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Citation: Cocean, A.; Postolachi, C.;
Cocean, G.; Bulai, G.; Munteanu, B.S.;
Cimpoesu, N.; Cocean, I.; Gurlui, S.
The Origin and Physico-Chemical
Properties of Some Unusual Earth
Rock Fragments. Appl. Sci. 2022,12,
983. https://doi.org/10.3390/
app12030983
Academic Editor: Fabrizio Balsamo
Received: 26 November 2021
Accepted: 12 January 2022
Published: 19 January 2022
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applied
sciences
Article
The Origin and Physico-Chemical Properties of Some Unusual
Earth Rock Fragments
Alexandru Cocean 1, Cristina Postolachi 1, Georgiana Cocean 1,2, Georgiana Bulai 3,
Bogdanel Silvestru Munteanu 1, Nicanor Cimpoesu 1,4, Iuliana Cocean 1and Silviu Gurlui 1, *
1Faculty of Physics, Alexandru Ioan Cuza University of Iasi, 11 Carol I Bld., 700506 Iasi, Romania;
alexcocean@yahoo.com (A.C.); tina.postolaki@gmail.com (C.P.); cocean.georgiana@yahoo.com (G.C.);
muntb@uaic.ro (B.S.M.); nicanor.cimpoesu@tuiasi.ro (N.C.); iulianacocean@hotmail.com (I.C.)
2Rehabilitation Hospital Borsa, 1 Floare de Colt Street, 435200 Borsa, Romania
3Integrated Center of Environmental Science Studies in the North-Eastern Development Region (CERNESIM),
Department of Exact and Natural Sciences, Institute of Interdisciplinary Research, Alexandru Ioan Cuza
University of Iasi, 700506 Iasi, Romania; georgiana.bulai@uaic.ro
4Faculty of Material Science and Engineering, Gheorghe Asachi Technical University of Iasi,
59A Mangeron Bld., 700050 Iasi, Romania
*Correspondence: sgurlui@uaic.ro
Abstract:
In this paper, several researches were undertaken related to a violent phenomenon, char-
acterized by a sonic boom, felt on an area of at least 500 km
2
, shortly followed by the fall of rock
fragments that were then recovered from the ground. These presented different appearance char-
acteristics from those of the materials and rocks specific to the respective area. Spectroscopic and
petrographic analyses were performed to identify the composition, morphological and crystallinity
characteristics in order to elucidate the nature of the collected rock samples. Using FTIR spectroscopy
functional groups, as those reported in the literature for Murchison, Bells and Allende, carbonaceous
chondrite meteorites were identified. The fragments evidenced topography and morphology that can
be assigned to the chondrules and chondrites of carbonaceous meteorites (CMs). The material in the
fragments proved to be as insoluble organic material (IOM), being insoluble in water and organic
solvents. Its crystalline structure was also evidenced by XRD analysis and FTIR spectrum. These
physico-chemical properties, in relation to the sonic boom perceived in the area from where they
were collected, indicate the spatial origin of the fragments of rock as possible meteorite fragments.
Keywords:
chemical and petrographic fingerprint; carbonaceous chondrite; meteorites; LIBS; volatile
meteorites; crystallinity
1. Introduction
Meteorites are an invaluable source of information about both extraterrestrial bodies
and the matter in their composition, as well as physico-chemical interactions that take
place in extreme conditions, clearly different from those on earth. The study of meteorites
also seeks answers related to the origin of organic matter and life on Earth. Among the
categories of meteorites identified so far, that of carbonaceous chondrites is a study material
of great interest, with researchers suggesting that, by establishing the connection with the
parent body and identifying the physico-chemical phenomena associated with the synthesis
of materials, the origin of life can be deciphered [
1
,
2
]. In a broader sense, it is about trying
to explain the evolution of organic matter and its formation [
2
–
5
]. The weathering of
carbonaceous chondrite (CC) meteorites by liquid water has also been studied [
1
,
6
]. From
the category of representative CC meteorites, the Murchison, Bell and Allende meteorites,
in which the content of organic material was highlighted by FTIR, SEM-EDS and XRD
techniques and classical analytical values (such as density and solubility) [
4
,
7
–
11
], were
intensively studied. The methods to detect traces of elements in meteorites, such as
Appl. Sci. 2022,12, 983. https://doi.org/10.3390/app12030983 https://www.mdpi.com/journal/applsci
Appl. Sci. 2022,12, 983 2 of 17
thorium, have been set up during [
12
] the use of neutron activation analysis. The content
of uranium and thorium in chondrite meteorites (CMs) was also studied by Lovering and
Morgan in 1979, by the same neutron activation method [
13
]. The primitive carbonaceous
chondrite, Acfer 094, was analyzed using synchrotron radiation-based X-ray computed
nanotomography for a good preservation of the material [
14
]. In 2014, Coulson et al. [
15
]
proved in a simulation model that fragile types of meteorites, i.e., volatile meteorites, may
survive at low altitudes due to their protective outgassing sheath of volatile ices and organic
material that protect the meteorite from direct atmospheric heating during its fall. The
Maribo carbonaceous chondrite meteorite that fell in 2009 in Denmark, contained organic
components very similar to the Murchison meteorite, but also specific characteristics, such
as components rich in nitrogen as well as trapped noble gases [16].
The most significant carbon content was identified in IDPs (interplanetary dust parti-
cles) with 45 wt% and in UCAMMs (ultra-carbonaceous Antarctic micrometeorites), the
latter containing the highest amounts of organic compounds, up to 90 wt% [17–19].
This work aims to identify the chemical composition, topography, morphology and
crystallinity of two space fragments of rocks that fell to the ground as a result of a large
supersonic boom. In order to elucidate the origin of the analyzed pieces, the results were
compared with those reported for the carbonaceous chondrite meteorites. The analyses
showed similarities with the meteorites presented in the literature, but also certain par-
ticularities of special importance. If some of the characteristics are common to a category
of meteorites from the same parental body, there are also individual “traits” that have
formed under particular conditions and interactions. Thus, an individual profile of the
space rock fragments was established based on these particularities and which constitute
their chemical and petrographic fingerprint similar to genetic for living beings.
2. Materials and Methods
On May 2020, a large sonic boom was felt in Iasi County, with a large number of
people confirming this. The press and social networks were the active means of immediate
communication of the unusual phenomenon. Two rock fragments that fell from space
immediately after that sonic boom were recovered from the Ipate area of Iasi County
(Figure 1).
