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American Mineralogist, Volume 98, pages xxx–xxx, 2013Property of MSA. Do not post to web site
0003-004X/13/0010–xxx$05.00/DOI: http://dx.doi.org/10.2138/am.2013.4416	 xxxx
Darrellhenryite, Na(LiAl2)Al6(BO3)3Si6O18(OH)3O, a new mineral from the tourmaline
supergroup
Milan Novák1,
*, Andreas Ertl2
, Pavel Povondra3
, Michaela Vašinová Galiová4,5
,
George R. Rossman6
, Helmut Pristacz2
, Markus Prem2
, Gerald Giester2
, Petr Gadas1
and Radek Škoda1
1
Department of Geological Sciences, Masaryk University, Kotlářská 2, 611 37 Brno, Czech Republic
2
Institut für Mineralogie und Kristallographie, Geozentrum, Universität Wien, Althanstrasse 14, 1090 Wien, Austria
3
Department of Geochemistry, Mineralogy, and Natural Resources, Charles University, Albertov 6, 128 43 Praha 2, Czech Republic
4
Department of Chemistry, Masaryk University, Kotlářská 2, 611 37 Brno, Czech Republic
5
Central European Institute of Technology (CEITEC), Masaryk University, Kamenice 5, 625 00 Brno, Czech Republic
6
Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California 91125-2500, U.S.A.
Abstract
Darrellhenryite, Na(LiAl2)Al6(BO3)3Si6O18(OH)3O, a new member of the tourmaline supergroup
(related to the alkali-subgroup 4), is a new Li-bearing tourmaline species, which is closely related
to elbaite through the substitution Y
AlW
0.5O1
Y
LiW
–0.5(OH)–1. It occurs in a complex (Li-bearing) petalitesubtype
pegmatite with common lepidolite, Li-bearing tourmalines, and amblygonite at Nová Ves
near Český Krumlov, southern Bohemia, Moldanubian Zone, Czech Republic. This pegmatite dike
is zoned cross-cuts {{AU:? missing text?}} a serpentinite body enclosed in leucocratic granulites.
Pink darrellhenryite forms columnar crystals (sometimes in parallel arrangement) up to 3 cm long
and up 2 cm thick, associated with albite (var. cleavelandite), minor quartz, K-feldspar, petalite, rare
polylithionite, and locally rare pollucite. The optical properties and the single-crystal structure study
(R1 = 0.019) of darrellhenryite are consistent with trigonal symmetry, w = 1.636(2), e = 1.619(2),
birefringence: 0.017, space group R3m, a = 15.809(2), c = 7.089(1) Å, V = 1534.4(4) Å3
, and Z = 3.
The chemical analysis, in combination with the results from the single-crystal structure refinement,
gives the formula X
(Na0.58Ca0.01o0.41)1.00
Y
(Li1.05Al1.95)3.00
Z
Al6 (BO3)3
T
(Si6O18) V
(OH)3
W
(O0.66F0.34)1.00,
which can be simplified to an ideal formula of Na(LiAl2)Al6(BO3)3Si6O18(OH)3O. The strongest lines
of the powder pattern [d in Å (I, hkl)] are 4.180 (39, 211), 3.952 (54, 220), 3.431 (73, 012), 2.925
(100, 122), 2.555 (90, 051), 2.326 (42, 511), 2.029 (42, 223), 2.021 (42, 152), 1.901 (50, 342), 1.643
(49, 603). The density is Dmeas = 3.03(3) g/cm3
, Dcalc = 3.038 g/cm3
. Darrellhenryite is considered to
have crystallized in Li- and B-rich but F-moderate environments in complex pegmatites; no influence
of higher activity of O on the darrellhenryite formation is implied from its mineral assemblage. The
name is for Darrell J. Henry, Professor of Geology at the Louisiana State University, Baton Rouge,
U.S.A., an expert on the mineralogy, petrology, crystal chemistry, and nomenclature of tourmalinesupergroup
minerals.
Keywords: Darrellhenryite, tourmaline group, chemical analyses, crystal structure, Nová Ves,
Czech Republic
Introduction
Lithium-bearing tourmalines are of considerable scientific
interest because they reflect compositional trends in granitic pegmatites
(e.g., Selway et al. 1999, 2002), because of their complex
zoning (e.g., Lussier et al. 2011), and because of their unknown
stability field (e.g., London 2011). The current nomenclature of
the tourmaline supergroup includes eight Li-bearing tourmalines
(Henry et al. 2011), four of which are known to exist in nature:
elbaite (Vernadsky 1913), fluor-liddicoatite (Dunn et al. 1977),
rossmanite (Selway et al. 1998), and fluor-elbaite (Bosi et al.
2013) and four hypothetical species (Table 1). Darrellhenryite,
Na(LiAl2)Al6(BO3)3Si6O18(OH)3O, represents a new Li-bearing
tourmaline species, which belongs to the oxy-tourmaline series
as do povondraite and chromo-alumino-povondraite (Henry et
al. 2011) and the more recently described minerals, oxy-schorl
(Bačík et al. 2013) and oxy-dravite (Bosi and Skogby 2012). In
this contribution, we present chemical analyses, the description
of the crystal structure, spectroscopic data, and discuss paragenetic
position of darrellhenryite in complex granitic pegmatites.
