0.25
0.25
0.25
0.01
0.04
0.02
0.06
0.04
0.07
0.04
9.66
9.66
9.62
9.64
9.64
9.70
9.70
92.02
92.34
91.79
91.67
92.7
91.87
91.92
101.68 102.00 101.41 101.31 102.34 101.57 101.62
94/c9 159/c1 160/c1 161/c1 166/c1 167/c1 171/c1
%
%
%
%
%
%
%
46.14
46.11
46.11
46.07
45.31
46.59
46.12
30.88
29.29
29.29
29.32
26.38
26.75
26.45
15.31
16.82
16.82
16.6
19.47
19.37
19.26
0.29
0.14
0.14
0.14
0.06
0.07
0.06
0.04
0.04
0.04
0.03
0.05
0.03
0.03
9.69
9.68
9.69
9.68
9.51
9.79
9.69
92.66
92.4
92.4
92.16
91.27
92.81
91.92
102.35 102.08 102.09 101.84 100.78 102.60 101.61
9/c2
1PO4
1
0.660
0.327
0.011
0
0.999
10/c2
1PO4
1
0.663
0.329
0.010
0.001
0.998
11/c2
1PO4
1
0.657
0.332
0.011
0
0.998
19/c4
1PO4
1
0.65
0.331
0.009
0.001
0.997
20/c4
1PO4
1
0.654
0.324
0.009
0.001
0.998
39/c12
1PO4
1
0.633
0.338
0.009
0.001
0.995
40/c12
1PO4
1
0.63
0.346
0.009
0.001
0.997
94/c9
1PO4
1
0.660
0.332
0.011
0.001
0.998
159/c1
1PO4
1
0.627
0.364
0.005
0.001
0.998
160/c1
1PO4
1
0.627
0.364
0.005
0.001
0.998
161/c1
1PO4
1
0.628
0.360
0.005
0
0.998
166/c1
1PO4
1
0.575
0.429
0.002
0.001
0.997
167/c1
1PO4
1
0.567
0.416
0.002
0
0.998
171/c1
1PO4
1
0.566
0.419
0.002
0
0.998
P2O5
FeO
MnO
MgO
CaO
Li2O
Total 1
total 2
Ferrisicklerite
P2O5
FeO
MnO
MgO
CaO
Li2O
Total 1
total 2
42/c1
43/c1
47/c1
56/c3
57/c3
59/c3
60/c3
71/c6
%
%
%
%
%
%
%
%
44,67
43,95
43,28
45,14
44,54
43,98
42,87
41,79
30,00
31,03
30,17
30,69
30,94
30,9
31,68
32,11
18,83
18,78
19,61
18,36
18,49
18,73
19,36
19,72
0,10
0,11
0,1
0,1
0,11
0,11
0,11
0,11
0,52
0,37
0,66
0,28
0,29
0,36
0,46
0,53
9,13
9,06
8,76
9,35
9,22
9,07
8,78
8,52
94,12
94,24
93,82
94,57
94,37
94,08
94,48
94,26
103,25 103,30 102,58 103,92 103,59 103,15 103,26 102,78
72/c6
79/c7
81/c7 84/c10 125/c9 158/c1 174/c6 175/c6
%
%
%
%
%
%
%
%
45,13
43,3
44,14
44,31
42,93
45,21
43,66
42,56
30,65
31,13
30,39
30,77
30,15
29,76
29,42
30,12
18,58
18,96
18,71
18,65
19,77
17,74
19,71
20,04
0,09
0,12
0,12
0,1
0,09
0,15
0,08
0,06
0,25
0,74
0,44
0,38
0,27
0,79
0,42
0,53
9,37
8,72
9,20
9,13
8,89
9,10
8,97
8,68
94,7
94,25
93,8
94,21
93,21
93,65
93,29
93,31
104,07 102,97 103,00 103,34 102,10 102,75 102,26 101,99
Ferrisicklerite
P
Fe
Mn
Mg
Ca
Li
Ferrisicklerite
P
Fe
Mn
Mg
Ca
Li
42/c1
PO4
1
0,663
0,421
0,003
0,014
0,970
43/c1
PO4
1
0,697
0,427
0,004
0,010
0,978
47/c1
PO4
1
0,688
0,453
0,003
0,019
0,961
56/c3
PO4
1
0,671
0,406
0,003
0,007
0,984
57/c3
PO4
1
0,687
0,415
0,004
0,008
0,983
59/c3
PO4
1
0,693
0,426
0,004
0,010
0,979
60/c3
PO4
1
0,729
0,451
0,004
0,013
0,973
71/c6
PO4
1
0,758
0,472
0,004
0,015
0,968
72/c6
PO4
1
0,670
0,411
0,003
0,006
0,986
79/c7
PO4
1
0,710
0,438
0,004
0,021
0,957
81/c7
PO4
1
0,679
0,424
0,004
0,004
0,990
84/c10
PO4
1
0,685
0,421
0,003
0,010
0,978
125/c9
PO4
1
0,693
0,460
0,003
0,007
0,984
158/c1
PO4
1
0,650
0,392
0,005
0,021
0,956
174/c6
PO4
1
0,665
0,451
0,003
0,012
0,975
175/c6
