The photo-stimulated reductive dissolution of semiconducting iron (hydro)oxides plays a vital role in iron (bio)geochemistry processes. Epitaxial twinned goethite (Goe-Hem), a typical goethite twin composed of a hematite center with acicular goethite outgrowths, is widely distributed in natural environment. Nevertheless, studies exploring the photochemical activity of Goe-Hem remain limited. In this study, photo-stimulated reductive dissolution process of Goe-Hem were investigated in depth. Physicochemical characterization revealed that Goe-Hem consists of twinned goethite crystals with a hematite core, containing 73% goethite and 27% hematite. In the presence of fulvic acid, the concentration of photo-stimulated reductively dissolved Fe2+(aq) from Goe-Hem was higher than that from goethite. Consequently, Goe-Hem exhibited superior photo-stimulated reductive ability than goethite. This enhanced activity was ascribed to the stronger visible light absorption, narrower band gap energy and more negative conduction band energy of Goe-Hem relative to goethite. The photo-stimulated reductively dissolved Fe2+(aq) from Goe-Hem play a vital role in iron cycling and biological iron acquisition in nature.

Talc plays an essential role in transporting water into the mantle via subduction zones. The compressional behavior of triclinic (C) talc under high pressure was investigated by a combination of synchrotron X-ray diffraction (XRD), infrared (IR) spectroscopy, and density functional theory (DFT) calculations. Talc exhibited exceptional structural stability with no observable crystallographic phase transitions up to similar to 20 GPa, as determined by synchrotron-based high-pressure XRD. However, a notable change occurs in the hydroxyl groups above similar to 10 GPa: the OH bond length, which plateaus at similar to 0.9687 & Aring; below this pressure, shows a subsequent linear decrease. The structure of talc shows strong anisotropic compressibility: the decrease of a-, b-, and c-axis is 4.4 %, 5.0 %, and 9.0 % throughout the investigated pressure regime, respectively. Most of the compression is taken up by the weakly bonded interlayer regions below similar to 10 GPa. The unit-cell volume changed continuously with pressure, but the F-f(E) plot indicates a change in compressibility around similar to 10 GPa. The PV data below and above 10 GPa were fitted separately using the third-order Birch-Murnaghan equation of state. The derived parameters are as follows: K-0 = 55.0(67) GPa and K ' = 11.0(52) below 10 GPa, and K-0 = 59.2(19) GPa and K ' = 5.2(4) above 10 GPa for XRD results with V-0 fitted as 455.5(9) & Aring;(3); V-0 = 451.4(5) & Aring;(3), K-0 = 41.2(18) GPa, and K ' = 8.2(8) below 10 GPa, and V-0 = 445.2(8) & Aring;(3), K-0 = 56.9(14) GPa, and K ' = 5.1(1) above 10 GPa for DFT results. Our findings contribute to a better understanding of hydroxyl groups in response to pressure in layered-structure silicates, offering insights into talc's roles in geological processes and the deep-Earth water cycle.

The duration and dynamic evolution of surface water on Mars are key to understanding its past habitability. Utopia Planitia, Mars' largest northern basin, preserves mineralogical signatures of ancient aqueous activity that remains chronologically unconstrained. Here, we present the quantitative reconstruction of the Hesperian Ocean's lifecycle using spectral analysis of manganese (Mn) (hydr)oxides as paleohydrological markers. Our innovative Spectral Contrastive-Aware Network, a deep learning framework trained on 13,742 infrared spectra of Martian soil simulants, decodes short-wave infrared data from China's Zhurong rover and orbiters operated by ESA and NASA. We identify altitude-dependent Mn (hydr)oxides enrichment that forms a distinctive mineralogical "bathtub ring", indicating an ancient ocean with defined boundaries. By quantitative mapping the spatiotemporal distribution of these minerals, we reconstruct the ocean's origin, expansion, regression, and extinction. Depositional modeling constrains its lifespan to 0.8-1.5 million years, providing the chronometrically constrained evidence for sustained surface water stability during the Hesperian.

