345

The Canadian Mineralogist

Vol. 53, pp. 345-356 (2015)
DOI: 10.3749/canmin.1400068

Mn-BEARING HELLANDITE-(Y) FROM THE HEFTETJERN PEGMATITE,

TRDAL, NORWAY

RITSURO MIYAWAKI, KOICHI MOMMA, KAZUMI YOKOYAMA, MASAKO SHIGEOKA, AND

SATOSHI MATSUBARA
Department of Geology and Paleontology, National Museum of Nature and Science, 4-1-1, Amakubo,
Tsukuba 305-0005, Japan

MIKU ITO AND IZUMI NAKAI

Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku, Tokyo 162-8601, Japan

ROY KRISTIANSEN
PO Box 32, N-1650 Sellebakk, Norway

ABSTRACT

Mn-bearing hellandite-(Y) occurs as pinkish yellow granular crystals (up to sub mm) in the Sc-rich granite pegmatite at
Heftetjern, Trdal, Telemark, Norway. Associated minerals are quartz, albite, Sc- and Ce-bearing epidote, hingganite-(Y), and
an undetermined Ca-bearing hingganite-related mineral. Electron microprobe analyses give an empirical formula as
Ca1.34Mn1.07Y2.75Ce0.02Nd0.02Sm0.01Gd0.01Dy0.05Er0.05Yb0.15Al0.94Fe0.08Si3.99B4.33O22.00(OH)2.00 on the basis of Al+Fe+Si =
5 and 24 anions per formula unit. The lattice parameters were refined from diffraction data obtained using a Gandolfi camera
with an imaging plate and Ni filtered CuK; a 18.693(17), b 4.651(3), c 10.178(7) , = 111.37(6), V 824.1(10) 3. The
crystal structure was refined from single-crystal XRD data obtained with a CCD-diffractometer and graphite-monochromated
MoK. The refinement with anisotropic atomic displacement parameters converged to R1 = 0.0269 for 1567 reflections [I >
2(I)] and 0.0318 for all 1768 reflections, resulting in the structural formula M3(Ca0.56Mn0.44)2M4(Y0.43
Ca0.23Ln0.14 0.20)2M 2(Y0.94Ln0.06)2M1(Al0.92Fe0.08)Si4B4O21.21(OH)2.79. In this hellandite-(Y), Mn2+ replaces Ca2+ at the M3
site and there is a significant vacancy at the M4 site. The T site is vacant, and, instead, the O5 position is occupied by (OH).

Keywords: hellandite-(Y), borosilicate, manganese, Heftetjern, Norway.

INTRODUCTION (at the X and Y sites) and Al octahedra (the Z site)

to form a three-dimensional structure. Mazzi et al.
Hellandite-(Y) is the premier member of the hel- (1979) pointed out that filling the vacant site tetra-
landite group, which consists of borosilicate minerals hedrally surrounded by 4 O atoms between the
having the general formula (Oberti et al. 2002), chains would transform the chain structure into a
X4Y2ZT2Si4B4O22W2 or M32M42M22M1T2Si4B4O22 sheet structure related to semenovite-(Ce) and gadol-
(OH,F,O)2, where X = M3 + M4; M3 = Ca2+, Y3+; inite. The additional tetrahedrally coordinated site
M4 = Na+, Ca2+, Y3+, Ln3+ (lanthanoids, LaLu); Y = (T) is occupied by Be and/or Li; partially in hellan-
M2 = Y3+, Ln3+, Th4+, U4+, Ca2+; Z = M1 = Mg, Al3+, dite-(Y) (Oberti et al. 1999) and considerably in
Fe3+, Mn3+, Ti4+; T = Li+, Be2+, (vacancy), (H). mottanaite-(Ce) (Della Ventura et al. 2002). A vari-
The distinguishing feature of the crystal structure of ety of isomorphous substitutions are observed in
hellandite-(Y) is B4Si4O22 chains of five-membered hellandite-(Y). Cations Th4+, U4+, and Na+ substi-
Si- and B-tetrahedra (Mellini & Merlino 1977). The tute for the essential constituents of hellandite-(Y),
chains are connected by eight-coordinated polyhedra REE3+ and Ca2+, at the X and Y sites. The REE3+/
of Ca and rare earth elements (REE: Y + Ln) Ca2+ ratio varies from the ideal ratio of hellandite-

Corresponding author e-mail address: miyawaki@[Link]