PO4
1
0,699
0,471
0,002
0,015
0,968
a(Å)
b(Å)
c(Å)
9,100(7) 17,992(9) 5,702(8)
9,098(3) 18,017(3) 5,688(2)
9,103(3) 18,019(6) 5,685(9)
9,110
18,032
5,692
9,097(2)
18,002
5,693(2)
P2O5
Fe2O3
Mn2O3
MgO
CaO
Total
Heterosite
P2O5
Fe2O3
Mn2O3
MgO
CaO
Total
Heterosite
P
Fe3+
Mn3+
Mg
Ca
Heterosite
P
Fe3+
Mn3+
Mg
Ca
44/c1
%
46,65
33,09
20,33
0,11
0,23
100,41
45/c1
%
45,42
33,16
20,58
0,08
0,33
99,578
48/c1
%
46,75
31,95
19,99
0,12
0,38
99,19
58/c3
%
46,85
32,70
19,90
0,11
0,28
99,85
61/c3
%
46,87
32,76
20,018
0,07
0,23
99,95
62/c3
%
46,79
33,47
19,38
0,10
0,35
100,09
63/c3
%
47,19
33,17
20,10
0,07
0,18
100,72
64/c3
%
47
33,18
19,70
0,08
0,17
100,14
65/c3
%
46,14
33,16
20,60
0,06
0,27
100,24
70/c6
%
46,25
32,69
19,52
0,1
0,53
99,10
74/c7
%
47,08
32,24
19,49
0,09
0,59
99,49
75/c7
%
47,42
32,72
19,50
0,09
0,42
100,16
76/c7
%
46,21
32,26
19,18
0,08
0,52
98,25
77/c7
%
47,69
33,15
19,57
0,09
0,16
100,66
78/c7
%
47,17
32,58
19,38
0,09
0,29
99,51
80/c7
%
47,22
33,36
19,85
0,09
0,14
100,66
83/c10
%
46,27
34,61
19,72
0,09
0,14
100,84
149/c1
%
44,95
31,49
19,55
0,14
2,01
98,14
153/c1
%
45,63
32,35
18,90
0,12
0,58
97,58
44/c1
1PO4
1
0,630
0,391
0,004
0,006
45/c1
1PO4
1
0,649
0,407
0,003
0,009
48/c1
1PO4
1
0,607
0,384
0,004
0,010
58/c3
1PO4
1
0,620
0,381
0,004
0,007
61/c3
1PO4
1
0,595
0,368
0,002
0,005
62/c3
1PO4
1
0,635
0,372
0,003
0,009
63/c3
1PO4
1
0,624
0,383
0,002
0,004
64/c3
1PO4
1
0,627
0,377
0,003
0,004
65/c3
1PO4
1
0,638
0,401
0,002
0,007
70/c6
1PO4
1
0,628
0,379
0,003
0,014
74/c7
1PO4
1
0,608
0,372
0,003
0,015
75/c7
1PO4
1
0,613
0,369
0,003
0,011
76/c7
1PO4
1
0,620
0,373
0,003
0,014
77/c7
1PO4
1
0,617
0,368
0,003
0,004
78/c7
1PO4
1
0,614
80/c7
1PO4
1
0,627
83/c10
1PO4
1
0,665
149/c1
1PO4
1
0,622
153/c1
1PO4
1
0,630
13/c4
14/c4
15/c4
16/c4
17/c4
18/c4
120/c6
121/c6
122/c6
124/c6
Ca0,009 (Fe3,083 Mn1,855 Mg0,021)4,959 (PO4)2 (OH)4
Ca0,004 (Fe2,877 Mn2,030 Mg0,053)4,960 (PO4)2 (OH)4
(Fe2,793 Mn2,117 Mg0,055)4,965 (PO4)2 (OH)4
Ca0,0018 (Fe2,9631 Mn1,9575 Mg0,0355)4,9562 (PO4)2 (OH)4
Ca0,0034 (Fe2,7353 Mn1,7171 Mg0,0424)4,4949 (PO4)2 (OH)4
(Fe2,9897 Mn1,9335 Mg0,0237)4,9470 (PO4)2 (OH)4
Ca0,0047 (Fe3,7168 Mn1,2523 Mg0,0265)4,9956 (PO4)2 (OH)4
Ca0,0028 (Fe3,6019 Mn1,3550 Mg0,0247)4,9818 (PO4)2 (OH)4
Ca0,0009 (Fe3,5570 Mn1,3776 Mg0,0382)4,9730 (PO4)2 (OH)4
Ca0,0018 (Fe3,5819 Mn1,3569 Mg0,0250)4,9640 (PO4)2 (OH)4
te
l eri
Table 9. Representative electron-microprobe analysis of ferrogatehouseite
(FeMn)5(PO4)2(OH)4
albite
fe rr
k
isic
albite
c(Å)
4.765(4)
4.773(6)
4.768(9)
4.770(3)
4.777(2)
4.772(3)
4.783(6)
4.773(2)
4.773(2)
4.776(2)
4.773(6)
4.782(8)
4.774(4)
Table 8. Chemical structural formulas of
ferrogatehouseite
k
isic
albite
Heterosite
Table 7. Unit-cell parameters for gatehouseite
f err
Electron-microprobe analyses of this mineral, identified as iron-rich