The evolutionary record of redox-sensitive manganese (Mn) minerals encodes critical information about Earth's oxygenation history. By building a global Mn mineral dataset (144 200 entries across 25 feature dimensions), we developed a URD (Unequal-size feature matrix, Recoupling relationship, and Disaccord labels) deep-learning model to reconstruct continuous atmospheric oxygen level (pO2) changes over 4.0 billion years. Our results provide robust mineralogical evidence linking the timing and tempo of oxygenation to planetary-scale tectonics and biosphere evolution. Specially, the reconstruction reveals two distinct oxygenation modes: a protracted and gradual increase during the Paleoproterozoic-Mesoproterozoic, reflected in the moderately progressive evolution of Mn mineral assemblages; and a more rapid rise preceding and following the Neoproterozoic, coincided with supercontinent breakup and convergence, respectively-a pattern potentially driven by tectonic modulation of Mn supply and demand. This study introduces a mineral-informatic framework for decoding complex, high-dimensional mineral records, offering a transformative approach for systematically interrogating Earth's long-term evolution.

The pore structure in coals plays a crucial role in the storage and transportation of coalbed methane (CBM). This study selected six samples of different rank coals to investigate the pore structure and fractal properties using mercury intrusion porosimetry (MIP), micro-computed tomography, low-temperature N-2 adsorption, and CO2 adsorption techniques. The full-size pore structure and fractal characteristics of coal were obtained using multiple methods, and the factors influencing fractal characteristics were analyzed utilizing the grayscale correlation method. The findings indicate that the overall pore volume of the coal samples under investigation is determined primarily by micropores (0.3 to 1 nm) and macropores (50 nm to 1 mu m). Low-rank coals exhibit a dominant pore size range in macropores, while medium- to high-rank coals show a dominant pore size range. Moreover, as the degree of coalification increases, the pore volume demonstrates a U-shaped trend, decreasing initially and then increasing. The specific surface area of pores is mainly determined by micropores, with medium-rank coals showing an average contribution of 10.5% from mesopores and micropores contributing up to 99% of the specific surface area in high-rank coals. The fractal dimension calculation results indicate that the pore structure becomes more complex as pore size increases. The overall fractal dimension decreases with increasing coal rank, suggesting reduced pore structure heterogeneity with deeper coalification. Grey correlation analysis ranks the influencing factors of fractal dimensions in different rank coals, with fixed carbon content (FCad) exerting the most significant influence on multiscale comprehensive fractal dimensions. Maximum vitrinite reflectance (R-o,R-max), micropore volume V-1, and micropore specific surface area S-1 are substantial factors affecting multiscale comprehensive fractal dimensions. The findings can provide an experimental basis for the efficient extraction of CBM in the study area.

Biosignature detection remains a key challenge in astrobiology, yet robust mineral biosignatures remain limited. Raman spectroscopy is increasingly applied in planetary exploration, but its high-dimensional spectral information has not yet been fully exploited for biosignature discrimination using data-driven approaches. Here, we integrate Raman spectroscopy with interpretable machine learning to distinguish biotic from abiotic apatite, a ubiquitous phosphate mineral in terrestrial and extraterrestrial environments. We compile 331 apatite Raman spectra from abiotic and biotic sources and extract 21 band-resolved spectral features. Principal component analysis reveals systematic separation between abiotic and biotic endmembers. A random forest classifier achieves 96.8% accuracy on an independent test set. Robustness is confirmed by multiple validation schemes, including leave-one-source-out cross-validation across 60 independent data sources, indicating that model performance generalizes beyond source- or instrument-specific artifacts. Feature importance identifies two dominant controls: phosphate-band broadening as a structural indicator of disorder and the carbonate-band intensity as a chemical signature of substitution. Density-functional calculations reproduce these features in simulated spectra and indicate that carbonate substitution doubles phosphate-tetrahedral distortion and increases formation energies by two orders of magnitude. Mechanically, higher carbonate contents during biomineral apatite formation reduce crystallinity and broaden Raman bands. We propose that the trained machine-learning model and a two-feature decision map enable the rapid probabilistic discrimination of unknown apatite samples. Our Raman-based machine-learning framework establishes a broadly applicable and mission-relevant strategy for deep-time archives and future planetary missions.

