Boletín de la Sociedad Geológica Mexicana / 74 (3) / A200722 / 2022 / 1

Subducted iron and glassy spherules in the upper mantle?

¿Esférulas de hierro y vítreas subducidas en el manto superior?

ABSTRACT
José M. González-Jiménez1,2,*, Ivanina Sergeeva3, Thomas N. Kerestedjian3, Fernando Gervilla1,2

1
Instituto Andaluz de Ciencias de la Tierra, ABSTRACT RESUMEN
Consejo Superior de Investigaciones Científi-
cas (CSIC)-Universidad de Granada, Avda.
de las Palmeras 4, 18100, Armilla, Granada, Spherules are documented in ophiol- Rocas del manto superior ofiolitico tales
Spain. itic mantle rocks such as peridotites como peridotitas y cromititas contienen esfe-
and associated chromitites. They ras. Estas consisten de: (1) hierro native con
2
Departamento de Mineralogía y Petrología, consist of: (1) native iron having cantidades variables de Ni con y sin inclu-
Facultad de Ciencias, Universidad de Grana-
da, Avda. Fuentenueva s/n, 18002, Granada, variable amounts of Ni with/without siones de vidrio silicatdo y óxidos (wüstite),
Spain. inclusions of silicate glass or oxides (2) intercrecimientos dendríticos de óxidos
(wüstite), (2) dendritic intergrowth of (magnetita, wüstita y hematites) con o sin
3
Geological Institute, Bulgarian Academy of oxides (magnetite, wüstite and hema- vidrio silicatado y, (2) vidrio silicatado.
Sciences, 24 Georgi Bonchev Str., 1113, Sofia,
Bulgaria. tite) with/without silicate glass and, Unísonamente, estas esferulas se interpretan
(3) silicate glass. Consensually, they como indígenas a las cromititas y relacio-
* Corresponding author: (J.M. González- are interpreted as indigenous to chro- nadas con procesos de alta temperatura que
Jiménez) [email protected] mitites and related with high-tem- tienen lugar en el manto superior terrestre.
perature processes operating in the Sin embargo, su parecido con aquellas esferas
Earth’s upper mantle. However, their de origen terrestre y extraterrestre descritas en
similarity with terrestrial and extra- otros contextos geológicos es reseñable. En
terrestrial spherules found in other este trabajo cuestionamos el origen autóc-
settings of the geological record is tono de las esferas en las rocas mantélicas,
remarkable. We raise the question on interpretándolas como material de origen
such indigenous origin, relating them volcánico y cósmico que ha sido reciclado
to volcanic and cosmic material recy- atraves de la cuña de manto superior donde

Subducted iron and glassy spherules in the upper mantle?

How to cite this article: cled back to the mantle wedge where ser forman las cromititas durante los procesos
González-Jiménez, J.M., Sergeeva, I., chromitites form during subduction. de subducción.
Kerestedjian, T.N., Gervilla, F., 2022,
Subducted iron and glassy spherules in the Keywords: spherules, iron, Palabras clave: esferas, metal,
upper mantle?: Boletín de la Sociedad Geológica glass, upper mantle, chromitite, vidrio, manto superior, cro-
Mexicana, 74 (3), A200722. http://dx.doi. subduction. mitita, subducción.
org/10.18268/BSGM2022v74n3a200722

Manuscript received: June 26, 2022.

Corrected manuscript received: July 19, 2022.
Manuscript accepted: July 24, 2022.

Peer Reviewing under the responsibility of

Universidad Nacional Autónoma de México.