gatehouseite (sample 14/c4), yielded (in wt.% oxides): P2O5 = 26.76, FeO
albite
= 38.97, MnO = 27.15, MgO = 0.41, CaO = 0.05, H2O (calculated for charge
balance) = 6.79, total =100.13. The crystal-chemical formula which
results from this composition is: (Fe2.877Mn2.030Mg0.053Ca0.004)(PO4)2(OH)4,
which is related to the one of gatehouseite but with Fe > Mn. Chemical
analyses on two other samples yielded similar empiric formulae, i.e.,
(Fe3.083Mn1.855Mg0.021Ca0.009)(PO4)2(OH)4 and (Fe2.735Mn1.717Mg0.042Ca0.003)
ferrisicklerite
(PO4)2(OH)4 (samples 13/c4 and 17/c4, respectively).
P2O5
Fe2O3
Mn2O3
MgO
CaO
Total
P
Fe3+
albite
ferrisicklerite
Heterosite
Heterosite
Sample
23 C1
10 C
Ci 58 F
ICDD 01-070-0516
Pring and Birch (1993)
b(Å)
9.765(5)
9.749(4)
9.757(8)
9.756(6)
9.748(1)
9.718(7)
9.758(3)
9.742(4)
9.778(6)
9.811(9)
9.775(2)
9.763(1)
9.76(5)
Table 6. Representative electron-microprobe
analysis of heterosite
Table 4. Representative electron-microprobe
analysis of ferrisicklerite
Table 2. Representative electron-microprobe
analysis of triphylite
Triphylite
Table 3. Unit-cell parameters for ferrisicklerite
a(Å)
5.841(9)
5.829(2)
5.837(4)
5.835(3)
5.824(3)
5.833(6)
5.810(5)
5.810(4)
5.844(5)
5.857(1)
5.824(9)
5.821(3)
5.830(5)
te
l eri
Further investigations by FTIR and micro-Raman are needed to acquire
albite
more details about the H2O content of this potential ferrous homologue
of gatehouseite. The petrographic texture indicates that
“ferrogatehouseite” as well as wolfeite, partially replaced triphylite
Photomicrograph of ferrisicklerite in
along its cleavage plane during the hydrothermal stage.
association with feldspars. Plane polarized
13/c4
14/c4
15/c4
16/c4
17/c4
18/c4
120/c6
121/c6
122/c6
124/c6
%
%
%
%
%
%
%
%
%
%
P2O5
26,6
26,76
26,81
26,73
29,05
26,69
26,54
26,58
26,71
26,69
FeO
41,51
38,97
37,91
40,09
40,22
40,39
49,93
48,46
48,09
48,39
MnO
24,66
27,15
28,37
26,15
24,93
25,79
16,61
18
18,39
18,1
MgO
0,16
0,41
0,42
0,27
0,35
0,18
0,2
0,187
0,29
0,19
CaO
0,1
0,05
0
0,02
0,04
0
0,05
0,03
0,01
0,02
H2O
6,75
6,79
6,80
6,78
7,37
6,77
6,73
6,74
6,77
6,77
Total 1
93,03
93,34
93,51
93,26
94,59
93,05
93,33
93,26
93,49
93,39
total 2
99,78
100,13
100,31
100,04
101,96
99,82
100,06
100,00
100,27
100,16
2PO4
2PO4
2PO4
2PO4
2PO4
2PO4
2PO4
2PO4
2PO4
2PO4
P
2
2
2
2
2
2
2
2
2
2
Fe
3,083
2,877
2,793
2,963
2,735
2,989
3,716
3,601
3,557
3,581
Mn
1,855
2,030
2,117
1,957
1,717
1,933
1,252
1,355
1,377
1,356
Mg
0,021
0,053
0,055
0,035
0,042
0,023
0,026
0,024
0,038
0,025
Ca
0,009
0,004
0
0,001
0,003
0
0,004
0,002
0,000
0,001
H2O
4
4
4
4
4
4
4
4
4
4
light. Crossed nicols.
triphylite
triphylite
triphylite
triphylite
“ferrogatehouseite”
ferrogatehouseite
ferrogatehouseite
“ferrogatehouseite”
Photomicrograph of triphylite sample with inclusion of
ferrogatehouseite. Plane polarized light. Crossed nicols.