Appl. Sci. 2022, 12, x FOR PEER REVIEW 2 of 16
[4,7–11], were intensively studied. The methods to detect traces of elements in meteorites,
such as thorium, have been set up during [12] the use of neutron activation analysis. The
content of uranium and thorium in chondrite meteorites (CMs) was also studied by Lov-
ering and Morgan in 1979, by the same neutron activation method [13]. The primitive car-
bonaceous chondrite, Acfer 094, was analyzed using synchrotron radiation-based X-ray
computed nanotomography for a good preservation of the material [14]. In 2014, Coulson
et al. [15] proved in a simulation model that fragile types of meteorites, i.e., volatile mete-
orites, may survive at low altitudes due to their protective outgassing sheath of volatile
ices and organic material that protect the meteorite from direct atmospheric heating dur-
ing its fall. The Maribo carbonaceous chondrite meteorite that fell in 2009 in Denmark,
contained organic components very similar to the Murchison meteorite, but also specific
characteristics, such as components rich in nitrogen as well as trapped noble gases [16].
The most significant carbon content was identified in IDPs (interplanetary dust par-
ticles) with 45 wt% and in UCAMMs (ultra-carbonaceous Antarctic micrometeorites), the
latter containing the highest amounts of organic compounds, up to 90 wt% [17–19].
This work aims to identify the chemical composition, topography, morphology and
crystallinity of two space fragments of rocks that fell to the ground as a result of a large
supersonic boom. In order to elucidate the origin of the analyzed pieces, the results were
compared with those reported for the carbonaceous chondrite meteorites. The analyses
showed similarities with the meteorites presented in the literature, but also certain partic-
ularities of special importance. If some of the characteristics are common to a category of
meteorites from the same parental body, there are also individual “traits” that have
formed under particular conditions and interactions. Thus, an individual profile of the
space rock fragments was established based on these particularities and which constitute
their chemical and petrographic fingerprint similar to genetic for living beings.
2. Materials and Methods
On May 2020, a large sonic boom was felt in Iasi County, with a large number of
people confirming this. The press and social networks were the active means of immediate
communication of the unusual phenomenon. Two rock fragments that fell from space im-
mediately after that sonic boom were recovered from the Ipate area of Iasi County (Figure
1).
(a) (b) (c)
Figure 1. The two fragments of space rocks found in Ipate (Iasi county of Romania). (a) P1 frag-
ment; (b) P2 fragment and (c) P1 and P2 fragments with a measuring device.
The fragments were brought to our laboratory and subjected to analyses and inves-
tigations that would establish their chemical composition and other characteristics, based
on which the comparison with meteorites reported by the literature can be made.
The material was first collected from the two fragments of rock, namely sample P1
and sample P2, and was investigated using optical microscopy, Fourier transform infrared
spectroscopy (FTIR), scanning electron microscopy (SEM) coupled with energy-disper-
sive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) methods. Pieces of about 3–5
Figure 1.
The two fragments of space rocks found in Ipate (Iasi county of Romania). (
a
) P1 fragment;
(b) P2 fragment and (c) P1 and P2 fragments with a measuring device.
The fragments were brought to our laboratory and subjected to analyses and investi-
gations that would establish their chemical composition and other characteristics, based on
which the comparison with meteorites reported by the literature can be made.
The material was first collected from the two fragments of rock, namely sample
P1 and sample P2, and was investigated using optical microscopy, Fourier transform
infrared spectroscopy (FTIR), scanning electron microscopy (SEM) coupled with energy-
dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) methods. Pieces of about
Appl. Sci. 2022,12, 983 3 of 17
3–5 mm
edges size were removed from different sides of each of the fragments, P1 and
P2, respectively. The pieces of material were first observed by optical microscopy. The
resulting pieces of material were then crushed, creating grains of about 0.1–0.2 mm size.
The chemical composition was studied with a Versatile FT-IR Laboratory Spectrometer
MB3000 used on dry powder samples. For the FTIR analysis, about 10 mg of crushed
material from each of the fragments, P1 and P2, was finely ground. From the resulting fine
powders, about 1 mg of each sample was incorporated into about 200 mg of potassium
bromide (KBr) used as suspension media, and compressed into a stainless steel ring under
100 atm of pressure, as per the method described by Cocean et al. Appl. Sci., 2021 [
20
]. In
the SEM-EDS investigation with Bruker AXS Microanalysis GmbH, both the bulk material
of about 3–5 mm edges size (from sample P1) and about 200 mg of powder from both
samples, P1 and P2, was analyzed. The crystalline structure of the powders resulting from
the crushing of the material of each of the two fragments was analyzed by X-ray diffraction
using a Shimadzu LabX XRD-6000 Diffractometer with a Cu K
α
radiation (
λ
= 1.54 Å).
About 200 mg of crushed material of each of the samples, P1 and P2, was used for analysis
by the XRD technique. The diffraction patterns were recorded in the 10
◦
–80
◦
2
θ
range with
a 2 deg/min scanning speed.
The dissolution was tested in water and in ethanol 90%, with the maximum exposure
time of the samples of powder from the fragments of rock being two months in glass tubes
with a stopper, so that the liquid did not evaporate. For each test, 2 mg of crushed material
of each sample was used in 1 mL of liquid.
The rock fragments were then wrapped in food foil and immersed in water to deter-
mine their volume. For this purpose, a graduated glass vessel filled with water was used.
To determine the mass, the analytical balance with 3 decimals was used. The density was
further calculated based on the measured volume and mass.
3. Results and Discussions
3.1. Solubility and Density
When trying to dissolve the sample of the material, it was found that the dissolution
did not take place, not even partially; the two phases (the water and solid granules in
the sample) did not mix, and the particles were only dispersed by stirring. The water
remained clear at all times. The result was the same in the alcohol, in which the granules
of the samples also did not dissolve. Insoluble organic matter (IOM) has been reported
in the case of the Murchison meteorite, in which the highest proportion of organic carbon
is similar to that of kerosene (similar to terrestrial kerogen). An elemental formula has
been established for the Murchison meteorite C
100
H
46
N
10
O
15
S
4.5
, being a material with a
complex composition, but which is not fully elucidated at the molecular level. [
8
]. After a
period of several weeks, the agglomeration of the particles in the water and those in the
alcohol was observed, in a formation with a structure similar to that of the initial sample.
This may be due to fullerenes, but also to other special structural features of the constituent
materials. Additionally, the tendency of the particles to aggregate in the liquid (as observed
during the dissolution test) shows the role of water and ethyl alcohol in this regard.
