Characterization and quantification of iron species in the banded iron formations (BIFs) in China Craton to explore the potential for H2 production using XRD and Mössbauer spectroscopy

Hyo-Im Kim; Inkyeong Moon; Minkyeong Kim; Hyuk Jun Lee; Hyunkyung Choi; Young Rang Uhm; Lei Liu; Jonguk Kim; Wonnyon Kim

doi:10.1371/journal.pone.0316540

Abstract

Banded iron formations (BIFs), significant iron ore deposits formed approximately 2.3 billion years ago under low-oxygen conditions, have recently gained attention as potential geological sources for evaluating hydrogen (H₂) production. BIFs are characterized by high concentrations of iron oxide (20 to 40 wt.%) and low Fe³⁺/Fe_tot ratios, representing a major source of ferrous iron on Earth. This study investigates the mineralogical and geochemical characteristics of iron ore samples from the Wugang and Hengyang BIFs in China using X-ray diffraction (XRD) and Mössbauer spectroscopy to examine H₂ generation potential. XRD analysis and microscopic observations showed that the magnetite and hematite are the primary ore minerals in BIFs in China Craton. Mössbauer spectroscopic results provided the quantified information on the fractions of each iron species in varying minerals. Particularly, the Fe³⁺ tetrahedral sites and octahedral sites occupied by both Fe²⁺ and Fe³⁺ in magnetite and Fe³⁺ octahedral sites in hematite were determined. We estimated H₂ production potential by calculating the relative fraction of Fe²⁺ in magnetite relative to total number of iron atoms in the bulk samples from the Mössbauer results. The pyroxene-bearing BIF in Wugang (P-BIF) contains magnetite predominantly (~30.4 wt%), and the fraction of Fe²⁺ in magnetite is ~26%. Based on the quantified values, the maximum potential for H₂ generation from P-BIF in Wugang could be ~630 mmol H₂/kg rock. Due to the variation of mineralogical composition depending on the types and locations of occurrence of BIF, the H₂ generation potential also varies. For example, contrast to P-BIF in Wugang, the hematite-rich BIF from Hengyang, containing ~6.0 wt% of magnetite, showed significantly lower Fe²⁺ fraction in magnetite (~5%), resulting in low H₂ potential (~120 mmol H₂/kg rock). This study presents that a prevalence of magnetite in BIFs has considerable potential for H₂ production due to low Fe³⁺/Fe_tot, suggesting that the magnetite-rich iron ore can be effectively utilized as the source of stimulated hydrogen production. The current results also highlight that the Mössbauer spectroscopy is essential to provide the database of relative fractions for each iron species in BIFs, which allows us to estimate the quantity of H₂ released from BIFs.

Citation: Kim H-I, Moon I, Kim M, Lee HJ, Choi H, Uhm YR, et al. (2025) Characterization and quantification of iron species in the banded iron formations (BIFs) in China Craton to explore the potential for H₂ production using XRD and Mössbauer spectroscopy. PLoS ONE 20(1): e0316540. https://doi.org/10.1371/journal.pone.0316540

Editor: Hesham M.H. Zakaly, Ural Federal University named after the first President of Russia B N Yeltsin Institute of Physics and Technology: Ural’skij federal’nyj universitet imeni pervogo Prezidenta Rossii B N El’cina Fiziko-tehnologiceskij institut, RUSSIAN FEDERATION

Received: August 30, 2024; Accepted: December 12, 2024; Published: January 24, 2025

Copyright: © 2025 Kim et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

Data Availability: All relevant data are within the manuscript.

Funding: This research was funded by the Korea Institute of Ocean Science & Technology (KIOST) research program (PEA0213). The work was also supported by the Ministry of Science and ICT of Korea (NRF-2022R1C1C1003385) and the Ministry of Education of Korea (RS-2023-00301974).

Competing interests: The authors have declared that no competing interests exist.

Introduction

Explorations of geological hydrogen (H₂) in diverse settings have garnered tremendous attention due to its potential to provide a sustainable and clean energy source as a promising alternative to fossil fuels [1–3]. Recent studies have discovered large accumulations and releases of natural H₂ in regions such as Mali in Africa [4], Oman in West Asia [5–7], Kansas in United States [8], and etc. [3]. Along with the exploration of natural H₂, the efforts to proactively generate H₂ from geological source rock (i.e., stimulated geological hydrogen) have been initiated to facilitate the large-scale and sustainable hydrogen production [6, 9].

