81
The Canadian Mineralogist
Vol. 57, pp. 81-90 (2019)
DOI: 10.3749/canmin.1800057

FERRIERITE-NH4, (NH4,Mg0.5)5(Al5Si31O72)22H2O, A NEW ZEOLITE FROM NORTHERN
BOHEMIA, CZECH REPUBLIC
NIKITA V. CHUKANOV§
Faculty of Geology, Moscow State University, Leninskie Gory, Moscow, 119991, Russia
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region, 142432, Russia

IGOR V. PEKOV
Faculty of Geology, Moscow State University, Vorobievy Gory, Moscow, 119991, Russia

JIŘÍ SEJKORA
Department of Mineralogy and Petrology, National Museum, Cirkusová 1740, 193 00 Praha 9, Czech Republic

JAKUB PLÁŠIL
Institute of Physics, Academy of Sciences of the Czech Republic v.v.i, Na Slovance 2, 182 21 Prague 8, Czech Republic

DMITRIY I. BELAKOVSKIY
Fersman Mineralogical Museum of Russian Academy of Sciences, Leninskiy Prospekt 18-2, Moscow, 119071, Russia

SERGEY N. BRITVIN
Department of Crystallography, Saint Petersburg State University, University Embankment 7/9, 199034 Saint Petersburg, Russia

ABSTRACTThe new zeolite ferrierite-NH4, ideally (NH4,Mg0.5)5(Al5Si31O72)22H2O, was discovered in open pits at Libouš and Bı́lı́na
in the Miocene Most Basin, which is situated in the Czech Republic. The associated minerals are calcite, siderite, whewellite,
quartz, opal, baryte, and clay minerals (at Libouš) and marcasite, pyrite, baryte, sphalerite, and gypsum (at Bı́lı́na). FerrieriteNH4 forms white radiating aggregates up to 2 mm across consisting of thin flattened prismatic crystals. Density calculated fromthe empirical formula is 2.154 g/cm3. Ferrierite-NH4 is optically biaxial, positive, a ¼ 1.518(2), b ¼ 1.520(2), c ¼ 1.522(2) (k ¼
589 nm). The IR spectrum shows the presence of the NH4þ cation. The chemical composition of the holotype sample is (wt.%;
electron microprobe, H and N analyzed by gas chromatography of products of ignition): (NH4)2O 2.7, Na2O 0.24, MgO 1.63,
Al 2 O 3 10.48, SiO 2 69.44, H 2 O 14.8, total 99.29. The empirical formula based on 36 SiþAl pfu is
H0.35[(NH4)2.74Mg1.07Na0.21](Al5.44Si30.56O72)21.55H2O. Ferrierite-NH4 is orthorhombic, space group Immm, with a
19.10(1) Å, b 14.15(1) Å, c 7.489(3) Å, V 2024(3) Å3, and Z ¼ 1. The strongest lines of the powder X-ray diffraction
pattern [d, Å (I, %) (hkl)] are: 9.52 (97) (200), 6.95 (28) (101), 6.60 (19) (011), 3.988 (61) (321, 031, 420), 3.784 (19) (330),
3.547 (73) (112, 040), 3.482 (100) (202), 3.143 (37) (141, 312).

Keywords: ferrierite-NH4, zeolite, ammonium, new mineral, Libouš, Bı́lina, Most Basin, Czech Republic.

§

Corresponding author e-mail address: chukanov@icp.ac.ru

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82

THE CANADIAN MINERALOGISTINTRODUCTION
This paper describes a new zeolite, ferrierite-NH4,
which was found as a relatively abundant mineralphase in two different areas of the Miocene Most
Basin (northern Bohemia), also formerly called theNorth Bohemian Brown-Coal Basin, in the Czech
Republic. The new mineral was named by analogy
with other ferrierite-series zeolites: ferrierite-Na,
ferrierite-K, and ferrierite-Mg. The sufﬁx modiﬁer-NH4 indicates that ammonium is the prevailing extraframework cation.
The mineral and its name have been approved by
the IMA Commission on New Minerals, Nomenclature
and Classiﬁcation (IMA no. 2017-099). The holotype
specimen of ferrierite-NH4 is deposited in thecollections of the Fersman Mineralogical Museum of
the Russian Academy of Sciences, Moscow, Russia,
with the registration number 5120/1.