Secondary minerals, such as clay minerals and Fe-Mn oxides, commonly form through aqueous processes mediated by microbial activity, making them key biosignature targets. Microbial proteins can be preserved within these minerals. Although Mars return samples are expected to be rich in secondary phases, the nanoscale distribution and preservation of proteins within them remain poorly known. Using atom probe tomography combined with complementary techniques, we investigate natural Mars-analog secondary minerals and their protein preservation capacity. We achieve in situ, near-atomic-scale characterization of protein-mineral interactions in natural samples. Our results show that clay minerals and Fe-Mn oxides form intimately mixed assemblages with homogeneous spatial associations at the nanometer to subnanometer scale. Proteinaceous residues are preserved within these minerals, commonly distributed along the inner and outer edges of relatively large mineral grains. Incorporation into the mineral lattice likely contributes to their preservation. In contrast, smaller secondary mineral grains (<5 nm) generally retain little protein-related signal and may adsorb only limited amino acid fragments. These findings provide direct nanoscale insights into protein-mineral associations in natural settings, with important implications for detecting potential biosignatures in extraterrestrial samples, such as those returned from Mars.

The marine iron cycle is now recognized as fast and dynamic, partly fueled by vast particulate iron inputs. Yet the mechanisms that activate this reservoir to sustain productivity remain unresolved. Here we show that mineral photocatalysis, an overlooked abiotic process, provides a key activation pathway for Fe(II) production. Laboratory experiments using synthetic iron oxides and anatase in artificial seawater demonstrate that anatase (TiO2) drives rapid Fe(III)-to-Fe(II) cycling at rates up to fourfold higher than current model assumptions. We propose this process explains the paradox of persistent Fe(II) in sunlit waters as a high-flux steady state of photochemical production coupled with biological uptake. Our findings establish mineral photocatalysis as a key driver in the ocean iron cycle, indicating that bioavailable iron fluxes from particles have been underestimated. Integrating photo-geochemical pathways into ocean models will improve predictions of iron recycling and ecosystem responses.

Electron transfer between birnessite and organic compounds (OC) plays a dominant role in the coupling cycle of manganese (Mn) and carbon across diverse environmental settings. While previous studies have extensively investigated individual processes of interface Mn reduction, surface Mn2+ adsorption, and surface-to-interior electron transfer, the dynamic interplay among these reactions and the mechanisms regulating subtle changes in surface and interior Mn states remained poorly understood. Additionally, existing models have not adequately captured electron transfer kinetics in multivariable systems involving pH, Mn2+ concentration, electron donor type, etc. In this study, we investigated the reduction kinetics of birnessite under the influence of multiple environmental variables by employing three typical OC: formic acid (HCOOH), formaldehyde (HCHO), and methanol (CH3OH). Time-series analysis revealed kinetic discrepancy and time lag between the alteration of the average Mn oxidation state (AMOS) within the solid and the release of Mn2+ from the reductive dissolution of birnessite, indicating a two-stage electron transfer mechanism occurring at the interface between birnessite and OC. X-ray absorption fine structure spectra revealed a rapid increase in corner-sharing MnO6 octahedra and a decline in AMOS during the initial stage, followed by a slight decrease in AMOS and substantial mineral dissolution to release Mn2+ in the subsequent stage. The transition point between the two stages is primarily influenced by the concentration of surface MnII under pH regulation, as confirmed by soft X-ray absorption spectroscopy and density functional theory calculations. Based on these findings, the adsorption equilibrium and electron transfer rate were modeled by a machine learning framework (JAX), which is influenced by three main factors: pH, Mn2+ concentration, and OC types. The adsorption equilibrium constant for HCHO was one order of magnitude lower than for HCOOH, yet displayed a faster reaction rate due to higher electron transfer rates. Competitive adsorption of OC and Mn2+ on reactive sites was influenced by both pH and Mn2+ concentrations. Combining these parameters, we created a 3D surface plot that comprehensively considered the interplay between different elementary reactions, including competitive adsorption and redox reaction rates, thereby visualizing the kinetic regulation mechanisms in multivariable systems. Furthermore, a comprehensive rate equation for the reduction of birnessite by OC was developed to predict its behavior in natural settings. With an electron storage capacity of 2.7x1023 electrons/mol Mn before structural decomposition or dissolution, we propose that birnessite can act as a geobattery driving cryptic elemental biogeochemical cycling. Our findings also suggest that the highly reversible redox reactivity of birnessite and the kinetics discrepancy in multi-step electron transfer reactions enable it to facilitate energy conversion among OC, sunlight, and microbes across a variety of temporal and spatial scales.