The oxidation of Fe²⁺ in the iron-rich rocks via water-rock interaction is considered a key process to in both natural H₂ and generating H₂ [10, 11]. Particularly, serpentinization, a well-known geological process that produces natural H₂ in association with the mafic and ultramafic rocks, occurs when Fe²⁺ in ferromagnesian minerals (such as olivine, pyroxene, and etc.) is oxidized to Fe³⁺, resulting in the reduction of H₂O [7, 12, 13]. Due to the significance of serpentinization, the previous and ongoing explorations for naturally released H₂ have focused on the geological contexts related to tectonic boundaries associated with oceanic lithosphere and mantle rocks such as ophiolite system [7, 14–16], mid-ocean ridges [17–19], and active vents [20–22]. In this context, the injection of fluid into rock containing Fe²⁺-bearing minerals can promote the oxidation reactions that involve H₂ emission, with chemical reaction of 2FeO_(rock) + H₂O → Fe₂O_3(rock) + H₂ [9, 23]. By constraining the geochemical conditions of fluids, the production of H₂ from the source rocks can become more efficient. For the determination of the source rock for obtaining H₂, the accurate description of geological targeted rocks including mineralogical identification and quantification of iron-bearing oxide minerals are necessary.

Recently, banded iron formations (BIFs) have re-emerged as a source rock for production of H₂ [24, 25] due to the prevalence of iron oxide phases. BIFs, which consist primarily of iron oxide minerals such as magnetite and hematite with high total Fe₂O₃ contents (~20–50 wt%), formed during the Precambrian era between 3.8 and 1.8 billion years ago [11] through the oxidation of dissolved Fe²⁺ (aq) in the oceanic water into Fe³⁺ [26]. The mineral phases constituting BIFs vary depending on the redox conditions, chemical compositions, material sources and microbial activities of the ancient aqueous system. Meanwhile, magnetite (Fe₃O₄) is considered to be a key mineral involved in the generation of H₂: magnetite has an inverse-spinel structure characterized by the general stoichiometry (Fe³⁺)^A[Fe²⁺Fe³⁺]^BO₄, where A sites are tetrahedrally coordinated (Td^M) and B sites are octahedrally coordinated (Oh^M), which are randomly occupied by approximately equal numbers of Fe³⁺ and Fe²⁺ [27, 28].

Until recently, magnetite was regarded as a by-product of the serpentinization process, resulting from the alteration of Fe²⁺-bearing silicate minerals to Fe³⁺-bearing serpentine and/or catalysts of H₂-production reactions [11, 12, 24, 29, 30]. A recent study suggests that the presence of magnetite in reactants (i.e., source rock) can promote oxidation reactions under low-temperature conditions due to its spinel crystal structure, which facilitates electron transfer on the octahedron sites in spinel structures [30]. Taking into account the stability of BIFs which formed in the Precambrian era, the formation of large-scale accumulation of naturally generated H₂ from BIFs is considered to be kinetically unfavored in the ambient condition. However, the experimental studies for water-rock interaction using magnetite on low-temperature conditions (under 200°C) controlling the temperature, pH, specific surface area and mineral composition of source rock showed that considerable amount of H₂ can be released from magnetite [24, 29, 30]: for example, about 6.3 μmol/g of H₂ were generated from natural magnetite at the temperature of ~5–20°C [29]. These previous results suggest that the magnetite could be a promising candidate for H₂ production with low amount of energy consumption during the engineering process for stimulated geological hydrogen. Therefore, the BIFs, which are abundant in magnetite and contain high total Fe content, could be deliberated its potential as a source for H₂ generation.

The application of the natural magnetite for hydrogen production offers several advantages compared to other methods. Unlike conventional approaches such as water electrolysis and fossil fuel reforming, the development of stimulated hydrogen production using magnetite can significantly reduce energy consumption and CO₂ emission during H₂ production process, contributing to a carbon-neutral and environmentally sustainable process. Moreover, magnetite-based H₂ production methods are potentially more reliable and consistent than H₂ production from biomass and solar photocatalysis, given the widespread availability of magnetite in various geological settings [24, 25]. While it is necessary to study the efficient conditions for H₂ generation from magnetite and identify suitable geological sites to achieve cost-effectiveness, H₂ production using magnetite in natural rock samples remains a highly promising approach, considering these advantages.

To evaluate the potential of BIFs as a source rock of H₂, the possible amount of H₂ release should be estimated based on the geochemical and mineralogical characterizations. Specifically, identification of iron-bearing mineral phases and quantification of their fractions in BIFs are necessary to determine the Fe²⁺ contents which can be involved in the oxidation reaction that produces H₂. X-ray diffraction (XRD) is an effective experimental tool for identifying the mineral species in the bulk rock samples, thus, previous studies have utilized XRD to investigate the mineral compositions in BIFs from diverse regions [31–33]. To better constrain the varying iron species, Mössbauer spectroscopy which a powerful technique for quantifying crystallographically distinct iron sites in diverse phases is necessary [34, 35]. This nuclear spectroscopic technique has widely utilized in the studies of natural and synthetic materials such as volcanic rocks in Earth and Mars [36–39], silicate glasses [40, 41], and BIFs [33, 42, 43] via quantifying the relative fractions of iron-bearing phases including magnetite and hematite.