An explanation of the aggregation phenomenon could be given by the formation
of hydrogen bonds or Van der Waal interactions in the presence of hydroxyl ions, but
also in the conditions of partial dissolution (dissolution of carbonates, sulfates and other
metal salts). Furthermore, the dissolution of soluble compounds, such as metal salts,
can have the effect of a phenomenon of the complexation of metal ions with insoluble
organic compounds, resulting in the aggregation of molecules according to the pattern of
precipitation and flocculation.
The density of the sample material was calculated based on the measurements of the
volume and mass as it states in Table 1.
Appl. Sci. 2022,12, 983 4 of 17
Table 1. Volume, mass and density of the two fragments of space rocks.
Sample VT
[mL]
VH2O
[mL]
VP = VT −VH2O
[mL]
M
[g]
ρ= M/VP
[g/cm3]
VT
[mL]
P1 53.08 40 13.08 13.573 1.037 70
P2 70 46.16 23.84 20.30 0.851 0.535
ρav =ρ1/ρ2
[g/cm3]0.944
3.2. FTIR Spectra Analysis
FTIR spectra analysis (Figure 2) was performed on material collected from the two
samples (P1 and P2) presumed as being meteoritic material. The vibrational bands of the
two spectra were compared with those obtained for the Murchison and Bells meteorites [
7
]
and the results are presented in Table 2.
Appl. Sci. 2022, 12, x FOR PEER REVIEW 4 of 16
The density of the sample material was calculated based on the measurements of the
volume and mass as it states in Table 1.
Table 1. Volume, mass and density of the two fragments of space rocks.
Sample VT
[mL]
VH2O
[mL]
VP= VT-VH2O
[mL]
M
[g]
ρ= M/VP
[g/cm3]
VT
[mL]
P1 53.08 40 13.08 13.573 1.037 70
P2 70 46.16 23.84 20.30 0.851 0.535
ρav = ρ1/ρ2
[g/cm3] 0.944
3.2. FTIR Spectra Analysis
FTIR spectra analysis (Figure 2) was performed on material collected from the two
samples (P1 and P2) presumed as being meteoritic material. The vibrational bands of the
two spectra were compared with those obtained for the Murchison and Bells meteorites
[7] and the results are presented in Table 2.
(a) (b)
Figure 2. FTIR spectra of the material extracted from the two fragments of rocks: (a) in the wave-
number range of 4000 to 580 cm-1 and (b) zoom on the wavenumber range of 1000 to 580 cm-1.
Table 2. Compared FTIR spectra of the samples and the Murchison and Bells mete-
orites (* Vibration modes that are not reported for Murchison, Allende and Bells Meteor-
ites.)
Vibration Bands in the Sample
Spectra [cm−1] Functional Groups In Meteorites
P1 P2
3805 3805
• O–H stretching, free (not H-bonded),
from adsorbed water bounded [21]
• In the same range, silanol groups Si–H
stretching [20,21]
*
Figure 2.
FTIR spectra of the material extracted from the two fragments of rocks: (
a
) in the wavenum-
ber range of 4000 to 580 cm−1and (b) zoom on the wavenumber range of 1000 to 580 cm−1.
Table 2.
Compared FTIR spectra of the samples and the Murchison and Bells meteorites (* Vibration
modes that are not reported for Murchison, Allende and Bells Meteorites.)
Vibration Bands in the
Sample Spectra [cm−1]Functional Groups In Meteorites
P1 P2
3805 3805
•
O–H stretching, free (not H-bonded), from adsorbed
water bounded [21]
•In the same range, silanol groups Si–H
stretching [20,21]
*
Appl. Sci. 2022,12, 983 5 of 17
Table 2. Cont.
Vibration Bands in the
Sample Spectra [cm−1]Functional Groups In Meteorites
P1 P2
3750
(sharp) 3750
(doublet)
•Terminal groups of silanol Si-OH bond to a polymer
chain [21,22]*
3545 3545
(doublet)
•
O–H stretching, free (not H-bonded), from adsorbed
water bounded [21]*
3425 3425
•OH groups, free or H-bonded denote water
molecules, but also COOH [21]
•Possible amino groups (N–H)
Murchison Meteorite: ∼3400 and
1640 cm−1, and are assigned to
structural and/or absorbed H2O of
hydrous silicates
Bells Meteorite: 3400 cm−1
corresponding to OH [7]
3382 3382
•
OH groups specific to carboxylic acids (in the COOH
group) [21]
•Possible amino groups (N–H) *
3306; 3252 3317; 3252 •
OH groups specific to carboxylic acids (in the COOH
group) [21]*
3121 3121 •Chelated structures in CaCO3[21,23]*
*3056 •(ar)C–C groups specific to aromatic compounds [21]*
2839 2860
•C–H in aliphatic compounds [21]
•Parent fullerene stretching bonds for C60H36.27 [24].
Murchison Meteorite: 2960, 2930, and
2860 cm−1; assigned to the aliphatic
C–H stretching modes
Bells Meteorite: 2950 cm−1assigned to
aliphatic C–H [7]
Fullerenes identified in Murchison and
Allende carbonaceous chondrite
meteorites [9];
2764 2764 •Parent fullerene stretching bonds for C60H36.27 [24]. Fullerenes identified in Murchison and
Allende carbonaceous chondrite
meteorites [9]
2340 2361 •Adsorbed CO2[25]*
* * *
Murchison Meteorite: 1730 cm−1
corresponding to C=O
Bells Meteorite: ∼1730 cm−1assigned
to C=O [7]
1905–1699 1905–1699
•Stretching vibrations of C–O bonds in COOH [21]
•Arenes overtones due to mono-substitution (689 cm−1
band) meta di-substitution (864 cm−1band)
*
1656 1656
•O–H group in absorbed molecules of water and/or
structural molecules of water of hydrous silicates [
7
]
•Stretching vibration modes of C=O involved in
hydrogen bonds in amides, as well as amino groups
(N–H), assigned to NHC=O amides I free and
H-bonded [21,26].
•In the same range, C=C stretching modes in arenes
Murchison Meteorite: at ∼3400 and
1640 cm−1, and are assigned to
structural and/or absorbed H2O of
hydrous silicates [7]
Appl. Sci. 2022,12, 983 6 of 17
Table 2. Cont.
Vibration Bands in the
Sample Spectra [cm−1]Functional Groups In Meteorites
P1 P2
1656 1656
•O–H group in absorbed molecules of water and/or
structural molecules of water of hydrous silicates [
7
]
•Stretching vibration modes of C=O involved in
hydrogen bonds in amides, as well as amino groups
(N–H), assigned to NHC=O amides I free and
H-bonded [21,26].