OCCURRENCE
The Miocene Most Basin is the largest of fourbasins in the Ohře (Eger) graben system in the Czech
Republic and is located in the central part of thesystem. Its total area is about 1400 km2 (Rajchl et al.
2009) and the basin ﬁll remnants are preserved over an
area of about 870 km2 (Kvaček et al. 2004). The
maximum total thickness of the preserved freshwater
sediments is 500 m (Grygar & Mach 2013). The
majority is composed of clastic sediments (clays andsands), but the economically important part is organic
matter in the form of coal seams. The main coal seam,
covering more than half of the basin, has a thickness of
20–30 m. In the remaining area of the basin the coalseam is absent or is split into several coal seams byclastic interlayers (Dvořák et al. 2012). About 63
mineral species have been described from here
(Dvořák et al. 2012), including the new minerals
humboldtine (Breithaupt 1822), tschermigite (Kobell1853), and bı́linite (Šebor 1913).
Specimens containing the new mineral ferrieriteNH4 were collected from two large, active open coalpits: the Libouš open pit (the Doly Nástup Tušimice
mine, Fig. 1) in the western part of the Most basin, andthe Bı́lina open pit (the Doly Bı́lina mine) in theeastern part of the basin. The distance between theseoccurrences is more than 40 km. The ﬁrst analyzed
samples and the holotype were found by Oldřich
Janeček in 2004 at the eastern margin of the Libouš
open pit (the cadastre of the former village of Krbice,50.41285008 N, 13.38150368 E). They were collectedfrom the base of the main coal seam and occur there asradiating aggregates of elongated tabular crystals(described below as sample Li1x) or ﬁne ﬁbrous

FIG. 1. Occurrence of ferrierite-NH4 in the hanging wall of themain coal seam (Li2) at the eastern margin of the Libouš
open pit. During coal mining, the occurrences offerrierite-NH4 were observed over an area of several
thousand m2. Photo by T. Novotný, 2017.

aggregates (Li1f) in fractures in abundant pelosiderite
nodules in association with calcite, siderite, whewellite, quartz, opal, baryte, and clay minerals. Later,
occurrences of ferrierite-NH4 were also discovered at
the eastern margin of the Libouš open pit (50.4252517
N, 13.3812767 E) in the hanging wall of the main coalseam (Li2). Above the coal seam there is a 1.5 m thicklayer of dark brown carbonaceous shale with abundantsmall siderite concretions bearing radiating aggregatesof ferrierite-NH4.
In the southern part of the Bı́lina open pit (thecadastre of the former village of Jenišův Újezd),
ferrierite-NH4 was found by Roman Gramblička in asomewhat different geological situation. It is foundonly in the proximity of the Bı́lina fault, and it isobserved in fractures of carbonate concretions, as wellas in siderite and sandstone bands in the base of themain coal seam. Associated minerals are marcasite,
pyrite, baryte, sphalerite, and supergene gypsum. The
analyzed samples were found in 2011 (Bi1), 2012
(Bi2), and 2017 (Bi3) in a line between GPS
coordinates 508 33.09558 0 N, 138 43.02042 0 E and508 33.11767 0 N, 138 42.85205 0 E.

