Harada and Tsujimori ﻿Progress in Earth and Planetary Science(2024) 11:6
https://doi.org/10.1186/s40645-024-00609-y

RESEARCH ARTICLE

Progress in Earth andPlanetary Science

Open Access

Methane genesis within olivine‑hosted fluidinclusions in dolomitic marble of the Hida Belt,
Japan
Hironobu Harada1*   and Tatsuki Tsujimori1,2

Abstract
Abiotic synthesis of hydrocarbon-bearing fluids during geological processes has a significant impact on the evolution of both the Earth’s biosphere and the solid Earth. Aqueous alteration of ultramafic rocks, i.e., serpentinization,
which forms serpentinite, is one of the geological processes generating abiotic methane (­ CH4). However, abiotic­CH4 generation is not limited to the serpentinization of mafic and ultramafic lithologies. Metasedimentary dolomitic
marble from the Hida Belt, Japan, is characterized by the presence of forsterite-rich olivine (­ Fo~89–93), and olivine
crystals contain abundant fluid inclusions (<1 to 10 μm in size). Raman spectroscopic analyses of olivine-hosted fluidinclusions found that both primary and secondary fluid inclusions contain ­CH4, lizardite/chrysotile, and brucite. This
indicates that micro-scale interactions between COH fluid and host olivine produced C­ H4 through the reductionof ­CO2 by ­H2 released during local serpentinization within inclusions. Our observation implies that the dolomitic marble has the potential to be a key lithology for the synthesis and storage of abiotic C­ H4 in a shallower crustal portionof orogenic belts.
Keywords Dolomitic marble, Fluid inclusion, Olivine, Abiotic methane synthesis, Hida Belt
1 Introduction
Serpentinization of ultramafic rocks is one of the mostcommon abiotic methane (­CH4) generation processes.
The process involves the oxidation of ferrous iron contained in primary olivine to ferric iron in secondary
minerals, such as serpentine, brucite, and magnetite.
Consequently, this oxidation leads to the generation ofhydrogen ­(H2)-bearing reduced fluids, and the production of ­CH4 during serpentinization results from thereduction of C
­ O2 by these ­H2-bearing fluids (e.g., McCollom and Bach 2009; Sleep et al. 2004; Suda et al. 2014). In*Correspondence:
Hironobu Harada
hironobu.harada.s7@dc.tohoku.ac.jp
1
Department of Earth Science, Graduate School of Science, Tohoku
University, Aoba‑ku, Sendai 980‑8578, Japan
2
Center for Northeast Asian Studies, Tohoku University, Aoba‑ku,
Sendai 980‑8576, Japanthe natural environment, the presence of hydrocarbonbearing serpentinite-related fluids has been observed atseafloor hydrothermal fields and ophiolites (e.g., Kelley
et al. 2005; Miller et al. 2016; Proskurowski et al. 2008).
Although it has been known that shallow low-temperature serpentinization generates ­H2-bearing reduced fluids (e.g., Etiope et al. 2011; Etiope and Sherwood Lollar
2013; Kelley et al. 2005; Mottl et al. 2003; Ohara et al.
2012; Proskurowski et al. 2008), Evans (2010) showed thatdeep high-temperature and high-temperature serpentinization forming antigorite does not generate ­H2-bearing
reduced fluids. Nevertheless, recent natural observations
revealed that high-temperature serpentinization enables the generation of reduced fluids (Boutier et al. 2021;
Vitale Brovarone et al. 2020; Zhang et al. 2021). Recent
studies have reported abiotic ­CH4 synthesis in subduction zone lithologies (Spránitz et al. 2022; Tao et al. 2018;
Wang et al. 2022); ­CH4-rich fluid inclusions in omphacite from carbonated eclogite of SW Tianshan, China are© The Author(s) 2024. Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which
permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to theoriginal author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images orother third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line
to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory
regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of thislicence, visit http://creativecommons.org/licenses/by/4.0/.