Mössbauer spectroscopy which has been applied to diverse BIFs from various depositional terrains (e.g., West Greenland, Canada, Australia, North China and etc.) provides detailed insights into the paleoenvironmental conditions during BIF formation, diagenetic and/or metamorphic pathways, and the degree of weathering [33, 44, 45]. More recently, a study utilizing Mössbauer spectroscopy attempted to quantify the mineral species in BIF samples from the Pilbara Craton in Australia to calculate the potential of H₂ production [25]. To identify suitable BIFs for H₂ production, the database of the quantified magnetite contents in diverse natural BIFs are required.

In this paper, we performed XRD and Mössbauer spectroscopy to identify and quantify the iron-bearing mineral phases in BIFs from the Wugang and Hengyang, located in the North and South China Cratons, respectively. It is well known that the North China Craton (NCC) contains primarily Neoarchean-Paleoproterozoic BIF deposits and the BIF types vary with the specific locations [46–48]. Although the details of BIFs in South China Craton (SCC) remain to be explored, a recent study has reported that Mesoarchean BIFs are deposited in the SCC [49]. This study provides the database of relative fractions for each iron species in BIFs, which allows us to estimate the quantity of H₂ released from BIFs. We then discuss the potential of BIFs in China Craton as the source of H₂ production.

Geological setting

China hosts three major Precambrian cratons: The NCC, the SCC, and the Tarim Craton (Fig 1A), each with a geological history spanning billions of years [50]. NCC is consist of Archean to Paleoproterozoic metamorphosed basement with Mesoproterozoic to Phanerozoic unmetamorphosed sedimentary cover. The basement rock of craton is primarily composed of Neoarchean tonalitic–trondhjemitic–granodioritic (TTG) gneisses and metamorphosed supracrustal rocks. In contrast, Paleoarchean and Mesoarchean rocks are largely confined to the eastern regions of the craton, particularly in eastern Hebei Province and Anshan in Liaoning Province, where rocks dating back to 3.85 billion years have been identified [51–53] (Fig 1B). The South China Craton is partitioned into two distinct geological blocks: the Yangtze Block in the north and the Cathaysia Block in the south, each characterized by unique crustal ages and tectonic histories [42, 54–56]. The basement of the Yangtze Block is composed of Archean rocks [57, 58], whereas the Cathaysian Block primarily contains Paleo-Mesoproterozoic rocks with some Late Archean elements [59]. The collision between these two blocks led to the Sibao Orogeny, dated between 0.9 and 1.3 billion years ago, which aligns with the global Grenville orogeny [60–62] (Fig 1C).

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Fig 1. Geological map of the study area.

(a) The schematic tectonic map of China showing the major Precambrian blocks [North China Craton (NCC) and South China Craton (SCC)] [63]. Geological maps of (b) NCC [64, 65] and (c) SCC [66] with sampling locations of the Wugang BIF within the NCC and the Hengyang BIF within the SCC.

https://doi.org/10.1371/journal.pone.0316540.g001

In this study, the iron ore samples were collected from the Wugang BIF in the North China Craton (NCC) and the Hengyang BIF in the South China Craton (SCC) (Fig 1). The Wugang BIF is located in the Neoarchean Taihua complex in the Wugang area and is considered one of the representative iron ores in the Central Plains [48]. The Taihua complex is discretely exposed along the southern margin of the north-south striking TNCO and consists of early Precambrian medium-high grade metamorphic rocks with TTG gneisses, amphibolites, supracrustal rocks and so forth. The area is primarily comprising the Neoarchean blocks of Huashan, Xiaoshan, Luoning, Lushan, and Wugang from northwest to southeast. Among the blocks, BIFs are distributed in the Wugang and Lushan areas. In this study, we focused Wugang BIF which possessed more than 600 million tons. The iron source was provided by mixture of high-T hydrothermal fluid and seawater with negligible effect of detrital contamination in an anoxic marine environment [64, 67]. Detrital zircon U-Pb dating provides an age constraint between 2.40 and 2.47 Ga [54]. Combined the features of geological condition, related host rock, and geochemical data, Wugang BIF have Superior-type affinity and deposited in near-shore continental-shelf or back-arc basin environments [48].

The Hengyang basins are located within the South China Craton, at the border between the Yangtze Block and the Cathaysian Block [68]. The geological data for the Hengyang BIF has only been documented in domestic publications. This study area is located in the central segment of the Qin-Hang Belt, adjacent to the western part of the Hengyang Basin. The region features a complex geological structure, with exposed strata including the Proterozoic Nanhuan Group, Sinian System, Cambrian and Ordovician systems from the Lower Paleozoic, and the Devonian, Carboniferous, and Permian systems from the Upper Paleozoic, as well as the Triassic, Jurassic, Cretaceous systems from the Mesozoic, and Quaternary deposits from the Cenozoic [69]. The samples are from the Fulu Formation of the Gaojian Group within the Nanhua System, characterized by a marine transgression from shallow to deep water (720–635 Ma). Stratigraphic evidence from drilling supports the assignment to the Fulu Formation, showing consistent thickness despite faulting (unpublished data).

