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<p>Grotto heritage sites are irreplaceable cultural treasures of global significance, and the limestone serving as their carrier is distinct from conventional engineering limestone due to its inherent cultural heritage attributes and complex environmental stressors. Specifically, limestone grottoes in the Central Plains region of China are predominantly threatened by weathering induced by the unique coupling effect of “salt and seasonal freeze–thaw cycles”—characterized by frequent seasonal temperature fluctuations and cumulative salt erosion. This paper proposes a multi-scale characteristic approach (nm ~ m) to investigate the correlation between weathering effects and the characteristics of micron-scale and meso-scale pore structures in this specific environment. The study process involved several steps: (1) Analyzing the pore structure of macro-scale sample (mm ~ m) in limestone through the laboratory tests, (2) using scanning electron microscopy (SEM), digital processing techniques (μm ~ mm), and mercury intrusion porosimetry (MIP) (nm ~ μm) to explore the damage evolution of the internal and external pore structure of the limestone under the coupling effect of salt freeze–thaw, and (3) quantify the irregularity of pore networks through the fractal theory, thereby clarifying the correlation between cycle numbers and damage mechanisms. Results indicated a positive correlation between cycle numbers and both porosity and cumulative mercury intrusion volume. The salt freeze–thaw damage was most pronounced in the early stage (0 ~ 15days) and gradually weakened thereafter. Medium pores (100 ~ 1000&#xa0;nm) and large pores (&gt; 1000&#xa0;nm) accounted for over 85% of the total pore volume, acting as the key drivers of limestone deterioration. These findings underscore the necessity of strengthening targeted detection and implementing protection measures against salt, temperature fluctuations, and water seepage for grottoes in the Central Plains region of China. This study fills the gap in systematic research on the micro-, meso-mechanism of salt freeze–thaw damage to limestone grottoes in this specific climatic zone, and provides a scientific, theoretical, and practical basis for the precise protection and restoration of such cultural heritage sites.</p>

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Multi-scale Characterization of Pore Structure Damage in Limestone Grottoes Under the Coupling Effect of Salt Freeze–Thaw

  • 期刊论文

  • 发表日期：

    2026年2月6日

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  • Zhiliu Wang,
  • Mengxin Hu,
  • Jiabao Tang,
  • Yulong Wang,
  • Xinming Li,
  • Song Yin,
  • Kebin Ren,
  • Chaolong Ma

摘要

Grotto heritage sites are irreplaceable cultural treasures of global significance, and the limestone serving as their carrier is distinct from conventional engineering limestone due to its inherent cultural heritage attributes and complex environmental stressors. Specifically, limestone grottoes in the Central Plains region of China are predominantly threatened by weathering induced by the unique coupling effect of “salt and seasonal freeze–thaw cycles”—characterized by frequent seasonal temperature fluctuations and cumulative salt erosion. This paper proposes a multi-scale characteristic approach (nm ~ m) to investigate the correlation between weathering effects and the characteristics of micron-scale and meso-scale pore structures in this specific environment. The study process involved several steps: (1) Analyzing the pore structure of macro-scale sample (mm ~ m) in limestone through the laboratory tests, (2) using scanning electron microscopy (SEM), digital processing techniques (μm ~ mm), and mercury intrusion porosimetry (MIP) (nm ~ μm) to explore the damage evolution of the internal and external pore structure of the limestone under the coupling effect of salt freeze–thaw, and (3) quantify the irregularity of pore networks through the fractal theory, thereby clarifying the correlation between cycle numbers and damage mechanisms. Results indicated a positive correlation between cycle numbers and both porosity and cumulative mercury intrusion volume. The salt freeze–thaw damage was most pronounced in the early stage (0 ~ 15days) and gradually weakened thereafter. Medium pores (100 ~ 1000 nm) and large pores (> 1000 nm) accounted for over 85% of the total pore volume, acting as the key drivers of limestone deterioration. These findings underscore the necessity of strengthening targeted detection and implementing protection measures against salt, temperature fluctuations, and water seepage for grottoes in the Central Plains region of China. This study fills the gap in systematic research on the micro-, meso-mechanism of salt freeze–thaw damage to limestone grottoes in this specific climatic zone, and provides a scientific, theoretical, and practical basis for the precise protection and restoration of such cultural heritage sites.