This is an open access article under the CC BY-NC-SA

license(https://creativecommons.org/licenses/by-nc-sa/4.0/)
 http://dx.doi.org/10.18268/BSGM2022v74n3a200722

2 / Boletín de la Sociedad Geológica Mexicana / 74 (3) / A200722 / 2022

INTRODUCTION

1. Introduction and volcanic origin that originally landed on the

deep-sea floor were recycled back to the mantle
Millimetric to (sub)-microscopic metallic-sili- during subduction. Our discovery offers an inno-
cate-oxide spherules of both extraterrestrial and vative alternative to foster the current debate of
terrestrial origins are present in the fossil and cur- exotic minerals in ophiolitic rocks while unravel-
rent geological record. The extraterrestrial ones ling geodynamic processes that operate in subduc-
are part of the huge number of micrometeorites tion-zone settings.
and cosmic dust that rains on the Earth annually
resulting from the fragmentation of asteroids
and released from comets (Peucker-Ehrenbrink, 2. Analytical methods
2001). Such extraterrestrial material enters the
atmosphere and partially melts and oxidizes to 2.1. MINERAL CONCENTRATES
form tiny (<2 mm) spheroidal bodies consisting of
iron or iron-nickel oxides and/or alloys (I-type), A small chip from each of the four samples ana-
Fe oxide dendrites within silicate glass (G-type) or lyzed in this study (GK1C-1 and GK3A-1 from
mainly silicate (S-type; with the V subtype made Golyamo Kamenyane and J-410m and Y-409m
up only of silicate glass) (Genge et al., 2008). On from Yakovitsa) was pre-grounded in agate mor-
Earth, metallic-silicate-glass spherules may form tar, washed with ethanol and then dried at room
by: (1) high-temperature processes but related with temperature for few minutes (until complete evap-
volcanism (i.e., cloud-to-ground lightning strikes oration of the ethanol). Dry material was then
or eruptions of low-viscosity magmas; Genaerau divided into sub fractions by handheld magnet,
et al., 2015; Nyström et al., 2016), (2) meteor- pre-insulated from direct contact with the material
itic impact (i.e., crystallization from the splash to avoid contamination, and purified several times.
ejecta or condensation from rock-vapor plumes; In order to avoid potential contamination, the
Velázquez et al., 2021), (3) biogenic hydrothermal manipulations of washing with ethanol were done
activity (Agarwal et al., 2021), and (3) diagenesis in glass Petri dish and the acid treatment in PTFE
(Suk et al., 1990). Likewise, un-natural anthropo- containers (100 ml tanks). This way, two fractions
genetic industrial processes may also manufacture were separated – non-magnetic, silicate one, and
spherules (Niyogi et al., 2011; McCloy, 2019). magnetic chromite one. As a precaution, the mate-
Subducted iron and glassy spherules in the upper mantle?

Metallic-oxide-silicate spherules are also found rial was inspected under a binocular microscope
in mantle rocks (peridotites and chromitites) from at each step of the separation process and no
a few ophiolites (Bai et al., 2004; Robinson et al., spherules were detected at this stage. Each frac-
2004; Xu et al., 2009; Xu et al., 2015; Yang et al. tion was subsequently separated by granulometry
2015; Griffin et al., 2016), although its origin is using 200 mesh disposable sieves while the frac-
highly controversial. They are interpreted to from tion 70-100 µm was again checked for spherules,
within mantle itself by melt immiscibility under although they were not identified. The chromite
the highly reducing conditions (e.g., Griffin et al., fractions were further treated with a mixture of
2016; Xiong et al., 2017) or to be solid products HF and HCl acid, heated to 160° C. The insoluble
of molten droplets originated by lightning strikes residue was then washed with deionized water sev-
on the mantle rocks when exposed to Earth’s sur- eral times and dried at room temperature reveal-
face (Ballhaus et al., 2017). Here we provide the ing the presence of spherules when recognized
first-ever thoughtful comparative study of metal- under binocular microscope. Once recognized,
lic-oxide-silicate spherules from ophiolitic upper the spherules were hand-picked and sticked on a
mantle rocks with others present in the geological wire of carbon tape on a SEM pin stub holder to
record, raising the possibility that they could cor- be imaged under scanning electron microscopy.
respond to recycled airborne spherules of cosmic Subsequent to this preliminary analysis of the
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Boletín de la Sociedad Geológica Mexicana / 74 (3) / A200722 / 2022 / 3