Methods

Samples

A total of 10 samples, including four iron ore samples from the Wugang BIF, two paragneiss samples associated with Wugang BIF, and four iron ore samples from the Hengyang BIF, were selected for this study. The samples were collected from natural outcrops of the BIFs, which were exposed at the surface, enabling easy access for direct sampling without the need for excavation or drilling. Since the BIFs are not operational, the iron ore sampling was conducted without a permit. The analysis for chemical composition of bulk rocks and XRD experiments were conducted on all 10 samples. For the Mössbauer experiments, three samples from Wugang and two samples from Hengyang with high Fe₂O₃ contents (> 30 wt%), representative of each petrological characteristic, were chosen.

Whole-rock analysis

Whole rock analysis was performed by at Activation Laboratories (Actlabs Canada) with “4 Litho” research analytical protocol. Major and trace elements were analyzed by Fusion ICP-OES (with an error range of ± ~0.1 wt%) and Fusion ICP-MS (with an error range of ± ~2%), respectively (Table 1). Note that the total values of major elements obtained by ICP-OES may exceed or fall short of 100% due to intrinsic factors during experiment such as presence of volatiles, variations of metal oxidation states, and matrix effects. Total values of major elements within the range of 99–101% are considered acceptable.

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Table 1. Whole-rock compositions of the BIFs and paragneiss.

https://doi.org/10.1371/journal.pone.0316540.t001

X-ray diffraction

X-ray diffraction (XRD) patterns for BIF samples including two paragneiss samples associated with Wugang BIF were collected on Bruker D8 advance X-ray diffractometer at the Department of Geology, Gyeongsang National University. The Cu Kα X-ray source (λ = 1.541 Å) with a voltage of 40 kV and a current of 40 mA was used to obtain the diffraction patterns ranging from 10° to 80° with a step size of 0.02°, and a step time of 0.4 s.

Mössbauer spectroscopy

The detailed description of iron oxide species in the BIF samples were analyzed using the room-temperature ⁵⁷Fe resonant absorption Mössbauer spectrometer in Korea Atomic Energy Research Institute (KAERI). Five powdered samples with high Fe₂O₃ contents (over 30 wt%) were prepared for the Mössbauer experiment. The Mössbauer experiments were conducted with a radioactivity of 50 mCi ⁵⁷Co/Rh source operating in the constant acceleration mode between -12 and 12 mm/s in transmission geometry. The spectrometer was calibrated with a 4 μm-thick α-Fe foil as the reference absorber. The isomer shifts (δ, mm/s) are reported relative to α-Fe metal at room temperature (298 K).

Result and discussion

Sample description

The iron ores from the Wugang BIF have relict layering texture (Fig 2A and 2B) and massive texture (Fig 2C) are primarily composed of magnetite, hematite, and quartz, with minor amounts of clinopyroxene and plagioclase, and rare occurrences of talc. Under microscopic observation, quartz occurs as irregular aggregates, displaying subhedral to anhedral forms, with sizes up to approximately 60 μm. Additionally, magnetite appears as single anhedral crystals or aggregates ranging from 10 to 60 μm in size (Fig 3A–3D). The iron ore from Hengyang BIF exhibit massive texture (Fig 2D and 2E) and are composed of magnetite, hematite, quartz with minor K-feldspar. The magnetite displays euhedral to subhedral shapes, with sizes less than 20 μm (Fig 3E–3F). In particular, the magnetite in Hengyang BIF is disseminated and partially replaced by hematite with white-pinkish oxide stripped by brighter edge, indicative of an oxidation process (Fig 3E and 3F).

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Fig 2. Representative photographs of samples used in this study.

(a-c) Wugang BIFs. (d-e) Hengyang BIFs. (f) paragneiss associated with Wugang BIF. The iron ores from samples (a, b) exhibit a distinctive layered texture. The darker layers are composed of magnetite and pyroxene, while the lighter layers consist of quartz. In contrast, the remaining ores exhibit a massive texture (c-e).

https://doi.org/10.1371/journal.pone.0316540.g002

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Fig 3.