Harada and Tsujimori ﻿Progress in Earth and Planetary Science(2024) 11:6

considered to be formed by the redox reactions of Febearing carbonates in water (Tao et al. 2018; Wang et al.
2022). Abiotic C­ H4 synthesis in such lithologies is rare,
and serpentinization has attracted interest as a major
abiotic ­CH4 production process. However, as reported inthis study, abiotic ­CH4 production during serpentinization is not limited to the ultramafic lithologies found inabyssal peridotite and ophiolite. Reconnaissance studies
for the abiotic ­CH4 production in supracrustal metasedimentary rocks in the continental crust have just begun.
In this paper, we present the occurrence of olivinehosted fluid inclusions containing ­CH4 from a dolomitic
marble from the Hida Belt, Japan. Based on the mineralinclusions associated with those fluid inclusions, we propose that abiotic ­CH4 synthesis in fluid inclusions is not
limited to ultramafic lithologies but also occurs in nonultramafic lithologies within the middle crustal section of
the continental margin.

2 Geological background
The Hida Belt of central Japan (Fig. 1a, b) is a continental fragment, which was once a part of a crustal basementof the East Asian continental margin prior to the backarc opening of the Japan Sea in the mid-Miocene (e.g.,
Isozaki et al. 2010, 2023). It consists mainly of PermoTriassic granite-gneiss complexes with Jurassic granitic
intrusions. The metamorphic lithologies of the Hida Belt
are mainly of granitic gneiss, amphibolite, marble, calcareous gneiss, quartzofeldspathic gneiss, and minor pelitic
gneiss (cf., Ehiro et al. 2016). The timing of the upper
amphibolite- to granulite-facies regional metamorphism
has been dated as ~260–230 Ma (e.g., Cho et al. 2021;
Horie et al. 2018; Takahashi et al. 2018).
In the Hida Belt, a large amount of metacarbonate
rocks occur accompanying gneissose rocks (Kano 1998).
The protolith has been regarded to be continental platform carbonates (e.g., Isozaki 1996, 1997; Sohma andKunugiza 1993). The sedimentary origin of the metacarbonate rocks is supported by their C–O–Sr isotope
compositions (Harada et al. 2021b). Most of the metacarbonate rocks in the Hida Belt consist mainly of calcite(i.e., calcite marble) with a minor amount of clinopyroxene, quartz, and titanite, whereas dolomitic marble
which consists mainly of Mg-rich calcite and dolomite israre (e.g., Harada et al. 2021b; Kano 1998). The calcite–
dolomite solvus thermometry from calcite–dolomite
intergrowth in dolomitic marble gives a temperature of~600 °C (Imai et al. 1977; Kano 1998).
3 Analytical methods
Micro Raman spectroscopic analyses were performed tocharacterize fluid inclusions. Unpolarized Raman spectra were obtained by a laser Raman spectrometer, thePage 2 of 13

HORIBA Jobin Yvon LabRAM300 at Tohoku University,connected to a 1024 × 256-pixel charge-coupled device(CCD) detector. The measurements used a 488 nm solidstate laser with a confocal hole of 200 μm, a slit widthof 100 μm. The laser was focused through an Olympus
MPlan 100 × objective lens (N.A. = 0.9). The laser output
was 25 mW at the source and approximately 5.0 mW at
the sample surface. The laser spot size was approximately
1 μm. Grating with 600 lines/mm and 1800 lines/mm wasused for analyses. The spectral resolution is ~5 ­cm−1 for
600 lines/mm grating and ~2 ­cm−1 for 1800 lines/mm
grating. The pixel resolution of this Raman spectrometer
when using a grating of 600 lines/mm is 5.5 ­cm−1/pixel
and 4.1 ­cm−1/pixel at about 1000 ­cm−1 and 3650 ­cm−1,
respectively, and the resolution when using a grating of1800 lines/mm is 1.8 ­cm−1/pixel and 1.3 ­cm−1/pixel ataround 1000 ­cm−1 and 3650 ­cm−1, respectively. Two
accumulations of 10–120 s were collected for each spectrum. The calibration of the spectrometer was performed
using a Si crystal and a diamond. The spectral baselines
were corrected, and the spectra were fitted using the software package PeakFit v4.12 (SeaSolve Software Inc.).

