Mineralogical Magazine, February 2011, Vol. 75(1), pp. 135–144

Bariopharmacoalumite, a new mineral species
from Cap Garonne, France and Mina Grande, Chile
S. J. MILLS1,*, M. S. RUMSEY2, G. FAVREAU3, J. SPRATT2, M. RAUDSEPP1 AND M. DINI4
1

2
3
4

Department of Earth and Ocean Sciences, University of British Columbia, 6339 Stores Rd, Vancouver, British
Columbia, Canada, V6T 1Z4
Department of Mineralogy, Natural History Museum, Cromwell Road, London SW7 5BD, UK
421 Avenue Jean Monnet, 13090 Aix-en-Provence, France
Escuela de Sociologı́a, Universidad Central, Av. Francisco de Aguirre 0405, La Serena, Chile[Received 10 November 2010; Accepted 27 January 2011]

ABSTR ACT

Bariopharmacoalumite, ideally Ba0.5Al4(AsO4)3(OH)4·4H2O, is a new mineral from Cap Garonne,
France. It occurs in several places within the mine as colourless to pale yellow interpenetrating cubes
up to 0.5 mm across. Bariopharmacoalumite is transparent to translucent, with a white streak, has anadamantine lustre and imperfect cleavage on {001}. The Vickers hardness is 234.35 and the Mohs
harness is 3.5. Bariopharmacoalumite is isotropic, with n = 1.573 (upper estimate) [calculated fromreflectance values at 589 nm using Fresnel Equations]. The empirical formula, based on 20 oxygen
atoms, is: (Ba0.54Cu0.03K0.01)S0.58(Al3.99Fe0.02)S4.01(AsO4)3.00(OH)3.85O0.15·4H2O and the calculated
density (on the basis of the empirical formula and single-crystal unit cell) is 2.580 g/cm3. The fourstrongest lines in the X-ray powder diffraction pattern are [dobs(Å), Iobs,(hkl)]: 7.759, 100, (001); 5.485,
27, (011); 3.878, 27, (002); 4.454, 18, (011). Bariopharmacoalumite from Cap Garonne is cubic, spacegroup P4̄3m with a = 7.742(4) Å, V = 464.2(4) Å3 and Z = 1. The crystal structure was solved bydirect methods and refined to R1 = 0.0705 for 215 reflections with I > 4s(I) and is consistent withmembers of the pharmacosiderite supergroup. Data are also presented from zoned bariopharmacoalumite bariopharmacosiderite crystals found at the Mina Grande mine, Chile.

K EY WORDS : bariopharmacoalumite, bariopharmacosiderite, crystal structure, Cap Garonne, new mineral, Mina
Grande mine, pharmacosiderite supergroup, Chile.

Introduction
THE pharmacosiderite supergroup of minerals(Rumsey et al., 2010) has been thoroughly
investigated recently to determine the crystal
structure and exchange properties of members of
the supergroup (e.g. Mills et al., 2010a,b; Rumsey* E-mail: smills@nhm.org
Present address: Mineral Sciences Department, Natural
History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, California 9007, USA
DOI: 10.1180/minmag.2011.075.1.135# 2011 The Mineralogical Society

et al., 2010). During these investigations, several
new species have been discovered: includinghydroniumpharmacosiderite (Mills et al., 2010b)
and natropharmacoalumite (Rumsey et al., 2010),
while several species of ‘‘ivanyukites’’, also partof the supergroup, were described by
Yakovenchuk et al. (2009). Here we present thethird new member in our series of reports:
bariopharmacoalumite. The mineral and name
(IMA 2010-041) were approved by the IMA
Commission on New Minerals, Nomenclature andClassiﬁcation prior to publication. The holotype ispreserved in the collections of the Natural History
Museum, London, under the registration number
BM 2010,82. Material removed from thisS. J. MILLS ET AL.

specimen and prepared for optical and chemical
analysis is additionally registered as P16907.
Further co-type material from the same ﬁnd isregistered as BM 2010,83 and material from the
Mina Grande mine (which is not considered typebut discussed in this paper) is registered as BM
2010,84.

