Biochar amendments are effective in stabilizing soil aggregates and improving soil organic carbon (SOC) content. However, the effects of biochar on highly acidic soil and their relation with soil SOC stability remain understudied. The study aimed to investigate the impact of biochar on changes of aggregate distribution and SOC stability in a highly acidic tea plantation soils over an eight-year period. Soil samples were collected from plots with varying biochar application amounts (0, 2.5 t ha−1, 5 t ha−1, 10 t ha−1, 20 t ha−1 and 40 t ha−1). The content of SOC, iron bound organic carbon (OC-Fe), particulate organic carbon (POC), mineral-associated organic carbon (MAOC) and the functional group composition of SOC was analyzed. The results indicated that in the biochar application treatments, the value of soil pH, SOC, POC and MAOC contents were increased from 3.92 to 4.28, 6.68%–187.02%, 8.31%–66.78% and 13.07%–236.47% respectively, compared with CK, while the content of macro-aggregate (particle size>0.25 mm) and soil aggregates mean weight diameter (MWD) significantly increased with higher biochar application amounts. But dissolved organic carbon (DOC) and OC-Fe content exhibited downward trend, decreased from 2.43% to 6.97% and 4.18%–19.91%. Furthermore, aromatic-C levels increased, with increased biochar application amounts. The integration of biochar not only bolstered soil aggregate stability but also amplified the presence of aromatic-C, thereby enhancing the resilience of organic carbon in highly acidic tea garden soil (BC40 > BC20 > BC5>BC2.5 > BC10 > CK), with increases ranging from 6% to 47%. The principal component analysis and structural equation modeling identified soil pH, TN, SOC, POC, MAOC, R > 0.25 and MWD as key factors of soil organic carbon stability. These findings provide crucial insights into the mechanism underlying biochar's efficiency in fortifying organic carbon stability, particularly in the context of highly acidic soil.
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