Back-scattered image
of ferrogatehouseite in triphylite.
Photomicrograph of ferrogatehouseite
( 30 µm in length, 20µm in width) on cleavage .
References:
ANDERSSON, A. S., KALSKA, B., HÄGGSTRÖM, L. and THOMAS, J. O. (2000): Lithium extraction/insertion in LiFePO4:
An X – ray diffraction and Mössbauer spectroscopy study. Solid State Ionics, 130, 41 – 52.
LOSEY, A., RAKOVAN, J. and HUGHES, J. M., FRANCIS, C. A., DYAR, M. D. (2004): Structural variation in the
lithiophilite – triphylite series and other olivine group structures. The Canadian Mineralogist, Vol. 42, pp.
1105 – 1115.
PRING, A., AND BIRCH, W. D. (1993): Gatehouseite, a new manganese hydroxy phosphate from Iron Monarch,
South Australia. Mineral. Mag., 57, 309 – 313.
SABAU, G., ILINCA, G., MARINCEA, S., ROBU, L. (1990): Evaluation of the lithium potential of the Romanian
pegmatites and of the possibilities of use. I. South Carpathians (Cibin Mountains). Unpubl. Report,
Geological Institute of Romania, 65 pp.
Acknowledgements
This research was supported by the Executive Agency for Higer Education, Research,
Development and inovation Funding (UEFISCDI), Ministry of National Education in Romania,
through the projects IDEI PN-II-ID-PCE-2013-3-0023 and ERA-MIN PT 339, 25.03.2014.
ferrisicklerite
heterosite
quartz
heterosite
ferrisicklerite
Photomicrograph showing the association ferrisicklerite - heterosite - quartz.
Heterosite has an obvious pleochroism in tints of mauve and yellow, whereas ferrisicklerite has more
evident pleochroism in tents.
A POSSIBLE NEW MINERAL SPECIES, “FERROGATEHOUSEITE”
(Fe,Mg)5(PO4)2(OH)4 FROM CONTU PEGMATITE, ROMÂNIA
1906
IGR
1
2
2
1
1
2
N. CALIN , A-M. FRANSOLET , M. BAIJOT , S. MARINCEA , D-G. DUMITRAS , F. HATERT ,
1
1
M.A. ANASON , A.M. IANCU
1. Department INI, Geological Institute of Romania, 1 Caransebes Str. , RO-012271, Bucharest, Romania,
nicolae_cln@yahoo.com
2. Université de Liège, Laboratoire de Minéralogie, B18, Sart Tilman, 4000, Belgique.
phosphate
Gatehouseite, Mn5(PO4)2(OH)4, is a rare Mn-bearing
phosphate, since this mineral is only reported in a
sedimentary iron ore deposit in Australia (Pring and
Birch, 1993). Like in many Mn-bearing phosphates
structures, Fe may replace Mn and a complete solid
solution often exists between the Mn- and Fe-bearing
end-members. One more time, our work leads us to
consider the existence of an hypothetic new species,
“ferrogatehouseite”, which would be the iron
dominant equivalent species of gatehouseite.
quartz
phosphate
muscovite
muscovite
albite
feldspar
albite
quartz
feldspar
muscovite
quartz
muscovite
phosphate
phosphate
Hand specimens of pegmatites from Contu
During the research on the Li-bearing pegmatites from
Contu (Cibin Mountains, South Carpathians, Romania) a
rich phosphate association, including heterosite –
purpurite, lithiophilite – triphylite, sicklerite –
ferrisicklerite, fluorapatite, vivianite, monazite, wolfeite
was identified. Other associated minerals include
spodumene, quartz, muscovite, K-feldspar, plagioclase,
beryl, cassiterite, columbite group minerals, lepidolite,
rutile, scarce schorl, uraninite, topaz, spessartine,
sillimanite, titanite. Pegmatites from Contu are hosted
by micaschists and gneisses related to the Sebes - Lotru
Series.
0
50
1 = schists and muscovite-bearing gneisses;
2 = kyanite schists; 3 = staurolit schists;
4 = garnet-bearing schists;
5 = amphibolites, gneisses and schists;
6 = pegmatites quartzo-feldspathic;
7 = albite and spodumene-bearing pegmatites;
8 = graphic pegmatites.