New occurrences
Cap Garonne
The old copper mine of Cap Garonne is locatednear the town of Le Pradet, Var, France. It was
operated between 1862 and 1917 through thetechnique of ‘chambers and pillars’. Two mines
were opened
the North and South mines,
working sub-horizontal veins of conglomerates
and sandstones of Triassic age. The minerals
present are mainly secondary species derivingfrom the breakdown of tetrahedrite/tennantite andgalena, usually developing in fractures or more
rarely in cavities within the country rock (e.g.
perroudite/capgaronnite/iltisite and ktenasite/
guarinoite/theresemagnanite). Part of the Northmine now hosts a museum dedicated to theHistory
A number of bariopharmacoalumite occurrences
has been reported in the literature over the past
50 years under different names. These aredescribed brieﬂy below:‘Barium-alumopharmacosiderite’
Walenta (1966) ﬁrst reported a sample of‘‘barium-alumopharmacosiderite’’ from theancient copper mines of Neubulach, Black
Forest, Germany. The ‘‘barium-alumopharmacosiderite’’ samples were all Fe-bearing and zoned,
but in all instances were Al-dominant. The
mineral forms as crusts of pale yellow crystals
on mansﬁeldite and is associated with arsenocrandallite. The crystals form as cubes [{001}] up
to 50 mm across, with the form {111} rarely
observed. Refractive indices show n = 1.650 (rim)and n = 1.62 (core). Walenta (1966) also observed
anomalous bluish to brownish interference
colours and noted sector zoning. The celldimension (determined from powder data) was:a = 7.89 Å, with the probable space group P4̄3m.
The mineral and its description were neversubmitted to the IMA for approval.
Wittern (2001) also reported ‘‘barium-alumopharmacosiderite’’ from the Michael mine,
Weiler, Black Forest, Germany.
‘‘Barium-zinc-alumopharmacosiderite’’‘‘Barium-zinc-alumopharmacosiderite’’ was also
published without approval by Sarp et al. (1994)
from Cap Garonne, France. Sarp et al. (1994)
reported the ideal formula as: Ba0.5Cu0.5Al4(AsO4)3(OH)5·5H2O, and associated minerals
including weilerite, mansﬁeldite, zeunerite, metazeunerite, cornubite, parnauite and olivenite. The
crystals are colourless and pseudocubic, with amaximum dimension of 0.3 mm across. The
crystal system was reported as tetragonal, withspace group I4̄2m and cell a = 15.476(2) and c =15.675(4) Å.

FIG. 1. Schematic map of the North mine, Cap Garonne,
showing the position of the type locality (red arrow).

136

BARIOPHARMACOALUMITE, A NEW MINERAL

FIG. 2. View of pillar 44b, Cap Garonne mine. Arrow indicates the site where the type specimens were found.

mining history of the site, collaborating with the
Association des Amis de la mine de Cap Garonne(AAMCG) to develop knowledge regarding themineralogy of the mine.
Cap Garonne is the type locality for 12 species(camerolaite, capgaronnite, deloryite, geminite,guarinoite, iltisite, mahnertite, perroudite, pradetite, pushcharovskite, theresemagnanite, andzdenekite), and was the subject of two PhD
studies (Guillemin, 1952; Chiappero, 1993). The
latter introduced a systematic numbering of thepillars of the North mine, now used to locate
accurately the origin of specimens. This
numbering was extended by the AAMCG to
include the walls at the periphery of the mine.
The type specimen of bariopharmacoalumite
was collected in one of these new pillars, named
44b (Fig. 1). A long fracture in the conglomerate
extends vertically from the lead-bearing levels(here associated with iron) at the top of themineralized vein, down to copper-bearing levels
at the bottom. Several aluminium-bearing
minerals are observed in this fracture, including
mansﬁeldite and philipsbornite. Other minerals
present include: beudantite, carminite, duftite,
mimetite, and scorodite in the Fe/Pb area, andolivenite and lavendulan in the Cu area (Fig. 2).
The mineral has also been found at four otherplaces in the Cap Garonne mines. One in the
North mine, where it was found opposite the pillar
that produced the type specimen, in pillar 44, as