346 Mn-BEARING HELLANDITE-(Y) FROM THE HEFTETJERN PEGMATITE

has been reported as a minor constituent of hellan-

dite-(Y), e.g., with only 0.41 wt.% MnO in
Norwegian material (Oftedal 1965), 0.58 wt.% in
Canadian material (Hogarth et al. 1972), and
0.70 wt.% in an Italian sample (Mellini & Merlino
1977). Mellini & Merlino (1977) described the
minor Mn (less than 0.1 apfu) as the divalent
(Mn2+) substituent for Ca2+ in hellandite-(Y). On
the other hand, Oberti et al. (1999) and Della
Ventura et al. (2002) considered the slight amounts
of Mn (not greater than 0.02 apfu) to be trivalent
(Mn3+) substituting for Al3+ at the Z (M1) site in
hellandite-(Y) and ciprianiite.
Here, we describe Mn-bearing (greater than 1
apfu) hellandite-(Y) occurring as tiny pinkish yellow
granular crystals (Fig. 1) in the Sc-rich granite peg-
matite at Heftetjern, Trdal, Telemark, Norway.
FIG. 1. A photomicrograph of Mn-bearing hellandite-(Y).
OCCURRENCE AND GEOLOGICAL BACKGROUND
(Y) and hellandite-(Ce) (3/3) towards those of tadz-
hikite-(Ce) (2/4) and mottanaite-(Ce) (1/5). The Heftetjern cleavelandite-amazonite pegmatite
Replacements of Al3+ by Fe3+, Ti4+, and Mg2+ are (Bergstl & Juve 1988, Juve & Bergstl 1990) is
usually observed in hellandite-(Y). The charge bal- situated in a marshy area between Hydalen and
ance for substitutions between heterovalent cations Skarsfjell in Trdal, Telemark county, southern
is maintained by coupled substitutions to form solid Norway, at an altitude of ~650 m above sea level, at
solutions with complex chemistry. Tadzhikite-(Ce) 598.6 N, 845.4 E (Fig. 2). A striking geochemical
(Chernitsova et al. 1982), ciprianiite, and motta- feature of the Heftetjern pegmatite is the high level of
naite-(Ce) (Della Ventura et al. 2002) are the other Sc. Beryllium, Y, Sn, and Ta are also characteristic
endmembers of solid solution series, and are inde- elements. The mineralogy and geochemistry of the
pendent species in the hellandite group. Manganese Heftetjern pegmatite have been reported and

FIG. 2. Regional geological sketch-maps of Heftetjern, Trdal, Telemark, Norway, reproduced after Segalstad & Raade (2003).
Stippled lines separate zones with pegmatites dominated by green amazonite, white K-feldspar, and pink K-feldspar.
 THE CANADIAN MINERALOGIST 347

TABLE 1. CHEMICAL COMPOSITION OF Mn-BEARING HELLANDITE-(Y)

wt.% 1 2 3 4 5 6 mean s.d. Tahara** Predazzo*** Wakefield****

Al2O3 4.78 4.73 4.96 4.92 4.88 4.85 4.85 0.08 3.82 3.04 3.42
Fe2O3 0.54 0.62 0.69 0.60 0.70 0.59 0.62 0.06 0.45 3.77 1.70
TiO2 0 0 0 0 0 0 0 0.85 <0.2 0.117
Mn2O3 0.478
CaO 7.62 7.79 7.64 7.66 7.65 7.56 7.65 0.07 16.64 15.22 12.74
SrO 0 0 0 0 0 0 0 0.059
MnO 7.72 7.65 7.72 7.78 7.61 7.78 7.71 0.06 0.92 0.70
Y2O3 31.85 31.86 30.77 30.94 32.17 32.02 31.60 0.54 21.58 18.07 28.11
La2O3 0.08 0 0.01 0 0.13 0 0.04 0.05 0 16.0 0.113
Ce2O3 0.44 0.24 0.31 0.31 0.13 0.33 0.29 0.09 1.10 0.133
Pr2O3 0 0 0 0 0 0 0 0 0.162
Nd2O3 0.37 0.36 0.37 0.41 0.34 0.40 0.37 0.02 2.09 1.90
Sm2O3 0.16 0.22 0.23 0.31 0.18 0.39 0.25 0.08 1.10 1.89
Eu2O3 0 0 0 0 0 0 0 0 0.092
Gd2O3 0.39 0.08 0.25 0.15 0.24 0.02 0.19 0.12 1.49 3.23
Dy2O3 0.81 0.94 0.78 1.29 0.88 0.70 0.90 0.19 1.97 3.56
Ho2O3 0 0 0 0 0 0 0 0.58
Er2O3 1.00 0.92 0.73 1.14 0.82 0.95 0.93 0.13 1.32 2.42
Yb2O3 2.88 3.05 2.74 3.38 2.83 3.06 2.99 0.21 1.50 1.96
ThO2 0 0 0.15 0.17 0 0.24 0.09 0.10 0 0.885
UO2 0 0 0 0 0 0 0 0 0.130
SiO2 24.55 24.51 24.46 24.27 24.05 24.27 24.35 0.17 24.84 25.57 22.25
B2O3 15.97 16.12 15.53 14.06 15.81 14.45 15.32 0.78 14.39 14.85 12.88
BeO 0.041
Li2O 0.003
H2O 1.28c 1.14c 2.20c 2.78c 1.25c 2.31c 1.83c 3.62c 4.50c 1.40
F 0 0 0 0 0 0 0 0.216
O=F 0.091
Total 100.44 100.23 99.54 100.17 99.67 99.92 99.98 98.26 99.74
apfu 1 2 3 4 5 6 Mean
Al 0.92 0.91 0.95 0.95 0.95 0.94 0.94 0.73 0.56 0.712
Fe 0.07 0.08 0.08 0.07 0.09 0.07 0.08 0.06 0.45 0.226
Ti 0 0 0 0 0 0 0 0.11 <0.03 0.016
Mn 0.021
AlFe 0.99 0.99 1.03 1.02 1.04 1.01 1.01 0.90 1.04 0.975
Ca 1.33 1.37 1.33 1.34 1.35 1.33 1.34 2.88 2.55 2.412
Sr 0 0 0 0 0 0 0 0.002
Mn 1.07 1.06 1.06 1.08 1.06 1.08 1.07 0.13 0.09
CaMn 2.40 2.43 2.39 2.42 2.41 2.41 2.41 3.01 2.64 2.414
Y 2.77 2.77 2.66 2.70 2.82 2.80 2.75 1.85 1.51 2.640
La 0.00 0 0.00 0 0.01 0 0.00 0 0.78 0.007
Ce 0.03 0.01 0.02 0.02 0.01 0.02 0.02 0.55 0.009
Pr 0 0 0 0 0 0 0 0 0.010
Nd 0.02 0.02 0.02 0.02 0.02 0.02 0.02 1.05 0.120
Sm 0.01 0.01 0.01 0.02 0.01 0.02 0.01 0.06 0.115
Eu 0 0 0 0 0 0 0 0 0.006
Gd 0.02 0.00 0.01 0.01 0.01 0.00 0.01 0.08 0.189
Dy 0.04 0.05 0.04 0.07 0.05 0.04 0.05 0.11 0.203
Ho 0 0 0 0 0 0 0 0.03
Er 0.05 0.05 0.04 0.06 0.04 0.05 0.05 0.07 0.135
Yb 0.14 0.15 0.14 0.17 0.14 0.15 0.15 0.08 0.105
348 Mn-BEARING HELLANDITE-(Y) FROM THE HEFTETJERN PEGMATITE

