ISSN 1063-7745, Crystallography Reports, 2021, Vol. 66, No. 1, pp. 2–9. © The Author(s), 2021.

This article is an open access publication, corrected publication, 2021.

Russian Text © The Author(s), 2021, published in Kristallografiya, 2021, Vol. 66, No. 1, pp. 4–12.

MINERALOGICAL
CRYSTALLOGRAPHY

Mineralogical Crystallography:
Look in the Past, New Trends, and Highlights
D. Yu. Pushcharovskya,*
aFaculty of Geology, Moscow State University, Moscow, 119899 Russia
*e-mail: [email protected]
Received April 10, 2020; revised May 18, 2020; accepted May 18, 2020

Abstract—Many urgent problems of modern mineralogical crystallography, to which the papers of this the-
matic issue of the journal Kristallografiya (Crystallography Reports) are devoted, have been considered. It is
shown how the use of advanced physicochemical methods enriches scientific concepts about the real struc-
tures of minerals and nature-like compounds, structural conditionality of their physical properties, forms of
concentration of chemical elements in terrestrial shells, crystallogenesis conditions, structural transforma-
tions in deep geospheres, relationships between structure types, and their interpretations based on modern
concepts.

DOI: 10.1134/S1063774521010132

It is well known that minerals are important in both lection by Ferraris, professor of the Turin Univer-
industry and scientific research, aimed, in particular, sity [2].
at revealing the history of the evolution of planets, the Almost immediately after the discovery of X-ray
Solar System, and the Universe as a whole. Currently, diffraction (XRD) by M. Laue in 1912, it became obvi-
the knowledge about minerals cannot be developed ous that XRD data concern not only geology but also
without detailed crystallochemical information. It is materials science; in the second half of the XX cen-
provided by structural studies, which are carried out tury, their importance for biology became obvious.
on crystals of increasingly complex compositions and Hence, it is not surprising that crystallography is
constitutions. Along with accumulation of crystal- included in the courses of most of Russian universities
lochemical data, the purpose of these studies is to pre- as an important component of physics, materials sci-
dict the behavior of crystalline phases under different ence, chemistry, and biology (let alone its conven-
physicochemical conditions. tional relationship with mineralogy). It is sufficient to
mention that, even in the pre-X-ray epoch of science
The results of the fundamental research in the field development, the first out of four volumes of the fun-
of mineralogical crystallography are of key impor- damental treatise by Amedeo Carlo Avogadro Solid-
tance for not only the development of the concepts State Physics was devoted entirely to crystallography
about natural crystalline materials. They are necessary (Fisica de’ corpi ponderabili, 4 volumi, Torino 1837–
for understanding the processes of formation and evo- 1841 (Physics of Ponderable Bodies (Matter), 4 vols.)
lution of geological objects at all levels: minerals, (Fig. 1).
rocks, and ores. Detailed knowledge of the structural The 19th volume of the Notes in Mineralogy [3],
principles of minerals with various compositions and which are regularly published by the European Miner-
structures is necessary for designing new functional alogy Union starting with 1994, is devoted to deep
materials with specified optical, magnetic, electric, analysis of the modern approaches to understanding
mechanical, catalytic, sorption, electrochemical, and the real structures of minerals and the nature of the
other properties. In addition, structural data on min- effects complicating them. The results of the use of
erals allow to understand better the phenomena occur- most advanced physicochemical methods, which
ring in technosphere and ecosphere in the crystalline facilitate investigation of very small crystals (including
compounds entering the composition of most of nanoparticles), weakly crystallized samples, and dis-
building and structural materials and present in com- ordered and aperiodic structures, as well as the solu-
mercial wastes. Some of recent results related to the tions of some other scientific problems were reported
solution of the aforementioned problems are consid- in the articles of that volume. Undoubtedly, many of
ered in the collection of articles Highlights in Miner- the results obtained will be developed in future crystal-
alogical Crystallographу [1] and the review of this col- lographic studies.

2
 MINERALOGICAL CRYSTALLOGRAPHY 3

(а) (b) (c)

Fig. 1. (a) Bust of А. Avogadro in Vercelli (Piemonte, Italy). (b) Portrait of А. Avogadro, lithography, 1856. (c) Cover of Avoga-
dro’s treatise Solid-State Physics (1837).