small (0.3 mm) white cubes covering fractures of
the conglomerate, where it is associated witholivenite, arsentsumebite and philipsbornite, andthree in the South mine, from pillars that are not
yet numbered. One of these South-mine occurrences is already famous among collectors for the
discovery of deloryite (Sarp and Chiappero,
1992). At this locality, bariopharmacoalumite
was collected in isolated white cubes (to0.5 mm) in fractures containing zeunerite andmansﬁeldite. In the other two occurrences of theSouth mine, bariopharmacoalumite is found withlavendulan, mansﬁeldite and olivenite.
A bariopharmacoalumite-bearing specimen of
unknown origin from within Cap Garonne mine isalso present in the collections of the NHM,
London registered originally as mansﬁeldite (BM1965,346). This is a large 15 cm615 cm piece(Fig. 3) of fracture surface that was collected
before the pillar numbering system was implemented. It shows rich encrustations of pale yellow
bariopharmacoalumite cubes associated with
mansﬁeldite, sky-blue arsenogorceixite andolivenite.
Mina Grande mine

137

The mine consists of two claims, Mina Grandeand San Antonio, both now largely made up of old
dumps and rock piles. The Mina Grande wasworked for secondary copper ore by artisan

S. J. MILLS ET AL.

F IG . 3. Sample 1965,346 showing pale yellow
bariopharmacoalumite cubes associated with mansﬁeldite, sky-blue arsenogorceixite and olivenite. Field ofview: 16 cm across.

miners known locally as ‘pirquineros’1, and bothproperties, notably Mina Grande, were worked forprimary Cu (bornite and chalcopyrite) and Ag
before 1840.
The local geology is dominated by andesitic
breccias, which, according to Domeyko (1848),
can be described as brecciated porphyric rock(‘‘porphyre bigarré’’). Geological interpretation of
the site shows nearly horizontal mineralized strata(locally called ‘‘mantos’’) that are probably
sedimentary or volcanic in origin. This unit
consists of bands of ﬁnely crystalline siliceousand calcareous rock, alternating with bands ofmore coarsely crystalline calcareous rock and it iswithin the latter, that most of the mineralization isfound. The mantos are cut by vertical fault-related
fractures that also carry signiﬁcant mineralization
and both of these mineralized features are cut bylater non-mineralized basic dykes (Wilmot, 1960).
There are two main veins recognized at Mina
Grande Veta Negra and Veta Blanca, both foundin the west fault fracture. The main gangue mineral
here is baryte, which is found in large quantities on
the outer boundaries of the mineralized veins(Benitez, 1949). Other gangue materials include:

1

quartz, jasper and other undifferentiated brecciatedcarbonates. Near the surface, oxidized mineralization can still be observed in the form of secondary
copper minerals including carbonates (malachite
and azurite), silicates (chrysocolla), sulphates(brochantite) and arsenates (cornubite and olivenite). Domeyko (1848) also reported secondary Pb
minerals including mimetite and pyromorphite.
Bariopharmacoalumite occurs here as zones
within bariopharmacosiderite crystals. Due to themode of occurrence, we were unable to determine
all the physical properties of the mineral and so
this occurrence could not be considered for cotype status. The bariopharmacoalumite–bariopharmacosiderite crystals are associatedwith quartz and chalcedony on a limonite-goethitematrix, which occurs close to the siliceouscalcareous strata.
Physical and optical properties
Cap Garonne
Bariopharmacoalumite typically occurs as radial
growths of colourless to pale yellow interpenetrating cubes up to several millimetres across(Figs 4, 5). Individual cubes are generally<100 mm in size and some exhibit stepped
growth features. Some cubes are elongated,giving a rectangular outline. The only form
observed is {001}. Bariopharmacoalumite istransparent to translucent, with a white streak,has an adamantine lustre and imperfect cleavage
on {001}. The tenacity is brittle, fracture irregularand is non-ﬂuorescent. The Vickers hardness is234.35 (load 245.75 mN) with a range(10 measurements) of 165.24 327.38, which isequivalent to 3.5 on the Mohs scale. The calculated
density (on the basis of the empirical formula andsingle-crystal unit cell) is 2.580 g/cm3.
Bariopharmacoalumite is isotropic, with n =1.573 (upper estimate) [calculated from reﬂectance values at 589 nm using Fresnel Equations].
A determination from individual fragments was
attempted using refractive index oils; the results
proved inconsistent however, probably due tominor chemical zonation. Bariopharmacoalumiteshows anomalous extinction, typical of membersof the supergroup and deep blue internal
reﬂections probably due to twinning.
Mina Grande mine

Pirquineros is the Chilean word meaning free handcraft
miners, who worked together in small cooperatives orinformal groups.

138

Bariopharmacoalumite occurs as thin growthzones within bariopharmacosiderite crystals

BARIOPHARMACOALUMITE, A NEW MINERAL

FIG. 4. BSE image of interpenetrating cubes of bariopharmacoalumite from Cap Garonne (South mine). Field ofview: ~150 mm across.

3 mm62 mm fragment from Cap Garonne
consisting of ~100 intergrown crystals, using a
Cameca SX100 electron microprobe at the
Natural History Museum, London. The operating
conditions were: 10 kV, 4 nA and a 30 mm beam
diameter. Si, Ca, Na, P, Ti, Sr, Cl and F were

(Figure 6). The crystals range in colour fromyellow to orange to light brown and in size from
0.1 to 0.5 mm across. {001} is the only form
observed. The crystals are opaque, have an orange
streak and a dull lustre.
Chemical composition
Quantitative wavelength-dispersive EMP analyses(sixteen points) were carried out on a

FIG. 5. Radial growths of yellowish interpenetrating
cubes of bariopharmacoalumite from Cap Garonne(pillar 44b). Field of view: 1 mm across (photo
Jean-Marc Johannet).

FIG. 6. Backscattered SEM image showing zoning in asingle bariopharmacoalumite-bariopharmacosiderite
crystal from the Grande mine, Chile. The brighter areas
are bariopharmacoalumite. The crystal is ~200 mm
across.

139

S. J. MILLS ET AL.

TABLE 1. Analytical data for bariopharmacoalumite from Cap Garonne.

K2O
BaO
CuO
Al2O3
Fe2O3
As2O5
H2O*
Total

Wt.%

Range

SD

Standards

0.07
11.35
0.35
27.89
0.19
47.28
14.58
101.71

0.0 0.19
10.80 11.91
0.26 0.46
26.72 28.75
0.0 1.21
46.43 47.83
11.87 13.72

0.06
0.28
0.06
0.64
0.38
0.28
0.54

KBr
BaryteCopper metal
Corundum
Fayalite
GaAs* Calculated for the tetrahydrate.

sought for but were below the detection limit. The
presence of OH and H2O were conﬁrmed by the
crystal-structure analysis, but insufﬁcient material
was available for a direct determination of H2O.
H2O was thus calculated from the results of thecrystal-structure determination. Analytical data
are given in Table 1. It should be noted that theslightly high total is attributed to the sensitivity ofthe mineral in the electron beam.
The empirical formula (based on 20 O atoms)
is: (Ba 0.54 Cu 0.03 K 0.01 ) S0.58 (Al 3.99 Fe 0.02 ) S4.01(AsO4)3.00(OH)3.85O0.15·4H2O. It is noted thatthe charge of (Ba 0.54 Cu 0.03 K0.01) is 1.15 + ,necessitating the deprotonation of 0.15 p.f.u. of
the bridging OH ions. The simpliﬁed and ideal
end-member formula of bariopharmacoalumite is:
Ba 0.5Al4(OH) 4(AsO4 )3.4H 2O, which requires
BaO 10.45, Al2O3 27.87, As2O5 47.00, H2O
14.74, total 100.00 wt.%.

