Lignin turnover kinetics in an agricultural soil is monomer specific

Lignin transformation and decomposition products are generally considered a major source of stable soil organic matter (SOM). Nevertheless this process remains poorly understood in part because lignin is a heterogeneous biopolymer composed of several types of phenol monomers, which potentially display specific and contrasting decomposition kinetics in soils. Here, we compared the specific in situ turnover kinetics of individual lignin monomers in a Paris-basin loamy soil through natural 13C labeling of SOM generated in a series of 1–9-year chronosequences of maize monoculture (C4, δ 13C −12‰) replacing wheat (C3, −27‰). Lignin monomers were released by CuO oxidation, quantified by gas chromatography (GC)/flame ionization detection (FID) and their 13C content was determined by GC coupled via a combustion interface to isotope ratio mass spectrometry (GC/C-IRMS). We calculated the proportion of C4-derived OC in lignin monomer pools by applying the isotopic mass balance equation to each lignin monomer. Individual C4-derived phenols displayed contrasting accumulation rates in soils over time, confirming the monomer-specific nature of their transformation kinetics. In proportion to total lignin phenols in soils, syringyl (S) and cinnamyl (C) phenols from maize accumulated faster than their vanillyl (V) counterparts. Consequently, the turnover kinetics of lignin-derived V-moieties may be slower than those of S and C ones. Incorporation of maize-derived carbon was faster in the aldehyde than in the acid pool for V-type units, while the opposite was observed for S-units. These in situ trends for phenol monomers and V-, S- and C-moieties were remarkably similar to the trends described in the literature with laboratory incubation or litterbag studies. None of the observed kinetics had a linear shape. Using only the extreme points of the chronosequence to calculate the kinetic parameters would result, for all the lignin monomers, in underestimating the turnover kinetics at the beginning of the kinetics and overestimating it for longer times. This observation underlines the importance of comprehensive 13C time-sequence labelling experiments such as provided at the Closeaux site, to accurately compute the kinetic parameters of SOM for the 1st years after the vegetation change.