TABLE 1. (CONTINUED)

wt.% 1 2 3 4 5 6 mean s.d. Tahara** Predazzo*** Wakefield****

Th 0 0 0.01 0.01 0 0.01 0.00 0 0.036

U 0 0 0 0 0 0 0 0 0.005
REE 3.08 3.06 2.95 3.08 3.11 3.11 3.06 2.45 2.29 3.580
Si 4.01 4.01 3.97 3.98 3.96 3.99 3.99 4 4 3.933
B 4.51 4.55 4.35 3.98 4.50 4.10 4.33 4 4 3.930
Be 0.017
Li 0.002
H 1.39 1.25 2.38 3.04 1.37 2.54 2.00 3.89 2.34 1.647
F 0 0 0 0 0 0 0 0.121
*
Present study. **Miyawaki et al. (1987). ***Mellini & Merlino (1977). ****Oberti et al. (2002).

Under the detection limit, <0.1 wt.% for F and <0.01 wt.% for the others. Total Ln, lanthanoids, LaLu.
c
Calculated.

discussed on several occasions (Raade et al. 2002, cassiterite are the most common Li- and Sn-minerals,
Cooper et al. 2006, Lussier et al. 2009, Kristiansen respectively.
2009, Kolitsch et al. 2010). The numerous granite The Heftetjern pegmatite is famous for its unique
pegmatites of the Trdal area are situated within the assemblage of Sc-minerals and Sc-bearing minerals,
Nissedal volcano-sedimentary outlier. Both the outlier such as the new species kristiansenite (Raade et al.
(13001200 Ma) and the older basement gneiss 2002), oftedalite (Cooper et al. 2006), and heftetjernite
(15201500 Ma) are intruded by the Trdal granite (Kolitsch et al. 2010), as well as bazzite (Juve &
(960850 Ma), which is regarded as the source of the Bergstl 1990), scandiobabingtonite and cascandite
pegmatite swarms (Bergstl & Juve 1988). The Rb-Sr (Raade & Erambert 1999), and thortveitite (Kristiansen
dating of lepidolite and microcline from the Skarsfjell 2009); the latter is also intimately intergrown with three
pegmatite gave ages between 950 and 880 Ma of the former (Raade et al. 2004). According to the
(Neumann 1960), but Kulp et al. (1963) estimated the classification of ern (1992), the Trdal pegmatites
age to be closer to 1000 Ma. From trace-element ana- are of mixed LCT-NYF (Li, Cs, Ta - Nb, Y, F) affinity.
lyses of different rock types it has been suggested
that some of the tin and a major part of the scandium
CHEMICAL COMPOSITION
in the cleavelandite-amazonite pegmatites of the area
probably have their source in the volcanogenic rocks
The chemical composition was determined by
of the Nissedal outlier, which were penetrated by the
means of a JEOL 8800M electron microprobe analy-
pegmatitic fluids (Bergstl & Juve 1988). The Trdal
zer (WDS mode, 15 kV, 20 nA, and 2 m beam dia-
area in Telemark is geochemically different from the
meter) employing standard materials as follows;
other granite pegmatite areas in south Norway, being
wollastonite for Ca and Si, rhodonite for Mn, silli-
characterized by tin, scandium, yttrium, beryllium,
manite for Al, fayalite for Fe, danburite for B,
and lithium. The cleavelandite-amazonite pegmatites
REEP5O14 for each rare earth element (Y and lantha-
at the nearby Hydalen and at Skarsfjell were
noids, LaLu), ThO2 for Th, and UO2 for U. The
described by Oftedal (1942). Here, zinnwaldite and
BK analytical line was monochromatized by the
LDE2 layered dispersion element on the spectrometer.
No other element with atomic number 5, except for
C from carbon coating and O as a constituent, was
detected. The results of chemical analyses with ZAF
corrections for six points within the fragment used for
the Gandolfi X-ray diffraction investigation are given
together with the mean values in Table 1. A few sets
of chemical data for Mn-bearing hellandite-(Y) from
the literature are also given for comparison. The
empirical formula derived from the mean data is
Ca1.34Mn1.07Y2.75Ce0.02Nd0.02Sm0.01Gd0.01Dy0.05Er0.05
Yb0.15Al0.94Fe0.08Si3.99B4.33O22.00(OH)2.00 on the basis
of Al + Fe + Si = 5 and 24 anions per formula unit.
FIG. 3. Chondrite-normalized lanthanoid distribution patterns Oberti et al. (2002) pointed out that the hellandite
of Mn-bearing hellandite-(Y). group minerals show an almost constant 4 Si and 4 B
 THE CANADIAN MINERALOGIST 349