British Columbia (Table 3). A single, cubeshaped fragment from a larger crystal mass wasused for collection of intensity data at 293 K. The
data were processed using the Bruker Apex
program suite (Bruker, 2003), with data reduction
using the SAINT program and absorption correction by the multi-scan method using SADABS(Bruker, 2003).
The structure was solved in space group P4̄3m
by direct methods using SHELXS-97 andsubsequent difference Fourier syntheses followed
by full-matrix least-squares reﬁnement on F2
using SHELXL-97 (Seldrick, 2008). The initial
location of the framework ions Fe/Al, As, O1 andO2 revealed that they were located in similar
positions to those reported by Zemann (1947,
1948) and Buerger et al. (1967) for the generalpharmacosiderite structure. The O atoms of the

Crystallography
Cap Garonne
X-ray powder diffraction data for Cap Garonne
bariopharmacoalumite were obtained on a Bruker
D8 powder diffractometer, utilizing Co-Ka
radiation at the Department of Earth and Ocean
Sciences, University of British Colombia,
Canada. Data collected on a ﬂat plate, areshown in Table 2. The reﬁned unit-cell parameters using Checkcell (Laugier and Bochu,
2004) were: a = 7.742(4) Å and V =464.2(4) Å3, which correspond well to thesingle-crystal data (see below).
The single-crystal study was carried out using a
Bruker X8 ApexII single-crystal diffractometer at
the Department of Chemistry, University of

TABLE 2. Powder X-ray data for bariopharmacoalumite from Cap Garonne.
hkl

dobs

Iobs

dcalc

Icalc

001
011
111
002
012
112
022
003
103

7.759
5.485
4.454
3.878
3.456
3.159
2.738
2.582
2.452

100
27
18
27
14
16
16
10
12

7.738
5.471
4.467
3.869
3.460
3.159
2.736
2.580
2.447

100
12
24
24
8
34
51
6
44

The four strongest lines are in bold.

140

BARIOPHARMACOALUMITE, A NEW MINERALTABLE 3. Crystallographic data and reﬁnement parameters for bariopharmacoalumite.
Cap Garonne

Mina Grande

Crystal data
Ideal formula
Crystal system
Space group
Unit-cell parameters, a (Å)
Unit-cell volume, V (Å3)
Z
Calculated density (g/cm3)
Absorption coefficient (mm 1)
Crystal size (mm)Ba0.5(Al,Fe)4(OH)4(AsO4)3.4H2O
cubic
P4̄3m
7.772(2)469.4(2)
1
2.58
7.827
0.1560.1560.15

Ba0.5(Al,Fe)4(OH)4(AsO4)3.4H2O
cubic
P4̄3m
7.850(2)483.7(2)
1
2.61
8.802
0.2060.2560.15

Data collection
Diffractometer
Temperature (K)Radiation, wavelength (Å)
y range for data collection (º)
h, k, l ranges
Total reflections collected
Unique reflections
Unique reflections F > 4s(F)Data completeness to ymax (%)

Bruker X8 ApexII
293
Mo-Ka, 0.71073
2.62 26.32
7 ? 9; 3 ? 9;
1230
215
168
99.2

Bruker X8 ApexII
293
Mo-Ka, 0.71073
2.59 28.77
8 ? 8; 10 ? 2;
853
266
192
98.8

Structure refinement
Refinement method
No. of refined parameters, restraints
Weighting coefficients a, b *Extinction coefficient
Data/restraints/parameters
R1 [F > 4s(F)], wR2 [F > 4s(F)],R1 all, wR2 allGoodness-of-fit on F2
Largest diff. peak and hole ( e/Å3)