4 Results
4.1 Sample description and petrography

The investigated dolomitic marble samples were collectedfrom an outcrop along the Takahara River, Kamioka
area, Gifu Prefecture (Fig. 1a, b). Although the dolomitic marble occurs surrounded by gneissose rocks andleucogranite, the contact between dolomitic marble andsurrounding lithologies cannot be observed in the field.
The dark-colored partially serpentinized olivine occurs
as layers with a variety of widths (up to several tens ofcentimeters) in white carbonate minerals (Fig. 1c, d). The
dolomitic marble exhibits variations in both the modal
abundance and grain size of olivines.
The investigated dolomitic marble shows no remarkable foliation and commonly shows granoblastic texture. It
consists mainly of Mg-rich calcite, dolomite, and olivine­(Fo~89–93), with a small amount of tremolite, clinohumite,and phlogopite along with trace apatite (Fig. 2a). Carbonate minerals (calcite and dolomite) occur in a wide rangeof sizes (up to ~3 mm). The major carbonate minerals of
the olivine-rich layer and carbonate-rich part are calcite
and dolomite, respectively. Abundant tiny rectangulardolomite crystals were observed in calcite, suggesting
the exsolution of dolomite from calcite. Olivine occurs
as granular-shaped crystals with a wide range in size
(up to ~3 mm). Almost all olivine crystals have partly orcompletely suffered serpentinization, forming serpentine,brucite, and magnetite (Fig. 2b). Olivine contains calcite, dolomite, and abundant fluid inclusions (Fig. 2c, d).
Mesh texture after olivine is commonly observed. Raman

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Fig. 1 Geological maps (a, b) and photographs of investigated dolomitic marble (c, d). a Simplified geological map of the Hokuriku region,
showing locations of the Kamioka area (modified after Harada et al. 2021a,b). Hd, Hida Belt; HG, Hida-Gaien Belt; I.S.T.L., Itoigawa–Shizuoka Tectonic
Line; M–T, Mino–Tamba Belt; Ry, Ryoke Belt. b A geological map of the Kamioka area, showing sample localities (modified after Harada et al.
2021a,b). c The field occurrence of the dolomitic marble (Kamioka area, the Hida Belt). d A sample slab of dolomitic marble. Black minerals are
partially or completely serpentinized olivine

spectroscopic analyses show that the serpentines are lizardite and chrysotile.

4.2 Description of olivine‑hosted fluid inclusions

Fluid inclusion analyses were performed on both thinsections and epoxy-mounted olivine crystals. Olivine

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Fig. 2 Photomicrographs of investigated dolomitic marble. a Cross-polarized light (XPL) image of dolomitic marble. b XPL image of partiallyserpentinized olivine crystals in dolomitic marble. Serpentinization forms serpentine (lizardite) and magnetite. c, d Plane-polarized light (PPL) imageof olivine crystals rich in fluid inclusions. e PPL image of olivine-hosted fluid inclusions with secondary nature. f PPL image of olivine-hosted primary
fluid inclusion that contains calcite and dolomite. Mineral abbreviations follow Warr (2021)

grains were separated from sieved whole-rock powder using magnetic and heavy liquid techniques.
Hand-picked olivine grains under a binocular microscope were mounted in 1-inch round epoxy resin
discs. Olivine crystals in the investigated dolomitic
marble often contain dark-colored fluid inclusions.
The fluid inclusions vary from <1 to 10 μm in sizeand show irregular shape. There are two major typesof olivine-hosted fluid inclusions, although discriminating between most inclusions is difficult. Primary
fluid inclusions trapped during olivine growth occur
as isolated inclusions, while secondary fluid inclusions, formed by fluid infiltration after olivine crystallization, occur as trails in olivine crystals (Fig. 2e).
However, most inclusions are hard to discriminate as
primary or secondary.

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Fig. 3 Representative Raman spectra of olivine-hosted fluid inclusions in dolomitic marble from the Hida Belt. a, b Raman spectraof the olivine-hosted fluid inclusions. c–e Raman spectra of olivine-hosted fluid inclusion (c), lizardite in olivine rim (d), and host olivine (e) in low
wavenumber spectral range (110–750 ­cm−1). f, g Raman spectra of olivine-hosted fluid inclusion in high wavenumber spectral range (2800–
3800 ­cm−1). h, i Raman spectra of lizardite (h) and olivine-hosted fluid inclusion (i) in O–H stretching region (3600–3750 ­cm−1)