TABLE 2. POWDER X-RAY DIFFRACTION DATA FOR THE Mn-BEARING HELLANDITE-(Y)

Heftetjern Tahara Miyawaki Predazzo Mellini &

Present Study et al. (1987) Merlino (1977)

I /I0 dmeas dcalc h k l I d Icalc dcalc

2 9.50 9.44 0 0 1
2 8.73 8.66 2 0 0 vw 8.60 13 8.84
5 8.03 8.01 2 0 1
10 5.48 5.46 2 0 1 w 5.49 9 5.57
10 5.00 4.98 2 0 2 vw 5.03 1 5.06
60 4.66 4.63 0 1 0 s 4.69 43 4.72
3 4.53 4.56 3 0 2
5 4.23 4.20 1 1 1 1 4.27
11 4.11 4.08 2 1 0 m 4.12 24 4.16
6 4.04 4.01 2 1 1
3 3.68 3.67 3 1 1 3 3.73
3 3.64 3.62 2 0 2 1 3.69
4 3.55 3.53 2 1 1
21 3.50 3.48 4 0 1 w 3.53 13 3.55
66 3.41 3.39 2 1 2 s 3.42 74 3.45
7 3.33 3.31 0 1 2 11 3.36
4 3.27 3.25 3 1 2 2 3.31
35 3.17 3.16 4 1 0 s 3.19 84 3.22
3.15 4 0 3 20 3.20
3.15 0 0 3 12 3.20
3.10 6 0 1 w 3.14 13 3.16
63 3.04 3.03 4 1 2 s 3.08 74 3.08
63 2.87 2.85 2 1 2 s 2.89 100 2.91
87 2.80 2.78 4 1 1 s 2.82 85 2.84
5 2.75 2.73 2 1 3 1 2.78
10 2.67 2.66 2 0 3 9 2.71
100 2.62 2.61 4 1 3 s 2.64 76 2.65
2.60 0 1 3 72 2.65
59 2.59 2.57 6 1 1 s 2.62 80 2.62
10 2.53 2.52 2 0 4 w 2.56 12 2.56
2.52 6 1 2 4 2.57
7 2.46 2.45 6 1 0 vw 2.48 11 2.50
17 2.37 2.36 0 0 4 vw 2.39 16 2.40
33 2.33 2.32 0 2 0 m 2.34 13 2.36
11 2.29 2.31 8 0 2 20 2.36
14 2.27 2.28 6 0 4 vw 2.31 13 2.32
14 2.23 2.22 3 1 4 w 2.25 22 2.26
16 2.19 2.18 7 1 0 w 2.21 23 2.23
43 2.15 2.15 7 1 3 m 2.17 23 2.19
2.14 6 0 2 18 2.18
2.14 3 1 3 25 2.18
15 2.11 2.10 0 1 4 w 2.13 8 2.14
12 2.08 2.07 8 1 2 vw 2.10 6 2.11
7 2.06 2.06 8 1 1 4 2.10
2.05 6 1 4 4 2.08
8 2.01 2.00 4 2 2 3 2.04
31 1.936 1.941 6 1 2 10 1.979
1.928 4 2 1 m 1.950 24 1.964
46 1.871 1.866 4 2 3 s 1.886 34 1.899
1.865 0 2 3 30 1.897
1.854 6 2 1 36 1.889
350 Mn-BEARING HELLANDITE-(Y) FROM THE HEFTETJERN PEGMATITE

TABLE 2. (CONTINUED)

Heftetjern Tahara Miyawaki Predazzo Mellini &

Present Study et al. (1987) Merlino (1977)