GENERAL APPEARANCE AND PHYSICAL PROPERTIESAt the ﬁrst (holotype, Li1x) occurrence ferrieriteNH4 forms white radiating aggregates with silky luster
up to 1.5 mm across (Fig. 2a, b) consisting of very thin
ﬂattened prismatic crystals (Fig. 3) elongated along(001) and growing on pelosiderite rocks consisting ofsiderite, opal, kaolinite, goethite, and organic matter.
Individual brittle to ﬂexible crystals are transparent
and exhibit vitreous luster. At the same place,abundant white aggregates of ferrierite-NH4 (Li1f)

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FERRIERITE-NH4, A NEW ZEOLITE MINERAL

83

composed of ﬂexible ﬁbers 1 to 5 lm thick (Fig. 4)
were also observed. In other occurrences in the Libouš(Li2) and Bı́lina (Bi1–3) open pits, radiating aggregates of ferrierite-NH4 up to 2 mm across are mostcommon, but there are also random aggregates of thinﬁbers covering an area of several cm2.
Cleavage is not observed. Density calculated using
the empirical formula is 2.154 g/cm3. Ferrierite-NH4
exhibits intense bluish white ﬂuorescence under both
short- (254 nm) and long-wave (366 nm) UV
radiation; such ﬂuorescence is unusual for zeolitegroup minerals.
Ferrierite-NH4 is optically biaxial, positive, a ¼
1.518(2), b ¼ 1.520(2), c ¼ 1.522(2) (k ¼ 589 nm). 2V(calc.) ’ 908. The optical orientation is Z ¼ c. Under
the microscope ferrierite-NH4 is colorless and nonpleochroic.

INFRARED SPECTROSCOPY

FIG. 2. (a) Radiating aggregate of ferrierite-NH4 crystals on arock consisting of siderite, opal, kaolinite, goethite, andorganic matter; Libouš open pit (Li1). Photo by A.
Kasatkin. Field of view 2 mm. (b) White radiating
aggregates of ferrierite-NH4 crystals in association withtiny grey siderite crystals on pelosiderite; Libouš open pit(Li1). Field of view 5 mm.

FIG. 3. Elongated ﬂattened prismatic crystals of ferrieriteNH4; Libouš open pit (Li1x). SEM photo. Field of view
300 lm.

In order to obtain an IR absorption spectrum,
ferrierite-NH4 powder was mixed with anhydrous KBr,
pelletized, and analyzed using an ALPHA FTIR
spectrometer (Bruker Optics) at a resolution of 4
cm–1. A total of 16 scans were collected. The IR
spectrum of an analogous pellet of pure KBr was used
as a reference.
Absorption bands in the IR spectrum of ferrieriteNH4 (Fig. 5) and their assignments are as follows(cm–1; s – strong band, w – weak band, sh – shoulder):3610, 3565sh, 3360w (O–H stretching vibrations of
H2O molecules); 3250, 3220sh (N–H stretchingvibrations of ammonium cations); 1646 (bending
vibrations of H2O molecules); 1474 (bending vibrations of ammonium cations); 1216s, 1076s, 1060sh(stretching vibrations of the tetrahedral framework);
791, 730, 707, 681, 647w, 564s, 530sh (mixed
vibrations of the tetrahedral framework); 474s, 435s

FIG. 4. Bundles of ﬂexible ﬁbers of ferrierite-NH4; Libouš
open pit (Li1f). SEM photo. Field of view 400 lm.

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84

THE CANADIAN MINERALOGIST

FIG. 5. Powder IR absorption spectra of (a) ferrierite-NH4 and (b) ferrierite-K, (K1.69Mg1.18Ca0.27Ba0.17Na0.13)(Si30.92
Al5.08O72)nH2O, from a post-magmatic hydrothermal assemblage uncovered near the village of Austa, Kyrdzhali region,
Eastern Rhodopes, Bulgaria.

(lattice modes involving predominantly bending vibrations of the tetrahedral framework and librational
vibrations of H2O molecules).
TABLE 2. CHEMICAL COMPOSITION OF
FERRIERITE-NH4 (wt.%) FROM THE MOST BASIN

CHEMICAL DATA
Five electron-microprobe compositions of theholotype sample were obtained using a Tescan
VEGA-II XMU digital scanning electron microscopewith an INCA Energy 450 energy-dispersive spectrometer (EDS) (EDS mode, 20 kV, 600 pA).
Hydrogen and N were analyzed by gas chromatography of the products of ignition at 1200 8C in an