Representative photomicrographs of the iron ores from Wugang BIF (a-d) and Hengyang BIF (e-j). (a-d) Coarse-grained magnetite and quartz with minor pyroxene. (e-f) Photomicrograph of relict of magnetite replaced by hematite and (h-i) subhedral to euhedral magnetite with sizes of up to 40 μm. Abbreviations: Mag: magnetite; Px: pyroxene; Qz: quartz.

https://doi.org/10.1371/journal.pone.0316540.g003

Chemical compositions: Major and trace elements

Table 1 shows the major and trace element composition of 8 BIF samples, comprising 4 samples from Wugang (WG) and 4 samples from Hengyang (MC). The chemical compositions of two paragneiss samples associated with the Wugang BIFs are also presented. The Wugang BIF displays the typical characteristics of Archean BIF, composed of high SiO₂ + Fe₂O₃^T content of 86.4–91.1 wt%. Note that Fe₂O₃^T refers the weight percent of total iron oxide. The major compositions of Wugang BIF samples in the current study are largely consistent with previously reported values [48, 70]. The Wugang BIFs have two different types of iron ores: pyroxene-rich BIF (i.e., P-BIF) and quartz-rich BIF (i.e., Q-BIF). In the outcrop, P-BIFs are located in the outer part of the ore body, while Q-BIFs are found in the central part [49]. The Wugang P-BIF samples contain relatively higher SiO₂ (51.3–53.4 wt%) and lower Fe₂O₃^T contents (33.0–38.6 wt%), compared to the Wugang Q-BIF samples which have SiO₂ contents with 42.0–43.8 wt% and Fe₂O₃^T contents with 44.6–49.1 wt%. The CaO contents in P-BIFs (8.1–9.4 wt%) are significantly higher than those in Q-BIFs (1.2–1.6 wt%), indicating the presence of Ca-rich pyroxene in the P-BIF samples, as shown in the XRD results (see Section ‘Major mineral phases: XRD results’). In both Wugang BIF samples, Na₂O, K₂O, and TiO₂ contents are under 1 wt%. Meanwhile, the paragneiss samples obtained from the vicinity of Wugang BIFs exhibit low Fe₂O₃^T contents of approximately 3–4 wt%, while their Al₂O₃ contents are significantly higher (~14.5 wt%), with respect to the BIF samples (0.13–1.1 wt%).

The Hengyang BIF samples have high Fe₂O₃^T contents of 30.4–40.4 wt% with SiO₂ contents of 49.7–62.1 wt%, while the one sample unit shows considerably low Fe₂O₃^T content of 11.7 wt% and high SiO₂ content of 72.1 wt%. The Al₂O₃ contents of Hengyang BIF samples (> 4 wt%) are notably higher than those of Wugang BIF samples (< 1 wt%), suggesting the possibility of crustal contamination [71] in Hengyang BIF.

The trace and rare earth element (REE) compositions of the BIF samples show distinct differences depending on the sampling locations. For Wugang BIF samples, the contents of trace and REE elements are mostly below the detection limit, regardless of the type. The lack of trace elements such as Hf, Zr, and Sc indicates that the involvement of clastic detritus into BIFs can be negligible in the Wugang area [72]. The remarkably high Sr contents (8–16 ppm) are consistent with the previously reported values [48]. On the other hand, the contents of trace and REE elements in the Hengyang BIF samples are significantly higher than those in Wugang BIFs. The total REE concentrations in the Hengyang BIF range from approximately 83 to 110 ppm, whereas those in the Wugang BIF ranges from about 4 to 12 ppm, indicating a distinct difference in the formation mechanisms between the Hengyang and Wugang BIFs. In particular, the remarkable high contents of Hf (1.4–4.7 ppm), Zr (50–189 ppm), and Sr (6–10 ppm) suggest significant contamination from terrigenous inputs into Hengyang BIFs.

Major mineral phases: XRD results

Fig 4 presents the X-ray diffraction (XRD) patterns for Wugang BIF and two associated paragneiss samples, showing the predominance of quartz in all samples and the presence of iron oxide minerals [i.e., magnetite (Fe₃O₄) and hematite (Fe₂O₃)] in BIF samples, consistent with the microscopic observations. The XRD patterns for P-BIFs exhibit the distinct diffraction peaks corresponding to magnetite (JCPDS No. 19–0629), with the main peak occurring at a 2θ of ~36° for the (311) plane [73, 74]. Additionally, the clinopyroxene [i.e., augite, (Ca,Mg)₂Si₂O₆] is observed in XRD patterns for P-BIF [75] with quartz [76]. While the diffraction peaks for magnetite are clear and evident, those for hematite is absent in the XRD patterns for P-BIF, indicating that the magnetite is major iron oxide phase in P-BIFs. For Q-BIFs, the coexistence of hematite and magnetite is confirmed in the XRD patterns. Note that the main diffraction peak of hematite appears at a 2θ of ~33° for the (104) plane (JCPDS No. 33–0664) [77, 78]. The paragneiss samples associated with the Wugang BIFs are primarily composed of quartz and plagioclase, with no other iron oxide phases observed in the XRD patterns. The XRD patterns for BIF samples from Hengyang are shown in Fig 5. Two samples collected from Hengyang basin (23MC-3-a and 23MC-3-b) contain both magnetite and hematite as the iron oxide phase, with the quartz as a dominant mineral phase. The other two samples (23MC-2-A-a and 23MC-2-A-b) contain the quartz and hematite with K-feldspar [79] as a minor phase. In these samples, the diffraction patterns for magnetite were not observed.

