Contribution of lignin and polysaccharides to the refractory carbon pool in C-depleted arable soils

We assessed the contribution of polysaccharides and lignin, major components of plant residues, to the refractory pool of soil organic carbon (SOC) in arable soils. Soil samples from two contrasting treatment types of European long-term agroecosystem experiments, i.e. conventionally managed (fertilized) and C-depleted plots, enriched in refractory compounds, were compared. Bulk samples from eight experimental sites and particle-size fractions of two of the sites were investigated. The CuO oxidation technique was used as a relative measure of lignin and its degree of structural alteration. The contents and composition of polysaccharides were determined following hydrolysis with trifluoroacetic acid (TFA). For the bulk samples, the amount of lignin phenols declined more than the total OC in the course of C-depletion. The contribution of lignin phenols to total OC was thus lower in the C-depleted versus the fertilized plots. A greater lignin biodegradation was found in the bulk samples of the depleted plots compared with the fertilized plots. The analysis of size fractions revealed lower OC-normalized contents of lignin phenols and a higher degree of lignin alteration in fractions <63 μm of the depleted versus the fertilized plots. These findings indicate that lignin does not accumulate within the refractory C pool of arable soils. The refractory SOC pool shows a lower contribution of lignin as compared with more labile fractions of SOC. If lignin-derived carbon is present in the stable pool it has been extensively modified so that it can no longer be identified as phenolic CuO oxidation products. OC-normalized contents of polysaccharides (neutral sugars and galacturonic acid) were similar in bulk samples of the C-depleted and fertilized plots. The contrasting treatments showed similar polysaccharide contents especially in separates <6 μm. The separates <6 μm in the C-depleted plots retained between 50 and 100% of the polysaccharide amounts in the fertilized plots. The mass ratio of (galactose+mannose)-to-(arabinose+xylose) (GM/AX) was higher in bulk samples of the C-depleted versus the fertilized plots, indicating a higher relative contribution of microbial sugars. Within a particular soil, the fine separates were those with the highest GM/AX ratio. These results indicate that the refractory C pool has a similar proportion of polysaccharides as the labile C pool, but refractory polysaccharides are mainly associated with fine separates and show a dominant contribution of microbial sugars. Our results provide evidence that polysaccharides, mainly those of microbial origin, are stabilized over the long-term within fine separates of arable soils. In contrast, CuO lignin is associated mainly with the coarse fractions and does not contribute to the refractory C pool.