Re-oxidation of Cr(III) in treated Cr-contaminated sites poses a considerable source of Cr(VI) pollution, necessitating stable treatment solutions for long-term control. This study explores the immobilization of Cr(VI) into chromite, the most stable and weathering-resistant Cr-bearing mineral, under ambient conditions. Batch experiments demonstrate chromite formation at pH above 7 and Fe(III)/Cr(III) ratios exceeding 1, with Fe(III) occupying all tetrahedral sites, essential for stability. A theoretical model is developed to evaluate the effects of pH and Fe(III)/Cr(III) ratios on chromite crystallinity, resulting in AI4Min-Cr, a publicly accessible platform offering real-time intelligent remediation strategies. To tackle the complexities of non-point source Cr pollution, we employ microbial methods to regulate on-site Eh and pH, optimizing chromite precipitation. Long-term stability tests confirm that chromite remained stable for over 180 days, with potential for magnetic separation recovery. This study presents a mineralogical strategy to address re-oxidation and Cr resource recovery in Cr-contaminated water and soil.

The extreme pressure and temperature conditions of the deep Earth,reaching up to～350 gigapascals(GPa)and 6000 K,pose major challenges for in-situ detection and the investigation of physical and chemical processes[1].Although numerous theoreti-cal simulations and experiments have been conducted under extreme deep-Earth conditions,a centralized platform with practi-cal tools for predicting the reactivity of substances on Earth and beyond is still lacking.Such tools are crucial for advancing our understanding of Earth's structure,composition,energy exchange,and long-term evolution.

Our work reveals that frequency-doubling upconversion in sulfide min-erals,particularly chalcopyrite,can generate visible light in deep-sea hy-drothermal environments.Spectroscopic measurements demonstrate that this mechanism produces blue-green photon fluxes that are three orders of magnitude higher than the intrinsic thermal radia-tion from vents.

In the rock–soil–biology–water ecosystem, rock weathering provides essential plant nutrients. However, its supply is insufficient for rising crop demands under population growth and climate change, while excessive fertilizer causes soil degradation and pollution. This study innovatively irrigated with carbonate rock leachates to enhance soil nutrient availability. A pot experiment with lettuce showed that irrigation significantly increased soil NO3−-N (+102.20%), available K (+16.45%), available P (+17.95%), Ca (+6.04%), Mg (+11.65%), and Fe (+11.60%), and elevated the relative abundance of Firmicutes. Lettuce biomass per plant rose by 23.78%, with higher leaf minerals (P, K, Ca, and Mg) and antioxidants (carotenoids and ascorbic acid). A field experiment further confirmed improvement of soil nutrient availability and peanut yield. This carbonate rock leachate irrigation technique effectively enhances soil quality and crop productivity/quality, offering a sustainable approach for green agriculture.

Industrial activities in chromate factories have significantly released chromium sludge into the environment, posing severe risks to local ecosystems and human health. Cr(VI), the most toxic and mobile form of chromium, possesses strong oxidizing capacity and confirmed carcinogenicity, posing serious risks to microbial communities and environmental health. Chromium (Cr) stress significantly affects microbial diversity, composition, and assembly, which is essential for evaluating ecological risks and resilience at contaminated sites. This study conducted comprehensive environmental factor testing and microbial analysis at a contaminated site, to elucidate the mechanisms by which Cr stress affects microbial communities. Cr concentration in the Source Zone (SZ) reached 1458.7 mg/kg. Actinobacteriota, Proteobacteria and Chloroflexi were identified as the dominant phyla. Environmental factors, including Cr, Cr(VI), pH, Zn, Ni and sulfate, significantly influence microbial community structure. In the Control Zone (CZ) and Precautionary Zone (PZ), community assembly was primarily influenced by stochastic processes, whereas deterministic factors exerted a greater impact in SZ. High heavy metal content is the primary factors driving the reduction in microbial diversity and abundance in SZ, leading to complex co-occurrence patterns and closer interactions among the remaining microbial communities. This research enhances the understanding of microbial dynamics in chromium-contaminated sites and lays the groundwork for effective ecological restoration strategies, emphasizing the need for tailored intervention strategies to enhance community resilience and improve remediation efforts in each specific area.