I /I0 dmeas dcalc h k l I d Icalc dcalc

12 1.829 1.826 1 0 0 1 4 1.864

11 1.825 1.825 1 0 0 3 4 1.861
9 1.790 1.782 8 0 5 w 1.816 12 1.813
18 1.739 1.741 8 0 2 w 1.766 16 1.776
1.732 10 0 0 12 1.768
1.731 1 0 0 4 11 1.763
6 1.713 1.718 2 0 5 11 1.747
20 1.695 1.691 4 0 6 w 1.714 16 1.717
1.687 4 1 4 14 1.718
10 1.669 1.663 8 1 5 6 1.692
10 1.661 1.653 0 2 4 13 1.681
1.637 8 2 2 18 1.668
1.622 10 1 0 m 1.645 21 1.656
21 1.594 1.588 4 1 6 w 1.613 31 1.613
19 1.577 1.571 6 2 2 w 1.590 22 1.601
7 1.552 1.552 2 2 4 2 1.579
1.544 0 3 0 7 1.572
3 1.533 1.539 8 0 3
3 1.517 1.512 1 2 0 1 3 1.543
3 1.505 1.499 1 2 0 4 2 1.529
6 1.464 1.464 1 2 1 3
1.440 4 3 2 vw 1.454 4 1.466
1.437 1 2 1 1 4 1.467
6 1.433 1.427 1 2 1 4 8 1.454
7 1.418 1.412 8 2 5 vw 1.429 2 1.437
2 1.407 1.386 4 3 3 w 1.402 9 1.411
17 1.392 1.386 0 3 3 8 1.410

apfu. The excess B in the present analysis possibly 0.05Tb, 0.04Eu, and 0.03Pr apfu. The chemical formula
comes from errors in the ZAF corrections, especially an including the infinitesimal lanthanoids with charge com-
overestimation for the absorption (A) correction, in pensating H is Ca1.34Mn1.07Y2.75Ln0.38Al0.94Fe0.08
addition to the relatively large standard deviation (0.78 Si3.99B4O21.23(OH)2.77, which was used for the occu-
for B2O3 in Table 1). A proforma calculation based on pancy parameters in the crystal structure refinement.
B = 4, Al + Fe + Si = 5 and 24 anions per formula unit Hellandite-(Y) from the Heftetjern pegmatite,
gave lower B2O3, 14.16 wt.%, and increased H2O, 2.73 Trdal, Norway, shows a notable chemical feature in
wt.%, with 99.73 total %, leading to the formula the enrichment of Mn with deficiency of Ca
Ca1.34Mn1.07Y2.75Ce0.02Nd0.02Sm0.01Gd0.01Dy0.05Er0.05 (Table 1). As the amounts of Al and Fe are sufficient
Yb0.15Al0.94Fe0.08Si3.99B4O21.02(OH)2.98. to fill the octahedral M1 (or Z) site, Mn probably
The chondrite-normalized lanthanoid distribution occupies the M2, M3, and/or M4 (X, Y) sites together
patterns of Mn-bearing hellandite-(Y) show an increas- with Ca, Y, and Ln (lanthanoids; LaLu). The distri-
ing trend with enrichment of heavy REEs having smaller bution of the cations among the M sites was exam-
ionic radii comparable to Y (Fig. 3). This trend can typic- ined in the crystallographic investigation as described
ally be observed in many of the Y-predominant REE below. The valence of Mn was estimated as divalent
minerals. Nevertheless, the trend is not a simple slope, after a bond-valence calculation based on the crystal
but shows the second peak at Pr, one of the light REEs. chemistry, i.e., the isomorphous substitution between
The lanthanoids content, which was not determined with Ca and Mn. Our microprobe analyses show a defi-
the electron microprobe, was estimated by means of inter- ciency of the cations at the M2, M3, and M4 sites,
polation with those of the determined lanthanoids having (Ca1.34Mn1.07Y2.75Ln0.38)5.54, relative to the ideal
neighboring atomic numbers; 0.03Lu, 0.02Tm, 0.01Ho, 6 apfu.
 THE CANADIAN MINERALOGIST 351

TABLE 3. CRYSTAL DATA, DATA COLLECTION INFORMATION, AND REFINEMENT

DETAILS

Chemical formula Ca1.34Mn1.07Y2.75Yb0.38Al0.92Fe0.08Si4B4O21.21(OH)2.79

Temperature 296 K
Wavelength 0.71073
Crystal system Monoclinic
Space group P2/a (# 13)
Unit cell parameters a = 18.609(8)
b = 4.6307(19)
c = 10.143(4)
= 111.475(4)
V = 813.4(6) 3
Z=2
Density (calculated) 4.06 Mg/m3
Absorption coefficient 13.70 mm1
F(000) 944
Crystal size 0.12 0.07 0.05 mm3
Oscillation width 0.5 (in )
Exposure time per flame 5s
Theta range for data 2.35 to 27.18
collection ()
Index ranges 1 7 h 23, 5 k 4, 1 2 l 12
Reflections collected 4089
Independent reflections 1768
Reflections [I > 2(I)] 1567
Rint 0.0208
Refinement method Full-matrix least-squares on F 2
restraints / parameters 6 / 191
Goodness-of-fit on F2 0.784
Final R indices [I > 2(I)] R1 = 0.0269, wR2 = 0.0879
R indices (all data) R1 = 0.0318, wR2 = 0.0934
Largest diff. peak and hole 1.082 and 1.013 e/3