100Km
Geological map of Romania
Table 5. Unit-cell parameter for heterosite
Sample
N 113
N 107 b
29 B
N 109
N 114 A
N 128
Ci_1d
Ce. 1C
Ce. 2D
N 129
N 122
N 120
Mean
Table 1. Unit-cell parameters for triphylite
Sample
a(Å)
b(Å)
c(Å)
23C1
4,719(1)
10,368(6)
6,035(5)
65CI
4,718(4)
10,366(3)
6,031(2)
9E
4,712(4)
10,379(6) 6,039(10)
29B
4,718(1)
10,378(3)
6,033(4)
Ci 1D
4,712(8)
10,375(7)
6,047(6)
Ci 1D1
4,713(7)
10,380(6)
6,038(7)
Mean
4,715(4)
10,374(5)
6,037(6)
Sabau et.al. (1990)
4,698(4)
10,365(5)
6,034(9)
Anderson et al. (2000) 4.6908(2) 10.3290(3) 6.0065(2)
Losey et al. (2004)
4,7138(6) 10,3826(1) 6,0499(5)
To achive this the goals of this work, a series of analytical
methods were used as follows:(1)optical study with Leica and
Jenapol-U polarizing microscopes; (2) X-ray powder diffraction
using a Bruker D8 Advance diffractometer (Ni-filtred Cu Ka
radiation, = 1.54060Å, accelerating voltage 40 Kv, beam
current 40 mA); (3) electron-microprobe analyses, using
CAMECA SX 50 device in wavelength-dispersive mode.
P2O5
FeO
MnO
MgO
CaO
Li2O
Total 1
Total 2
Triphylite
Phosphates belonging to the triphylite - lithiophilite series
generally occur as nests in the spodumene and feldspar
masses. They from granular masses of greenish gray
color that turns locally into dark or black, due to the
weathering. Both optical and scanning electron microscope
studies show that triphylite abundantly contains inclusions
of wolfeite and of a gatehouseite - like phase, the later
occurring on the (001) perfect cleavage plane of triphylite.
P2O5
FeO
MnO
MgO
CaO
Li2O
Total 1
Total 2
Triphylite
X-ray powder data were obtained on a representative sample
and indexed according to ICDD file 01-070-0516, belonging
to gatehouseite. These data allow the refinement of the
unit-cell parameters, in the space group P212121(19). The
refined parameters are: a = 9.103(3) Å, b = 18.019(6) Å and
c = 5.685(9) Å. The a and b parameters are slightly larger
while c is slightly smaller compared to those of gatehouseite,
given by Pring and Birch (1993), i.e., a = 9.097(2) Å,
b = 18.002(3) Å and c = 5.693(2) Å.
P
Fe2+
Mn
Mg
Ca
Li
Triphylite
P
Fe2+
Mn
Mg
Ca
Li
Sample
N 103
Ce 59
23C1
N 112
Mean
ICDD 00-033-0802
a(Å)
b(Å)
c(Å)
5,945(6)
5,941(7)
5,943(9)
5,945(4)
5,944(7)
5,946
10,076(8)
10,061(5)
10,056(8)
10,061(9)
10,064(8)
10,063
4,793(1)
4,791(8)
4,796(2)
4,797(7)
4,794(5)
4,793
Ferrisicklerite
9/c2
10/c2
11/c2
19/c4
20/c4 39/c12 40/c12
%
%
%
%
%
%
%
45.94
45.98
45.79
45.93
46.51
46.26
46.18
30.73
30.9
30.46
30.23
30.8
29.64
29.45
15.04
15.14
15.23
15.21
15.1
15.65
16
0.3
0.28
0.29
0.24
0.25
0.25
0.25
0.01
0.04
0.02
0.06
0.04
0.07
0.04
9.66
9.66
9.62
9.64
9.64
9.70
9.70
92.02
92.34
91.79
91.67
92.7
91.87
91.92
101.68 102.00 101.41 101.31 102.34 101.57 101.62
94/c9 159/c1 160/c1 161/c1 166/c1 167/c1 171/c1
%
%
%
%
%
%
%
46.14
46.11
46.11
46.07
45.31
46.59
46.12
30.88
29.29
29.29
29.32
26.38
26.75
26.45
15.31
16.82
16.82