4.3 Raman spectroscopic analyses of olivine‑hosted fluidinclusions

We performed Raman spectroscopic analyses for over
100 olivine-hosted fluid inclusions. Raman spectraof olivine-hosted fluid inclusions show a strong bandat ~2913–2918 ­cm−1 (Figs. 3, 4, Additional file 1: Figure S1). This band can be assigned to the symmetric
C–H stretching band of ­C H4 vapor (e.g., Brunsgaard
Hansen et al. 2001; Lu et al. 2007; Seitz et al. 1996).
In addition to C
­ H4, several bands were observed in
the high wavenumber region (~3600–3800 ­cm−1)(Figs. 3,4, Additional file 1: Figure S1). These bands are
originated from O–H stretching vibrations of hydrous
minerals. On the low wavenumber region, Raman spectra of fluid inclusions show several bands in addition to
the bands of the host olivine (Fig. 3c, e). The ~280 ­cm−1and ~444 ­cm−1 bands (Fig. 3c) can be assigned to lattice vibrational modes of brucite (e.g., Dawson et al.
1973; Duffy et al. 1995; Zhu et al. 2019). Since brucite
has a strong band at ~3650 ­cm−1 derived from O–H
stretching vibration (e.g., Dawson et al. 1973; Duffyet al. 1995; Zhu et al. 2019), the ~3652 ­cm−1 band of

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Fig. 4 Representative Raman spectra of olivine-hosted fluid inclusions. a PPL image of olivine-hosted fluid inclusions. b, c Raman spectraof the olivine-hosted fluid inclusions shown in (b). d, e Raman spectra of olivine-hosted fluid inclusions that contain carbonate minerals. Inclusionof d contains calcite and dolomite, and inclusions of e contains calcite

the fluid inclusion is attributed to brucite. In addition to olivine and brucite, Raman spectra of olivinehosted fluid inclusions show ~130 ­cm−1, 230 ­cm−1,−1−1
390 ­cm , and ~690 ­cm bands (Fig. 3c). Similar peaks
are also observed in matrix serpentine that occurs
in rims and clacks of olivine crystals (Fig. 3d). We
assigned these bands to serpentine minerals of lizardite or chrysotile (e.g., Auzende et al. 2004; Compagnoni
et al. 2021; Groppo et al. 2006; Petriglieri et al. 2015;
Rinaudo et al. 2003; Rooney et al. 2018; Tarling et al.
2018). Although lizardite and chrysotile have similar
Raman spectra in the low wavenumber region, they
can be distinguished by their O–H stretching bands
in the high wavenumber spectral range (e.g., Auzende
et al. 2004; Compagnoni et al. 2021; Petriglieri et al.
2015; Rooney et al. 2018; Tarling et al. 2018); lizardite has two major peaks while chrysotile has one peakwith a slightly low wavenumber shoulder. Based on
the presence of ~3685 ­cm−1 and ~3706 ­cm−1 peaksof the obtained spectrum (Fig. 3f, g, i), we consideredthat the serpentine in olivine-hosted fluid inclusions
is lizardite. Raman spectrum of lizardite in high wavenumber spectral range consists of multiple bands (e.g.,
Auzende et al. 2004; Compagnoni et al. 2021). Compagnoni et al. (2021) obtained Raman spectra of lizardite under three different crystal orientations anddeconvolved the O–H stretching region of lizardite
into six bands. They reported that lizardite shows different Raman spectra and intensities for each orientation. Since we analyzed lizardite in fluid inclusions,
it is difficult to perform a deconvolution that is completely consistent with the literature. Therefore, asprevious studies have shown (Auzende et al. 2004;
Petriglieri et al. 2015; Rooney et al. 2018; Tarling et al.
2018), we regarded that the Raman spectrum of lizardite in the O–H stretching region is characterized by
two intense peaks at ~3680 ­
cm−1 and >~3700 ­cm−1(Fig. 3i). Although lizardite has a band of ~3650 ­cm−1, it
is not strong (Fig. 3h; Compagnoni et al. 2021; Rooneyet al. 2018; Tarling et al. 2018). Hence, the intense peakHarada and Tsujimori ﻿Progress in Earth and Planetary Science(2024) 11:6