TABLE 1. CHEMICAL COMPOSITION OF THE
HOLOTYPE SAMPLE OF FERRIERITE-NH4 (wt.%)

Constituent(NH4)2O
Na2O
MgO
Al2O3
SiO2
H2O
Total

Mean

Range

2.7 6 0.2
0.24
0–0.43
1.63
1.52–1.74
10.48
10.14–10.79
69.44
69.07–69.81
14.8 6 0.6*
99.29

Standard Probedeviation standard
0.17
0.08
0.24
0.29

AlbiteDiopside
AlbiteSiO2* This value obtained by subtraction of H2O formed as aresult of oxidation of NH4þ from the total measured watercontent.

Libouš
n*

Li1x
35

Li1f
14

Bı́lina
Li2
19

Bi1
15

Bi2
16

Bi3
3

2.15
2.25 2.35
2.38
2.20 2.18(NH4)2O
0.34
0.14 0.29
0.07
0.31 0.38
Na2O
K2O
0.13
0.10 0.00
0.21
0.26 0.17
MgO
1.71
1.74 1.46
1.40
1.41 1.32
Al2O3
10.14 10.41 9.64
9.52
9.59 9.35
71.62 71.52 70.26 72.07 71.88 71.19
SiO2
H2O**
15.47 15.58 15.11 15.43 15.40 15.23
total
101.56 101.74 99.11 101.08 101.05 99.82
NH4
2.14
2.22 2.40
2.37
2.20 2.20
Na
0.29
0.11 0.25
0.06
0.26 0.33
K
0.07
0.06 0.00
0.12
0.14 0.09
Mg
1.10
1.12 0.96
0.90
0.91 0.86
Al
5.15
5.27 5.01
4.85
4.89 4.83
Si
30.85 30.73 30.99 31.15 31.11 31.17
H2O
22.00 22.00 22.00 22.00 22.00 22.00
H***
0.45
0.64 0.45
0.50
0.46 0.48
Si/Al
6.00
5.83 6.18
6.42
6.36 6.46
TSi
0.86
0.85 0.86
0.87
0.86 0.87
Note: * n – number of spot analyses; ** H2O calculatedon the basis of theoretical content of 22 H2O molecules
pfu; *** Excessive H calculated for charge balance.

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FERRIERITE-NH4, A NEW ZEOLITE MINERAL

85

FIG. 6. NH4 (pfu) versus Mg (apfu) for studied ferrierite-NH4 samples from the Libouš and Bı́lina open pits: 1 – Libouš
holotype, 2 – Libouš Li1x, 3 – Libouš Li1f, 4 – Libouš Li2, 5 – Bı́lina Bi1, 6 – Bı́lina Bi2, 7 – Bı́lina Bi3.

oxygen ﬂow. Analytical data are given in Table 1.
Contents of other elements with atomic numbers .8
are below detection limits. The Gladstone-Dalecompatibility is 1 – (Kp/Kc) ¼ –0.028 (excellent).

The charge-balanced empirical formula (based on 36
SiþAl pfu) is H0.35[(NH4)2.74Mg1.07Na0.21](Al5.44
Si30.56O72)21.55H2O. The simpliﬁed formula is(NH4,Mg0.5)5(Al5Si31O72)22H2O.

FIG. 7. Ternary graph for extra-framework cations (pfu) for studied ferrierite-NH4 samples from the Libouš and Bı́lina open pits.
Legend as in Figure 6.