•In the same range, C=C stretching modes in arenes
Murchison Meteorite: at ∼3400 and
1640 cm−1, and are assigned to
structural and/or absorbed H2O of
hydrous silicates [7]
1536 *
•Skeletal vibrations of aromatic bonds C=C [21]
• −(COO)−stretching asymmetric [20]
•Amides II NHC=O free and H-bonded;
polypeptides [21]
Bells Meteorite: ∼1600 cm−1assigned
to aromatic C=C [7]
1429 1438
•CO32−(in CaCO3) [23]
•Crystalline structure [27–29]
•C60 in fullerenes [30]
Murchison Meteorite: around
1435 cm−1; assigned to CO32−
of carbonates
Bells Meteorite: 1450 cm−1assigned to
carbonates [7]
1453 [30]
CH2deformation mode in
CH2–C=C [20]
* 1093
•C–O in carboxylic acids (~1100 cm−1) [21]
•in fullerenes (1050 cm−1) [24]
•SO42−in FeSO4(1090 cm−1) [23]
•Si–O–Si stretching [21]
Murchison Meteorite: 1150 cm−1;
assigned to SO42−of sulfates
Bells Meteorite: 1124 cm−1
corresponding to sulfates [7]
950
853; 804 950
830; 804
•Si-O stretching [7,21]
•Si-(CH3)2skeletal vibration and Si–O–C stretching
(both in the same range of ~850; ~800) [21]
Murchison Meteorite: around
1000 cm−1, assigned to the Si–O
stretching modes of silicates
Bells Meteorite: silicate peaks at
around 1000 cm−1; 1010 cm−1
corresponding to SiO [7]
874 874
•Carbonate ions CO32−with bending modes out of
plane [23,28,29,31]
•Skeletal vibrations C–O [21,29]*
(900-650)
734 (900-650)
734
•Th–O and Th (IV) [32]*
650 650 •S–O stretching vibrations in CaSO3[25]*
669; 661 669; 661 •S–O stretching vibrations in CaSO4[25]*
(874-689)
689 (874-689)
689
•S–O stretching in sulfites [21]*
689 689
•C–H aromatic bending out of plane modes [21]
•In the same range, adsorbed molecular CO2[25]*
612 611 •S–O stretching vibrations in FeSO4[25]*
597 597 •C60 in fullerenes [30]
•stretching modes of C–Si [21]*
Appl. Sci. 2022,12, 983 7 of 17
The summary of the evidenced chemical compounds in the FTIR spectra (Figure 2) is
as follows:
â
Carboxylic acids and/or amino acids (also in the Murchison and Bells carbonaceous
chondrite meteorites);
âAmines, amides I and II;
â
Aliphatic (also in the Murchison and Bells carbonaceous chondrite meteorites) and
aromatic compounds (also in the Bells carbonaceous chondrite meteorite);
âFullerenes (also in the Allende carbonaceous chondrite meteorite);
â
Carbonates (also in the Murchison and Bells carbonaceous chondrite meteorites)
as calcium carbonate in a crystalline state = calcite (the strong peak at 1429 and
1438 cm−1;
â
Sulfates (also in the Murchison and Bells carbonaceous chondrite meteorites) as
calcium sulfate (CaSO4and FeSO4) and sulfites as calcium sulfite (CaSO3);
âThorium oxides (Th IV);
â
Silicates (also in the Murchison and Bells carbonaceous chondrite meteorites) and
silanol groups (Si–OH) as terminal groups bonded to the polymeric chain;
â
Adsorbed water free molecules and H-bonded (also in the Murchison and Bells
carbonaceous chondrite meteorites);
â
Absorbed and structural water in hydrous silicates (also in the Murchison and Bells
carbonaceous chondrite meteorites);
âAdsorbed carbon dioxide (CO2) on the fragments’ surface;
âSulfur may also be included in the organic compounds as sulfones and sulfoxides;
â
The shape of the baseline of the two FTIR spectra that drops off at both edges indicates
a scattering effect, due to crystalline structures. (See the bands at 1429 cm
−1
in P1
and at 1438 cm
−1
in P2). The shift of the peak between the two samples is due to
the influence of the other two crystalline components in sample P1 (SiO
2
—moganite
and CaSO
4
—anhydrite) to the specific vibration of crystalline CaCO3, compared with
sample P2 where only crystalline CaCO3(calcite) was detected by XRD.
Absorbed water on the surface of the material is evidenced in both P1 and P2 by the
bands at 3805 cm
−1
(P1), 3545 cm
−1
(P1, P2), denoting free O–H groups and 3425 cm
−1
(P1, P2) assigned to O–H groups that can be free or hydrogen bounded [
20
,
21
]. Noisy
spectra denote H
2
O absorbed into the analyzed samples or hydrated compounds. The
water absorbed into the meteoritic material or adsorbed onto the surface of the fragment
or of the pores is in accordance with Coulson et al. [
15
], who consider the meteorite as
a “coherent carbonaceous matrix with pores filled with water ice and volatile organics”.
Kebukawa et al. [
7
] reported bands at
∼
3400 cm
−1
for the Murchison and Bells FTIR spectra
assigned to H
2
O absorbed of the hydrous silicates. The band at 3805 cm
−1
may also indicate
silanol groups (Si–OH) [
21
]. Vibrations at 3750 cm
−1
(P1, P2), known as specific to silanol
bonding to a polymer chain [
22
], confirmed the Si–OH groups. Chemical structures with
silicon are also denoted by the vibrational band at 950 cm
−1
, which is assigned to Si–O
stretching [
7
,
20
,
21
] and the bands at 853 cm
−1
and 804 cm
−1
are assigned to Si–(CH
3
)
2
skeletal vibration and Si–O–C stretching, both in the same range of ~850; ~800 [21].
Vibrational bands at 3382 cm
−1
(P1, P2), 3306 cm
−1
(P1) and 3317 cm
−1
(P2) and
3252 cm−1
(P1, P2), indicate the OH groups specific to carboxylic acids in the COOH func-
tional group, but also the possible amino groups (N–H) [
21
] denoting possible amino acids.
The large band in the range of 1905 cm
−1
–1699 cm
−1
(P1, P2) is assigned to carbonyl groups,
but also to the stretching vibrations of the bonds C–O in the group COOH of carboxylic
acids [
21
]. The bond C–O was also confirmed by the band at 1093 cm
−1
(P2), as well as the
864 cm
−1
band (P2) [
21
]. In the same range of 1905 cm
−1
–1699 cm
−1
, the arenes overtones
due to mono-substitution (coupled with the 689 cm
−1
band) and meta di-substitution (coupled
with the 864 cm
−1
band) were also identified. Aromatic compounds are denoted in the
P2 FTIR spectrum by the 3056 cm
−1
band (P2) specific to (ar)C–C groups [
21
] and the
1536 cm
−1
band specific to the skeletal vibrations of the aromatic bonds, C=C, reported in
literature as being in the range of 1610 cm
−1
–1550 cm
−1
(P1) [
21
]. In the spectrum of the
Appl. Sci. 2022,12, 983 8 of 17
Bells meteorite, the vibrations specific to aromatic C=C were found at about 1600 cm
−1
[
7
].