Rock varnish is widely distributed across Earth's various climatic zones, especially prevalent in arid environments similar to Mars. Its potential presence on Mars has made it a significant Mars analog for planetary research. The primary components of rock varnish are clay minerals and iron-manganese oxyhydroxides, with clay minerals possibly playing a crucial role in the enrichment of iron and manganese. However, there has been scarce in-depth and detailed research on these clay minerals within rock varnish. To better understand the formation and transformation mechanisms, as well as the influencing factors of clay minerals in rock varnish, we conducted X-ray diffraction (XRD) analyses on clay minerals isolated from rock varnish samples collected across different climatic regions in China. Additionally, in situ visible to near-infrared spectroscopy (Vis-NIR), scanning electron microscopy (SEM), and focused ion beam high-resolution transmission electron microscopy (FIB-HRTEM) were performed on the rock varnish samples. The results revealed the presence of illite in all rock varnish samples, while the selective occurrence of other clay minerals was closely correlated with climatic backgrounds. Furthermore, the crystallinity of illite was significantly influenced by climatic conditions. Illite found in rock varnish existed as both detrital and authigenic forms. Generally, the detrital illite in rock varnish was thicker than the nanometer-scale authigenic illite and exhibited distinct differences in chemical composition (e.g., Si/Al, K/Al ratios) and nanoscale morphology. In many cases, the possible transformation of illite to chlorite was observed, either internally within illite particles or through the formation of regular or irregular interstratified structures between illite and chlorite. Both interlayer brucitization and talc brucitization mechanisms may be involved in the chloritization (brucitization) of illite in rock varnish. Such transformations are generally uncommon in surface environments and are more frequently associated with low-grade metamorphism, suggesting that the environment at the illuminated rock surfaces, akin to metamorphic conditions, might provide the energy needed for these reactions. Considering the strong solar irradiance characteristic of Mars and its abundance of Mg- and Fe-rich rocks, it is plausible to expect the continued occurrence of chloritization on the martian surface and even within martian rock varnish. Our findings are significant for better understanding the formation and transformation of clay minerals on the martian surface and martian rock varnish, and climate-controlled water-rock interactions on Mars.

Efficient and safe extraction of coalbed methane is essential for reshaping China’s energy composition. This study integrates CO2 adsorption, N2 adsorption, and corrected mercury intrusion porosimetry (MIP) data to analyze the full pore size distribution (PSD) of six coal samples from the Qinshui and Tiefa Basins. By applying multifractal theory, we identified key heterogeneity features across different coal ranks, followed by a discussion of the factors influencing these parameters. The results indicate the following: (1) Coal matrix compressibility significantly impacts MIP results when mercury intrusion pressure exceeds 10 MPa, with corrected mesopore and macropore volume reductions ranging from 59.85–96.31% and 3.11–15.53%, respectively. (2) Pore volume distribution varies with coal rank, as macropores dominate in low-rank coal, while micropores contribute most in medium- and high-rank coal, accounting for over 90% of the total specific surface area. Multifractal analysis of CO2, N2, and corrected MIP data confirms notable multifractal characteristics across the full pore size range. (3) As the degree of coalification increases, as indicated by the rise in the Ro,max value, there is a notable negative correlation observed among the multifractal parameters Dmin-D0, D0-Dmax, Δα, and H. A positive correlation exists between moisture content and volatile matter content with Dmin-D0, Δα, and H, while a significant negative correlation is shown between the concentration of minerals and Dmin-D0, Δα, and H. There exists a favorable correlation between inertinite concentration and D0-Dmax. This work presents a theoretical foundation and empirical proof for the secure and effective extraction of coalbed methane in the researched region.

Iron plays a critical role in marine primary production by regulating biological processes such as photosynthesis and nitrogen fixation. However, the mechanisms by which semiconducting iron oxides influence microbial communities in the euphotic zone remain poorly understood. This study investigated hematite-mediated photoreduction processes and their indirect regulatory effects on marine microbial communities. Hematite nanoparticles and electrodes were synthesized and characterized using XRD, Raman spectroscopy, AFM, and electrochemical methods. Hematite exhibited n-type semiconductor behavior with a narrow bandgap (2.08 eV), generating photoelectrons that reduced structural Fe(III) to soluble Fe2+ at 0.0970 mu mol/L/day under visible light. This process elevated Fe2+/L Fe ratios by 8-fold compared to dark controls. High-throughput 16S rRNA sequencing demonstrated that Fe2+ enrichment selectively shaped microbial community structures, favoring iron-metabolizing genera such as Marinobacter, Rhodococcus, and Marivita. These results establish that hematite semiconductors drive iron cycling through photoelectron transfer, indirectly shaping microbial community structure and metabolic functions via Fe2+ bioavailability. This work bridges mineral photogeochemistry with microbial ecology, advancing understanding of abiotic-biotic interactions in marine iron cycling and their implications for biogeochemical processes.