Full-matrix least-squares on F224, 10.1424, 0.99
0.12(3)215/1/24
0.0705, 0.1737
0.0929, 0.1924
1.007
3.31, 0.62

7 ? 7

6 ?7

Full-matrix least-squares on F226, 10.163, 0.156
0266/1/26
0.1004, 0.2459
0.1348, 0.2657
1.177
1.80, 2.565* Sheldrick (2008)

fractionally occupied H2O molecules (O3 and O4)
and the hydrogen for the hydroxyl atom (H2)were then added to the structure based on
inspection of the difference Fourier map(Table 4). Reﬁnement of the Ba site gave
0.41 a.p.f.u. though attempts to reﬁne K on thesite resulted in an unstable reﬁnement. The
R-factor increased in both cases; therefore weconstrained the site at 0.5 a.p.f.u.. Reﬁnement of
the Al site gave an Al:Fe ratio of 0.78(4):0.22(4),which is more Fe-rich than the crystals analysedby electron probe pharmacosiderite supergroupminerals tend to be zoned and can vary greatly
from crystal to crystal. With the occupancies forO3 and O4 ﬁxed at their previously reﬁned values
and with their thermal parameters constrained to
be isotropic, due to the partial occupancy of these141

atoms, an anisotropic reﬁnement converged to R1= 0.0650. The structure reported herein is
inverted; however, this gives atomic coordinates
which are more easily comparable to all
previously reported structures. This treatment is
consistent with the structural reports for othermembers of the pharmacosiderite supergroup.
The average bond lengths (Table 5) for<As O> and <Al O> are fairly typical (1.665
and 1.933 Å), while the distance between O2 andO4 is 2.72 Å, which is indicative of H-bonding.
The average bond length for the Ba site is3.197 Å, which is in 12-fold coordination, isalso very typical. All these values are consistent
with the previous structure reports for thesupergroup (e.g. Buerger et al., 1967; Mills etal., 2010a,b; Rumsey et al., 2010).

00.1421(5)0.1421(5)0.3809(16)0.8881(13)0.829(2)^0.120(8)0.686(5)00.1427(5)0.1427(5)0.393(2)0.8878(19)0.829(2)^0.137(13)0.690(10)Mina Grande
As1
^
Al1
0.1427(5)Fe10.1427(5)O10.127(2)O20.8878(19)H20.829(2)
Ba1
0
O3
^
O4
0.690(10)y/b

Cap Garonne
As1
^
Al1
0.1421(5)Fe10.1421(5)O10.1259(12)O20.8881(13)H20.829(2)
Ba1
0
O3
^
O4
0.686(5)

x/a

142
0
0.1427(5)0.1427(5)0.127(2)0.8878(19)0.829(2)^^0.690(10)00.1421(5)0.1421(5)0.1259(12)0.8881(13)0.829(2)^^0.686(5)z/c10.58(5)0.42(5)
1
1
1
0.17
0.2
0.2

1
0.78(4)0.22(4)
1
1
1
0.17
0.19
0.44

Occ.

0.0237(14)0.0115(18)0.0115(18)0.040(5)0.023(8)0.028
0.031(3)0.02(2)0.02(3)0.0315(13)0.028(3)0.028(3)0.038(4)0.026(5)0.031
0.049(3)0.017(12)0.051(13)

Ueq or Uiso

0.019(2)0.0115(18)0.0115(18)0.047(8)0.023(8)0.0258(17)0.028(3)0.028(3)0.036(4)U110.0259(18)0.0115(18)0.0115(18)0.026(10)0.023(8)0.0344(15)0.028(3)0.028(3)0.036(4)U220.0259(18)0.0115(18)0.0115(18)0.047(8)0.023(8)0.0344(15)0.028(3)0.028(3)0.043(7)U33

00.0017(16)0.0017(16)0.001(6)0.006(6)00.0039(17)0.0039(17)0.004(4)U2300.0017(16)0.0017(16)0.009(10)0.006(6)00.0039(17)0.0039(17)0.004(4)U13

TABLE 4. Final atom coordinates, site occupancies and atom displacement parameters (Å2) for bariopharmacoalumite.