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Fig 4. XRD patterns for BIF and paragneiss samples from Wugang (WG) region.

M and H refers to magnetite (JCPDS No. 19–0629) and hematite (JCPDS No. 33–0664), respectively (closed circles: quartz [76]; open diamonds: clinopyroxene [75]; closed squares: plagioclase [80]; closed triangles: talc [81]).

https://doi.org/10.1371/journal.pone.0316540.g004

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Fig 5. XRD patterns for BIF and paragneiss samples from Hengyang (MC) regions.

M and H refers to magnetite (JCPDS No. 19–0629) and hematite (JCPDS No. 33–0664), respectively (closed circles: quartz [76] and open squares: K-feldspar [79]).

https://doi.org/10.1371/journal.pone.0316540.g005

By combining microscopic observation with XRD analysis, magnetite is dominant in Wugang BIF, whereas hematite is primary phases in the Hengyang BIF. Since the presence of Fe²⁺ in BIF is essential to produce H₂ during alteration and hydration processes, the relative fraction of magnetite can be a major factor in estimating the amount of H₂ released from BIF. Therefore, the variation in the composition of iron oxide minerals across different regions suggests that the potential for H₂ production depends on the types and locations of occurrence of BIFs. To obtain more quantified data on the potential of H₂ release, we attempt to yield quantitative fraction of iron species in the banded iron formation samples using Mössbauer spectroscopy.

Quantification of iron species in the BIFs: Mössbauer spectroscopy

The Mössbauer spectra for BIF samples can be deconvoluted into multiple sextets and doublets, each characterized by specific hyperfine parameters [i.e., isomer shift (δ), quadrupole splitting (Δ), and hyperfine field (kOe)] that depend on their crystallographic structures [34, 82]. For the minerals with magnetic ordering, such as ferromagnetic magnetite and antiferromagnetic hematite, the sextet in Mössbauer spectra arises due to the magnetic hyperfine fields around iron nuclei. The iron sites in oxide minerals (i.e., tetrahedral and octahedral sites in magnetite, Fe³⁺ in hematite) can be effectively distinguished through hyperfine parameters: for example, the isomer shifts for the tetrahedral (occupied by Fe³⁺, Td^M) and octahedral [occupied by Fe²⁺ and Fe³⁺ with equal proportion (i.e., Fe^2.5+), Oh^M] sites in magnetite are ~0.26 mm/s and ~0.67 mm/s, respectively, and those for octahedral sites in hematite are ~0.37 mm/s [34, 82]. The Td^M, Oh^M, and Oh^H sites have hyperfine fields of ~490, ~460, and 520 kOe, respectively [34, 82].

Figs 6 and 7 show the Mössbauer spectra and fitting results for Wugang and Hengyang BIF samples, respectively. The hyperfine parameters for each iron species in varying minerals obtained from the fitting of the experimental data are shown in Table 2. For the Wugang P-BIF (20WG-24-b), the spectrum was deconvoluted with two sextets and three doublets. The former corresponds to the magnetite: the outer sextet with δ = 0.26 mm/s, Δ = 0.00 mm/s, and H_hf = 489.8 kOe and the inner sextet with δ = 0.66 mm/s, Δ = 0.00 mm/s, and H_hf = 459.5 kOe are assigned to Fe³⁺ tetrahedral site and Fe^2.5+ octahedral site (which is mixed valence Fe site with both Fe²⁺ and Fe³⁺), respectively. Note that the ratio of area between Td^M and Oh^M for all samples is ~0.67 (i.e., Td^M:Oh^M = 2:1), which is consistent with the general stoichiometry of magnetite, showing the robustness of the current fitting procedure. The latter is typical characteristics of silicate minerals, consisting of two Fe²⁺ doublets (δ = 1.23 mm/s, Δ = 2.30 mm/s and δ = 1.15 mm/s, Δ = 2.00 mm/s, and one Fe³⁺ doublet (δ = 0.24 mm/s, Δ = 0.85 mm/s)). The doublets can be assigned to clinopyroxene which have three distinct Fe sites (i.e., M1, M2, and Oh^P sites) [83]. We note that hematite is not observed in the Mössbauer spectra for P-BIF, which is consistent with the current XRD results. Based on the values of relative area for Oh^M with respect to total area of Mössbauer spectra (~52.2%), the calculated Fe²⁺ in magnetite with respect to total iron atoms is about 26.1% in the P-BIF sample. The Fe²⁺ fraction of magnetite relative to total number of iron atoms (Fe²⁺_M, %) can be calculated as a half of the area of Oh^M site, because the Oh^M sites occupied by Fe²⁺ and Fe³⁺ with approximately equal proportions [27, 28]. The Mössbauer spectra for Wugang Q-BIF samples (20WG-23-2-a and 20WG-23-2-b) show three sextets corresponding to Td^M, Oh^M, and Oh^H and one doublet associated with Fe²⁺-bearing silicate mineral. A doublet was fitted with δ = 1.16 mm/s and Δ = 2.63 mm/s for 20WG-23-2-a, and δ = 1.13 mm/s, Δ = 2.63 mm/s for 20WG-23-2-b. Based on the hyperfine parameters, the doublet represents talc observed in XRD patterns [84]. Contrary to P-BIF, the presence of hematite is noticeable in the Mössbauer spectra for Q-BIF samples, consistent with XRD results. The fractions of Fe²⁺ in magnetite for Q-BIFs are ~15–16%, which are considerably lower than those for P-BIF.

