Previous research has shown that long-term intensive cropping of irrigated lowland rice has led to significant grain-yield declines in field trials. The yield decline was attributed to decreased availability of soil nitrogen, which is held mostly in the soil organic matter. By advanced solid-state NMR spectroscopy, we have detected significant amounts of amide nitrogen directly bonded to aromatic rings in a humic acid fraction extracted from a continually submerged, triple-cropped rice soil. Because nitrogen bonded to aromatics is not readily plant-available, this observation can explain the yield decline. Quantitative 13 C NMR combined with advanced spectral editing showed that this humic acid is rich in lignin derivatives (>45% of all carbon), whereas the corresponding humic acid fraction extracted from an aerobic, single-cropped rice soil contains less lignin and less nitrogen bonded to aromatics. C ultivation of two or three rice crops annually in irrigated lowland soils has been the foundation of Asia's rice supply since such intensive cropping first became possible in the 1960s. Currently, approximately one quarter of global rice production comes from multiple annual cropping of lowland rice, and this central role in the food supply will expand in the future as Asian populations continue to increase. In long-term field trials in which initial yield levels of lowland rice approached the yieldpotential ceiling, yields declined by Ͼ35% during 20-30 years of double and triple cropping (1). The search for mitigation options that will reverse this yield decline and thus improve the food supply for a significant portion of the world's population requires an understanding of the underlying processes.Agronomic data indicate that this yield decline resulted primarily from decreased crop uptake of soil nitrogen (1), which is distinct from fertilizer nitrogen and is held mostly in the soil organic matter. However, total soil nitrogen did not decrease in quantity as yields declined. We propose that the apparent decrease in availability of soil nitrogen is caused by the chemical stabilization of nitrogenous compounds by bonding to aromatic rings in lignin residues, probably via phenolic functionalities. Lignin residues accumulate in soils that are intensively cropped to irrigated lowland rice (1) because of their slow decomposition under the characteristically anaerobic conditions and their high input rates through multiple incorporations annually of crop residues. Nitrogen directly bonded to or in aromatic rings has been found to be less bioavailable than nitrogen in peptides, based on its rate of degradation through soil microbial processes under laboratory conditions (2-4), but 15 N NMR spectroscopy has been unable to detect significant fractions of nitrogen bonded to aromatic carbons in the organic matter of these rice soils or any other soils (5), raising doubts as to whether nitrogen can be bonded to aromatic carbons under field conditions. Recent developments in solid-state NMR pulse sequences have greatly advanc...