ANALYTICAL METHODS
spherule surface, then they were imbibed in 2.4. ELECTRON MICROPROBE ANALYSIS (EPMA)
epoxy resin and polished. Considering the small
size and their softness, the largest iron spherule The major element composition of magnetite
identified from the Yakovitsa chromitite was the was determined on the polished surface for the
only to survive the polishing process. Spherule 1 using a Cameca SX-100 microprobe
in CIC of University of Grana, Spain.
2.2. FIELD EMISSION SCANNING ELECTRON EPMA data were obtained using an excitation
MICROSCOPY (FE-SEM) voltage of 20 kVand a beamcurrent of 20 nA, with
a beam 2–3 μm in diameter. Monitored spectral
Spherules were preliminarily characterized and lines were MgKα, FeKa, AlKα, CrKα, SiKα,
imaged using a Leo Gemini Field Emission TiKα, MnKα, NiKα, CoKα, ZnKα and VKα.
Scanning Electron Microscope (FE-SEM) at the Standards used were MgO, Fe2O3, Al2O3, Cr2O3,
Centro de Instrumentación Científica (CIC) of SiO2, CoO, ZnO, TiO2, MnTiO3, NiO and
the Universidad de Granada, Spain. The instru- Pb5(VO4)3Cl.
ment was equipped with an Energy Dispersive
Spectra (EDS) detector. Accelerating voltage was 2.5. FOCUSED ION BEAM (FIB) HIGH-RESOLUTION
20 kV and beam current optimized for an ade- TRANSMISSION ELECTRON MICROSCOPY (HRTEM)
quate number of counts for each EDS analysis.
The unpolished spherules were firstly inspected A thin-foil sample was prepared and extracted
on the secondary electron mode (SE) in an effort from the polished Spherule-1 from the Yakovitsa
to better define their morphological characteris- chromitite by using a Focused Ion Beam Scanning
tics and chemistry by EDX, where once polished Electron Microscope (FIB-SEM) in the Labora-
they were checked again under FESEM but torio de Microscopías Avanzadas (LMA) at the
using the back-scattered electron mode (BSE), Instituto de Nanociencia de Aragón (INA) – Uni-
although only one of the spherules survived (i.e., versity of Zaragoza, Spain. The TEM thin foil
Spherule 1 from Yakovitsa shown in Figure 2 of preparation was performed using a Dual Beam
the main text). FEI Thermo-Fisher Scientific, model Helios
650. The selected region of interest was first cov-
2.3. MICRO-RAMAN ered by a thin strip (~300 nm) of C by focused

Subducted iron and glassy spherules in the upper mantle?

electron beam induced deposition (FEBID) and
The micro-Raman spectra of silicate and oxide subsequently with a second strip (~1 µm) of Pt.
component of the spherules were obtained by These strips act as protection during the milling,
means of JASCO NRS-5100 micro-Raman spec- polishing, and extraction process of the thin foils.
trometer, equipped with an Olympus microscope The bulk material was first removed on both sides
with x5, x20, and x100 objectives belonging to of the lamella by a rough Ga+ ion milling with
the CIC of University of Granada, Spain. The a 30 kV current at 2.5 nA and the subsequent
532 nm laser excitation was used as an excitation polishing with a 30 kV current at 0.23 nA. The
source with a spectral resolution of 2.08 cm-1. final polishing step was performed on the sample’s
The minimum lateral resolution was about 1 μm inclusions until the electron transparency was
(with the 100× objective). The spectrometer was achieved. This was completed by subsequently
calibrated using the 520.6 cm-1 Raman peak of milling the thin foil with a 5 kV current at 68 pA.
silicon before each experimental measurement. The electron transparency was monitored by an
The spectra were collected using the 100× objec- Everhart-Thornley SE detector and using a 5 kV
tive with repeated acquisition: 2 acquisitions for electron beam. After achieving the electron trans-
100 s. Obtained Raman spectra were compared parency, the thin foil was rapidly polished using a
with those of the RRUFF database. low energy 5 kV current at 10 pA to reduce the
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ANALYTICAL METHODS

Table 1. Chemical composition of magnetite.