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Fig 6. Mössbauer spectra (grey dots) and fitting results (black line) of Wugang BIFs at 298 K.

The spectra with three sextets (corresponding to magnetite and hematite) and doublets (corresponding to silicate minerals), as labeled.

https://doi.org/10.1371/journal.pone.0316540.g006

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Fig 7. Mössbauer spectra (grey dots) and fitting results (black line) of Hengyang BIFs at 298 K.

The spectra with three sextets (corresponding to magnetite and hematite) and doublets (corresponding to silicate minerals), as labeled.

https://doi.org/10.1371/journal.pone.0316540.g007

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Table 2. Hyperfine parameters and relative fractions of each iron species obtained from Mössbauer spectroscopy.

https://doi.org/10.1371/journal.pone.0316540.t002

The Mössbauer spectra for BIF samples from the Hengyang region are also deconvoluted into two sextets for magnetite, one sextet for hematite, and one doublet for Fe²⁺-bearing silicate mineral, while the relative area of each component varies among samples. Detailed fitting parameters are presented in Table 2. For 23MC-3-a, the relative fraction of the sextet for octahedral site of magnetite (Fe^2.5+) is approximately 50.9%, indicating that Fe²⁺ in magnetite (Fe²⁺_M) is about 25.5%. Notably, the predominance of hematite (~81.9%) are observed in the 23MC-2-A-a, indicating the lack of magnetite in this sample.

Magnetite in BIFs: The potential source for H₂

Recent pioneering study has explored the potential process for natural H₂ generation via weathering and alteration of natural BIFs with aqueous fluids, based on the systematic analysis of their petrological, mineralogical, and geochemical characteristics [24]. This study suggests that the oxidation of Fe²⁺ in ferrous minerals including magnetite, can release natural H₂, occurring near the surface under low-temperature conditions. Furthermore, the several water-rock interaction experiments have reported that the magnetite can produce considerable amounts of H₂ in relatively lower temperature conditions (< 100°C) than hydrothermal processes such as serpentinization [25, 30]. These studies indicate that magnetite can be a main source of hydrogen both in naturally released and stimulated production.

Based on the generic redox Eq (1) that describes iron oxidation and H₂ generation [25], the potential for H₂ production from Fe²⁺ in magnetite can be estimated. The mechanism involves a redox reaction occurring in anoxic environments, where water oxidizes Fe²⁺ to Fe³⁺ and is itself reduced to form H₂. Furthermore, the oxidation of magnetite within BIFs to hematite, induced by water-rock interaction, plays the crucial role in promoting H₂ production in this process.

(1)

To estimate the potential of H₂ release from magnetite in the BIFs, quantification of the fractions of individual iron species using Mössbauer spectroscopy is necessary. Table 3 shows the total Fe contents in bulk sample (Fe^T, wt%), the relative fraction of Fe²⁺ in magnetite (Fe²⁺_Mag, %) and that of Fe atoms in magnetite with respect to total iron atoms (Fe_Mag, which is the sum of Fe²⁺ and Fe³⁺, %), and the proportion of magnetite in the bulk sample (X_Mag, wt%). Here, n typically represents the number of moles, while X is used in a chemical context to denote either a percentage or a weight fraction. As mentioned in above, the Fe²⁺_Mag can be obtained by the half of Oh^M area, and Fe_Mag can be calculated by the sum of areas for Oh^M and Td^M. Note that X_Mag (wt%) can be calculated by multiplying Fe^T (wt%) by Fe_Mag (%) and then dividing by 0.72, where 0.72 represents the ratio of the mass of iron atoms to the total mass of Fe₃O₄, accounting for the three Fe atoms present in each formula unit of magnetite. The maximum H₂ potentials (mmol/kg) which can be produced from Fe²⁺ in magnetite were obtained by following the previously reported calculation steps [25]. Based on Eq (1), one mole of H₂ can be produced for every two moles of Fe²⁺O in magnetite, indicating the necessity to determine the number of moles of Fe²⁺ in magnetite within 1 kg of bulk BIF samples (nFeO_Mag). The weight percent of Fe²⁺ in magnetite (XFe²⁺_Mag) relative to the bulk sample is calculated by multiplying the total Fe content (Fe^T, wt%) by the percentage of Fe²⁺ in magnetite (Fe²⁺_Mag, %). The weight percent of Fe²⁺O in magnetite (XFe²⁺O_Mag) is then obtained by multiplying XFe²⁺_Mag by 0.78, which represents the molar mass ratio of Fe to FeO. Using the molar mass of FeO (71.844 g/mol), XFe²⁺O_Mag is further converted to moles of nFeO_Mag per unit mass of rock. Finally, the number of moles of H₂ can be determined by dividing nFeO_Mag by 2 and then converted to millimoles in kilogram to obtain the final result [25].