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Fig. 5 Photomicrographs and representative Raman spectra of fluid inclusions in carbonate minerals. a PPL image of fluid inclusions
in dolomite. b Raman spectrum of fluid inclusion in dolomite. Raman spectra of most fluid inclusions in calcite and dolomite show a broad bandfrom around 2700–3800 ­cm−1, which originates from O–H stretching modes of liquid water. c Enlarged view of O–H stretching region in the Raman
spectrum of (b). PPL image (d) and Raman spectrum (e) of dolomite-hosted fluid inclusions that propagate from the serpentinized rim of olivine
crystalat ~3650 ­cm−1 can be considered to be that of brucite.
Based on the above consideration, this study treats theRaman spectra of olivine-hosted fluid inclusions in thehigh wavenumber region as follows: The presence of
brucite is characterized by the strong ~3650 ­cm−1 band,
while other bands is derived from lizardite. Lizardite
is characterized by two intense peaks at ~3680 ­cm−1and >~3700 ­cm−1. The ­CO2, ­H2O, and ­H2 were notdetected from investigated olivine-hosted fluid inclusions. The inclusion assemblage that contains ­C H 4,
lizardite, and brucite was ubiquitously observed ininvestigated olivine-hosted fluid inclusions. In addition
to the described inclusion assemblage, some primary
fluid inclusions also contained carbonate minerals(Figs. 2f, 4d, e). Carbonate minerals in fluid inclusions
show ~155 ­cm−1, ~281 ­cm−1, and ~714 ­cm−1 bands−1with a strong ~1088 ­cm band (Fig. 4d, e) and are considered to be calcite. The peak position of the strong
band of investigated carbonate mineral (~1088 ­cm−1)
was slightly higher than that of calcite in the literature (~1085 ­cm−1: e.g., Bischoff et al. 1985; Dufresne
et al. 2018; Gillet et al. 1993). The slight upshift of theband has been reported from Mg-calcite (e.g., Bischoff
et al. 1985; Borromeo et al. 2017; Burke 2001), andthe observed bands can be attributed to Mg-calcite.
The ~1088 ­cm−1 band of Mg-calcite in fluid inclusions
sometimes has a shoulder at a higher wavenumber side(~1098 ­cm−1) (Fig. 4e), suggesting the presence of dolomite (e.g., Bischoff et al. 1985; Gillet et al. 1993). Since
calcite and dolomite also occur as inclusion minerals in

the olivine, carbonate minerals in fluid inclusions are
considered an accidentally trapped mineral during hostolivine growth.
4.4 Fluid inclusions in carbonate minerals

Calcite and dolomite also contained fluid inclusions(Fig. 5a, d). Raman spectra of most fluid inclusions incalcite and dolomite show a broad band from around2700–3800 ­cm−1 (Fig. 5b, c), which is attributed to O–H
stretching modes of liquid water (e.g., Walrafen 1964).
Secondary fluid inclusions that propagate from the serpentinized rim of olivine crystals were rare and contained ­CH4 (Fig. 5d, e). Note that these secondary ­CH4
fluid inclusions in carbonate minerals lack ­H2O.

5 Discussion
5.1 Origin of ­CH4‑bearing olivine‑hosted fluid inclusions

Raman spectroscopic analysis of olivine-hosted fluidinclusions in dolomitic marble found the presence of­CH4, lizardite, and brucite (Figs. 3, 4, Additional file 1:
Figure S1). The presence of serpentine and brucite in
fluid inclusions is robust evidence that serpentinization
occurred within olivine-hosted fluid inclusions as theresult of the reaction between trapped fluid and host olivine crystals (Fig. 6). Therefore, it is reasonable to consider that the C­ H4 was produced via the reduction of­CO2 by H­ 2 that originated from internal serpentinization
within fluid inclusions (Grozeva et al. 2020; Klein et al.
2019; Miura et al. 2011; Zhang et al. 2021, 2022).