N Al2O3 Cr2O3 Fe2O3 FeO MnO CoO NiO Total

1 0.04 0.10 69.49 30.58 0.57 0.16 0.03 100.96
2 0.04 0.05 69.92 30.71 0.60 0.16 0.04 101.53
3 0.03 0.11 69.88 30.74 0.57 0.17 0.04 101.53
4 0.05 0.14 69.93 30.81 0.58 0.16 0.03 101.71
5 0.04 0.14 69.77 30.71 0.60 0.15 0.02 101.44
6 0.04 0.10 69.66 30.63 0.59 0.17 0.03 101.22
7 0.04 0.14 69.51 30.59 0.60 0.14 0.04 101.08
8 0.04 0.12 69.39 30.50 0.58 0.17 0.06 100.88
9 0.04 0.12 69.53 30.62 0.56 0.17 0.02 101.06
10 0.04 0.12 69.60 30.61 0.59 0.17 0.03 101.15
11 0.04 0.15 69.29 30.49 0.58 0.16 0.05 100.76
13 0.04 0.16 69.17 30.47 0.57 0.16 0.03 100.61
14 0.04 0.13 69.20 30.44 0.59 0.16 0.03 100.59
15 0.04 0.13 69.44 30.60 0.56 0.17 0.02 100.95
20 0.04 0.16 69.43 30.56 0.58 0.17 0.04 100.98
22 0.03 0.07 69.62 30.61 0.58 0.17 0.02 101.11
23 0.04 0.13 69.61 30.61 0.59 0.16 0.05 101.18
24 0.04 0.12 69.50 30.57 0.59 0.17 0.03 101.02
26 0.03 0.03 69.35 30.54 0.54 0.17 0.01 100.66
28 0.04 0.09 69.54 30.56 0.61 0.16 0.02 101.02
Atoms per formula unit
N Al Cr Fe3+ Fe2+ Mn Co Ni
1 0.00 0.00 2.00 0.98 0.02 0.00 0.00
2 0.00 0.00 2.00 0.97 0.02 0.00 0.00
3 0.00 0.00 2.00 0.98 0.02 0.01 0.00
4 0.00 0.00 1.99 0.98 0.02 0.00 0.00
5 0.00 0.00 1.99 0.98 0.02 0.00 0.00
6 0.00 0.00 1.99 0.97 0.02 0.01 0.00
7 0.00 0.00 1.99 0.98 0.02 0.00 0.00
8 0.00 0.00 1.99 0.97 0.02 0.01 0.00
9 0.00 0.00 1.99 0.98 0.02 0.01 0.00
10 0.00 0.00 1.99 0.97 0.02 0.01 0.00
11 0.00 0.00 1.99 0.97 0.02 0.01 0.00
13 0.00 0.00 1.99 0.98 0.02 0.01 0.00
Subducted iron and glassy spherules in the upper mantle?

14 0.00 0.00 1.99 0.97 0.02 0.00 0.00

15 0.00 0.00 1.99 0.98 0.02 0.01 0.00
20 0.00 0.00 1.99 0.98 0.02 0.01 0.00
22 0.00 0.00 2.00 0.98 0.02 0.01 0.00
23 0.00 0.00 1.99 0.97 0.02 0.00 0.00
24 0.00 0.00 1.99 0.98 0.02 0.01 0.00
26 0.00 0.00 2.00 0.98 0.02 0.01 0.00
28 0.00 0.00 2.00 0.97 0.02 0.00 0.00
SiO2 is always below 0.5wt. %
TiO2, V2O3, MgO and ZnO are below detection limit.

amorphization until a final thin foil thickness of A FEI Titan G2 transmission electron microscope
~90 nm was attained. Subsequently, the thin foil (TEM) equipped with Field Emission gun XFEG
was undercut with a 30 kV at 2.5 nA current, lifted was used to analyze the thin-foil at the Centro de
out, and transferred from the sample to a TEM Instrumentation Científica of the University of
grid using an OmniProbe nano-manipulator with Granada, Spain. The FEI Titan G2 microscope
a tungsten tip. To weld the thin foil to the tungsten is equipped with 4 energy dispersive analyses of
tip and the TEM grid, an ion-beam assisted Pt X-rays (EDX) detectors (FEI microanalysis Super
deposition was performed. X) and a high-angle annular dark-field detector
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Boletín de la Sociedad Geológica Mexicana / 74 (3) / A200722 / 2022 / 5