X-RAY CRYSTALLOGRAPHY Refinement of the crystal structure

X-ray diffraction The X-ray diffraction data for crystal structure

analysis were collected from a single crystal of the
The powder X-ray diffraction pattern was Mn-bearing hellandite, which was picked from the
obtained from Debye rings recorded on an imaging thin section used for the electron microprobe ana-
plate in a Gandolfi camera with a diameter of lyses. The measurements were obtained with a Bruker
114.6 mm using Ni filtered CuK radiation. The AXS SMART APEX 2 diffractometer equipped with
data were processed with a Fuji BAS-2500 bio- a CCD area-detector using -scans (0.5/min) and
image analyzer using a computer program written utilizing graphite-monochromated MoK radiation
by Nakamuta (1999). The lattice parameters were ( = 0.71073 ) with 7 seconds per frame exposure
refined with diffraction angle data calibrated with a time. The reduction and correction for the Lorentz-
Si-standard reference material (NBS #640b) and polarization factors and background effects were car-
using a computer program by Toraya (1993). Table ried out as well as an empirical correction for
2 shows the X-ray powder diffraction data for Mn- absorption (SAINTPLUS and SADABS). The lattice
bearing hellandite-(Y). The lattice parameters were parameters and diffraction experimental conditions are
refined in the monoclinic system from the diffrac- summarized in Table 3.
tion data: a 18.693(17), b 4.651(3), c 10.178(7) , The structure was solved using direct methods and
A 111.37(6), V 824.1(10) 3, which are very close referencing the results of the crystal structure analysis
to those of hellandite-(Y) in the published literature by Mellini & Merlino (1977) and was refined with
(e.g., Mellini & Merlino 1977, Oberti et al. 1999, the SHELXTL program (Sheldrick 2008). A full-mat-
Oberti et al. 2002). rix least-squares refinement with anisotropic atomic
352 Mn-BEARING HELLANDITE-(Y) FROM THE HEFTETJERN PEGMATITE

TABLE 4. OCCUPANCY PARAMETERS, ATOMIC FRACTIONAL COORDINATES, EQUIVALENT ISOTROPIC

AND ANISOTROPIC ATOMIC DISPLACEMENT PARAMETERS (2)

Occupancy x y z Ueq

Al1 0.92Al 0.08Fe 0 0 0 0.0138(3)

Y2 0.943(2)Y 0.0567(17)Yb 0.042313(17) 0.02021(7) 0.35947(3) 0.00774(16)
Ca3 0.560(8)Ca 0.440(8)Mn 0.24672(4) 0.00215(12) 0.65778(7) 0.0104(2)
Y4 0.433(3)Y 0.231(8)Ca 0.15507(3) 0.04275(10) 0.92895(5) 0.01532(18)
0.1365(15)Yb 0.000(8)Mn
Si1 Si 0.09970(5) 0.48676(18) 0.64705(9) 0.0092(3)
Si2 Si 0.11117(6) 0.49617(18) 0.16171(11) 0.0106(2)
B1 B 0.1710(2) 0.5301(8) 0.4522(5) 0.0108(8)
B2 B 0.2544(2) 0.4559(8) 0.1348(4) 0.0102(8)
O1 O 0.03942(13) 0.2433(5) 0.5624(2) 0.0116(5)
O2 O 0.17507(13) 0.3119(5) 0.7570(3) 0.0156(5)
O3 O 0.06910(13) 0.2935(5) 0.7363(2) 0.0139(5)
O4 O 0.13177(14) 0.3257(5) 0.5423(3) 0.0148(5)
O5 O 0.03821(13) 0.1900(6) 0.8705(2) 0.0127(5)
O6 O 0.24417(13) 0.2388(5) 0.8603(3) 0.0149(5)
O7 O 0.16602(13) 0.2257(5) 0.4484(2) 0.0133(5)
O8 O 0.12932(15) 0.6732(5) 0.3096(3) 0.0191(6)
O9 O 0.18864(14) 0.3301(6) 0.1646(3) 0.0252(7)
O10 O 0.08544(13) 0.7371(5) 0.0408(3) 0.0129(5)
O11 O 0.05237(13) 0.2411(5) 0.1547(2) 0.0127(5)
O12 O 0.25 0.3245(8) 0 0.0266(9)
O13 O 0.25 0.6503(8) 0.5 0.0184(8)
H5 H 0.036(5) 0.427(19) 0.882(9) 0.14(4) Uiso
U11 U22 U33 U23 U13 U12
Al1 0.0153(8) 0.0146(7) 0.0125(8) 0.0006(5) 0.0064(6) 0.0006(5)
Y2 0.0059(2) 0.0096(2) 0.0084(2) 0.00031(9) 0.00347(16) 0.00046(9)
Ca3 0.0111(4) 0.0096(3) 0.0099(4) 0.00089(19) 0.0033(3) 0.0001(2)
Y4 0.0147(3) 0.0167(3) 0.0185(3) 0.00353(15) 0.0107(2) 0.00422(15)
Si1 0.0076(6) 0.0106(5) 0.0099(6) 0.0000(3) 0.0040(5) 0.0002(3)
Si2 0.0081(5) 0.0119(5) 0.0113(5) 0.0002(3) 0.0031(4) 0.0001(3)
B1 0.0102(19) 0.0083(18) 0.015(2) 0.0018(13) 0.0055(16) 0.0000(13)
B2 0.0086(19) 0.0108(19) 0.0117(19) 0.0001(14) 0.0041(15) 0.0013(13)
O1 0.0111(11) 0.0108(12) 0.0127(12) 0.0004(9) 0.0041(9) 0.0012(9)
O2 0.0087(12) 0.0128(12) 0.0217(13) 0.0007(10) 0.0014(10) 0.0013(9)
O3 0.0110(12) 0.0158(12) 0.0156(12) 0.0000(10) 0.0058(10) 0.0028(9)
O4 0.0145(12) 0.0124(12) 0.0196(13) 0.0017(10) 0.0089(10) 0.0011(9)
O5 0.0113(12) 0.0142(13) 0.0146(12) 0.0018(9) 0.0069(10) 0.0008(9)
O6 0.0126(12) 0.0124(13) 0.0199(13) 0.0014(10) 0.0063(10) 0.0018(9)
O7 0.0100(11) 0.0124(13) 0.0162(13) 0.0012(9) 0.0033(10) 0.0021(9)
O8 0.0250(14) 0.0131(13) 0.0140(12) 0.0014(10) 0.0009(11) 0.0036(11)
O9 0.0121(13) 0.0203(14) 0.0480(18) 0.0152(13) 0.0169(12) 0.0056(11)
O10 0.0079(11) 0.0155(12) 0.0144(12) 0.0016(9) 0.0029(9) 0.0017(9)
O11 0.0099(11) 0.0165(12) 0.0113(12) 0.0006(9) 0.0032(9) 0.0036(9)
O12 0.054(3) 0.0130(19) 0.0133(18) 0 0.0128(18) 0
O13 0.0126(17) 0.0144(18) 0.030(2) 0 0.0094(15) 0