Harada and Tsujimori ﻿Progress in Earth and Planetary Science(2024) 11:6

Fig. 6 Schematic diagram illustrating a model of serpentinization
and accompanying ­CH4 generation within olivine-hosted fluidinclusions. a Petrography of olivine-bearing dolomitic marble. b
Olivine-hosted fluid inclusions originally contained ­H2O and ­CO2
(COH fluid) when they were trapped. c The decrease in temperatureduring the early stages of exhumation causes serpentinization of hostolivine by trapped fluid and ­H2 generation. d Generated ­H2 reduced­CO2 and formed C­ H4

Based on the observation, we postulate that olivinehosted fluid inclusions originally contained ­H2O and ­CO2
(COH fluid) when they were trapped. As temperatures
decreased upon exhumation, the trapped fluid caused
serpentinization of the host olivine crystal and formed lizardite and brucite as step-daughter minerals. The serpentinization reaction generated H­ 2, and then the ­H2 reduced­CO2 and formed ­CH4. The origin of ­CO2 in the trapped
fluid can be attributed to metamorphic decarbonation
and/or carbonate dissolution. The entrapment of primary
fluid inclusions occurred during olivine growth in theupper-amphibolite to granulite facies peak metamorphic
conditions of the Hida Belt. Since the formation of serpentine in fluid inclusions occurred after the fluid entrapment, the secondary fluid inclusions must have been
trapped at conditions under which olivine is stable in thepresence of H
­ 2O. In other words, the fluid entrapment
occurred prior to the matrix serpentinization of the hostolivine crystal. Therefore, we can rule out the possibility
that the ­CH4 was derived from matrix serpentinization
and was present in the fluid when it was trapped.
Although typical serpentinization reactions accompany
the oxidation of iron and form magnetite, resulting in ­H2generation, the mineral inclusion assemblage of investigated olivine crystals lacks magnetite (Figs. 3, 4). However, there is a possibility that nanometer-sized magnetite

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crystals that cannot be detected by Raman spectroscopic
analyses may be present in inclusions. Even if not, magnetite formation is not essential in ­H2 production during serpentinization. Serpentine can accommodate asignificant amount of ferric iron ­(Fe3+) (e.g., Andreani
et al. 2013; Fuchs et al. 1998; Klein et al. 2009; O’Hanley
and Dyar 1993). Serpentine produced by the hydrationof magnesium (Mg)-rich olivine contains Fe with a high­Fe3+/(Fe3+ + ­Fe2+) ratio (Klein et al. 2013). The mineral assemblage formed by serpentinization depends on
conditions such as temperature and water to rock ratio;
magnetite may not be produced by the serpentinizationof Fe-bearing olivine (Klein et al. 2013). In that case, the­Fe3+ in serpentine contributes to the ­H2 generation (e.g.,Andreani et al. 2013; Klein et al. 2013; Marcaillou et al.
2011; Seyfried et al. 2007). Therefore, the absence of magnetite does not exclude the possibility of ­H2-generation
via serpentinization within fluid inclusions.
Secondary fluid inclusions in carbonate minerals that
propagate from serpentine contained ­CH4 and lacked­H2O. In contrast, the ubiquitous occurrence of hydrous
minerals like serpentine and brucite in olivine-hosted
fluid inclusions indicates that the inclusions initially contained ­H2O. The contrast regarding the presence of waterin fluid inclusions in olivine and carbonate minerals may
reflect differences in the original fluid composition. Since­CH4 secondary fluid inclusions in calcite and dolomite
propagate from serpentine, the origin of C
­ H4 in carbonate minerals can be attributed to the matrix serpentinization of olivine crystals, which formed serpentine
minerals of olivine rim and clacks. Therefore, the entrapment timing of ­CH4-bearing fluid inclusions hosted inolivine and carbonate minerals would have been different: Olivine-hosted fluid inclusions were trapped prior
to the matrix serpentinization, whereas C­ H4 secondary
fluid inclusions in calcite and dolomite were formed during or after the serpentinization. Raman spectra of mostof the fluid inclusions in calcite and dolomite show thepresence of liquid H­ 2O. If these inclusions were formed
during regional metamorphism, metamorphic fluid
would not have contained C­ H4. Fluid inclusions in carbonate minerals may support the abiotic C­ H4 generation
within olivine-hosted fluid inclusions. The possibility thatthe ­CH4 in olivine-hosted fluid inclusions is of biologicalorigin cannot be completely ruled out without measuring
the carbon isotope compositions of the ­CH4. However,the presence of ­H2O-rich fluid inclusions in carbonate minerals and the mineralogy of olivine-hosted fluidinclusions indicate that the abiotic synthesis during internal serpentinization within fluid inclusions is a plausible
origin of ­CH4 in olivine-hosted fluid inclusions of dolomitic marble.