Darrellhenryite has been approved by the IMA-CNMNC
(proposal no. 2012-026). Its chemical composition relates to the
alkali-subgroup 4 (Table 1; Henry et al. 2011), which requires a
new root name in this case, the name chosen is darrellhenryite,
in honor of Darrell J. Henry (born 1953), Professor of Geology
at the Louisiana State University, Baton Rouge, U.S.A., an expert
on the mineralogy, petrology, crystal chemistry, and nomenclature
of tourmaline-supergroup minerals. The type specimen is
deposited with the Department of Mineralogy and Petrography
of the Moravian Museum, Zelný trh 6, 659 37 Brno, Czech Republic,
catalog number B10661. Holotype material (the crystal* E-mail: mnovak@sci.muni.cz
{{AU: I’m not sure why some mineral names are in italic, but left
as-is. Same with site nomenclature. So proofread carefully.}}
NOVÁK ET AL.: DARRELLHENRYITE, A NEW MINERAL FROM THE TOURMALINE SUPERGROUP2
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chosen for structure refinement) is deposited at the Smithsonian
Institution, National Museum of Natural History, Washington
D.C., catalog number NMNH 175992, and co-type material is
also deposited at this museum, catalog number NMNH 175993.
Occurrence
Darrellhenryite was discovered in a complex (Li-bearing)
pegmatite at Nová Ves near Český Krumlov, southern Bohemia,
Czech Republic. The pegmatite belongs to the Moldanubian
pegmatite province along with about 100 other lepidolite- and
elbaite-subtype pegmatite bodies of the Variscan age (Novák
and Povondra 1995; Novák 2005; Breiter et al. 2010; Ertl et
al. 2004, 2012; Melleton et al. 2012). The pegmatite occurs as
a symmetrically zoned dike, up to 8 m thick and about 100 m
long, that cuts a serpentinite body (Teertstra et al. 1995; Novák
and Černý 1998), which is enclosed in leucocratic granulites of
the Blanský les Massif. From the contact inward, it consists of
(1) an outermost granitic unit with biotite, (2) a coarse-grained
albite unit locally with graphic intergrowths of Kfs + Qtz and
aggregates of Ms + Qtz + Tur; (3) blocky K-feldspar and blocky
petalite, and (4) an albite-lepidolite unit, the latter three units
also containing Li-bearing tourmalines. No pockets have been
found in the pegmatite. The Li-bearing primary minerals in the
pegmatite are: petalite > lepidolite (trilithionite > polylithionite)
> Li-bearing tourmalines (darrellhenryite > fluor-elbaite) >
amblygonite. Secondary spodumene + quartz aggregates after
petalite and secondary montebrasite after primary amblygonite
are also present. Accessory almandine-spessartine, fluorapatite,
beryl, zircon, pollucite, cassiterite, columbite, and microlitegroup
minerals (fluornatromicrolite to fluorcalciomicrolite)
were also found in the pegmatite. The pegmatite may be classified
as a complex (Li)-type, petalite-subtype following the
scheme proposed by Černý and Ercit (2005) but with substantial
amounts of lepidolite, Li-bearing tourmalines, and amblygonite.
The mineral assemblage and modal proportion of Li-bearing
minerals are similar to much larger pegmatites of the petalitesubtype
(e.g., Tanco, SE Manitoba, Canada: Stilling et al. 2006,
and Utö, Stockholm region, Sweden: Smeds and Černý 1989;
Selway et al. 2002{{AU:OK?}}). However, the overall amount
of Li-bearing minerals is much lower in the Nová Ves pegmatite
than in these pegmatites.
Darrellhenryite (holotype) forms subhedral, short, columnar
crystals and parallel aggregates, up to 3 cm long and up to 2 cm
thick, which occur exclusively in the cleavelandite-rich portions
of the albite-lepidolite unit in the central part of the dike. The associated
minerals also include minor quartz, relics of pale brown,
blocky K-feldspar and colorless blocky petalite, rare colorless
flakes of polylithionite and locally rare altered pollucite. Very
rare inclusions of late muscovite, visible only in BSE images,
occur within the aggregates of darrellhenryite.
Method
Chemical composition
Chemical analyses of darrellhenryite were carried out by various methods.