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86

THE CANADIAN MINERALOGISTTABLE 3. POWDER X-RAY DIFFRACTION DATA FOR FERRIERITE-NH4 FROM LUBOUŠ AND FERRIERITE-K
FROM AUSTA, KYRDZHALI REGION, EASTERN RHODOPES, BULGARIA (OUR DATA)
Ferrierite-K

Ferrierite-NH4
Imeas, %dmeas, Ådcalc, Å

hkl

Imeas, %dmeas, Å

7
97
28
19
8
n/d
10
2
61
16
19
14
17
73
100
9
8
37
10
6
9
2
6
4
n/d
4
4
4
2
1
2
2
2
5
2
2
8
3
4
12
3
5
1
1
2
2
3
2
2
2
2

11.34
9.52
6.95
6.60
5.79
n/d
4.960
4.835
3.988
3.864
3.784
3.741
3.680
3.547
3.482
3.396
3.315
3.143
3.062
2.949
2.899
2.861
2.719
2.649
n/d
2.571
2.483
2.423
2.361
2.317
2.264
2.245
2.184
2.150
2.118
2.037
2.004
1.952
1.932
1.873
1.840
1.782
1.743
1.716
1.678
1.669
1.658
1.631
1.616
1.587
1.565

11.370
9.550
6.972
6.619
5.806
n/d
4.966
4.851
4.001, 3.991, 3.958
3.872
3.790
3.744
3.682
3.557, 3.538
3.486
3.403
3.317, 3.310
3.155, 3.145
3.067, 3.062
2.966, 2.947
2.903, 2.899
2.858
2.720
2.647
n/d
2.572, 2.564
2.489, 2.483, 2.475
2.425
2.366, 2.362
2.315
2.264
2.246
2.186, 2.179
2.150
2.121, 2.115
2.042, 2.035
2.010, 2.004, 2.000, 1.998
1.952, 1.946
1.935, 1.927
1.872, 1.872
1.842, 1.841, 1.837, 1.837
1.787, 1.782, 1.782, 1.778
1.743, 1.740
1.719, 1.714, 1.713, 1.713
1.679, 1.678
1.669
1.655, 1.654
1.634, 1.630, 1.624
1.617, 1.614, 1.614
1.592, 1.584
1.569, 1.564, 1.564

110
200
101
011
310
220
121
301
321, 031, 420
411
330
002
231
112, 040202
501
240, 022
141, 312
521, 431
530, 402
620, 132
341
422
051
350
042, 701
631, 242, 103
602
640, 730
451
442
811
413, 712
233
361, 460
901, 651
170, 523, 642, 732
071, 613
930, 370
004, 053
703, 462, 204, 253
570, 723, 314, 224
453, 752
932, 181, 372, 813
334, 860
514
044, 10.2.2
743, 11.3.0, 770
903, 604, 653
12.0.0, 534
581, 563, 444

11
100
30
16
18
9
5
4
55
18
48
n/d
26
84
62
13
18
25
24
7
10
n/d
10
8
7
5
6
5
8
3
1
2
1
2
5
2, 2
8
3
5, 7
7
2, 2
7, 6
1
1, 1
1

11.36
9.54
7.01
6.61
5.80
5.68
4.962
4.840
3.985
3.873
3.789
n/d
3.690
3.541
3.484
3.405
3.317
3.145
3.067
2.949
2.898
n/d
2.720
2.648
2.584
2.571
2.483
2.424
2.365
2.316
2.262
2.244
2.185
2.150
2.115
2.043, 2.033
2.002
1.952
1.934, 1.927
1.872
1.847, 1.839
1.785, 1.774
1.741
1.723, 1.714
1.678
n/d
1.659
1.628
1.617
1.595, 1.583
1.565

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3
2
2
2, 1
1

87

FERRIERITE-NH4, A NEW ZEOLITE MINERALTABLE 3. CONTINUED.
Ferrierite-K

Ferrierite-NH4
Imeas, %dmeas, Ådcalc, Å

hkl

Imeas, %dmeas, Å

2
2
3
2
8
3
1

1.552
1.493
1.468
1.442
1.429
1.418
1.397

1.556, 1.553, 1.550, 1.549
1.494, 1.492, 1.490, 1.490
1.471, 1.467, 1.466, 1.465
1.445, 1.444, 1.442
1.429, 1.428
1.421, 1.415
1.397, 1.394

154, 12.2.0, 273, 10.5.1
11.3.2, 473, 772, 015
943, 734, 064, 491
192, 10.3.3, 824
682, 325
880, 0.10.0
11.2.3, 505

2
4
2, 5
2, 1
7
3
1

1.551
1.496
1.473, 1.467
1.446, 1.440
1.428
1.416
1.400

Note: hkl indices were chosen taking into account intensities of reflections of the calculated powder XRD patterns
based on the structure data for samples of K-enriched ferrierite (orthorhombic, Immm) reported by Alberti & Sabelli(1987) and Pickering et al. (1989). n/d ¼ not detected.