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a Mg0.9 , Fe0.1 2 SiO4 + bH2 O
Olivine3+→ c Mgx , Fe2+
y , FezFe3+
v , Siw O5 (OH)4

Serpentine

2(1)+ dMg(OH)2 +eH2 .
Brucitea Mg0.9 , Fe0.1 2 SiO4 + bH2 O
Olivine3+→ c Mgx , Fe2+
y , FezFe3+
v , Siw

Serpentine

2

O5 (OH)4(2)+ d Mgs , Fet (OH)2 +eH2 .
BruciteFig. 7 The estimation of the amount of ­CH4 produced
within olivine-hosted fluid inclusions. Assuming spherical fluidinclusions with a diameter of 10 μm, the amount of ­CH4 that could
be produced by serpentinization without magnetite formation
is calculated. The results of two simple reactions are shown; produced
brucite is a Fe-free brucite and b Fe-bearing brucite. The number
on the lines shows the assumed density of ­H2O (100–1000 kg/m3)

Assuming spherical fluid inclusions with a diameter of
10 μm, we estimated the amount of C
­ H4 that could be produced by the serpentinization without magnetite formation
as a function of F
­ e3+ content in serpentine (Fig. 7). Two
simple reactions were considered, one in which the productbrucite is a pure Mg end-member (Reaction 1) and one inwhich the product brucite contains Fe (Reaction 2).

For simplicity, the following assumptions were made.
(1) Generated H­ 2 is not lost by diffusion. (2) Trapped fluid
initially contains ­H2O and ­CO2, and the amount of ­CO2
is sufficient to react with the generated ­H2. (3) Amongthe products, only serpentine contains ­Fe3+. Since we2+
3+
3+
regard cronstedtite [(Fe 2Fe )3(Fe Si)2O5(OH)4] as the­Fe3+ end-member of serpentine (Evans 2008), the ­Fe3+/(Fe2+ + ­Fe3+) ratio of serpentine is up to 0.5. The serpentine formed by the serpentinization of F
­ o90 olivine has a­Fe3+/(Fe2+ + ­Fe3+) ratio up to ~0.35 (Klein et al. 2013).
Assuming the density of trapped ­H2O is 1000 kg/m3, each
fluid inclusion has the potential to produce a maximumof ~1.7 × ­10−13 mol ­CH4. This ­CH4 amount is comparable
to the ­CH4 content of olivine-hosted fluid inclusions inperidotite and gabbroic rocks (8.4 × ­10−14 to 1.2 × ­10−11 mol­CH4: Klein et al. 2019). Although the actual serpentinization reaction would be more complex, and this is a maximum estimation, it suggests the effective production of­CH4 in olivine-hosted fluid inclusions in dolomitic marble.
5.2 Implications for abiotic ­CH4 synthesis
during serpentinization

What is the significance of C
­ H4 synthesis in olivine-hosted
fluid inclusions? Thermodynamic calculations show that
serpentinization involving a small volume of fluid resultsin high H­ 2 concentration in fluids because the generated ­H2 is less diluted (Klein et al. 2013). Olivine-hosted
fluid inclusions can achieve a high H­ 2 concentration during serpentinization because the volume of trapped fluid
is much smaller than the volume of the host olivine crystal. In addition, the infiltration of external fluids would notoccur during serpentinization due to the isolated natureof the fluid inclusions within the olivine. This condition
would be suitable for the reduction of C
­ O2 and production of ­CH4. Experimental studies suggest that there aresubstantial kinetic barriers inhibiting abiotic C­ H4 synthesis
from the reduction of C
­ O2 unless certain catalysts, such asHarada and Tsujimori ﻿Progress in Earth and Planetary Science(2024) 11:6