These included a complete wet chemical analysis (Povondra et al. 1985); 13 EMP
analyses (using WDS) with a Cameca SX 100 electron microprobe, LA-ICP-MS
(Li; eight analyses); and a combination of wet chemical, near-IR, and thermogravimetric
analysis (TGA; 3 analyses) for H2O. To determine the OH content of
darrellhenryite, ~15 mg of the material was used for each analysis, performed on
a Mettler-Toledo TGA/SDTA851 (University of Vienna). The powder was heated
from 25 to 1100 °C (5 °C/min) in N2 gas (gas flow: 25 mL/min).Analytical data of
darrellhenryite, including standards for EMPA, are given in Table 2. A synthetic
multi-layered pseudocrystal (Si/W layers, d = 60 Å, PC1 in terms of Cameca) was
used as reflector for the fluorine analysis. It provides a much higher count rate
than the more commonly used TAP (thalium acid phtalate) crystal. The substantial
overlap of the FKa position with the shoulder of the FeLa,b peak on the pseudocrystal
(Witter and Kuehner 2004) is not significant due to very low Fe content in
darrellhenryite. The PHA settings of the detector were used in differential mode
(baseline 750 mV and window 3500 mV) to reduce the “Bremsstrahlung” intensity
and the influence of the second order of the AlKa peak on the low background
position. We chose a natural lepidolite with well-defined F content (8.45 wt% F)
as a standard. Prior to conducting the analysis, care was taken to determination
precise background positions and the peak maximum of the FKa line. The positions
of the FKa peak in darrellhenryite and lepidolite are identical. The fluorine
peak counting time was 60 and 30 s on each of the background positions, and the
exponential fit of background was used. Raw EMPAdata and B, H, and Li content
determined by Povondra et al. (1985), were corrected using the X-Phi (Merlet
1994) matrix procedure.
Concentration of Li and trace elements and were investigated by LA-ICPMS
(Department Chemistry, Masaryk University, Brno) using an Agilent 7500ce
(Agilent Technologies, Santa Clara, California, U.S.A.) quadrupole ICP-MS with
an attached UP 213 laser ablation system (New Wave Research, Inc., Fremont,
California, U.S.A.). The samples were placed into a SuperCell (New Wave Research,
Inc., Fremont, California, U.S.A.) having a volume of 33 cm3
and ablated
using a commercial Q-switched Nd:YAG laser operated at a wavelength of 213 nm
Table 1.	Theoretical compositions of olenite, along with known and
hypothetical Li-bearing tourmalines
	 1	2	 3	 4	 5	6	7	 8	9
SiO2	 39.03	38.65	38.49	38.40	38.12	38.12	38.2	37.84	37.41
Al2O3	 44.15	46.46	 40.82	 40.73	 43.12	37.73	37.81	 40.13	47.61
B2O3	 11.30	11.20	 11.15	 11.12	 11.04	11.04	11.06	 10.96	10.84
Li2O	1.62	0.80	 2.39	 2.39	 1.58	3.16	3.17	 2.35	 –
Na2O	–	 –	 3.31	 3.30	 3.28	 –	 –	 –	3.22
CaO	–	–	–	–	–	5.93	5.94	5.89	–
H2O	3.90	2.90	 3.85	 2.88	 2.86	2.86	3.82	 2.84	0.93
F	 –	 –		 2.02	 –	2.01	–	 –	 –
X site	 	 	 Na	 Na	 Na	 Ca	 Ca	 Ca	Na
Y site	 LiAl2	 Li0.5Al2.5	 Li1.5Al1.5	 Li1.5Al1.5	 Li1Al2	 Li2Al1	 Li2Al1	 Li1.5Al1.5	 Al3
Z site	 Al6	 Al6	 Al6	 Al6	 Al6	 Al6	 Al6	 Al6	 Al6
B site	 B3	 B3	 B3	 B3	 B3	 B3	 B3	 B3	 B3
T site	 Si6	 Si6	 Si6	 Si6	 Si6	 Si6	 Si6	 Si6	 Si6
V site	 (OH)3	 (OH)3	 (OH)3	 (OH)3	 (OH)3	 (OH)3	 (OH)3	 (OH)3	 O3
W site	 OH	 O	 OH	 F	 O	 F	 OH	 O	 OH
Notes: 1 = rossmanite (LiAl2)Al6Si6O18(BO3)3(OH)3OH; 2 = -Li-O root name
(Li0.5Al2.5)Al6Si6O18(BO3)3(OH)3O; 3 = elbaite Na(Li1.5Al1.5)Al6Si6O18(BO3)3(OH)3OH;
4 = fluor-elbaite Na(Li1.5Al1.5)Al6Si6O18(BO3)3(OH)3F; 5 = darrellhenryite Na(LiAl2)
Al6Si6O18(BO3)3(OH)3O; 6 = fluor-liddicoatite Ca(Li2Al)Al6Si6O18(BO3)3(OH)3F; 7 =
liddicoatite Ca(Li2Al)Al6Si6O18(BO3)3(OH)3OH; 8 = Ca-Li-O root name Ca(Li1.5Al1.5)
Al6Si6O18(BO3)3(OH)3O; 9 = olenite NaAl3Al6Si6O18(BO3)3(O)3OH; all formulas from
Henry et al. (2011).
Table 2. Analytical data for darrellhenryite
Constituent	wt%*	
wt%†	
Range†	
S.D.†	
Probe standard
SiO2	 37.94	38.38	38.69–38.12	0.17	 almandine
Al2O3	 42.77	43.49	43.75–43.10	0.16	 grossular
B2O3	 11.01	11.01*	
		
FeO	 0.17				 almandine
MnO	 0.02	 0.02	 0.11–0.00	 0.04	spessartine
CaO	 0.07	 0.05	 0.09–0.00	 0.03	fluorapatite
Li2O	 1.88	 1.63	 1.87–1.37	 0.21	 NIST 610
Na2O	 1.81	1.92	2.03–1.78	0.07	 albite
K2O	 0.12				 sanidine
H2O	 2.86	2.86*	
		
F	 0.64	0.71	0.78–0.61	0.07	 lepidolite
O=F	 –0.27	–0.30			
  Total	 99.02	99.77			
* Wet chemical analysis from Povondra et al. (1985).