Traditionally, structural identification is an complex. It should be reminded that, when studying the
important part of mineralogical crystallography. The first structures (in particular, K+Al3+(SO4)2 ⋅ 12H2O
scientific concepts of the structural chemistry of min- alum), the boundary between the science and art was
erals and main sections of their systematics have been at a level of determining 11 independent parameters.
enriched significantly due to the new instrumental Now, the number of refined parameters in modulated
possibilities and progress in software, thus facilitating structures reaches several hundreds and is three orders
further development of mineralogy and inorganic of magnitude larger for the structures of biological
chemistry. As is well known, in the first structural crystals as compared with minerals. To date, the com-
refinements of halite and diamond, which were per- plexity of crystal structures is estimated not only based
formed 85 years ago (in the “Bragg” epoch), crystals on the number of the refined parameters involved in
with sizes from 1 cm to several millimeters were refinement but also with application of the informa-
applied. In the 1920s–1930s (epoch of V. Taylor and tion-theory apparatus [4]. In the first approximation,
L. Pauling), crystals less than 1 mm in size could be this number increases with an increase in the number
analyzed due to the invention of hot-cathode tubes. of atoms per unit cell and with lowering of its symme-
Then, beginning with the 1960s, the progress in the try. For example, cation ordering in a unit cell is
software development and the use of more powerful accompanied by a transition to a superstructure having
X-ray systems made it possible to reduce the sizes of a higher information density in comparison with the
crystals studied to several hundredths of millimeter. initial cell.
Finally, since the 1970s, the possibilities of X-ray anal-
ysis have been expanded to a great extent due to the use Along with the broadening of possibilities for
of high-power synchrotron radiation, which makes it studying crystal structures of minerals, new approaches
possible to investigate micrometer-sized rare minerals in understanding their constitution, nature of their
and understand better the evolution history and crys- technologically important properties, and crystal-
tallization conditions of containing rocks. lochemical features of crystallogenesis have been
In this context, it should be noted that powder developed in the last decades. In this context, one
XRD analysis has been experienced a kind of revival should mention the concept of anion-centered com-
during the last decades; having become more than a plexes, many statements of which were developed by
simple “biometric image” of a specific mineral, it the researchers from the worldwide-known crystallo-
facilitates structural refinement, qualitative analysis of graphic school of St. Petersburg University [5]. Ini-
mixtures, and obtainment of structural information tially, these conclusions were based on the detailed
for samples under extreme conditions [3]. analysis of the crystal chemistry of a large group of
minerals, related to fumarole exhalations of the Great
New correlations between the structures and Tolbachik Fissure Eruption, which occurred on the
physical properties of crystals are being revealed. The Kamchatka peninsula in 1974–1975. As a result, a
objects under study have also become much more fairly voluminous series of Cu-bearing minerals was