16.6
19.47
19.37
19.26
0.29
0.14
0.14
0.14
0.06
0.07
0.06
0.04
0.04
0.04
0.03
0.05
0.03
0.03
9.69
9.68
9.69
9.68
9.51
9.79
9.69
92.66
92.4
92.4
92.16
91.27
92.81
91.92
102.35 102.08 102.09 101.84 100.78 102.60 101.61
9/c2
1PO4
1
0.660
0.327
0.011
0
0.999
10/c2
1PO4
1
0.663
0.329
0.010
0.001
0.998
11/c2
1PO4
1
0.657
0.332
0.011
0
0.998
19/c4
1PO4
1
0.65
0.331
0.009
0.001
0.997
20/c4
1PO4
1
0.654
0.324
0.009
0.001
0.998
39/c12
1PO4
1
0.633
0.338
0.009
0.001
0.995
40/c12
1PO4
1
0.63
0.346
0.009
0.001
0.997
94/c9
1PO4
1
0.660
0.332
0.011
0.001
0.998
159/c1
1PO4
1
0.627
0.364
0.005
0.001
0.998
160/c1
1PO4
1
0.627
0.364
0.005
0.001
0.998
161/c1
1PO4
1
0.628
0.360
0.005
0
0.998
166/c1
1PO4
1
0.575
0.429
0.002
0.001
0.997
167/c1
1PO4
1
0.567
0.416
0.002
0
0.998
171/c1
1PO4
1
0.566
0.419
0.002
0
0.998
P2O5
FeO
MnO
MgO
CaO
Li2O
Total 1
total 2
Ferrisicklerite
P2O5
FeO
MnO
MgO
CaO
Li2O
Total 1
total 2
42/c1
43/c1
47/c1
56/c3
57/c3
59/c3
60/c3
71/c6
%
%
%
%
%
%
%
%
44,67
43,95
43,28
45,14
44,54
43,98
42,87
41,79
30,00
31,03
30,17
30,69
30,94
30,9
31,68
32,11
18,83
18,78
19,61
18,36
18,49
18,73
19,36
19,72
0,10
0,11
0,1
0,1
0,11
0,11
0,11
0,11
0,52
0,37
0,66
0,28
0,29
0,36
0,46
0,53
9,13
9,06
8,76
9,35
9,22
9,07
8,78
8,52
94,12
94,24
93,82
94,57
94,37
94,08
94,48
94,26
103,25 103,30 102,58 103,92 103,59 103,15 103,26 102,78
72/c6
79/c7
81/c7 84/c10 125/c9 158/c1 174/c6 175/c6
%
%
%
%
%
%
%
%
45,13
43,3
44,14
44,31
42,93
45,21
43,66
42,56
30,65
31,13
30,39
30,77
30,15
29,76
29,42
30,12
18,58
18,96
18,71
18,65
19,77
17,74
19,71
20,04
0,09
0,12
0,12
0,1
0,09
0,15
0,08
0,06
0,25
0,74
0,44
0,38
0,27
0,79
0,42
0,53
9,37
8,72
9,20
9,13
8,89
9,10
8,97
8,68
94,7
94,25
93,8
94,21
93,21
93,65
93,29
93,31
104,07 102,97 103,00 103,34 102,10 102,75 102,26 101,99
Ferrisicklerite
P
Fe
Mn
Mg
Ca
Li
Ferrisicklerite
P
Fe
Mn
Mg
Ca
Li
42/c1
PO4
1
0,663
0,421
0,003
0,014
0,970
43/c1
PO4
1
0,697
0,427
0,004
0,010
0,978
47/c1
PO4
1
0,688
0,453
0,003
0,019
0,961
56/c3
PO4
1
0,671
0,406
0,003
0,007
0,984
57/c3
PO4
1
0,687
0,415
0,004
0,008
0,983
59/c3
PO4
1
0,693
0,426
0,004
0,010
0,979
60/c3
PO4
1
0,729
0,451
0,004
0,013
0,973
71/c6
PO4
1
0,758
0,472
0,004
0,015
0,968
72/c6
PO4
1
0,670
0,411
0,003
0,006
0,986
79/c7
PO4
1
0,710
0,438
0,004
0,021
0,957
81/c7
PO4
1
0,679
0,424
0,004
0,004
0,990
84/c10
PO4
1
0,685
0,421
0,003
0,010
0,978
125/c9
PO4
1
0,693
0,460
0,003
0,007
0,984
158/c1
PO4
1
0,650
0,392
0,005
0,021
0,956
174/c6
PO4
1
0,665
0,451
0,003
0,012
0,975
175/c6
PO4
1
0,699
0,471
0,002
0,015
0,968
a(Å)
b(Å)
c(Å)
9,100(7) 17,992(9) 5,702(8)
9,098(3) 18,017(3) 5,688(2)
9,103(3) 18,019(6) 5,685(9)
9,110
18,032
5,692
9,097(2)
18,002
5,693(2)
P2O5
Fe2O3
Mn2O3
MgO
CaO
Total
Heterosite
P2O5
Fe2O3
Mn2O3
MgO
CaO
Total
Heterosite
P
Fe3+
Mn3+
Mg
Ca
Heterosite
P
Fe3+
Mn3+
Mg
Ca
44/c1
%
46,65
33,09
20,33
0,11
0,23
100,41
45/c1
%
45,42
33,16
20,58
0,08
0,33
99,578
48/c1
%
46,75
31,95
19,99
0,12
0,38
99,19
58/c3
%
46,85