† Electron microprobe, LA-ICP-MS (Li2O), TGA: 2.9(1) wt% H2O, near-infrared
spectroscopy: 2.87 wt% H2O.
NOVÁK ET AL.: DARRELLHENRYITE, A NEW MINERAL FROM THE TOURMALINE SUPERGROUP 3
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(pulse duration 4.2 ns).Ablated material was transported from the sample chamber
using helium carrier gas (1 L/min-1
) and mixed with argon (0.6 L/min-1
) prior to
the torch. Optimization of LA-ICP-MS parameters (gas flow rates, sampling depth,
voltage of ion optics) was performed using glass reference material NIST SRM 612
to maximize the S/N ratio. Potential polyatomic interferences were minimized by a
collision reaction cell in He mode (2.5 mL/min-1
). {{auth: Lforliter, changes ok?}}
Crystal structure
The tourmaline of darrellheryite was studied on a Bruker AXS Kappa APEX
II CCD diffractometer equipped with a monocapillary optics collimator and
graphite-monochromatized MoKa radiation. Single-crystal X‑ray diffraction data
were collected at room temperature (out to ~80° 2q), integrated and corrected for
Lorentz and polarization factors and absorption correction by evaluation of partial
multiscans. The structure was refined (using a starting model; Ertl et al. 2010)
with SHELXL-97 (Sheldrick 1997) using scattering factors for neutral atoms. The
H atom bonded to the O3 atom was located from a difference-Fourier map and
subsequently refined. Refinement was performed with anisotropic displacement
parameters for all non-hydrogen atoms. Table 3 provides crystal data and details of
the structure refinement. Site occupancies were refined according to well-known
characteristics of the tourmaline structure (B, O1–O8, and H3 were constrained
to fully occupy their respective sites, Na was refined at the X site, Al and Li were
refined at the Y site; for other details see Table 4). The refinements converged at
R1(F) values of ~1.95% (Table 3). The atomic parameters and equivalent isotropic
displacement parameters are given in Table 4. In Table 5 we present selected
interatomic distances. (CIF1
is available on deposit.) {{auth: you can rephrase
and/or place elsewhere as you like}}
The X‑ray powder diffraction (XRD) data for darrellhenryite (pinkish white
powder) were collected on a PW 3710 Philips diffractometer using CuKa radiation
(40 kV, 40 mA), equipped with a secondary graphite monochromator. The irradiated
sample area was constantly 12 × 12 mm2
(automatic divergence slits gave
a constant area for each 2q angle). A sample of darrellhenryite was prepared on
a round zero-background silicon holder, dispersed in a few drops of acetone and
allowed to dry. The XRD data were collected [at 295(1) K] over the 2q range of
5–62° using 0.01° steps and a counting time of 1 s/step. Because of the very limited
amount of material with a composition close to the end-member of darrellhenryite,
the collection of high-quality data was limited to 2q less than 65° because of the low
quality of data at higher angles. Silicon SRM 640b was used as internal standard.
The powder diffraction data (indexing is based on the structure refinement and
only reflections with Icalc ≥ 1 are listed) are listed in Table 6.
Spectroscopic investigations
Near-infrared spectra were obtained with a Nicolet Magna 860 FTIR, a silica
beam splitter, and a tungsten-halogen source. Polarized spectra were obtained with
a LiIO3 crystal polarizer. The darrellhenryite sample was prepared as a doubly
polished 1.132 mm thick slab, in which the c axis is parallel to the section plane.
A small, clear area was located in the otherwise cracked sample through which
the spectrum could be obtained. The OH content was determined from the integrated
area of the OH overtone bands in the 6350 to 7300 cm–1
region. Because
a calibration of this method specific to this species does not exist, the calibration
used in Ertl et al. (2010) for elbaite-schorl series tourmalines was chosen for this
study. Optical spectra in the visible to near-infrared region were obtained with a
home-built microspectrometer based on diode-array technology, as described in
Taran and Rossman (2001).
Results
Physical and optical properties
Darrellhenryite has vitreous luster and a pinkish white streak.
