Commercial
humic acids mainly obtained from leonardite are in increasing
demand in agronomy, and their market size is growing rapidly because
these materials act as soil conditioners and direct stimulators of
plant growth and development. In nature, fungus-driven nonspecific
oxidations are believed to be a key to catabolizing recalcitrant plant
lignins, resulting in lignin humification. Here we demonstrated the
effective transformation of technical lignins derived from the Kraft
processing of woody biomass into humic-like plant fertilizers through
one-pot Fenton oxidations (i.e., artificially accelerated fungus reactions).
The lignin variants resulting from the Fenton reaction, and manufactured
using a few different ratios of FeSO4 to H2O2, successfully accelerated the germination of Arabidopsis thaliana seeds and increased the tolerance
of this plant to NaCl-induced abiotic stress; moreover, the extent
of the stimulation of the growth of this plant by these manufactured
lignin variants was comparable or superior to that induced by commercial
humic acids. The results of high-resolution (15 T) Fourier transform-ion
cyclotron resonance mass spectrometry, electrostatic force microscopy,
Fourier transform-infrared spectroscopy, and elemental analyses strongly
indicated that oxygen-based functional groups were incorporated into
the lignins. Moreover, analyses of the total phenolic contents of
the lignins and their sedimentation kinetics in water media together
with scanning electron microscopy- and Brunauer–Emmett–Teller-based
surface characterizations further suggested that polymer fragmentation
followed by modification of the phenolic groups on the lignin surfaces
was crucial for the humic-like activity of the lignins. A high similarity
between the lignin variants and commercial humic acids also resulted
from autonomous deposition of iron species into lignin particles during
the Fenton oxidation, although their short-term effects of plant stimulations
were maintained whether the iron species were present or absent. Finally,
we showed that lignins produced from an industrial-scale acid-induced
hydrolysis of wood chips were transformed with the similar enhancements
of the plant effects, indicating that our fungus-mimicking processes
could be a universal way for achieving effective lignin humification.