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Table 3. Total Fe contents (Fe^T, wt%), the fraction of Fe²⁺ in magnetite (Fe2+Mag, %), the fraction of Fe atoms in magnetite relative to total Fe atoms in the bulk sample (Fe_Mag, %), and the proportion of magnetite in the bulk sample (X_Mag, %).

The iron redox state of the bulk sample (Fe³⁺/Fe_tot) and estimated H₂ (mmol/kg) potential are also presented.

https://doi.org/10.1371/journal.pone.0316540.t003

The P-BIF sample from Wugang (20WG-24-b), which composed of predominantly magnetite, showed low Fe³⁺/Fe_tot ratio (~0.68) and high content of Fe²⁺ in magnetite (~26%). The estimated potential of H₂ production of magnetite-rich BIFs in China Craton is ~630 mmol H₂/kg rock. Meanwhile, the hematite-rich BIF sample from Hengyang (i.e., 23MC-2-A-a) have significantly lower Fe²⁺ fraction in magnetite (~5%), resulting in low H₂ potential (~120 mmol H₂/kg rock). Note that the unaltered BIFs from the Hamersley Province of Western Australia are thermodynamically estimated to produce 200 mmol H₂/kg [25]. Compared to the previous study, the secondary minerals such as goethite or maghemite were not observed, indicating that the BIFs in China Craton have significant potential to produce H₂ because these BIFs are rather fresh. The current results showed that the magnetite-rich BIF can be a probable candidate for H₂ production and H₂ generation potential varies with mineralogical compositions depending on the types and locations of occurrence of BIFs. The results of this study highlight that it is essential to prioritize the exploration of deposits with favorable geochemical and mineralogical conditions, particularly those with a dominance of magnetite. Experimental techniques, including Mössbauer spectroscopy, are effective for accurately quantifying iron species and providing details of mineral compositions from diverse geological settings. Additionally, laboratory experiments simulating subsurface conditions with natural BIF samples could further elucidate the reaction mechanisms and kinetics associated with hydrogen release, contributing to optimization of conditions for maximizing H₂ production. Establishing a mineralogical database focused on the relative fractions of iron species across various BIFs would also be valuable for guiding future exploration and resource development.

Conclusions

In this study, we investigated the mineralogical and geochemical characteristics of natural iron ore samples from the Wugang and Hengyang BIF in China. Specifically, we identified the mineral phases in the BIF samples and quantified the individual iron species in varying iron-bearing phases including magnetite and hematite, using XRD and Mössbauer spectroscopy. The current results allow us to evaluate the potential of H₂ production from Fe²⁺ species in the magnetite of BIFs. The details of mineral compositions in BIF vary with the types and locations of occurrence: particularly, the pyroxene-bearing BIF samples collected in Wugang showed the predominance of magnetite, while the hematite is dominant in the BIF samples from Hengyang region. The maximum potential of H₂ production of the sample with high content of Fe²⁺ in magnetite concerning total iron atoms (~26%) was calculated to be ~ 630 mmol H₂/kg rock, indicating that magnetite-rich BIF could be promising candidates for H₂ production. The current study highlights that the Mössbauer spectroscopy can be effectively utilized to characterize the geological source rocks for the future exploration of H₂ production sites. We believe that our findings can contribute to establish the mineralogical database of BIFs in the China Craton, providing a basis for assessing their potential for H₂ production.

Acknowledgments

The authors deeply appreciate their invaluable support of scientists of the Central South University during the geological sampling. We thank the editor and anonymous reviewers for their constructive and helpful suggestions.

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Figures

Abstract

Introduction

Geological setting

Methods

Samples

Whole-rock analysis

X-ray diffraction

Mössbauer spectroscopy

Result and discussion

Sample description

Chemical compositions: Major and trace elements

Major mineral phases: XRD results

Quantification of iron species in the BIFs: Mössbauer spectroscopy

Magnetite in BIFs: The potential source for H2

Conclusions

Acknowledgments

References

Magnetite in BIFs: The potential source for H₂