displacement parameters was carried out. Scattering lanthanoids. Site occupancy factors were fixed or
factors for neutral atoms were taken from the restrained on the basis of the chemical composition
International Tables for X-ray Crystallography and the cation ordering for hellandite described by
Volume C (Wilson 1992). The scattering factor curve Oberti et al. (2002). The occupancy of the Al1 (M1)
for Yb, the predominant lanthanoid in the crystal, was site was fixed at 0.92Al + 0.08Fe. The scattering fac-
adopted as the representative curve for all of the tors of Fe and Mn are similar, and gave no
 THE CANADIAN MINERALOGIST 353

FIG. 4. VESTA (Momma & Izumi 2011) illustration of the crystal structure of Mn-bearing hellandite-(Y). Sites are indicated
by colors as follows: green for Al1, orange for Ca3, yellow for Y2 and Y4, blue for Si, pink for B, red for O, and dark gray
for H. The Si, B, and T (vacant in this case) tetrahedra are illustrated in shades of blue, pink, and pale green, respectively.

TABLE 5. INTERATOMIC DISTANCES ()

Al1 O11 1.881(2) Y2 O1 2.305(2)

O11 1.881(2) O3 2.317(2)
O5 1.921(2) O1 2.322(3)
O5 1.921(2) O7 2.345(2)
O10 1.923(2) O11 2.383(2)
O10 1.923(2) O8 2.462(3)
mean 1.908 O5 2.464(2)
O4 2.553(2)
H5 O5 1.11(9) mean 2.394
Ca3 O13 2.300(3) Y4 O6 2.214(3)
O9 2.327(3) O10 2.254(2)
O7 2.346(2) O5 2.302(2)
O6 2.353(3) O3 2.332(2)
O2 2.414(3) O12 2.367(3)
O7 2.480(3) O6 2.444(3)
O4 2.534(3) O2 2.521(3)
O8 2.682(3) O9 2.827(3)
mean 2.430 mean 2.408
Si1 O3 1.599(3) Si2 O11 1.594(2)
O1 1.600(2) O10 1.596(3)
O4 1.644(3) O9 1.625(3)
O2 1.650(2) O8 1.633(3)
mean 1.623 mean 1.612
B1 O7 1.412(4) B2 O6 1.413(4)
O13 1.479(4) O12 1.470(4)
O4 1.517(5) O9 1.484(5)
O8 1.520(5) O2 1.522(5)
mean 1.482 mean 1.473
 354
TABLE 6. BOND-VALENCE TABLE FOR Mn-BEARING HELLANDITE-(Y)

Al1 Y2 Ca3 Y4 Si1 Si2 B1 B2

O1 0.458 1 1.067 1 1.962

1 1
0.437 1
1
O2 0.249 1 0.194 1 0.932 1 0.665 1 2.039
1 1 1 1
O3 0.443 1 0.323 1 1.070 1 1.836

Mn-BEARING HELLANDITE-(Y) FROM THE HEFTETJERN PEGMATITE

1 1 1
O4 0.234 1 0.180 1 0.947 1 0.674 1 2.035
1 1 1 1
O5 0.457 1 0.298 1 0.350 1 1.105
2 1 1
O6 0.293 1 0.444 1 0.888 1 1.863
1 1 1
0.238 1
1
O7 0.411 1 0.299 1 0.895 1 1.813
1 1 1
0.208 1
1
O8 0.300 1 0.121 1 0.976 1 0.669 1 2.065
1 1 1 1
O9 0.315 1 0.085 1 0.997 1 0.737 1 2.134
1 1 1 1
O10 0.459 1 0.398 1 1.079 1 1.936
2 1 1
O11 0.512 1 0.371 1 1.084 1 1.967
2 1 1
O12 0.293 2 0.765 2 2.117
1 1
O13 0.339 2 0.747 2 2.171
1 1
2.857 2.952 2.003 2.324 4.016 4.136 2.984 3.055
 THE CANADIAN MINERALOGIST 355