(HAADF). This FEI Titan G2 microscope also 3. Results

includes a spherical aberration corrector for the
objective lens. Selected mineral areas of interest Two iron-rich oxide and two silicate glass spherules

RESULTS
sampled within the thin-foil were imaged by the were recovered from two chromitites bodies hosted
FEI Titan G2 microscope using a combination of in the upper mantle section the Golyamo Kamen-
high-angle annular dark-field (HAADF) to obtain yane and Yakovitsa ultramafic massifs, in southern
Z high contrast images, and High-Resolution Bulgaria (Figure 1). These rocks belong to the
Transmission Electron (HRTEM) images to char- Rhodopean Ophiolite Association (Kolcheva et al.,
acterize the texture of the grains and to properly 2000), which correspond to a lithospheric section
define the ordering of the mineral aggregates. formed a mid-oceanic ridge that evolved to an
All these images were treated using the Digital island arc/back-arc setting in a supra-subduction
Micrograph® software in its Version 1.71.38 while zone (Colás et al., 2013).
maps were processed with the VELOX® software The largest iron-rich oxide spherule (~75-175
package. The FEI Titan G2 was running at 300 µm) was found in the Yakovitsa chromitite (Figure
kV working conditions while HRTEM images 2a-2l). It consists of an interlocking polygonal struc-
were acquired using Gatan CCD Camera. Ele- ture made up of micro-crystallites of magnetite
mental maps images were also processed using the with junctions, which are filled by a finely-grained
VELOX® software. symplectite of magnetite and amporphous Si glass

Subducted iron and glassy spherules in the upper mantle?

Figure 1 Simplified geological map of the Eastern Rhodope (adapted from Bonev, 2006) showing the localization of the ultramafic
massifs hosting the chromitite bodies investigated in this work. Equivalence keys: 1 (Kozhoukharov et al., 1988), 2 (Haydoutov et al.,
2001), 3 (Bonev, 2006), and 4 (Janák et al., 2011). Legends are in all cases inset in the figures.
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with trace amounts of P (Figure 2a-2l). Single-spot EDX analysis collected from the spherule surface
analyses obtained by EMPA show relatively (Figures 3d-3f). The discrete crystals of magnetite
RESULTS

homogenous composition of magnetite across the are small (<5 µm) faceted-equant grains with cubic
whole sphere with up to 93.47 wt.% FeOt, minor arrangement perpendicular to (111) crystal faces
Mn (0.54-0.61 wt%), CoO (0.14-0.17 wt%), Cr2O3 (Figure 3b), whereas rosaries of sub-micrometric
(0.03-0.16 wt%), Al2O3 (0.03–0.05 wt%), NiO spherules of magnetite occur widespread in the
(0.01-0.06 wt%), SiO2 (<0.5 wt%), and no TiO2, wüstite groundmass (Figure 3c).
MgO or CaO (Table 1). The smaller iron-rich oxide The glassy spherules are both colorless with
spherule identified in Golyamo Kamenyane (Fig- a smooth surface (Figures 4a and 4b) relatively
ures 3a-3c) consists of dendritic magnetite (Fe2O3) homogenous in composition dominated by SiO2
microcrystals within a wüstite (FeO) groundmass (~41 wt.%), CaO (31-34 wt-%) and Al2O3 (14-15
as determined by micro-RAMAN and FESEM- wt%), and lesser amounts of FeOt (~7 wt.%), MgO
Subducted iron and glassy spherules in the upper mantle?