CRYSTALLOGRAPHY REPORTS Vol. 66 No. 1 2021

4 PUSHCHAROVSKY

selected, which contained additional O anions (that Number of new minerals annually
are not involved in traditionally selected tetrahedral 140
complexes). Their tetrahedral coordination is formed Minerals submitted to the IMA Commission
by four Cu atoms; note that the Cu–O distances are 120
shorter in comparison with the conventional distances
in other structures. Later on, it was shown that [OCu4] 100
tetrahedra can be combined into topologically differ-
ent complexes. Based on these observations, Filatov 80
et al. concluded that [OCu4] tetrahedra are the main
60
conveyors of copper from the deep magmatic zone to
the terrestrial surface. By now, anion-centered com- 40
plexes have been found in minerals and inorganic
compounds of different compositions. Their analysis Approved
20
has revealed structural conditionality of physical Submissions
properties of many crystals. 0
1960 1970 1980 1990 2000 2010
The period from the beginning of the XX century is Year mineral was approved or submitted
characterized by great progress in the development of
scientific concepts about minerals. It is not a mere
Fig. 2. An increase in the number of new minerals in the
chance that Academician N.P. Yushkin (1936–2012) period from 1960 to 2015 [6].
wrote the following: “The most informative indicator
of mineralogy development is the number of known
mineral forms at a certain historical moment.” Before erals formed in hot zones of fumaroles (T > 473 K) and
1800, there were less than 100 known independent at moderate temperatures (T = 323–423 K) were
mineral forms. After this historical milestone, the rate determined. All high-temperature minerals do not
of discovering new minerals has been continuously contain hydrogen atoms, and Cu2+ cations are in the
increasing. For example, 87 minerals were discovered fourfold or fivefold coordination in them. In contrast,
in the period from 1800 to 1819. Then, in the period the second-group minerals contain generally OH
from 1820 to 1919, 185 minerals on average were dis- anions and/or water molecules, whereas Cu2+ cations
covered each 20 years. From 1920 to 1939, 256 new are prone to octahedral coordination [8].
minerals were described, and 342 minerals were added
in the period from 1940 to 1959. Since 1960, 40–50 Another example is the discovery of coesite (a rare
(and more than 100–150 in the last decade) new min- silica polymorph), which facilitated the interpretation
erals were discovered annually. Thus, to date, the total of high-pressure metamorphism and specific features
number of minerals found on the Earth exceeds 5600 of the petrology of surrounding rocks [9].
(Fig. 2). Obviously, this result is due to the fruitful Pekov, a discoverer of more than 200 new minerals,
cooperation of mineralogists and crystallographers. has outlined a set of conditions favorable for finding
The discovery of a new mineral is considered by the previously unknown minerals. First, this is a geo-
mineralogy community as a significant event. There chemical peculiarity of mineral-forming medium,
are relatively few regions on the Earth where new min- which leads to its enrichment with some rare elements.
erals are more likely to be found. These are, primarily, For example, at insignificant variations in the physi-
Khibiny and Lovozero alkaline complexes on the Kola cochemical conditions, boron can form compounds
peninsula, where 219 minerals were discovered [7]. with similar compositions but significantly different
The fumarole systems of the Tolbachik volcano structures.
(Kamchatka) added 129 new minerals. The next in the However paradoxical it may sound, a deficit of par-
list are the Långban deposit of iron–manganese ores ticular conventional chemical elements also leads to
(Värmland mining region, Sweden), where 75 miner- the formation of unusual natural compounds. This
als were found; Vesuvius potassium-rich lavas, skarn condition facilitates concentration of rarer elements
rocks, and fumaroles (Campania, Italy) with 66 new and crystallization of minerals with these elements in
minerals; Tsumeb polymetallic deposit in Namibia their composition. A deficit of silica leads to the for-
with 73 new minerals; etc. mation of oxides of Al, Mg, Be, and other elements,
The characterization of new minerals is an import- which usually enter the composition of silicates.
ant part of modern mineralogical crystallography. Ultrahigh pressures in deep geospheres or a combi-
Sometimes even rare minerals indicate unusual condi- nation of a high temperature and atmospheric pres-
tions of their crystallization. One of recent examples of sure, which is characteristic of the crystallization from
these conclusions is the analysis of the structural prin- fumarolic sublimates at the boundary between hot
ciples for 96 copper-containing minerals (oxysalts, lavas and carbonate rocks near Earth’s surface, may
chlorides, and oxides), related to volcanic fumaroles. also induce formation of minerals with unusual com-
As a result, the crystallochemical features of the min- positions or structures.