significant difference in the parameters correlating the refinement indicates that there is little Mn at the Y4(M4)
occupancies in the refinement. Ferric iron was site. It is noteworthy that the deficiency of the cations
adopted as the substituent for Al3+ in preference to was confirmed as a 0.2 vacancy at the Y4(M4) site.
Mn3+ at the Al1 (M1) site. However, Mn was consid- Oberti et al. (1999) concluded that no vacancies occur at
ered as Mn2+ replacing Ca2+ at the Ca3 (M3) and Y4 the M sites in hellandite-(Y) from Latium (Italy), after
(M4) sites in the refinement. The occupancy factors their complete chemical and structural analyses. On the
of Y + Yb at the Y2 (M2), Ca + Mn at the Ca3 contrary, the Mn-bearing hellandite-(Y) appears to have
(M3), and Y + Ca + Yb + Mn at the Y4 (M4) sites a vacancy at the Y4(M4) site.
were refined but were constrained on the basis of The cation chemistry of Mn-bearing hellandite-(Y)
chemical composition. The refinement converged to requires 2.77 (OH) for the 24 anions, namely 24 O in
R1 = 0.0286 for 1567 reflections [I > 2(I)] and the F-free hellandite-(Y), per formula unit.
0.0334 for all 1768 reflections. Approximately 2 (OH) can be at the O5 site. The
The final positional and displacement parameters bond-valence sum (Table 6) suggests that the residual
are listed in Table 4. Interatomic distances in the 0.77 (OH) may distribute among O3, O6, and O7,
coordination polyhedra are summarized in Table 5. having lower values 1.836, 1.863, and 1.813, respect-
Figure 4 shows an illustration of the crystal structure cre- ively. Although the O7 shows the lowest value, the
ated using VESTA (Momma & Izumi 2011). The bond other two, O3 and O7, bond to Y4(M4) and are
valences were calculated from the interatomic distances speculated to be occupied by (OH).
following the procedure of Brown & Altermatt (1985) The Mn ion in the Mn-bearing hellandite-(Y) from
and using the parameters of Brese & OKeeffe (1991). Heftetjern, Trdal, Telemark, Norway is divalent and
The values (Table 6) are weighted averages according replaces Ca at the eight-coordinated Ca3(M3) site in
to the occupancy parameters in the final refinement. the crystal structure. Many Mn-minerals have been
recognized in the Heftetjern pegmatite; helvine
DISCUSSION [Mn2+4Be3(SiO4)3S], spessartine [Mn2+ 3 Al2(SiO4)3],
scandiobabingtonite [Ca2(Fe2+,Mn)ScSi5O14(OH)],
Oberti et al. (2002) suggested that Li and/or Be 2+
and oftedalite [(Sc,Ca,Mn )2K(Be,Al)3Si12O30]
often occupy the T site in hellandite-(Y), instead of H (Cooper et al. 2006), of which the latter two show the
bonding to O at the O5 site, one of the four corners substitution of Mn for Ca. The Mn-bearing hellandite-
of the T tetrahedron. The difference-Fourier maps of (Y) suggests a potential occurrence of the Mn-analogue
the present crystal structure analysis indicated an elec- of hellandite-(Y), in which Mn2+ dominates over Ca2+,
tron density (0.9 e) with a distance of 0.98 to the ideally Mn2(YCa)Y2AlSi4B4O22(OH,F,O)2, which
O5 site. The final cycle of calculation, refining the means the M3 site is occupied by only Mn2+.
fractional coordinates and isotropic displacement para-
meters of H at this position, converged with the low-
est R factors and resulted in crystallographically
ACKNOWLEDGMENTS
reasonable interatomic distances. Several comparative
We are grateful to T.V. Segalstad and G. Raade,
calculations with electron density at the T site gave
no indication of Li or Be but might represent negli- University of Oslo, for their suggestions and permis-
gible small occupancies or drift from the H position sion to use the geological map in Figure 2. The
neighboring the O5 site. The average TO distance, authors thank Associate Editor Dr. Maria Franca
ca. 1.80 , corresponds to 3.5 electrons at the T site Brigatti and referees Dr. Luciano Secco and an
based on estimation of the (Li + Be) content at the T anonymous reviewer for their corrections and sugges-
site from the TO distance (Oberti et al. 2002). The tions. We would like to celebrate the 70th birthday of
distance between the T site and H neighboring O5 is Professor Edward S. Grew, the authority of boron
only 0.7 , indicating no simultaneous occupations of (and beryllium), with this description of hellandite-
H (and Li and/or Be) within the T tetrahedron. Oberti (Y), a borosilicate mineral. RK is happy to be a part
et al. (1999) pointed out that the presence of (Be, Li) of this tribute Ed Grew, and acknowledges the con-
at the T site is coupled with the substitution of F and/ structive collaboration of more than two decades.
or O for OH at the O5 position. Fluorine was not
detected in the electron microprobe analyses. The
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