Figure 2 Microphotographs of the iron spherule recovered from the Yakovitsa chromitite. (a-c) and (d) are images of the microtexture of
the spherule collected by FE-SEM previously and after polishing, respectively. (e-h) High-angle annular dark-field scanning transmission
electron microscopy (HAADF-STEM) image and corresponding TEM-EDS elemental map of the FIB thin foil (see location in (d)). (i-k)
High-resolution (HR)-TEM and high-magnification HRTEM images of the anatomy of the contact between magnetite microplates and
symplectite amorphous silica. (l) Selected area electron diffraction (SAED) image showing the amorphous nature of the silica sympletitice
and crystallinity of magnetite.
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Boletín de la Sociedad Geológica Mexicana / 74 (3) / A200722 / 2022 / 7

(2-4 wt.%) as well as Ti and K < 1.5 wt.% (see EDX shrinkage features such as bubble-like vesicles now
inset in Figure 4). These two spherules were partly filled with a suite of secondary minerals including

RESULTS
smashed during the mounting process, reveling magnetite, quartz, rutile or mixtures of them (Figure
internal continuity of the vitreous structure with 4b). Under high magnification magnetite exhibit
the typical conchoidal fractures of glassy materials rounded to octahedral-habit, whereas quartz is pris-
(Figures 4c and 4d). The spherule recovered from matic and rutile is needle-like to acicular crystals
the Golyamo Kamenyane chromitite displays grown perpendicular to the surface of the vesicle.

Subducted iron and glassy spherules in the upper mantle?

Figure 3 Microphotographs of the iron spherule recovered from the Golyamo Kamenyane chromitite. (a-b) Secondary electron (SE) FE-
SEM images of the unpolished spherule. (d-f) Representative spectrums of magnetite and wüstite collected micro-RAMAN and FESEM.
 http://dx.doi.org/10.18268/BSGM2022v74n3a200722
DISCUSSION AND CONCLUDING

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4. Discussion and concluding remarks Spherules having structures and textures similar to
4.1. IDENTIFYING SPHERULES IN MANTLE-DERIVED
ours - dendrite magnetite with interstitial silicate
REMARKS

ROCKS glass or wüstite groundmass and silicate glass only;

Figures 2-4 - have not been reported yet from
As noted above, metallic-silicate-oxide spherules ophiolitic mantle-derived rocks. Most spherules
found in natural rocks may have both natural and documented in peridotites and associated chro-
anthropogenetic origins. Some textural (magne- mitites from ophiolites (i.e., Tibet, Ray-Iz and
tite, rutile and quartz filling voids in the glassy Oman) consist of Ni-free native iron (α-Fe) with
spherule) and chemical features (very low Mn in cortex of dendritic wüstite, both having very small
the iron-rich spherule) of the spherules from the quantities (<<1 wt.%) of Mn, Ti and Si (Bai et
Bulgarian chromitites clearly rules out contami- al., 2004; Robinson et al., 2004; Xu et al., 2015;
nation by man-made spherules (Sulovsky, 2002; Griffin et al., 2016). Some spherules documented
Zhang et al., 2014; Shetye et al., 2019) during min- from Tibetan chromitites exhibit an additional
eral separation processes. thin layer of hematite separating the iron core and
Subducted iron and glassy spherules in the upper mantle?

Figure 4 Microphotographs collected by FESEM in SE mode of the glassy spherules recovered from the Yakovitsa (a) and Golyamo
Kamenenyane (b-h) chromitites. Representative FESEM-EDX spectrum of the glass are inset in the figure.
 http://dx.doi.org/10.18268/BSGM2022v74n3a200722

DISCUSSION AND CONCLUDING

Boletín de la Sociedad Geológica Mexicana / 74 (3) / A200722 / 2022 / 9

the wüstite rim (Xu et al., 2015), whereas some In addition, subsequent works showed that SuR-
others from Ray-Iz have iron core with drop-like UHP minerals might also form during low-pres-