00.0017(16)0.0017(16)0.001(6)00.0039(17)0.0039(17)0.004(5)U12

S. J. MILLS ET AL.

BARIOPHARMACOALUMITE, A NEW MINERALTABLE 5. Selected bond distances (Å) for bariopharmacoalumite.

As1
Al1
Al1
Ba1
Ba1
O2
O4

O1
O1
O2
O4
O1
H2
H2

Cap Garonne

Mina Grande

1.665(14)1.864(14)2.002(9)3.183(6)3.204(6)0.80(2)
1.92(4)1.64(2)
1.97(2)2.029(12)3.220(6)3.205(10)0.80(2)
1.89(9)

64
63
63
64
68

We have also conﬁrmed an additional locality
for bariopharmacoalumite from the Gambatesa
mine, Val Graveglia, Liguria, Italy, where it
occurs as very pale greenish cubes on white
schistose rock. The occurrence has been
conﬁrmed by single-crystal X-ray studies (Uwe
Kolitsch/SJM) [P4̄3m, a = 7.7515(10)] andSEM-EDS analyses (Corrado Balestra).
Acknowledgements
Associate Editor, G. Diego Gatta, Structures
Editor, Fernando Cámara, and two anonymous
reviewers are acknowledged for providing helpfulcomments on the manuscript. Uwe Kolitsch andCorrado Balestra are thanked for providing
information about the Italian sample. Jean-Marc
Johannet is thanked for taking photographs of thetype specimen and Harry Taylor of the NHM
photography unit for taking photographs of
specimen BM 1965,285.

Mina Grande mine
A single crystal from the Mina Grande mine wasalso studied and determined in the same manneras the Cap Garonne sample to R1 = 0.1004(Table 3). Because of the diffuse nature of the
spots, which correspond to the two different
minerals, the R-factor is slightly larger thanideal, though reﬁnement of the Al/Fe site canact as a proxy for bariopharmacoalumite:bariopharmacosiderite composition. In the case of thes t u d i e d ‘ cr y s t al ’ th e r e ﬁ n e d A l : F e i s
0.58(4):0.42(4) (Table 4), indicating that thezoning seen in Fig. 6 is pervasive throughout
the crystals, and that there is roughly an equal
proportion of bariopharmacoalumite and bariopharmacosiderite in the bulk crystal.
Discussion
All ‘‘barium-alumopharmacosiderite’’ and‘‘barium-zinc-alumopharmacosiderite’’ reports
constitute legitimate bariopharmacoalumite
occurrences in accordance to the nomenclaturescheme of the pharmacosiderite supergroup(Rumsey et al., 2010). The tetragonal ‘‘bariumzinc-alumopharmacosiderite’’ from Cap Garonne
can be considered bariopharmacoalumite-Qac
using polytypic nomenclature (where the cubic
polytypes are sufﬁxed Ca). It is of note that both
polytypes have also been reported for bariopharmacosiderite (Hager et al., 2010). The formula
reported by Sarp et al. (1994) for ‘‘barium-zincalumopharmacosiderite’’ is incorrect, as it isprobable that Ba+Zn = 0.5 a.p.f.u., and that(OH) 4 4. The instability of the mineral underthe microprobe is likely to be the source of theerrors in the reported totals. In the case where thetotal cation charge is >1+, deprotonation of OH
occurs, therefore (OH)5 is impossible.

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