CRYSTALLOGRAPHY REPORTS Vol. 66 No. 1 2021

 MINERALOGICAL CRYSTALLOGRAPHY 5

Techniques used in mineral discoveries

100
90
80
% of minerals discovered

70
60
50 Fig. 4. Three XRD patterns, which made it possible to
3 reveal the NaHF2 impurity in chemically pure (c.p.) NaF
40 1 2 agent [12].
30
20 samples obtained from mines and quarries or when
10 developing mineral deposits [11]. Lunar samples and
meteorites also produced some new minerals. There
0 are many new minerals in peralkaline rocks and vol-
1910 1930 1950 1970 1990 2010 cano-related fumaroles. The number of discoverers of
new minerals rises constantly; it increased by a factor
Fig. 3. Characteristic techniques used to describe new
minerals: (1) XRD analysis, (2) electron-probe analysis, of 4 in 70 years and amounts currently to six.
and (3) wet chemistry. Other curves are the data of ther- In the XIX century, minerals were identified based
mogravimetry/differential thermal analysis (TG/DTA), on chemical analysis and study of crystal morphology.
IR spectroscopy, and Raman spectroscopy [11].
All data were generalized in reference books (e.g.,
Dana’s System of Mineralogy, Goldschmidt’s Atlas of
Living organisms can also be in involved in min- Crystal Forms, etc.). The time when an experienced
eral-formation processes. These are primarily bacte- mineralogist could visually determine several tens of
ria, whose activity leads to selective separation of some mineral forms was left far in the past due to the discov-
chemical elements. This effect is especially pro- ery of XRD analysis, which changed radically the
nounced in the zones of surface oxidation of sulfide approach to characterization of minerals.
and arsenide ore deposits, where, in particular, mala- Successful diagnostics of an unknown mineral is
chite, azurite, and many copper arsenates with various primarily related to the presence of a sufficient
structures are formed. amount of standard reference data, containing the val-
Mineral formation involves 72 out of 118 chemical ues of diffraction reflection intensities I and interpla-
elements. According to the data of Krivovichev and nar spacings d. A need for creating reference databases
Charykova [10], the following elements are leaders in was understood immediately after the first XRD pat-
the number of mineral species (given in parentheses) terns were recorded. For example, an American
formed with their participation: oxygen (4041), hydro- researcher Hull, who analyzed an X-ray image of NaF
gen (2755), silicon (1448), calcium (1139), sulfur in 1919, revealed that this compound, considered pre-
(1025), aluminum (960), iron (917), sodium (914), viously as chemically pure, contained an impurity of
copper (616), phosphorus (580), arsenic (575), and NaHF2 [12].
magnesium (550). As Hull told, a NaF agent of chemically pure grade
There is no doubt that the impressive rate of dis- was delivered from stock and subjected to XRD analy-
covering minerals is related to the improvement of sis. Then the researchers synthesized NaF compound
physicochemical methods in use (Fig. 3). The data in of very high purity and also recorded its XRD pattern.
Fig. 3 indicate an increasing role of XRD, electron- A comparison of both images (Fig. 4) showed that the
probe, and spectroscopic studies at a significant first sample contained ~30–40% of impurities. To
decrease in the importance of wet chemistry in char- determine their compositions, XRD patterns of
acterization of new minerals. In the 100-year period Na2CO3, NaCl, NaHF2, and other chemically similar
(from 1917 to 2016), 4046 forms (three quarters of the compounds were obtained. Thus, it was found for the
total number of minerals) were discovered. first time that a commercial sample contained specif-
An analysis of these studies suggests that they are ically the NaHF2 impurity.
generally supported by state foundations. In the last The first XRD databases were created only in 1938,
100 years, minerals were revealed in different coun- when an American researcher Hanawalt and his colle-
tries; however, the number of the research groups guages published a paper [13] devoted to the XRD
involved in these studies did not exceed 20. Most of identification of materials, which contained calcu-
new minerals are discovered at universities and aca- lated powder XRD patterns for 100 compounds. Each
demic institutes (in total, 75%) and in museums powder XRD pattern started to be considered as a
(25%). Two thirds of new minerals were found in the “fingerprint” of the corresponding chemical com-