The sample P1 spectrum also indicated amides II, NHC=O free and H-bonded (in the same
range with C=C aromatic) [21].
The chelated structures are indicated by the bands at 3121 cm
−1
(P1, P2) and are
assigned to calcium carbonate, CaCO
3
, and the vibrations specific to CO
32−
at 1429 cm
−1
(P1) and 1438 cm
−1
(P2) [
31
] are also present in the FTIR spectra of the two samples.
Kebukawa et al. [
7
] reported bands assigned to carbonates at 1435 cm
−1
and 1450 cm
−1
in
the Murchison and Bells meteorite spectrum, respectively. The symmetric stretch modes of
the carbonate ions CO
32−
at 1093 cm
−1
(P2) and 874 cm
−1
(P1, P2) out-of-plane bending
modes [
22
,
27
,
28
,
30
] complete the information provided by the FTIR spectrum of the P2
sample, regarding the content in carbonates.
The strong peaks at 1429 cm
−1
(P1) and 1438 cm
−1
(P2) also denote the crystalline state
due to calcium carbonate in the samples of the materials.
The band at 1656 cm
−1
in both the P1 and P2 FTIR spectra are assigned to the O–H
group of absorbed water in hydrous silicates—as also reported by Kebukawa et al. [
7
] for the
Murchison meteorite. Correlating this with the multiple bands from 3805 cm
−1
, 3750 cm
−1
and 3545 cm
−1
, the first two may indicate the silanol groups in polymeric structures or even
additional to fullerenes. In the same range (1656 cm
−1
) there are stretching vibration modes
specific to carbonyl groups C=O involved in hydrogen bonds [
21
]. This would indicate
amides; hence, amino groups (N–H) are also in the same vibrations range [
25
] assigned
to amides I, NHC=O, free or H-bonded [
21
]. In the same range, C=C stretching modes in
arenes are reported in the literature [21].
Aliphatic C–H is identified in the bands at 2839 cm
−1
(P1) and 2860 cm
−1
(P2) [
20
].
Kebukawa et al. [
7
] reported stretching modes assigned to aliphatic C–H at 2960, 2930 and
2860 cm−1for the Murchison meteorite and 2950 cm−1for the Bells meteorite.
In the same range, the bands at 2839 cm
−1
, 2764 cm
−1
(P1), 2860 cm
−1
and 2764 cm
−1
(P2) denote the fullerene structures of the C
60
H
36.27
type [
24
]. C
60
in the fullerenes is also
indicated by the bands at 1430 cm
−1
and 597 cm
−1
[
30
] in both samples (P1, P2); in the same
range, the C–Si stretching modes are assigned in the literature [
21
]. The band at 1093 cm
−1
could also be assigned to C–O stretching in the fullerenes [
24
] as skeletal vibrations due to
C–O stretching [21]. Parent fullerene has been previously identified in the meteorites [9].
The band at 1093 cm
−1
denotes the sulfates and sulfites, SO
42−
and SO
32−
, in CuSO
4
,
CaSO
4
, CaSO
3
and in FeSO
4
. Based on the elemental composition determined by EDS
analysis, the 1093 cm
−1
is assigned to CaSO
4
, CaSO
3
and to FeSO
4
. This assignment also
takes into account the S–O stretching vibrations that CaSO
4
exhibits at 667 cm
−1
and
that are noticed in the P1 spectrum (669; 661 cm
−1
) and less intensely in the P2 spectrum
(669; 661 cm
−1
) and that FeSO
4
exhibits at 611 cm
−1
, which is noticed in the P1 spectrum
(
611 cm−1
) and P2 spectrum (612 cm
−1
) [
25
]. The band at 650 cm
−1
is assigned to S–O
stretching in calcium sulfite CaSO
3
in the P1 and P2 spectra [
25
] confirming sulfites. Calcium
sulfate is also confirmed by the difractogram of XRD analysis. Kebukawa et al. [
7
] have
reported SO42- in the Murchison and Bells meteorites.
Vibration modes at 2340 cm
−1
(P1) and 2361 cm
−1
(P2) and 689 cm
−1
(P1, P2) are
assigned to molecular adsorbed CO2[25].
According to Ali et al. [
31
], the bands in the range of 900
−
650 cm
−1
could be assigned
to thorium covalent bonds with oxygen (Th–O and O–Th–O) [
12
] also evidenced Thorium in
meteorites. It is important to notice that in the FTIR spectra of samples P1 and P2 is the
curved base line, which drops off at both the left and right sides, indicating the effects of
scattering, possibly due to the crystalline state of the particles analyzed, to the effect of carbon
black or to spherical particles. The shape of the baseline may also indicate the biological material
(DNA) causing Mie scattering, or the non-Lambert–Beer absorption behavior in biological
cells [33].
The FTIR spectra of the two samples (P1, P2) exhibit bands of similar wavenumbers as
those reported for the Murchison and Bells meteorites. The spectra of the P1 and P2 samples
exhibit fullerene structures that were not reported for the Murchison and Bells meteorites,
Appl. Sci. 2022,12, 983 9 of 17
but are reported by Becker et al. [
9
] as evidence for meteorites. Carbonates, silanol groups
and adsorbed CO
2
are also identified in the spectra of the P1 and P2 samples. Vibration
modes different to what was reported for the Murchison and Bells meteorites complete those
already reported by Kebukawa et al. [
7
], for the aromatic structures. Organic kerogen-like
matter, referred to as “Murchison Insoluble Organic Material (IOM)” by
Pizzarello et al. [8]
,
is evidenced when corroborating the FTIR spectra with the high insolubility of samples P1
and P2 in water and alcohol, as presented before.
The chemical components identified by FTIR spectroscopy are also confirmed by EDS
elemental analysis and XRD, the latter evidencing the crystalline structures of calcium
carbonate (CaCO3, CaSO4and SiO2).