All other studied samples were analyzed using a
Cameca SX-100 electron microprobe (National Museum, Prague) operating in the wavelength-dispersion
mode with an accelerating voltage of 15 kV, a beam
current on the specimen of 10 nA, and a beam
diameter of 5 lm. We also attempted analyticalconditions as mild as 1 nA current and 20 lm beam
diameter with the same results; the analytical conditions were veriﬁed using analyses of ferrierite-Mg
from Kamloops Lake, Canada (Graham 1918). The
following lines and standards were used: Ka: albite(Na), BN (N), hematite (Fe), sanidine (Al, Si, K),
diopside (Mg), rhodonite (Mn), wollastonite (Ca); La:
Cs glass (Cs), Rb glass (Rb); Lb: baryte (Ba), celestine(Sr); and Ma: vanadinite (Pb). Peak counting times(CT) were 20 s for the main elements and 60 s for theminor elements; CT for each background was one-halfof the peak time. The raw intensities were converted toconcentrations using the PAP (Pouchou & Pichoir1985) matrix-correction software. The elements Ba,
Cs, Fe, Mn, Rb, and Sr were sought, but found to be
below the detection limit (about 0.01–0.03 wt.%).
Chemical composition of all studied samples fromboth occurrences do not show signiﬁcant differences(Table 2); NH4 content varies in the range 1.8–3.0 pfu
and ammonium and NH4 as extra-framework cations
predominate over Mg (0.6–1.4 apfu, Fig. 6) and minor
Na þ K (up to 0.6 apfu, Fig. 7). The calculated valuesof TSi ¼ Si/(Si þ Al) (Table 2) agree very well withthose published for ferrierite series minerals (0.80–0.87) by Coombs et al. (1997).
The Gladstone-Dale compatibility index(Mandarino 1981) calculated for the holotype sample
is excellent: 1 – (Kp/Kc) ¼ –0.028.

X-RAY DIFFRACTION DATA
Powder X-ray data were obtained using a Rigaku
R-AXIS Rapid II single-crystal diffractometerequipped with a cylindrical image plate detector using
the Debye-Scherrer geometry (d ¼ 127.4 mm). Data (inÅ for CoKa) are given in Table 3.
The obtained diffraction pattern was indexed withan orthorhombic unit cell (space group Immm, by
analogy with ferrierite-K). Unit-cell parameters of theholotype sample reﬁned from the powder data are as
follows: a 19.10(1) Å, b 14.15(1) Å, c 7.489(3) Å, V
2024(3) Å3, Z ¼ 1.
A crystal fragment of ferrierite-NH4 (0.166 3 0.070
3 0.043 mm in size) was selected using an optical
microscope and mounted for single-crystal X-ray study
using an Oxford Diffraction Gemini single-crystal
diffractometer equipped with an Atlas CCD detector
using monochromated MoKa radiation from a sealed
X-ray tube. According to the single-crystal X-ray
diffraction data, ferrierite-NH4 is orthorhombic with
unit-cell parameters a 19.1444(18) Å, b 14.1633(13)Å, c 7.4905(5) Å, V 2031.0(2) Å3 (at room
temperature, from 1353 observed reﬂections) and a
19.0973(6) Å, b 14.1333(5) Å, c 7.4719(2) Å, V
2016.72(11) Å3 (at 120 K). The crystal structure could
not be solved because of the poor quality of theavailable crystals.