32,70
19,90
0,11
0,28
99,85
61/c3
%
46,87
32,76
20,018
0,07
0,23
99,95
62/c3
%
46,79
33,47
19,38
0,10
0,35
100,09
63/c3
%
47,19
33,17
20,10
0,07
0,18
100,72
64/c3
%
47
33,18
19,70
0,08
0,17
100,14
65/c3
%
46,14
33,16
20,60
0,06
0,27
100,24
70/c6
%
46,25
32,69
19,52
0,1
0,53
99,10
74/c7
%
47,08
32,24
19,49
0,09
0,59
99,49
75/c7
%
47,42
32,72
19,50
0,09
0,42
100,16
76/c7
%
46,21
32,26
19,18
0,08
0,52
98,25
77/c7
%
47,69
33,15
19,57
0,09
0,16
100,66
78/c7
%
47,17
32,58
19,38
0,09
0,29
99,51
80/c7
%
47,22
33,36
19,85
0,09
0,14
100,66
83/c10
%
46,27
34,61
19,72
0,09
0,14
100,84
149/c1
%
44,95
31,49
19,55
0,14
2,01
98,14
153/c1
%
45,63
32,35
18,90
0,12
0,58
97,58
44/c1
1PO4
1
0,630
0,391
0,004
0,006
45/c1
1PO4
1
0,649
0,407
0,003
0,009
48/c1
1PO4
1
0,607
0,384
0,004
0,010
58/c3
1PO4
1
0,620
0,381
0,004
0,007
61/c3
1PO4
1
0,595
0,368
0,002
0,005
62/c3
1PO4
1
0,635
0,372
0,003
0,009
63/c3
1PO4
1
0,624
0,383
0,002
0,004
64/c3
1PO4
1
0,627
0,377
0,003
0,004
65/c3
1PO4
1
0,638
0,401
0,002
0,007
70/c6
1PO4
1
0,628
0,379
0,003
0,014
74/c7
1PO4
1
0,608
0,372
0,003
0,015
75/c7
1PO4
1
0,613
0,369
0,003
0,011
76/c7
1PO4
1
0,620
0,373
0,003
0,014
77/c7
1PO4
1
0,617
0,368
0,003
0,004
78/c7
1PO4
1
0,614
80/c7
1PO4
1
0,627
83/c10
1PO4
1
0,665
149/c1
1PO4
1
0,622
153/c1
1PO4
1
0,630
13/c4
14/c4
15/c4
16/c4
17/c4
18/c4
120/c6
121/c6
122/c6
124/c6
Ca0,009 (Fe3,083 Mn1,855 Mg0,021)4,959 (PO4)2 (OH)4
Ca0,004 (Fe2,877 Mn2,030 Mg0,053)4,960 (PO4)2 (OH)4
(Fe2,793 Mn2,117 Mg0,055)4,965 (PO4)2 (OH)4
Ca0,0018 (Fe2,9631 Mn1,9575 Mg0,0355)4,9562 (PO4)2 (OH)4
Ca0,0034 (Fe2,7353 Mn1,7171 Mg0,0424)4,4949 (PO4)2 (OH)4
(Fe2,9897 Mn1,9335 Mg0,0237)4,9470 (PO4)2 (OH)4
Ca0,0047 (Fe3,7168 Mn1,2523 Mg0,0265)4,9956 (PO4)2 (OH)4
Ca0,0028 (Fe3,6019 Mn1,3550 Mg0,0247)4,9818 (PO4)2 (OH)4
Ca0,0009 (Fe3,5570 Mn1,3776 Mg0,0382)4,9730 (PO4)2 (OH)4
Ca0,0018 (Fe3,5819 Mn1,3569 Mg0,0250)4,9640 (PO4)2 (OH)4
te
l eri
Table 9. Representative electron-microprobe analysis of ferrogatehouseite
(FeMn)5(PO4)2(OH)4
albite
fe rr
k
isic
albite
c(Å)
4.765(4)
4.773(6)
4.768(9)
4.770(3)
4.777(2)
4.772(3)
4.783(6)
4.773(2)
4.773(2)
4.776(2)
4.773(6)
4.782(8)
4.774(4)
Table 8. Chemical structural formulas of
ferrogatehouseite
k
isic
albite
Heterosite
Table 7. Unit-cell parameters for gatehouseite
f err
Electron-microprobe analyses of this mineral, identified as iron-rich
gatehouseite (sample 14/c4), yielded (in wt.% oxides): P2O5 = 26.76, FeO
albite
= 38.97, MnO = 27.15, MgO = 0.41, CaO = 0.05, H2O (calculated for charge
balance) = 6.79, total =100.13. The crystal-chemical formula which
results from this composition is: (Fe2.877Mn2.030Mg0.053Ca0.004)(PO4)2(OH)4,
which is related to the one of gatehouseite but with Fe > Mn. Chemical
analyses on two other samples yielded similar empiric formulae, i.e.,
(Fe3.083Mn1.855Mg0.021Ca0.009)(PO4)2(OH)4 and (Fe2.735Mn1.717Mg0.042Ca0.003)
ferrisicklerite
(PO4)2(OH)4 (samples 13/c4 and 17/c4, respectively).