The Huxingshan tungsten deposit, located in the Jiangnan tungsten belt of South China, consists of scheelitequartz-muscovite-calcite (SQMC) and scheelite-quartz-muscovite-fluorite (SQMF) vein-type mineralization hosted by the Yalan-Yuantang fault and the Niutitang Formation carbonate rocks. The textures and compositions of Sch-A (from SQMC veins) and Sch-B (from SQMF veins) were revealed by cathodoluminescence (CL) imaging and in situ LA-ICP-MS to decipher the nature and origin of the ore-forming fluids. CL images show that Sch-A is homogeneous, while Sch-B exhibits oscillatory zoning. The presence of quartz-muscovite assemblages in both vein types-common in greisen and vein-type W-Sn deposits-and the LREE-enriched patterns in Sch-A/Sch-B cores jointly indicate a magmatic-hydrothermal origin for the ore-forming fluids. However, Sch-A and Sch-B exhibit different REE patterns and yield two markedly distinct compositional clusters, with Sch-B having lower Sr, Nb, Mo, and higher Mn and REE contents than Sch-A. These mineral chemical differences, combined with the fact that fluorite exclusively occurs in Sch-B-bearing SQMF veins, suggest that Sch-A and Sch-B formed from two distinct magmatic-hydrothermal fluid pulses: a F-poor pulse and a F-rich pulse. The cores of Sch-A and Sch-B provide the earliest records of the two mineralizing fluid pulses, showing that (1) both fluid pulses initially exhibited LREE-enriched patterns, with the F-rich fluid pulse having lower LREE/HREE ratios than the F-poor fluid pulse, and (2) the F-poor fluid pulse is Sr-rich and REE-poor, while the F-rich fluid pulse is Sr-poor and REErich. The shift from LREE-enriched to MREE-enriched patterns from core to rim in Sch-A and Sch-B grains, accompanied by progressively decreasing REE and Sr contents, results from closed-system crystallization of scheelite during the two mineralization pulses. Sch-A and Sch-B have low Mo content (4.9-203 ppm) with variable Eu anomalies (0.56-2.89 for Sch-A and 0.87-4.21 for Sch-B), similar to those of scheelite from reduced skarn, indicating reduced conditions of the ore-forming fluids. Based on published geochronological data of the Huxingshan district, the overlapping Y/Ho ratios of both scheelite types indicate the mineralizing fluid pulses were likely sequentially released from a concealed granitic magma system emplaced at ca. 132.9 Ma. Our study at Huxingshan reveals that pulsed ore formation by multiple magmatic-hydrothermal fluid pulses is likely crucial for the formation of intrusion-related tungsten deposits.

Pathological mineralizations in breast lesions are closely associated with disease progression and serves as a critical diagnostic indicator. However, systematic understanding remains lacking regarding the phase categories, distribution patterns, and proportional occurrences of mineral phases across different breast lesion types. The diagnostic implications of specific phases, such as calcium oxalate, for distinguishing benign and malignant lesions remain controversial. This study employed polarizing microscopy,environmental scanning electron microscopy（SEM） with energy dispersive spectroscopy（EDS）,transmission electron microscopy（TEM）, Fourier transform infrared spectroscopy（FTIR）, and Raman spectroscopy to analyze the phase composition of 61 mineralized samples from three lesion types:Invasive carcinoma, carcinoma in situ and benign lesions. Results demonstrate that breast lesion mineralizations predominantly comprise calcium phosphates, including hydroxyapatite（HA）, amorphous calcium phosphate（ACP）, and whitlockite, occasionally accompanied by calcium oxalate（monohydrate or dihydrate）. Distinct distribution patterns and proportional occurrences of minerals were observed among the three types of lesion mineralizations. HA, as the predominant phase, was ubiquitously present across all three lesion categories. ACP, a mineralization precursor phase, emerged during early mineralization stages across all lesion types. Notably, whitlockite exclusively occurred in benign lesions and carcinoma in situ, with higher prevalence in benign cases, suggesting a progressive decline in Mg 2+ concentration within the lesion microenvironment as malignancy advances. Calcium oxalate coexisted with HA in mineralized regions across all lesion types, and its presence in invasive carcinoma specimens warrants heightened clinical attention.