DISCUSSION
Orthorhombic symmetry was chosen for ferrieriteNH4 by analogy with ferrierite-K, taking into accountthe crystal-chemical similarity of Kþ and NH4þ.
Powder X-ray diffraction data for ferrierite-NH4(Table 3) are in agreement with this assumption.
Alberti et al. (1998) also chose orthorhombic symmetry (space group Immm) for synthetic NH4-exchanged
ferrierite. Properties of synthetic analogues of ferrierite-NH4 have been studied in numerous works(Fjellvåg et al. 1989, Sobalı́k et al. 1998, Datka et
al. 2003, Peixoto et al. 2003). These compounds are

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THE CANADIAN MINERALOGISTTABLE 4. COMPARATIVE DATA FOR FERRIERITE-SERIES MINERALS
Ferrierite-NH4

Ferrierite-Na

Ferrierite-K

Ferrierite-Mg

Crystal system(NH4,Mg0.5)5(Al5Si31O72)22H2O
Orthorhombic(K,Na,Mg0.5)5(Al5Si31O72)nH2O
Orthorhombic(Mg0.5,K,Na)7(Al7Si29O72)nH2O
Orthorhombic

Space group
a, Å
b, Å
c, Å
b, 8
V, Å3
Z

Immm
19.10
14.15
7.489
90
2024
1

(Na,K,Mg0.5)5(Al5Si31O72)nH2O
Orthorhombic ormonoclinic(pseudoorthorhombic)
Immm or P21/n
18.88614.1827.470’902000.81

Immm
18.97314.1407.478
902006.2
1

Immm
19.187–19.231
14.145–14.161
7.498–7.499
902037.3–2039.9
1Strong lines of thepowder X-ray
diffraction
pattern: d, Å (I,%)

9.52 (97)
6.95 (28)6.60 (19)3.988 (61)3.864 (16)3.784 (19)3.680 (17)3.547 (73)3.482 (100)9.60 (100)5.84 (18)4.01 (21)3.974 (28)3.797 (20)
3.708 (31)3.535 (26)3.493 (22)9.54 (100)7.01 (30)
3.985 (55)3.789 (48)3.690 (26)3.541 (84)3.484 (62)3.145 (25)
3.067 (24)No data

IR absorption
bands

3610, 3565sh,
3360w, 3250,
3220sh, 1646,
1474, 1216s,
1076s, 1060sh,
791, 730, 707, 681,
647w, 564s, 530sh,
474, 435s

No data

3629, 3375sh,
3276sh, 1652,
1223s, 1058s, 790,
730sh, 691, 655sh,
570, 464s, 436s

3625, 3500,
3270sh, 1700sh,
1645, 1220s,
1060s, 785sh,
740sh, 714, 572,
462s, 442s

Optical data

Biaxial (þ)
a ¼ 1.518
b ¼ 1.520
c ¼ 1.522

Biaxial (þ)
a ¼ 1.473
b ¼ 1.474
c ¼ 1.477

Biaxial (þ)
a ¼ 1.489
b ¼ 1.489
c ¼ 1.492

Biaxial (þ)
a ¼ 1.487
b ¼ 1.489
c ¼ 1.491

FormulaDensity, gcm–3
Sources

2.154 (calc.)
This work

2.06–2.23 (meas.)2.13 (calc.)
Wise & Tschernich(1976), GramlichMeier et al.
(1985), Gottardi& Galli (1985)

medium pore-size catalysts with strong shape-selective
properties.
Ferrierite-NH4 differs from ferrierite-Na, ferrieriteK, and ferrierite-Mg by exhibiting signiﬁcantly higher
refractive indices (Table 4). This is evidenced by avery high Gladstone-Dale constant k for (NH4)2O of

2.16 (calc.)
Wise & Tschernich(1976), Yajima &Nakamura(1971), Chukanov(2014), our PXRD
data

2.21 (meas.)
2.136
Alietti et al. (1967),
Alberti & Sabelli(1987), Deer etal. (2004),
Passaglia (1978),
Chukanov &Chervonnyi(2016)