REMARKS
inclusions wüstite, Fe–Ti alloys and/or silicate sure partial hydration of oceanic lithosphere
glass with up to 39 wt.% TiO2, 19 wt.% SiO2, 4 (Farré-de-Pablo et al., 2019; Pujol-Solà et al., 2018).
wt.% Al2O3, 22 wt.% FeO, 8 wt.% MnO, 6 wt.% Thus, a need for the inquiry on the generalized
Ca and 1 wt.% K2O (Yang et al., 2015). A subset deep mantle-related origin of for the alleged SuR-
of the spherules identified in-situ in chromites from UHP assemblage has arisen.
Tibet consist of Ni-Fe (formula Ni7.4 Fe2.6; Xu et al., The spherical morphologies along with the
2009) and host inclusions of pentlandite, periclase droplet-like shape of wüstite and/or silicate glass
and magnesium silicates. within iron cores reported in spherules from Ray-Iz
These spherules documented in mantle-de- are consistent with surface tension of unmixing
rived ophiolitic rocks were related to fluids/ metallic, oxide and silicate melts at high-tem-
melts of very high temperature (>1400-1500 ºC) perature. However, such mechanism itself cannot
and low f O2 (well below IW buffer) operating in satisfactorily explain the presence of silicate glass
the lower mantle or the Mantle Transition Zone found as both inclusions within native iron and
(i.e., MTZ > 610 km; Xu et al., 2015; Griffin et interstitial to dendritic magnetite and/or wüstite.
al., 2016). This interpretation was based on two Rather, silicate glass suggests melts quickly frozen
assumptions: (1) the assemblage iron + wüstite (quenched) as these are non-equilibrium materials
was also found in diamonds of deep-seated peri- that form due to fast kinetics preventing complete
dotites and kimberlites (e.g., Xu et al., 2015), and crystallization after melting with extremely high
(2) metallic-silicate-oxide spherules belong to the cooling rates (i.e., in the order of 107 ºC/min for
Super-reducing (SuR) mineral assemblage (e.g., hyper-quenched glasses; McCloy, 2019). There-
moissanite, carbides, nitrides and silicides) that is fore, it is unlikely that those spherules containing
usually found together with minerals that typically glasses were originated in-situ within the Earth’s
form at UHP (e.g., diamond and coesite) in these mantle. In fact, silicate glasses in mantle rocks
mantle rocks. Pioneering works suggested a com- can only be attributed to trapped interstitial melts
mon origin of the SuR and UHP during chromi- that have quenched during fast volcanic eruptions
tite crystallization from high-Cr melts within the (O’Reilly and Griffin, 2012). Interestingly, the

Subducted iron and glassy spherules in the upper mantle?

lower part of the upper mantle or MTZ (Yang et glass in these spherules from Ray-Iz has higher
al., 2007; Zhou et al., 2014; Zhang et al., 2016) or Ti than glasses in analogous volcanic and cosmic
metamorphism of recycled chromitites at these spherules. Its chemistry is, however, similar to that
high depths (McGowan et al., 2015; Griffin et al., of silicate-titanium-iron spherules reported from
2016). However, subsequent works (e.g., Xiong the Colônia impact crater in Brazil (Veláquez et al.,
et al., 2017) suggested that SuR minerals could 2021). However, these spherules lack of sculptur-
be incorporated into exhuming peridotites (and ing or impact marks (microcraters, pits with radial
associated chromitites) that already had UHP by cracks and star-shaped pit) as those of impact-re-
metasomatic slab-derived CH4 ± H2 fluids, or lated origin.
mantle melts that were supplied with such com- The patterns of iron nuclei and oxide cortex
ponent. Moreover, all spherules identified in these or dendritic magnetite in wüstite groundmass doc-
mantle-derived rocks, except the Ni-Fe bearing umented in the spherules from Tibet and Ray-Iz
isolated inclusions in chromite from Tibetan chro- and Golyamo Kamenyane ophiolites are very sim-
mitites, were found in mineral separates, therefore ilar to those reported in I-type cosmic spherules
do not provide the necessary direct connection (Genge et al., 2017). In contrast, the microtexture of
between the spherules and the other minerals of dendritic magnetite within Si-bearing glass of the
the SuR-UHP to confirm their true mantle origin. Yakovitsa spherule has been identified in volcanic
 http://dx.doi.org/10.18268/BSGM2022v74n3a200722
DISCUSSION AND CONCLUDING

10 / Boletín de la Sociedad Geológica Mexicana / 74 (3) / A200722 / 2022

(e.g., Ignimbrites of Southern Primorye in Rusia; that cosmic spherules could remain stable under
Grebennikov, 2011) and G-type cosmic spherules low-temperature and high-pressure conditions
REMARKS