The crystals are translucent to transparent with an intense to pale
pink color. The mineral is brittle with conchoidal fracture. Mohs
hardness is ~7. The measured density reported by Povondra et
al. (1985) is 3.03(3) g/cm3
. The calculated density is 3.041 g/
cm3
using the empirical formula given by Povondra et al. (1985)
and the present unit cell (single-crystal) data whereas the calculated
density is 3.038 g/cm3
using the present empirical formula
Table 3.	Crystallographic data and refinement details for darrellhen-
ryite
a, c (Å)	 15.809(2), 7.089(1)
V (Å3
)	1534.4(7)
Crystal dimensions (mm)	 0.15 × 0.15 × 0.10
Collection mode, 2θmax (°)	 full sphere, 79.95
h, k, l ranges	 –28/28, –28/27, –12/12
Number of frames	 620
Total reflections measured	 19944
Unique reflections	 2249
R1a
(F), wR2b
(F2
), Rint
c
(%)	 1.95%, 4.32%, 3.50%
Flack x parameter	 0.016(59)
“Observed”refls. [Fo > 4σ(Fo)]	2169
Extinct. coefficient	 0.00517(26)
No. of refined parameters	 95
Goodness-of-fitd	
1.065
Δσmin, Δσmax (e/Å3
)	 –0.57, 0.64
Note: X-ray radiation: MoKa (λ = 0.71073 Å); Z = 3; space group is R3m (no. 160);
multi-scan absorption correction; refinement on F2
. Frame width, scan time,
detector distance: 3°, 15 s, 35 mm. Scan mode: sets of ω and θ scans.
a
R1 = Σ||Fo| – |Fc||/Σ|Fo|.
b
wR2={Σ[w(Fo
2
–Fc
2
)2
]/Σ[w(Fo
2
)2
]}1/2
.w=1/[σ2
(Fo
2
)+(aP)2
+bP],P=[2Fc
2
+Max(Fo
2
,0)]/3.
c
Rint = Σ|Fo
2
– Fo
2
(mean)|/Σ[Fo
2
].
d
GooF = S = {Σ[w(Fo
2
– Fc
2
)2
]/(n–p)}1/2
.
Table 4. Table of atomic parameters in darrellhenryite
Site	 x	 y	 z	Ueq	 Occ.
X	 0	 0	 0.7509(3)	0.0199(6)	 Na0.56(1)
Y	 0.87800(4)	0.93900(2)	0.34846(7)	0.0068(2)	Al0.651(3)Li0.349
Z	 0.70347(2)	0.74017(2)	0.37588(3)	0.00539(5)	 A1.00
B	 0.89096(4)	0.78193(9)	 0.5307(2)	 0.0057(2)	 B1.00
T	 0.80823(1)	0.81027(2)	0.98406(3)	0.00450(4)	 Si1.00
H3	0.740(2)	0.870(1)	0.600(4)	0.051(8)	 H1.00
O1	 0	 0	 0.2079(2)	0.0252(6)	O0.66(4)F0.34
O2	0.93962(3)	 0.87924(7)	 0.4938(1)	 0.0125(2)	 O1.00
O3	0.73727(8)	 0.86864(4)	 0.4772(1)	 0.0124(2)	 O1.00
O4	0.90589(3)	 0.81179(7)	 0.9106(1)	 0.0085(1)	 O1.00
O5	0.81242(7)	 0.90621(4)	 0.8883(1)	 0.0091(1)	 O1.00
O6	0.80533(4)	0.81595(4)	0.21009(8)	0.0070(1)	 O1.00
O7	0.71341(4)	0.71375(4)	0.90703(7)	0.00641(9)	 O1.00
O8	0.79052(4)	0.72987(4)	0.54631(8)	0.0071(1)	 O1.00
Note: For the definition of Ueq see Fischer and Tillmanns (1988).
Table 5. Selected interatomic distances in darrellhenryite
X-O2 ×3	 2.461(2)
X-O5 ×3	 2.747(1)
X-O4 ×3	 2.815(1)
Mean	2.674(1)
Y-O1	1.9450(11)
Y-O2 ×2	 1.9552(7)
Y-O6 ×2	 1.9574(7)
Y-O3	2.1320(12)
Mean	1.9837(9)
Z-O6	1.8656(6)
Z-O7	1.8815(6)
Z-O8	1.8850(6)
Z-O8’	1.8985(7)
Z-O7’	1.9425(6)
Z-O3	1.9598(5)
Mean	1.9055(6)
T-O7	1.6069(7)
T-O6	1.6081(6)
T-O4	1.6180(4)
T-O5	1.6326(4)
Mean	1.6164(5)
B-O2	1.358(2)
B-O8 (×2)	 1.3799(9)
Mean	1.373(1)
Note: Standard deviation in parentheses.
1
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NOVÁK ET AL.: DARRELLHENRYITE, A NEW MINERAL FROM THE TOURMALINE SUPERGROUP4
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and unit-cell data (single-crystal data). Darrellhenryite is nonfluorescent
under long-, medium-, or short-wave UV light. It is
uniaxial (–), w = 1.636(2) (1.637), e = 1.619(2) (1.621) (590 nm);
birefringence: 0.017 (0.016) (data in parentheses from Povondra
et al. 1985). In thin section, it is colorless. Fragments about 1
cm thick show pleochroism that varies from near colorless (||c)
to pale pink (^c).
The color is caused primarily by an absorption band centered
at ~520 nm in the polarization direction perpendicular to c (Fig.