P2O5
Fe2O3
Mn2O3
MgO
CaO
Total
P
Fe3+
albite
ferrisicklerite
Heterosite
Heterosite
Sample
23 C1
10 C
Ci 58 F
ICDD 01-070-0516
Pring and Birch (1993)
b(Å)
9.765(5)
9.749(4)
9.757(8)
9.756(6)
9.748(1)
9.718(7)
9.758(3)
9.742(4)
9.778(6)
9.811(9)
9.775(2)
9.763(1)
9.76(5)
Table 6. Representative electron-microprobe
analysis of heterosite
Table 4. Representative electron-microprobe
analysis of ferrisicklerite
Table 2. Representative electron-microprobe
analysis of triphylite
Triphylite
Table 3. Unit-cell parameters for ferrisicklerite
a(Å)
5.841(9)
5.829(2)
5.837(4)
5.835(3)
5.824(3)
5.833(6)
5.810(5)
5.810(4)
5.844(5)
5.857(1)
5.824(9)
5.821(3)
5.830(5)
te
l eri
Further investigations by FTIR and micro-Raman are needed to acquire
albite
more details about the H2O content of this potential ferrous homologue
of gatehouseite. The petrographic texture indicates that
“ferrogatehouseite” as well as wolfeite, partially replaced triphylite
Photomicrograph of ferrisicklerite in
along its cleavage plane during the hydrothermal stage.
association with feldspars. Plane polarized
13/c4
14/c4
15/c4
16/c4
17/c4
18/c4
120/c6
121/c6
122/c6
124/c6
%
%
%
%
%
%
%
%
%
%
P2O5
26,6
26,76
26,81
26,73
29,05
26,69
26,54
26,58
26,71
26,69
FeO
41,51
38,97
37,91
40,09
40,22
40,39
49,93
48,46
48,09
48,39
MnO
24,66
27,15
28,37
26,15
24,93
25,79
16,61
18
18,39
18,1
MgO
0,16
0,41
0,42
0,27
0,35
0,18
0,2
0,187
0,29
0,19
CaO
0,1
0,05
0
0,02
0,04
0
0,05
0,03
0,01
0,02
H2O
6,75
6,79
6,80
6,78
7,37
6,77
6,73
6,74
6,77
6,77
Total 1
93,03
93,34
93,51
93,26
94,59
93,05
93,33
93,26
93,49
93,39
total 2
99,78
100,13
100,31
100,04
101,96
99,82
100,06
100,00
100,27
100,16
2PO4
2PO4
2PO4
2PO4
2PO4
2PO4
2PO4
2PO4
2PO4
2PO4
P
2
2
2
2
2
2
2
2
2
2
Fe
3,083
2,877
2,793
2,963
2,735
2,989
3,716
3,601
3,557
3,581
Mn
1,855
2,030
2,117
1,957
1,717
1,933
1,252
1,355
1,377
1,356
Mg
0,021
0,053
0,055
0,035
0,042
0,023
0,026
0,024
0,038
0,025
Ca
0,009
0,004
0
0,001
0,003
0
0,004
0,002
0,000
0,001
H2O
4
4
4
4
4
4
4
4
4
4
light. Crossed nicols.
triphylite
triphylite
triphylite
triphylite
“ferrogatehouseite”
ferrogatehouseite
ferrogatehouseite
“ferrogatehouseite”
Photomicrograph of triphylite sample with inclusion of
ferrogatehouseite. Plane polarized light. Crossed nicols.
Back-scattered image
of ferrogatehouseite in triphylite.
Photomicrograph of ferrogatehouseite
( 30 µm in length, 20µm in width) on cleavage .
References:
ANDERSSON, A. S., KALSKA, B., HÄGGSTRÖM, L. and THOMAS, J. O. (2000): Lithium extraction/insertion in LiFePO4:
An X – ray diffraction and Mössbauer spectroscopy study. Solid State Ionics, 130, 41 – 52.
LOSEY, A., RAKOVAN, J. and HUGHES, J. M., FRANCIS, C. A., DYAR, M. D. (2004): Structural variation in the
lithiophilite – triphylite series and other olivine group structures. The Canadian Mineralogist, Vol. 42, pp.
1105 – 1115.
PRING, A., AND BIRCH, W. D. (1993): Gatehouseite, a new manganese hydroxy phosphate from Iron Monarch,
South Australia. Mineral. Mag., 57, 309 – 313.
SABAU, G., ILINCA, G., MARINCEA, S., ROBU, L. (1990): Evaluation of the lithium potential of the Romanian
pegmatites and of the possibilities of use. I. South Carpathians (Cibin Mountains). Unpubl. Report,
Geological Institute of Romania, 65 pp.
Acknowledgements
This research was supported by the Executive Agency for Higer Education, Research,
Development and inovation Funding (UEFISCDI), Ministry of National Education in Romania,
through the projects IDEI PN-II-ID-PCE-2013-3-0023 and ERA-MIN PT 339, 25.03.2014.
ferrisicklerite
heterosite
quartz
heterosite
ferrisicklerite
Photomicrograph showing the association ferrisicklerite - heterosite - quartz.
Heterosite has an obvious pleochroism in tints of mauve and yellow, whereas ferrisicklerite has more
evident pleochroism in tents.