0.483 (for comparison: for Na2O k ¼ 0.190, for K2O k¼ 0.196, and for MgO k ¼ 0.200 – see Mandarino1981).
Ammonium-bearing aluminosilicates are very rarein nature. Ferrierite-NH4 is the second (after ammonioleucite, Hori et al. 1986) natural ammonium-

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89

FERRIERITE-NH4, A NEW ZEOLITE MINERAL

dominant zeolite and the ﬁrst hydrous zeolite-groupmineral with species-deﬁning ammonium. Two otherNH4-dominant aluminosilicate minerals are buddingtonite (NH4-analogue of sanidine) and tobelite (NH4analogue of muscovite).
The formation mechanism of ammonioleucite ispresumed to be related to a low-temperature hydrothermal reaction of the solution containing ammonium
ions with analcime (Hori et al. 1986). Buddingtonite at
its type locality, the Sulfur Bank mine, California,
USA (Erd et al. 1964), formed via low-temperature
replacement of plagioclase by ammonia-bearing hot
springs. Buddingtonite from the the Condor oil-shale
deposit near Proserpine, Queensland, Australia(Loughnan et al. 1983), is concluded to be ofdiagenetic origin; it developed in an ammonium-richenvironment. Tobelite from its type locality, theOhgidani pottery stone deposit near Tobe, Japan(Higashi 1982), is a product of hydrothermal alterationof a biotite andesite dike; the source of the ammonium
is unknown.
An interesting hydrothermal assemblage of nitrogen-bearing aluminosilicate minerals was describedfrom alpine-type veins in the headwaters of the
Shchugor river, near Man’-Khambo Ridge, Northern
Urals, Russia. These minerals are represented bytsaregorodtsevite, N(CH3)4(AlSi5O12), a sodalitegroup member with tetramethylammonium as a
species-deﬁning cation (Pautov et al. 1993), and an
NH4-enriched variety of chabazite-Ca (Karpenko et al.
2001b). As shown by geochemical study, nitrogen wasprobably mobilized during the formation of alpinetype veins from host mica-chlorite schists whichcontain ammonium-bearing muscovite (Karpenko et
al. 2001a, b).
All studied occurrences of ferrierite-NH4 in the
Libouš and Bı́lina open pits are situated in immediateproximity to the coal seam. This mineral was formed
in a sedimentary environment by low-temperature
diagenesis after formation and cracking of carbonate
concretions; there is no evidence of hydrothermal
processes. Most probably, organic matter in the
Miocene coal sediments was the source of theammonium. It has been shown experimentally(Townsend & Loizidou 1984) that natural K- andMg-bearing ferrierite-Na readily reacts with solutionsof ammonium salts to form the NH4-dominantanalogue of ferrierite-Na. The exchange was foundto be ternary in nature, involving sodium, ammonium,
and potassium. Therefore, it is possible to assume thatnatural ferrierite-NH4 formed either directly fromﬂuids with increased ammonium ion contents or as aresult of ion exchange reactions involving ferrierite-Naor ferrierite-K.

ACKNOWLEDGMENTS
The authors wish to express their thanks to
Oldřich Janeček (Doly Nástup Tušimice), Roman
Gramblička, and Zdeněk Dvořák (Doly Bı́lina) for
their kind support in this study. This work was
ﬁnancially supported by the Russian Foundation for
Basic Research, grants 18-05-00051-a (IR spectroscopy and determination of N and H2O) and 18-2912007-mk (powder X-ray diffraction and electron
microprobe analyses of the holotype sample andassociated minerals). The study of other samples was
supported by the Ministry of Culture of the Czech
Republic (DKRVO 2018/02; National Museum
00023272) to JS. Technical support by the X-Ray
Diffraction Resource Centre of Saint-Petersburg State
University is gratefully acknowledged. This research
was partly supported (to JP) by project No. LO1603
under the Ministry of Education, Youth and Sports
National sustainability program I of the Czech
Republic, by means of which some of the scientiﬁcequipment was purchased. The authors are grateful to
Pietro Vignola and an anonymous reviewer for usefulcomments.

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Received September 4, 2018. Revised manuscript accepted
January 7, 2019.

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