3.3. Crystallinity Analysis from XRD
The XRD analysis results in Figure 3, mainly show the crystalline structures of calcites,
which is in accordance with the FTIR spectra in which the peaks assigned to CO
32−
and
the chelate structure are noticed, including the strong peaks at 1429 cm
−1
(sample P1)
and
1438 cm−1
(sample P2) specific to CaCO
3
in the crystalline state. While the P2 sample
presented peaks that correspond to only the calcite phase, CaCO
3
hexagonal (reference
card ICSD 98-001-8166), the P1 sample presented two additional diffraction lines that were
associated with anhydride, CaSO
4
orthorhombic (reference card ICSD 98-000-1956) and
moganite, SiO2monoclinic (reference card ICSD 98-006-7669).
Appl. Sci. 2022, 12, x FOR PEER REVIEW 9 of 16
The XRD analysis results in Figure 3, mainly show the crystalline structures of cal-
cites, which is in accordance with the FTIR spectra in which the peaks assigned to CO32−
and the chelate structure are noticed, including the strong peaks at 1429 cm−1 (sample P1)
and 1438 cm−1 (sample P2) specific to CaCO3 in the crystalline state. While the P2 sample
presented peaks that correspond to only the calcite phase, CaCO3 hexagonal (reference
card ICSD 98-001-8166), the P1 sample presented two additional diffraction lines that were
associated with anhydride, CaSO4 orthorhombic (reference card ICSD 98-000-1956) and
moganite, SiO2 monoclinic (reference card ICSD 98-006-7669).
Figure 3. XRD Difractogram.
Calcium carbonate (CaCO3) in a crystalline state was identified in the Murray mete-
orite, but was identified as aragonites (CaCO3 orthorhombic) by Lee et al. [6].
3.4. Elemental Composition Analyzed with Energy Dispersive Spectroscopy (EDS)
Elemental composition performed with energy dispersive X-ray analysis on different
surfaces of the sample, proved the non-homogeneity of the material concerning the atomic
percentage, but with the constituting elements dispersed on all the surfaces, except for Si,
Pb and Mn, which are detected only on certain areas of the studied surface. Table 3 reflects
the results concerning the percentages of each component element on different surfaces.
Table 3. EDS analysis results on the elemental composition.
Element Atom [%]
s1 s2 s3
Carbon 85.9724 77.7475 80.3783
Oxygen 12.1562 20.4560 17.0068
Sulfur 1.4799 0.8755 0.5528
Calcium 0.3714 0.4666 1.6246
Silicon • 0.2580 0.2675
Thorium 0.0025 0.0117 0.0052
Magnesium 0.0065 0.0927 0.0823
Aluminum • 0.0542 0.0398
Iron 0.0045 0.0242 0.0229
Figure 3. XRD Difractogram.
Calcium carbonate (CaCO
3
) in a crystalline state was identified in the Murray mete-
orite, but was identified as aragonites (CaCO3orthorhombic) by Lee et al. [6].
3.4. Elemental Composition Analyzed with Energy Dispersive Spectroscopy (EDS)
Elemental composition performed with energy dispersive X-ray analysis on different
surfaces of the sample, proved the non-homogeneity of the material concerning the atomic
percentage, but with the constituting elements dispersed on all the surfaces, except for Si,
Pb and Mn, which are detected only on certain areas of the studied surface. Table 3reflects
the results concerning the percentages of each component element on different surfaces.
Appl. Sci. 2022,12, 983 10 of 17
Table 3. EDS analysis results on the elemental composition.
Element
Atom [%]
s1 s2 s3
Carbon 85.9724 77.7475 80.3783
Oxygen 12.1562 20.4560 17.0068
Sulfur 1.4799 0.8755 0.5528
Calcium 0.3714 0.4666 1.6246
Silicon •0.2580 0.2675
Thorium 0.0025 0.0117 0.0052
Magnesium 0.0065 0.0927 0.0823
Aluminum •0.0542 0.0398
Iron 0.0045 0.0242 0.0229
Nickel 0.0066 0.0137 0.0104
Lead •0.0009 •
Manganese • • 0.0093
100 100 100
The EDS spectra for the two fragments of rock are presented in Figure 4.
Appl. Sci. 2022, 12, x FOR PEER REVIEW 10 of 16
Nickel 0.0066 0.0137 0.0104
Lead • 0.0009 •
Manganese • • 0.0093
100 100 100
The EDS spectra for the two fragments of rock are presented in Figure 4.
(a) (b)
Figure 4. EDS spectra resulted on the analyzed areas (a,b), on areas of the samples of rocks S1 (a)
and S2 (b).
3.5. Petrography
The petrography of the fragments of rocks (P1 and P2) was studied based on optical
microscopy and SEM images and maps of elements.
3.5.1. Optical Microscopy Images
In the images acquired with the optical microscope (Figure 5), the metallic droplets
are evidenced, as well as other structures, such as granular- and needle-shaped structures,
that may be assigned to oxides or metal salts. In accordance with the XRD difractogram
(Figure 3), granular structures can be assigned to moganite (SiO
2
) and to calcites (CaCO
3
),
and the needle-shaped structures belong to anhydride (CaSO
4
).
(a) (b)
Figure 4.
EDS spectra resulted on the analyzed areas (
a
,
b
), on areas of the samples of rocks S1 (
a
) and
S2 (b).
3.5. Petrography
The petrography of the fragments of rocks (P1 and P2) was studied based on optical
microscopy and SEM images and maps of elements.
3.5.1. Optical Microscopy Images
In the images acquired with the optical microscope (Figure 5), the metallic droplets
are evidenced, as well as other structures, such as granular- and needle-shaped structures,
that may be assigned to oxides or metal salts. In accordance with the XRD difractogram
(Figure 3), granular structures can be assigned to moganite (SiO
2
) and to calcites (CaCO
3
),
and the needle-shaped structures belong to anhydride (CaSO4).
Appl. Sci. 2022,12, 983 11 of 17
Appl. Sci. 2022, 12, x FOR PEER REVIEW 10 of 16
Nickel 0.0066 0.0137 0.0104
Lead • 0.0009 •
Manganese • • 0.0093
100 100 100
The EDS spectra for the two fragments of rock are presented in Figure 4.
(a) (b)
Figure 4. EDS spectra resulted on the analyzed areas (a,b), on areas of the samples of rocks S1 (a)
and S2 (b).
3.5. Petrography
The petrography of the fragments of rocks (P1 and P2) was studied based on optical
microscopy and SEM images and maps of elements.
3.5.1. Optical Microscopy Images
In the images acquired with the optical microscope (Figure 5), the metallic droplets
are evidenced, as well as other structures, such as granular- and needle-shaped structures,
that may be assigned to oxides or metal salts. In accordance with the XRD difractogram
(Figure 3), granular structures can be assigned to moganite (SiO
2
) and to calcites (CaCO
3
),
and the needle-shaped structures belong to anhydride (CaSO
4
).