1). Weak, sharper features occur at 449 and 457 nm, and a hint of
a broad and weak band appears centered at ~700 nm.All of these
features and the band in the E||c direction are characteristic of most
pink tourmalines, which owe their color to Mn3+
believed to be
produced by the natural irradiation of Mn2+
in the tourmaline (Reinitz
and Rossman 1988). The sample is full of pervasive internal
fractures, which cause the wave-like appearance in the spectrum
(Fig. 1) due to interference fringes. A 10.4 mm thick air gap in
this particular sample would produce the fringes seen in Figure 1.
Spectra obtained from different areas in the sample had significant
differences in the intensity of the 520 nm band, attributed to Mn,
indicating an inhomogeneous distribution of this chromophore.
Chemical composition
The empirical formulas are calculated on the basis of 31
(O,OH,F): (Na0.55K0.02Ca0.01o0.42)S1.00 (Li1.19Fe0.02Al1.96)S3.17 Al6.00
(BO3)3.00 (Si5.99Al0.01)O18 (OH)3.00(O0.67F0.32OH0.01) from Povondra
et al. (1985){{AU:OK?}} and (Na0.58Ca0.01o0.41)S1.00 (Li1.03
Al2.02)S3.05 Al6.00 (BO3)2.98 Si6.01O18 (OH)3.00(O0.65F0.35), a combination
of EMPA, LA-ICP-MS (Li), TGA (H2O), and B2O3 taken
from Povondra et al. (1985).{{AU:OK?}} The ideal formula for
darrellhenryite is Na1.00 (Li1.00Al2.00)S3.00 Al6.00 (BO3)3.00 Si6.00 O18
(OH)3.00 O1.00. Very low concentrations of other elements (Fe, Mn,
K, Ca) are typical, as well as moderate contents of F (Table 2).
Analyses obtained using LA-ICP-MS indicate that most trace
elements are present at or below the detection limits (0.1–15
ppm) except for low contents (+ detection limits in parentheses)
of Be (≤17; 0.1), Ni (≤11; 0.3), Cu (≤13; 1), Zn (≤10; 3), and Sn
(≤77; 2) (all in ppm) and high contents of Ga (134–405 ppm; 2).
The Ga content is comparable to that of Cu-enriched Li-bearing
tourmalines from pegmatites in Brazil, Nigeria, and Mozambique
(Peretti et al. 2009), but higher than that of black tourmaline from
NYF-type pegmatites of the Třebíč Pluton, Czech Republic, with
Ga = 78–160 ppm (Novák et al. 2011), and black tourmaline
from common pegmatites of the Strážek Moldanubicum, Czech
Republic, with Ga = 2–212 ppm (Gadas et al. 2012).
Near-IR spectrum
Water content can be determined from the intensity of the OH
overtone absorptions in the 7000 cm–1
region of the near-infrared
spectrum (Fig. 2). The total integrated area of the spectrum (||c
+ 2×^c) in Figure 2 is 1092.5 per cm2
(normalized to 1 cm
thickness). Using the density of 3.038 g/cm3
and dividing by the
factor 113 (taken from Ertl et al. 2010), an H2O concentration of
2.87 wt% is determined. This is in remarkably close agreement
with the value in Table 2, 2.86 wt%, determined by classical wet
chemical methods and with the value determined by thermogravimetric
analysis (TGA) [2.9(1) wt%; Table 2]. This value is also
consistent with the proposed darrellhenryite formula.
Table 6. X-ray powder diffraction data for darrellhenryite
dmeas (Å)	 dcalc (Å)	 Imeas	 h	k	 l
7.906	 7.911	 5	 1	1	0
6.295	 6.299	 15	 1	0	1
4.924	 4.927	 18	 0	2	1
4.575	 4.578	 7	 3	0	0
4.180	4.183	 39	 2	1	1
3.952	3.954	 54	 2	2	0
3.431	3.434	 73	 0	1	2
3.353	 3.355	 18	 1	3	1
3.084	 3.086	 8	 4	0	1
2.989	 2.991	 14	 4	1	0
2.925	2.927	 100	 1	2	2
2.873	 2.875	 4	 3	2	1
2.592	 2.594	 11	 3	1	2
2.555	2.557	 90	 0	5	1
2.433	 2.435	 1	 2	4	1
2.364	 2.366	 38	 0	0	3
2.355	 2.356	 31	 2	3	2
2.326	2.328	 42	 5	1	1
2.284	 2.286	 3	 6	0	0
2.266	 2.267	 2	 1	1	3
2.168	 2.170	 13	 5	0	2
2.147	 2.148	 21	 4	3	1
2.100	 2.101	 25	 3	0	3
2.090	 2.091	 14	 4	2	2
2.029	2.030	 42	 2	2	3
2.021	2.023	 42	 1	5	2
2.004	 2.005	 10	 1	6	1
1.978	 1.979	 4	 4	4	0
1.901	1.902	 50	 3	4	2
1.887	 1.888	 6	 3	5	1
1.854	 1.855	 12	 4	1	3
1.835	 1.837	 9	 6	2	1
1.816	 1.817	 3	 7	1	0
1.802	 1.803	 1	 6	1	2
1.759	 1.760	 15	 1	0	4
1.718	 1.719	 5	 0	2	4
1.674	 1.675	 6	 2	6	2
1.643	1.644	 49	 6	0	3
1.629	 1.630	 27	 2	7	1
1.608	 1.609	 2	 5	2	3
1.582	 1.583	 20	 5	5	0
1.576	 1.577	 9	 4	0	4
1.565	 1.566	 4	 8	1	1
1.544	 1.545	 6	 3	2	4
1.534	 1.535	 8	 4	6	1
1.523	 1.524	 9	 9	0	0
1.514	 1.515	 11	 7	2	2
1.508	 1.508	 3	 7	3	1
Note: d-values in angstroms. The unit-cell data parameters refined from the
powder data (CuKa radiation) are a = 15.820(2), c = 7.093(1) Å.The 10 reflections
withthehighestintensityareinbold.Standarddeviationsformeasuredd-values
are 0.1%. {{Authors: correct value if needed. MK}}
Figure 1. Optical absorption spectrum of darrellhenyrite normalized
to 1.0 mm thickness. (Color online.)