(Folco and Cordier, 2015). A common feature of prevailing upon subduction, and therefore might
all spherules found in ophiolitic mantle rock is that be found in rocks related to slab-derive sediments
both magnetite and wüstite have Ni contents below in subduction zones. Interestingly, some spherules
1.0 wt.%. Low Ni in oxides is a common feature from Ray-Iz exhibit an identical pattern, raising
of cosmic spherules where Ni was separated from the possibility that cosmic spherules (and by exten-
the silicate-oxide melts towards metallic beads sion volcanic ones) now found in peridotites and
due to siderophile attraction display (Genge et al., chromitites from ophiolites could represent part of
2017). In fact, a population of spherules reported sediments that were incorporated into the upper
from Tibetan chromitites still contain Ni-Fe beads mantle via subduction. The recycling of crustal
or are solely Ni-Fe spherules, similarly to the vast material in the mantle and return pathways to
majority of I-type cosmic spherules reported in the the Earth’s surface has been already tracked by
geological record (Folco and Cordier, 2015; Genge xenocrystal zircons inherited from continental
et al., 2017). Nevertheless, cosmogenic nuclide and sources in supra-subduction zone ophiolitic and
noble gas analyses are not available for spherules juvenile intra-oceanic volcanic arc rocks (Proenza
associated with mantle peridotite and chromitites et al., 2018). In this scenario, it is expected that the
to confirm their extraterrestrial or terrestrial ori- spherules had experienced a series of events since
gin. This is clearly a green field for future research. their deposition in the deep sea including: modifi-
Silicate glass spherules from our chromitites cation during fly, alteration during diagenesis and
exhibit some common features with silicate-dom- transport with the oceanic slab into the subduction
inant volcanic and V-type cosmic spherules, zone, high P/T metasomatism/metamorphism,
including: (1) spherical morphology, with smooth heating by carrying fluids and melts involved in
external surface and internal conchoidal fractures mantle metasomatism and chromitite formation,
as is typical for quenched silicate-droplet glass, (2) and final exhumation. However, all the spherules
empty vesicles (now filled with secondary minerals) identified in ophiolitic mantle rocks are well-pre-
that may have been produced by degasification or served as their shapes and chemical composition
dissolution of pre-existing metal beads. However, were not obviously altered. Then, how can these
spherules could be transported and recycled into
Subducted iron and glassy spherules in the upper mantle?

their markedly higher Al and Ca but lower Mg dis-

tinguish them from cosmic ones. Overall, the con- the shallow oceanic mantle without affection?
centration of all the analyzed elements overlaps Subducted slabs can transport significant vol-
that of terrestrial basic basaltic glasses (McCloy, umes of sediments to depths greater than 50 km
2019; Cicconi and Neuville, 2019), suggesting (Scholl and von Huene, 2009) and these, in turn,
their possible volcanic-related origin. may be transferred to the mantle wedge by (1)
fluids/melts channelized in melt conduits or frac-
4.2. RECYCLING SPHERULES IN THE UPPER tures (González-Jiménez et al., 2017), and/or (2)
MANTLE? detachment and buoyancy-driven diapiric up flow
of plumes of slab-derived sediments (Gerya and
Shi et al. (2011) suggested an extraterrestrial ori- Yuen, 2003). The first mechanism links the trans-
gin for a suite of iron spherules they recognized fer of slab-derived spherules to the introduction of
in jadeitites from the Myanmar ophiolite. In silica- and alkali-rich fluids/melts due to the dehy-
these spherules with Fe isotopic composition dration/ anatexis of subducted sediments through
overlapping I-type cosmic spherules, core of fractures in mantle peridotites; it could be linked to
native iron is also overgrown by a rim made up of mechanism similar to those transferring spherules
dendritic crystal of wüstite. This discovery shows to jadeitites as observed in the Myanmar ophiolite.
 http://dx.doi.org/10.18268/BSGM2022v74n3a200722

Boletín de la Sociedad Geológica Mexicana / 74 (3) / A200722 / 2022 / 11

The second mechanism could be related with the Conflicts of interest

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cold plumes –partly molten crustal (including sed-
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rocks mixed on length scales from a few tens of
meters to hundreds of kilometers – contributing
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