Decadal application of mineral fertilizers alters the molecular composition and origins of organic matter in particulate and mineral-associated fractions

The extent to which long-term application of mineral fertilizers regulates the quantity, quality, and stability of soil organic matter (SOM) in soil matrices remains unclear. By combining four biomarkers, i.e., free and bound lipids, lignin phenols and amino sugars, we characterized the molecular composition, decomposition and origins of SOM in response to 10-year fertilization (400 kg N ha−1 yr−1, 120 kg P ha−1 yr−1 and 50 kg K ha−1 yr−1) in a cropland in North China. We focused on two contrasting fractions: particulate organic matter (POM), and mineral-associated organic matter (MAOM). Fertilization increased soil organic carbon (SOC) by 23% in MAOM, and altered its composition and origins, despite having a limited effect on bulk SOC levels. Fertilization increased plant-derived terpenoids by 46% in POM and long-chain lipids (≥C20) by 116% in MAOM but decreased short-chain lipids (<C20) by 54% in the former fraction. Fertilization reduced suberin-derived lipids by 56% in POM and 30% in MAOM but increased lignin-derived phenols by 74% in POM and 31% in MAOM, implying that crop residues were preferentially stored via the POM form. Fertilization decreased the contribution of microbial residues to SOC in both the fractions. Overall, mineral fertilizers tended to reduce certain labile components within POM (e.g., short-chain lipids), leading to the accrual of recalcitrant molecules (e.g., long-chain lipids, cutin-derived lipids, and lignin-derived phenols) in the MAOM fraction. Collectively, our study suggests that mineral fertilizers can increase SOM stability and persistence by modifying their molecular composition and preservation in the mineral-organic associations in a temperate agroecosystem.