NOVÁK ET AL.: DARRELLHENRYITE, A NEW MINERAL FROM THE TOURMALINE SUPERGROUP 5
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Crystallography
Single-crystal X‑ray studies gave the following data: trigonal
symmetry, space group: R3m, a = 15.809(2), c = 7.089(1) Å, V =
1534.4(4) Å3
, and Z = 3. Darrellhenryite is isotypic with elbaite
and other rhombohedral (R3m) members of the tourmaline supergroup.
The refined formula for darrellhenryite, X
(Na0.56o0.44)
Y
(Li1.05Al1.95)S3.00
Z
Al6
T
(Si6O18) (BO3)3
V
(OH)3
W
(O0.66F0.34), is
in reasonably good agreement with the empirical formula
X
(Na0.58Ca0.01o0.41) Y
(Li1.03Al2.02)S3.05
Z
Al6 (BO3)2.98
T
(Si6O18) V
(OH)3
W
(O0.65F0.35); slight differences are within the limits of the refinement
and may also reflect minor chemical zoning confirmed by
chemical analyses and different ways of formula elucidation.
An H atom (H3) at the site associated with O3 was easily
located in this refinement. Ertl et al. (2002) showed that the
bond-angle distortion (s2
oct) of the ZO6 octahedron in a tourmaline
is largely a function of the <Y-O> distance of that tourmaline,
although the occupant of the O(3) site (V position in the general
formula) also affects that distortion. The covariance, r, of <Y-O>
and s2
oct of the ZO6 octahedron is –0.99 (Fig. 2 in Ertl et al. 2005)
for all investigated tourmalines whose V site is occupied by 3
(OH) groups. Darrellhenryite (with Z
s2
oct = 52.85 and <Y-O> ≈
1.984; Table 5) lies exactly on the V site = 3 (OH) line. Hence,
the V site of darrellhenryite is completely occupied by (OH).
The refinement shows that the W site is occupied by (O0.66F0.34)
(Table 4, Fig. 3). Hence, this site is clearly dominated by oxygen,
considering also the chemical data (Table 2).
The T site is completely occupied by Si.Arefinement of Si ↔
B at the T site gives no clear indication for significant amounts
of [4]
B (>0.10 apfu). Hence, in the final refinement the T site was
refined only with Si (Table 4). Recently, Lussier et al. (2011)
investigated liddicoatite samples fromAnjanaboina, Madagascar,
which contain essentially no [4]
B. Most of these Al- and Li-rich
tourmalines have a <T-O> distance of 1.617(1) Å, which is in
good agreement with the <T-O> distance of ~1.616(1) Å in
darrellhenryite (Table 5).
The X‑ray powder diffraction data for darrellhenryite is presented
in Table 6. Unit-cell parameters refined from the powder
data (Table 6), obtained by a least-squares refinement of the
setting angles of all reflections, are as follows: a = 15.820(2), c
= 7.093(1) Å, V = 1537.4(6) Å3
, very similar to those from the
single-crystal X‑ray study and data of Povondra et al. (1985).
Compositional evolution of tourmalines from the Nová Ves
pegmatite and paragenetic position of darrellhenryite
Tourmaline is a common accessory mineral in complex
pegmatites of the Moldanubian Zone including the Nová Ves
pegmatite (Povondra et al. 1985; Novák and Povondra 1995;
Novák et al. 2004; Breiter et al. 2010). Its chemical composition
evolves during pegmatite crystallization: black Mg-poor
oxy-schorl from the outer albite unit → black oxy-schorl to
blue or green Fe-rich fluor-elbaite in muscovite + quartz aggregates
from the albite unit → green Fe-rich fluor-elbaite to
pink fluor-elbaite to darrellhenryite from outer parts of the
albite-lepidolite unit → pink to pinkish darrellhenryite in albite
(cleavelandite) from the inner part of the albite-lepidolite unit
(Fig. 3). The compositional trends (behavior of Na, Al, Fe, and
F) are similar to ordinary lepidolite-subtype pegmatites from the
Moldanubian Zone (Selway et al. 1999; Novák 2000); however,
most tourmalines from Nová Ves belong to the oxy series (Fig.