(a) (b)
Figure 5. Optical microscopy images: (a) P1 sample and (b) P2 sample.
3.5.2. Surface Morphology Analyzed with Scanning Electron Microscopy (SEM)
SEM images provide morphological and topographic information on the material of
meteorites. Similar structures were evidenced as being reported [
10
] for carbonaceous
chondrites. The grains of chondrules, droplets of metals or metal oxides in the carbonaceous
chondrite matrix can be distinguished, as indicated in the SEM images (a)–(f) in Figure 6.
The SEM image shows white grains of different sizes assigned to oxides and the
crystalline state, and the veins of a darker and lighter color indicating the relief of the
sample. The fullerene individual sheet is identified in Figure 6d [34].
3.5.3. Maps of Elements
The maps of the chemical elements (Figure 7) offer an image of the non-homogeneous
distribution of the chemical elements, indicating, at the same time, the identity of the
components that are also confirmed by FTIR and XRD analyses. In the sense of the above-
mentioned factors, we further present the mapping analysis and morphological aspect
(SEM images) on several areas studied from samples P1 and P2 of the rock fragments.
The maps of the elements of the area denoted as P1m-Ch1, which is part of the P1 frag-
ment in massive state, evidence carbon (C) that can be assigned to organic compounds: sul-
fur (S) in organics, as sulfones, also the sulfates/sulfites of calcium (CaSO
4
/CaSO
3
). Never-
theless, some of the calcium (Ca) in the P1m-Ch1 area may be part of the
calcium–aluminum
inclusions (CAI), as per the maps of the elements. A grain of a significant size of silicon
oxide (SiO
2
) is noticed in the right side of the area, while the silicon in the left side of the
area is assigned to Si–OH as a silanol bond to organics. Iron (Fe), similar to nickel (Ni), is in
the finely dispersed particles. The very low percentage of Fe and Ni makes it difficult to
estimate if they are part of the Kamacite structures (Fe–Ni). The grains of a more significant
size are noticed on the iron map. They can be assigned to iron oxides. It is not excluded that
some of the iron is involved in chemical structures, such as troilite (Fe-S) and iron sulfate
(FeSO4) chondrules.
The area denoted as P1m-Ch2, also part of the P1 fragment in massive state, exhibits on
the maps the disposal of the chemical elements indicating carbon (C) assigned to carbonates
(CaCO
3
), but also based on the XRD and FTIR analysis, supposed to be in organics or as
adsorbed CO
2
. Sulfur (S) can be assigned to sulfates, but also to organic compounds,
such as sulfones, when corroborating the maps with the FTIR and XRD analyses. The
area mapping P1m-Ch1 provides evidence of calcium sulfate (CaSO
4
). Other than above-
mentioned compounds with calcium, the maps of Ca and O, respectively, also indicate CaO
as well as possible CAI (calcium–aluminum inclusions).
Appl. Sci. 2022,12, 983 12 of 17
Appl. Sci. 2022, 12, x FOR PEER REVIEW 11 of 16
Figure 5. Optical microscopy images: (a) P1 sample and (b) P2 sample.
3.5.2. Surface Morphology Analyzed with Scanning Electron Microscopy (SEM)
SEM images provide morphological and topographic information on the material of
meteorites. Similar structures were evidenced as being reported [10] for carbonaceous
chondrites. The grains of chondrules, droplets of metals or metal oxides in the carbona-
ceous chondrite matrix can be distinguished, as indicated in the SEM images (a)–(f) in
Figure 6.
The SEM image shows white grains of different sizes assigned to oxides and the crys-
talline state, and the veins of a darker and lighter color indicating the relief of the sample.
The fullerene individual sheet is identified in Figure 6d [34].
(a) (b)
(c) (d)
Figure 6. Cont.
Appl. Sci. 2022,12, 983 13 of 17
Appl. Sci. 2022, 12, x FOR PEER REVIEW 12 of 16
(e) (f)
Figure 6. SEM images of the different areas on the fragments of rock: P1 sample in the (a–d) images
adnd P2 sample in the images (e,f).
3.5.3. Maps of Elements
The maps of the chemical elements (Figure 7) offer an image of the non-homogeneous
distribution of the chemical elements, indicating, at the same time, the identity of the com-
ponents that are also confirmed by FTIR and XRD analyses. In the sense of the above-
mentioned factors, we further present the mapping analysis and morphological aspect
(SEM images) on several areas studied from samples P1 and P2 of the rock fragments.
Figure 7. Maps of chemical element distribution on the different studied surfaces.
Figure 6.
SEM images of the different areas on the fragments of rock: P1 sample in the (
a
–
d
) images
adnd P2 sample in the images (e,f).
Appl. Sci. 2022, 12, x FOR PEER REVIEW 12 of 16
(e) (f)
Figure 6. SEM images of the different areas on the fragments of rock: P1 sample in the (a–d) images
adnd P2 sample in the images (e,f).
3.5.3. Maps of Elements
The maps of the chemical elements (Figure 7) offer an image of the non-homogeneous
distribution of the chemical elements, indicating, at the same time, the identity of the com-
ponents that are also confirmed by FTIR and XRD analyses. In the sense of the above-
mentioned factors, we further present the mapping analysis and morphological aspect
(SEM images) on several areas studied from samples P1 and P2 of the rock fragments.
Figure 7. Maps of chemical element distribution on the different studied surfaces.
Figure 7. Maps of chemical element distribution on the different studied surfaces.
Thorium (Th) may be assigned as thorium oxides (ThO
2
), as FTIR spectra also indicate
(Figure 2). Troilite (Fe-S), lead (Pb) and manganese (Mn) are also noticed. The SEM image
of this area of the massive/bulk material of the P1 fragment of rock, shows a high number
of large size grains in white color.
The fragments of rock P1 and P2 were also analyzed in a powder state obtained by
slight pressing due to their friability.
Appl. Sci. 2022,12, 983 14 of 17
The maps of the elements of the P1-Ch1area of P1 powder show carbon assigned to be
in organic compounds as sulfones and cloudy-disposed carboxylic acids, while calcium (Ca)
as oxide (CaO) is disposed in the veins. Particles of silicon oxide (SiO
2
) were finely dispersed
on all the studied surfaces, but also grains of significant sizes were noticed, among which
the grain in the center of the studied area of P1-Ch1 denotes aggregation in the chondrules
pattern. Due to the very low percentage of Mg, Al and Fe, it is difficult to estimate, but
the oxides of these elements might be in the area denoted as P1-Ch1. Manganese (Mn)
and nickel (Ni) are also noticed. The SEM image of the area shows grains and veins as
preserved structures after the fragment of rock was crushed for analysis. This fact confirms
the presence of structures with high mechanical resistance, such as a crystal lattice identified
by FTIR and XRD analysis. An analysis of the mechanical properties was not made, because
the study focused on the chemical composition, the existence of crystalline structures and
the arrangement of the compounds in chondrule-shaped agglomerations.