CRYSTALLOGRAPHY REPORTS Vol. 66 No. 1 2021

6 PUSHCHAROVSKY

pound. Then, the American Society for Testing and PDF-4 + entries with structures
Materials (ASTM) systematized the structural data. In 400
1941, all XRD spectra known by that time were pub-
lished (with participation of ASTM) in the form of a 350
file with a searching key proposed by Hanawalt. The 300
key included the data on the three strongest reflec-
tions, chemical formula, and the number of the card 250
with complete information about this compound. In 200
the next years, the file was expanded to 2500 com-
pounds. Thereafter, a committee on filling the file was 150
organized under the patronage of ASTM, being then 100
assisted by scientific organizations of the United
50
Kingdom, France, and Canada. Soon the committee
assumed the functions of an international organiza- 0
2008 2009 2010 2011 2012 2013 2014 2015 2016 2018
tion and became completely independent in 1969. The
database compiled by it started to be referred to as PDF-4 + entries Access to atomic coordinates
“Powder Diffraction File of the Joint Committee on
Powder Diffraction Standards” (PDF JCPDS). In Fig. 5. The increase in the number of compounds with
1978, 14 international and national scientific commu- XRD characteristics included in the ICSD database.
nities (primarily, from the United States, Germany,
Canada, Australia, France, the United Kingdom, and
Japan) established the International Center for Dif- who was the first chief executive officer of Apple
fraction Data (ICDD) under the patronage of the Computer (in the period from February 1977 to
International Union of Crystallography. The ICDD March 1981). He is also known as a gemstone expert.
database PDF-2 is assumed to be created in 1940. It In is of interest that the RRUFF project was named
consists of two independent parts, which include the after the sound imitating Scott’s cat purring.
data on inorganic and organic compounds. In 1985, In the modern Earth sciences, the XRD analysis at
the XRD data for all characterized compounds were high pressures is especially important, because the
computerized. The dynamics of filling the ICSD data- rocks located on the terrestrial surface and erupted
base with XRD data is shown in Fig. 5. from depths of less than 100 km make it possible to
By August 2019, the Inorganic Crystal Structure estimate the composition of only 0.02% of the Earth’s
Database (ICSD) of the University of Bonn included volume. In the last 50 years, the scientific concepts
426000 XRD patterns of inorganic crystals, 75% of about the mineralogy of deep geospheres have been
which contained structural data. Corundum numbers gradually expanded [14]. The results of these interdis-
(I/Ic), necessary for determining the quantitative ratios of ciplinary studies are shown in a generalized form in
minerals in mixtures, are given for 325900 structures. Fig. 6.
The data sample of minerals and their analogues con- From the point of view of mantle mineralogy, dia-
tains 47000 XRD patterns, with corundum numbers mond inclusions are of particular interest, because
(I/Ic) reported for 36 000 structures. The database they characterize the deep medium in which these
contains also 143636 XRD patterns of metals and high-pressure crystals grow. The recently found inclu-
alloys. sion of OH-containing ringwoodite Mg2SiO4 in dia-
It should be acknowledged that an attempt to mond (Fig. 7) (one of possible mantle components at
determine a mineral based on only the powder XRD depths in the range of 520–670 km [16]) indicates that
database, containing data on more than 5600 mineral diamond can be formed not only in the mantle but
forms, may be unsuccessful in the absence of any also in the transition zone with participation of hydro-
chemical information. Spectral data also help greatly gen-containing melts or fluids. It is assumed that there
to solve this problem, especially in gemology, where are vacancies of Mg2+ cations in OH-containing ring-
nondestructive experimental methods are highly woodite, which occupy the only site in oxygen octahe-
important. That is why the popularity of the high- dra in this high-symmetry structure, whose sites can
quality RRUFF database of IR and Raman spectra be occupied by the protons involved in the formation
constantly increases (along with that of the powder of OH groups. This isomorphism is quite possible in
XRD database, annually renewed by the ICDD) in the the wadsleyite structure; however, its lower-symmetry
mineralogical practice. This base contains XRD and structure contains only one out of four crystallograph-
spectral data on 7000 minerals (including their variet- ically nonequivalent Mg octahedra, into which pro-
ies) and 3500 mineral forms. This concept is accepted tons can be incorporated; therefore, its ability to accu-
for minerals characterized by structures of the same mulate water in the lower half of the mantle transition
type and chemically similar compositions. The orga- zone should be lower than that of ringwoodite. Never-
nization of RRUFF was sponsored by Michael Scott, theless, both minerals (ringwoodite and wadsleyite)

CRYSTALLOGRAPHY REPORTS Vol. 66 No. 1 2021

 MINERALOGICAL CRYSTALLOGRAPHY 7

Minerals of deep geospheres

Main chemical elements in deep geospheres:
Si, Mg, Fe, Al, Ca, and O

Upper olivine (Mg, Fe)2SiO4; orthorhombic and monoclinic

mantle pyroxenes (Mg, Fe)2Si2O6 (Pbca, P2/c);
garnet (pyrope (Mg, Fe, Ca)3(Al, Cr)2Si3O12
stishovite: TiO2 structure type; KAlSi3O8–hollandite structure type
Transition wadsleyite E-(Mg, Fe)2SiO4–asimovite Fe2SiO4 (wadsleyite structure type);
zone ringwoodite J-(Mg, Fe)2SiO4–arsenite Fe2(SiO4) spinel structure type;
akimotoite MgSiO3 (ilmenite structure type)–hemleite FeSiO3;
major garnet Mg3(Fe2+Si)(SiO4)3; (CaMg)AlSiO o hollandite structure type