3). Based on a large set of EMPanalyses, rossmanite, a common
accessory mineral in the lepidolite-subtype pegmatites from the
Moldanubian Zone, Czech Republic (Selway et al. 1998, 1999),
has not been identified from the Nová Ves locality.
Darrellhenryite is evidently the least common Li-bearing
tourmaline, and it is known only from the Nová Ves locality. The
mineral assemblage of darrellhenryite (holotype + other samples)
is characterized by abundant albite + minor quartz ± K-feldspar ±
petalite (or secondary spodumene + quartz) ± rare polylithionite
± pollucite. It differs from other pink Li-bearing tourmalines in
complex pegmatites of lepidolite-subtype and elbaite-subtype
from the Moldanubian Zone. In lepidolite-subtype pegmatites,
pink Li-bearing tourmaline (fluor-elbaite > rossmanite > elbaite;
Povondra et al. 1985; Selway et al. 1998, 1999; Novák 2000)
is typically associated with common Li-rich micas (trilithionite
> polylithionite; Černý et al. 1995) + albite ± quartz, and this
assemblage indicates high activity of F. In elbaite-subtype
pegmatites, red to pink Li-bearing tourmaline (fluor-elbaite >
fluor-liddicoatite; Povondra et al. 1985; Novák et al. 1999a,
2012) is commonly the only Li-bearing mineral, Li-rich micas
(polylithionite; Novák and Povondra 1995; Novák et al. 1999b;
Zahradníček and Novák 2012) being absent or very rare; hence, F
enters almost exclusively tourmaline. Consequently, composition
of associated Li-rich micas and their abundance play a crucial
role in the formation of darrellhenryite because they control activities
of Li and F in the system. Darrellhenryite is likely related
to Li- and B-rich but F-moderate environments characterized by
the assemblage albite ± quartz > Li-rich micas. No influence of
higher activity of O on the darrellhenryite formation is inferred
from the mineral assemblage, similar to the case of oxy-schorl
(Bačík et al. 2012).
Due to a low number of complete chemical analyses of Libearing
tourmalines and because we did not find any chemical
analysis of Li-bearing tourmaline corresponding to darrellhenryite,
we checked also electron microprobe analyses of Ca-poor
Li-bearing tourmalines published to date, where Li and H were
calculated using stoichiometric constraints: Li (apfu) = 15 – Σ
(Y+Z+T) and (OH+F) = 4 (e.g., Selway et al. 1999). Only a few
analyses of pink Li-bearing tourmalines show a combination of
Na, Al, and F contents (Na > 0.5 apfu, Al > 7.5 apfu, F < 0.5
apfu), which are indicative of darrellhenryite. The samples come
Figure 2. Near-IR spectrum of darrellhenryite (sample grr3075).
(Color online.)
NOVÁK ET AL.: DARRELLHENRYITE, A NEW MINERAL FROM THE TOURMALINE SUPERGROUP6
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from Dobrá Voda, Czech Republic (Selway et al. 1999, Table 1,
analysis no. 9{{AU: OK? clearer that it is their Table}}); Tanco,
SE Manitoba, Canada (Selway et al. 2000, Table 4, analysis
no. 5); Utö, Sweden (Selway et al. 2002, Table 2, analysis no.
7); and Bennet Mine, southern Maine (Wise and Brown 2010,
Table 8, analysis no. 8). They typically show high vacancies at
the X site (~0.43–0.48 pfu) and low to moderate F (0.23–0.39
apfu), so they are compositionally close to rossmanite (Selway
et al. 1998). Consequently, a detailed study (ideally including
EMPA, single-crystal X‑ray diffraction, LA-ICP-MS, SIMS, and
spectroscopic methods) is required to distinguish the Ca-poor
Li-bearing tourmalines—elbaite, fluor-elbaite, rossmanite, darrellhenryite,
and the hypothetical o-Li-O phase (Table 1) —in
{{auth: okay? From? Sentence seems to be missing something}}vacant
subgroup 4 (Henry et al. 2011).
Acknowledgments
We sincerely thank the reviewers A. McDonald and F. Colombo for their
careful reviews of the manuscript as well as the comments of the members of the
CNMNC of the IMA, which improved this manuscript significantly. This work was
funded by GAP 210/10/0743 (M.N., P.G., and R.Š.) and by the Austrian Science
Fund (FWF) project no. P23012-N19 (A.E.) with contributions from NSF grant
EAR-0947956 (G.R.R.). M.V.G. acknowledges the European Regional Development
Fund project “CEITEC” (CZ.1.05/1.1.00/02.0068).
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analyses (Povondra et al. 1985); square = black oxy-schorl; triangle = green Fe-rich fluor-elbaite; circles = pink darrellhenryite to darrellhenryite
= fluor-elbaite; star = type material data (Table 2, analysis b). {{AU:OK?}}
NOVÁK ET AL.: DARRELLHENRYITE, A NEW MINERAL FROM THE TOURMALINE SUPERGROUP 7
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Manuscript received November 26, 2012
Manuscript accepted May 27, 2013
Manuscript handled by Fernando Colombo