The maps of the elements on a second area of the powder of the P1 sample, denoted
as P1-Ch2, shows the arrangement of elements indicating carbonates (CaCO
3
), sulfates
(mainly CaSO
4
, and possibly MgSO
4
, FeSO
4
and Al
2
(SO
4
)
3
), carbon in organics, sulfur in
organics, a large number of chondrules containing silicon oxide and aluminum (SiO
2
/Al),
as well as a very low content in Fe and Ni. In addition to the granular structures, this
area studied at SEM on the P1 fragment powder shows porous structures associated with
carbon (according to mapping), which is part of the organic type IOM (insoluble organic
material), or fullerene C60. In fact, a transparent strand of what is identified as a fullerene
individual sheet is seen at the bottom of the image [34].
A third area of P1 powder sample, identified as P1-Ch3, is denoted by the maps of
element content of sulfates (CaSO
4
) and calcium oxide (CaO), as well as some calcium
carbonate (CaCO
3
) in a crystalline state. The calcium carbonate in the calcite grains may be
assigned to Tochilinite due to the content in sulfur evidenced in the same area. Transparent
sheet observed in the SEM image is assigned to individual fullerene sheets, fullerene C60
being evidenced by the FTIR spectra (Figure 2) similar to graphene transparent sheets,
evidenced by Khenfouch et al. [
34
], on the SEM images of synthesized graphene few-
layered sheets. The carbon in the organics with sulfur is also observed on the maps of
elements of the P1-Ch3 area of the sample. Grains of chondrules with SiO
2
in a crystalline
state are evidenced in CAIs. Finely dispersed silicon may be assigned to phyllosilicates
organized in parallel sheets as [Si
2
O
52
-]n. Finely dispersed Fe-Ni and Mn particles are
also observed.
On the maps of the P2-Ch1 area of the powder sample from fragment P2, the elements
calcium (Ca), carbon (C), oxygen (O) and sulfur are assigned to oxide, carbonate and sulfate
(CaO
2
, CaCO
3
and CaSO
4
). Calcium is also assigned to CAIs and carbon is also assigned to
organics with sulfur (sulfones). Grains of SiO
2
metallic iron (Fe) chondrules, and also finely
dispersed Fe-Ni particles, are noticed. Thorium (Th) is assigned to thorium oxides. The
SEM image of this area shows the structures with good mechanical strength, practically
those structures, such as chondrules.
The second studied area on the powder sample of fragment P2, denoted as P2-Ch2,
shows, based on the maps of elements corroborated with the FTIR spectrum, carbon (C) in
organic compounds and organic compounds with sulfur. The veins of calcium carbonate
(CaCO
3
) and grains of CaCO
3
assigned to calcites in tochilinite, due to sulfur observed, are
evidenced by the maps of the elements. However, it is obvious that sulfur areas overlap
the carbon areas in an almost identical pattern, indicating that the majority of the sulfur
is an organic bond. Chondrules with a content of silicon oxide (SiO
2
), magnesium (Mg),
aluminum (Al), manganese (Mn) and Fe-Ni particles are observed by element arrangements
in the maps. The SEM image of this area shows less brittle carbon structures than the
material as a whole, but with a tendency to crack following the mechanical stress to which
it was subjected.
Appl. Sci. 2022,12, 983 15 of 17
4. Conclusions
There are indications that the samples studied herein are part of a stony type of mete-
orite, subtype chondrites, class carbonaceous as per classification found in [
35
,
36
], which
went through a weathering process by liquid water [
1
,
6
] with a high content of organic
carbon, mainly IOM (insoluble organic matter) of the kerogen-type, but also fullerene.
Absorbed, carbon dioxide enhances the percentage of the carbon element determined by
EDS analysis. An explanation for the high content in carbon may be the accumulation of
IDPs. Detected water molecules by FTIR analysis are assigned to the remnant water of
a volatile ice sheath that used to protect the meteorite from direct atmospheric heating.
Thus, the fragments may be part of the category of volatile meteorites, as described in the
model of dynamics of volatile meteorites presented by Coulson et al. [
15
]. The metals in
oxides, carbonate and sulfate, but also being possible to enter in coordination with organic
substances, complete the image of the chemical composition of the fragments. Petrographic
analysis provides information on the elements dispersion within the material, but also
the aggregation in the chondrules type of particles or structured in veins. By comparing
the results obtained with the analyses of some meteorites long studied in the literature,
the similarities of composition and structure were found. The specific fingerprint of the
material in the two fragments is given by the high carbon content, as well as by the friability
of the bulk material compared to the hardness of the particles that result from crushing it.
The bulk friability can be considered to be caused by the loss of volatile organic compounds
and/or water, which has led to the weakening of the bonds between the particles. The
tendency of the particles to aggregate in the liquid (as observed during the dissolution
test), shows the role of water and ethyl alcohol in this regard. Although it can be attributed
to the partial dissolution and formation of hydrogen bonds, Van der Waals interactions
and/or coordination and complexation bonds, this phenomenon requires in-depth studies
to establish the exact nature of the connections that lead to the aggregation phenomenon.
Author Contributions:
Conceptualization, S.G. and I.C.; methodology, A.C., I.C., G.C. and S.G.; inves-
tigation, C.P., G.B., B.S.M. and N.C.; writing—original draft preparation, I.C. and S.G.;
writing—review
and editing, S.G.; supervision, S.G. All authors have read and agreed to the published version of
the manuscript.
Funding:
This research was funded by the Ministry of Research, Innovation and Digitization, project
FAIR_09/24.11.2020 and by the Executive Agency for Higher Education, Research, Development and
Innovation, UEFISCDI, ROBIM, project number PN-III-P4-ID-PCE2020-0332 and the Operational
Program Competitiveness 2014–2020, Axis 1, under POC/448/1/1, research infrastructure projects
for public R&D institutions/Sections F 2018, through the Research Center with Integrated Techniques
for Atmospheric Aerosol Investigation in Romania (RECENT AIR) project, under grant agreement
MySMIS no. 127324.
Acknowledgments:
The authors would like to thank Ciprian Ifteme from Ipatele (Iasi) for his help in
recovering these fragments.
Conflicts of Interest: The authors declare no conflict of interest.
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