Lower bridgmanite MgSiO3–hiroseite FeSiO3; periclase–wüstite (Mg, Fe)O;

mantle CaSiO3 (orthorhombic perovskite structure type); MgAl2O4, carnegiete
NaAlSiO4–CaFe2O4 structure type; stishovite SiO2–post-stishovite –
CaCl2 structure type ; seifertite SiO2–DPbO2 structure type;
interface with the D'' zone–MgSiO3 (post-perovskite structure type)

Fig. 6. Modern concepts about the mineral composition of the Earth’s mantle.

can be considered as important accumulators of water Recently, according to the opinion of some
in deep geospheres [17]. researchers, some major discoveries were made in a
relatively new line of research, related to quasicrystals.
Another discovery is related to the identified inclu- The formation and characterization of first quasicrys-
sions of metallic iron and cohenite Fe3C in diamond tals in 1984 were preceded by the description of
[18]. It suggested that the diamond crystals containing incommensurate periodicity. Thus, it was found that
these inclusions could be formed at much larger the periodicity of three-dimensional atomic distribu-
depths (~700 km) in comparison with the previously tion in real space is not a necessary property of crystals
investigated samples of this mineral. At the same time, (in contrast to the conservation of periodicity in the
the modern potential of XRD experiments in cham- reciprocal (diffraction) space). The relatively rare
bers with diamond anvils allows one to predict possi- manifestation of quasicrystallinity among synthetic
ble mineralogical phases in not only the Earth’s man- intermetallic compounds with nonclassical symme-
tle but also in the core of our planet. tries suggests that many quasicrystals are metastable
phases. However, the recent finding of three natural
New data indicate the existence of structural differ- quasicrystals in the meteorites from Chukotka (the
ences between the surface layers of different faces. The first quasicrystalline mineral icosahedrite (Al63Cu24Fe13)
need for achieving electrostatic balance of dangling
bonds leads to the fact that the structures of the crystal was discovered in 2009) and previously investigated
surface and crystal bulk have different geometries, synthetic intermetallic compounds left no doubt that
symmetries, and properties. Some surprising examples this form of matter is stable and important for the
(see below) confirm this conclusion. It is well known Earth sciences [20]. In addition to mineralogy, these
that diamond is a typical insulator (due to the two- data undoubtedly offer new prospects in many natural
electron covalent carbon interatomic bonds, which sciences: astrophysics (by expanding the ideas about
determine the wide band gap ΔE = 5.5 eV), whereas its possible processes in the early development stages of
surface with unsaturated bonds of carbon atoms, the Solar System), solid-state physics, and materials
doped with hydrogen atoms, exhibits pronounced science. It remains to be said that, from the point of
semiconductor properties [19]. A change in the elec- view of data capacity, quasicrystals can be considered
tronic structure of pyrite, caused by shortened Fe–S as a bridge from minerals to, on the one hand, inor-
bonds on its surface, is accompanied by the manifesta- ganic materials and, on the other hand, biocrystals.
tion of nonmetallic metalloid properties (with cova- A relationship between crystallography and mod-
lent type of interatomic interactions) at the crystal sur- ern biology and medicine was noted above. Currently,
face, in contrast to the semiconductor conductivity of no medical product can be recommended without
the crystal as a whole. It may seem surprising that crystallographic analysis of its structure. It can also be
magnetite, which is a semimetal with covalent bonds, assumed that argillaceous minerals and zeolites played
has ferromagnetic properties; however, their nature is a certain role in the origin of life on the Earth [21].
due to the exchange interaction between iron atoms. Some aspects of this extremely complex and intriguing