FeNi alloys and chromite, are present (e.g., Foustoukos andSeyfried 2004; Horita and Berndt 1999; Klein and McCollom 2013; Lazar et al. 2012; McCollom 2016; McCollom
and Seewald 2001); longer reaction times may be necessary
to produce a significant amount of abiotic C­ H4. However,fluid inclusions can retain high H­ 2 concentrations overmuch longer timescales than experimental studies. Therefore, internal serpentinization within fluid inclusions canbe an effective pathway of abiotic C­ H4 synthesis in the geological process.
High concentrations of geologically sourced hydrogen and hydrocarbon can have an impact on the Earth’s
biological activities. The microbial habitat extends tobeneath Earth’s surface, and Earth’s subsurface biosphere, which has a large biomass (Magnabosco et al.
2018), relies for metabolisms on ­H2 and ­C H4 producedby fluid-rock interactions (e.g., Colman et al. 2017;
Templeton and Caro 2023). In fact, some subsurface
microbial communities would use serpentinite-derived­H2 and ­C H4 (e.g., Schrenk et al. 2013). Recently, Vitale
Brovarone et al. (2020) found that serpentinization
generates reduced fluids, including ­H2, ­C H4, ­H2S, and­NH3, and they suggested that these fluids may supply to the subsurface biosphere in the forearc region.
In this study, we proposed the abiotic C­ H4 synthesis
in olivine-hosted fluid inclusions of dolomitic marble.
The presence of microorganisms with anaerobic methane oxidation has been reported from granitic rocks aswell as basalts and serpentinites (e.g., Ino et al. 2016;
Kraus et al. 2021; Lever et al. 2013; Nothaft et al. 2021).
If the olivine-hosted fluid is released, dolomitic marble
may have the potential to provide abiotic ­C H4 to thesubsurface biosphere in the continental crust.
Abiotic ­CH4 synthesis through internal serpentinization within olivine-hosted fluid inclusions has
been widely recognized in mafic and ultramafic rocks(Grozeva et al. 2020; Klein et al. 2019; Miura et al. 2011;
Zhang et al. 2021, 2022). This study provides the firstfinding of ­CH4-bearing olivine-hosted fluid inclusions inmetacarbonate rocks with sedimentary origin. We propose that serpentinization within olivine-hosted fluidinclusions is a ubiquitous process in olivine-bearing
lithologies, not only in ultramafic rocks. Furthermore,since olivine-bearing dolomitic marbles occur in various orogenic belts with a wide range of metamorphic
conditions (e.g., Kato et al. 1997; Liu et al. 2006; Ogasawara et al. 2000; Otsuji et al. 2013; Satish-Kumar et al.
2010; Yoshida et al. 2021), and even in contact metamorphic aureoles (e.g., Cook and Bowman 2000; Ferry
et al. 2002; Holness 1997; Rice 1977), the dolomitic
marble might have the potential to be the key lithology
for the synthesis and storage of abiotic ­CH4 in the continental crust and orogenic belts. In addition, the C­ H4Page 10 of 13

in olivine-hosted fluid inclusions can be released by theweathering of exhumed dolomitic marble, and it might
affect the atmospheric ­CH4. To further our understanding of the contributions to the impact of abiotic ­CH4
storage in the solid Earth, quantitative estimation of ­CH4
production is still required.

Supplementary Information
The online version contains supplementary material available at https://​doi.​
org/​10.​1186/​s40645-​024-​00609-y.
Additional file 1: Figure S1. Representative Raman spectra ofolivine-hosted fluid inclusions in high wavenumber spectral range(2800–3800 ­cm−1).
Acknowledgements
We appreciate Yoshihide Ogasawara for donating a micro-Raman facility anddolomitic marble samples to CNEAS. We extend our appreciation to Tan Furukawa and Isamu Morita for their field assistance. We thank Maureen Feinemanfor her constructive feedback. We are grateful for constructive comments from
two anonymous reviewers and thoughtful editorial handling by Madhusoodhan Satish-Kumar.
Author contributions
HH devised the project, conducted the analysis, and drafted the manuscript.
TT supervised the project and contributed to the writing of the manuscript.
All authors read and approved the final manuscript.
Funding
This research was supported by the Graduate School of Science and Center for
Northeast Asian Studies, Tohoku University, in part by grants from the MEXT/JSPS KAKENHI JP22J21064 to HH, JP21H01174 to TT, ERI JURP 2021-B-01 in
Earthquake Research Institute, the University of Tokyo, and the International
Joint Graduate Program in Earth and Environmental Sciences (GP-EES) of
Tohoku University.
Availability of data and materials
All data generated or analyzed during this study are included in this publishedarticle.

Declarations
Competing interests
The authors declare that they have no competing interest.
Received: 7 August 2023 Accepted: 2 February 2024

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