CRYSTALLOGRAPHY REPORTS Vol. 66 No. 1 2021

8 PUSHCHAROVSKY

Ringwoodite
inclusion

(а) 1 mm

Juina

Mato
Grosso

(b)
Fig. 8. Monograph by Rutten (1910–1970, the Nether-
Fig. 7. (a) Ringwoodite inclusion in the diamond crystal lands), devoted to the possibility of origin of life on the
and (b) map of Brazil with indication of the Juina kimber- Earth and in other regions of the Universe via gradual
lite pipe, where the diamond with ringwoodite inclusion transformations of inanimate nature.
was found [15].

axis of the structure. Triangular CO3 anions in the

problem were considered in the study Generated from structures of bastnäsite-(Ce) CeCO3F, parisite-(Ce)
Crystals? by Academician Yushkin [22]. He noted a Ce2CaF2(CO3)3, and synchysite-(Ce) CaREE(CO3)2F
surprising similarity between the simplest biosystems (REE is a rare-earth elements) have a similar vertical
and hydrocarbon crystals with similar structures. One orientation. Along with vaterite, these structures form
can obtain a real protoorganism by supplementing this a unified polysomatic family [24]; its representatives
mineral with protein components. Many geological illustrate the applicability of the modular concept for
aspects of the abiotic synthesis of organic materials their interpretation, due to which the relationships
and multimolecular systems using gradual transfor- between individual structure types can be understood
mations of inanimate nature were considered by Rut- better.
ten [23] (Fig. 8). The results considered above only partially charac-
Along with the transmission electron microscopy terize the range of problems crystallographers and
(TEM), a relatively new method of automatic XRD mineralogists currently deal with. In this context, it
tomography is being gradually introduced into the should be reminded that crystallography originated in
mineralogical practice. It is especially efficient for the XVIII century at the interface of mineralogy and
studying nanocrystals, including biominerals in living mathematics and continues to develop in many
organisms (including humans). New data were respects specifically due to the study of minerals. It is
obtained on vaterite, which is a polymorphic form of not surprising in this context that, at the initiative of
calcite present in the shells of gastropods; on hydrox- professor G. Ferraris (Italy) and the author of this
ylapatite in human dental enamel; and on silicon-con- study, a subdivision named as Mineralogical Crystal-
taining nanorods of primary sponges. Currently, dif- lography, focused on modern high-tech structural
ferent forms of proteins are under study. studies of minerals and nature-like compounds, was
In the aforementioned vaterite structure, planes established within the European Crystallographic
of CO3 triangles are almost parallel to the principal Association at the IUCr congress in Geneva in 2002.

CRYSTALLOGRAPHY REPORTS Vol. 66 No. 1 2021

 MINERALOGICAL CRYSTALLOGRAPHY 9

This fact is an additional confirmation of the postulate 6. E. S. Grew, G. Hystad, R. M. Hazen, et al., Am. Min-
that mineralogical crystallography is not static but eral. 102 (8), 1573 (2017).
actively developing line of research, the results of https://doi.org/10.2138/am-2017-5897
which expand the concepts in different fields of natu- 7. I. V. Pekov, Soros Obrazovat. Zh., No. 5, 65 (2001).
ral science. 8. I. V. Pekov, N. V. Zubkova, and D. Yu. Pushcharovsky,
Acta Crystallogr. B 74, 502 (2018).
https://doi.org/10.1107/S2052520618014403
FUNDING 9. C. Chopin, Contrib. Mineral. Petrol. 86, 107 (1984).
This study was supported by the Russian Foundation for 10. V. G. Krivovichev and M. V. Charykova, Zap. Ross.
Basic Research, project no. 18-05-00332. Mineral. O-va, No. 4, 1 (2015).
11. I. F. Barton, Am. Mineral. 104 (5), 641 (2019).
OPEN ACCESS 12. A. W. Hull, J. Am. Chem. Soc. 41 (8), 1168 (1919).
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13. J. D. Hanawalt, H. W. Rinn, and L. K. Frevel, Ind.
Attribution 4.0 International License, which permits use, Eng. Chem. Anal. Ed. 10 (9), 457 (1938).
sharing, adaptation, distribution and reproduction in any
14. D. Pushcharovsky and Yu. Pushcharovsky, Earth-Sci.
medium or format, as long as you give appropriate credit Rev. 113 (2), 94 (2012).
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https://doi.org/10.1021/cr3004696 Translated by Yu. Sin’kov

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