Added-Value Chemicals from Lignin Oxidation

Lignin is the second most abundant component, next to cellulose, in lignocellulosic biomass. Large amounts of this polymer are produced annually in the pulp and paper industries as a coproduct from the cooking process—most of it burned as fuel for energy. Strategies regarding lignin valorization have attracted significant attention over the recent decades due to lignin’s aromatic structure. Oxidative depolymerization allows converting lignin into added-value compounds, as phenolic monomers and/or dicarboxylic acids, which could be an excellent alternative to aromatic petrochemicals. However, the major challenge is to enhance the reactivity and selectivity of the lignin structure towards depolymerization and prevent condensation reactions. This review includes a comprehensive overview of the main contributions of lignin valorization through oxidative depolymerization to produce added-value compounds (vanillin and syringaldehyde) that have been developed over the recent decades in the LSRE group. An evaluation of the valuable products obtained from oxidation in an alkaline medium with oxygen of lignins and liquors from different sources and delignification processes is also provided. A review of C4 dicarboxylic acids obtained from lignin oxidation is also included, emphasizing catalytic conversion by O2 or H2O2 oxidation.

Lignin oxidation products in soil, dripwater and speleothems from four different sites in New Zealand

Lignin oxidation products (LOPs) are widely used as vegetation proxies in climate archives, such as sediment and peat cores. The total LOP concentration, Σ8, provides information on the abundance of vegetation, while the ratios C/V and S/V of the different LOP groups also provide information on the type of vegetation. Recently, LOP analysis has been successfully applied to speleothem archives. However, there are many open questions concerning the transport and microbial degradation of LOPs on their way from the soil into the cave system. These processes could potentially alter the original source-dependent LOP signals, in particular the C/V and S/V ratios, and thus complicate their interpretation in terms of past vegetation changes. We analyzed LOPs in leaf litter and different soil horizons as well as dripwater and flowstone samples from four different cave sites from different vegetation zones in New Zealand using ultrahigh-performance liquid chromatography coupled to high-resolution mass spectrometry. We test whether the original source-dependent LOP signal of the overlying vegetation is preserved and can be recovered from flowstone samples and investigate how the signal is altered by the transport from the soil to the cave. The LOP concentrations range from mg g−1 in the soil to ng g−1 in the flowstones. Our results demonstrate that, from the soil to the flowstone, the C/V and S/V ratios both increase, while the total lignin content, Σ8, strongly decreases. This shows that the LOP signal is strongly influenced by both transport and degradation processes. Nevertheless, the relative LOP signal from the overlying soil at the different cave sites is preserved in the flowstone. We emphasize that for the interpretation of C/V and S/V ratios in terms of past vegetation changes, it is important to compare only samples of the same type (e.g., speleothem, dripwater or soil) and to evaluate only relative variations.

Supported-Metal Catalysts in Upgrading Lignin to Aromatics by Oxidative Depolymerization

Supported gold and platinum particles on titanium oxide catalysts were evaluated in the oxidative depolymerization of lignins toward high added value aromatics under mild conditions (T: 150 °C, Pair: 20 bar, CNaOH: 10 g/L, 1 h). Kraft and ethanol Organosolv lignins were engaged in the study. Gold catalyst showed a strong tendency to further oxidize aromatics produced from lignin depolymerization to volatile compounds leading to very low yield in target molecules. On the contrary, platinum-based catalysts were allowed to observe enhanced yields that were attributed to its ability to preserve lignin’s substructure during the reaction. A kinetic model was constructed based on the results observed, which allowed us to identify the occurrence of condensation reactions during lignin oxidation and degradation of the produced aromatic compounds as the main limitations to reach high product yields. Insights on lignin oxidation and the catalyst’s role lead through this study would help to reach higher control over lignin valorization.

Photocatalytic Pretreatment of Commercial Lignin Using TiO2-ZnO Nanocomposite-Derived Advanced Oxidation Processes for Methane Production Synergy in Lab Scale Continuous Reactors

The photocatalytic pretreatment of lignocellulosic biomass to oxidize lignin and increase biomass stability has gained attention during the last few years. Conventional pretreatment methods are limited by the fact that they are expensive, non-renewable and contaminate the anaerobic digestate later on. The present study was focused to develop a metal-derived photocatalyst that can work with visible electromagnetic spectra light and oxidize commercial lignin liquor. During this project the advanced photocatalytic oxidation of lignin was achieved by using a quartz cube tungsten T3 Halogen 100 W lamp with a laboratory manufactured TiO2-ZnO nanoparticle (nanocomposite) in a self-designed apparatus. The products of lignin oxidation were confirmed to be vanillic acid (9.71 ± 0.23 mg/L), ferrulic acid (7.34 ± 0.16 mg/L), benzoic acid (6.12 ± 0.17 mg/L) and p-coumaric acid (3.80 ± 0.13 mg/L). These all products corresponded to 85% of the lignin oxidation products that were detectable, which is significantly more than any previously reported lignin pretreatment with even more intensity. Furthermore, all the pretreatment samples were supplemented in the form of feedstock diluent in uniformly operating continuously stirred tank reactors (CSTRs). The results of pretreatment revealed 85% lignin oxidation and later on these products did not hinder the CSTR performance at any stage. Moreover, the synergistic effects of pretreated lignin diluent were seen that resulted in 39% significant increase in the methane yield of the CSTR with constant operation. Finally, the visible light and nanoparticles alone could not pretreat lignin and when used as diluent, halted and reduced the methane yield by 37% during 4th HRT.

Lignin oxidation products in soil, dripwater and speleothems from four different sites in New Zealand

Lignin oxidation products (LOPs) are widely used as vegetation proxies in climate archives, such as sediment and peat cores. The total LOP concentration, Σ8, provides information on the abundance of vegetation, while the ratios C / V and S / V of the different LOP groups also provide information on the type of vegetation. Recently, LOP analysis has been successfully applied to speleothem archives. However, there are many open questions concerning the transport and microbial degradation of LOPs on their way from the soil into the cave system. These processes could potentially alter the original source-dependent LOP signals, in particular the C / V and S / V ratios, and thus complicate their interpretation in terms of past vegetation changes. We analyzed LOPs in leaf litter and different soil horizons as well as dripwater and flowstone samples from four different cave sites from different vegetation zones in New Zealand using ultrahigh performance liquid chromatography coupled to high resolution mass spectrometry. We test whether the original source-dependent LOP signal of the overlying vegetation is preserved and can be recovered from flowstone samples and investigate how the signal is altered by the transport from the soil to the cave. The LOP concentrations range from mg/g in the soil to ng/g in the flowstones. Our results demonstrate that, from the soil to the flowstone, the C / V and S / V ratios both increase, while the total lignin content, Σ8, strongly decreases. This shows that the LOP signal is strongly influenced by both transport and degradation processes. Nevertheless, the relative LOP signal from the overlying soil at the different cave sites is preserved in the flowstone. We emphasize that for the interpretation of C / V and S / V ratios in terms of past vegetation changes, it is important to compare only samples of the same type (e.g., speleothem, dripwater or soil) and to evaluate only relative variations.

Linking microbial genomes with their potential to degrade terrestrial organic matter in the Amazon River

Rivers connect the carbon cycle in land with that in aquatic ecosystems by transporting and transforming terrestrial organic matter (TeOM). The Amazon River receives huge loads of TeOM from the surrounding rainforest, promoting a substantial microbial heterotrophic activity and consequently, CO2 outgassing. In the Amazon River, microbes degrade up to 55% of the lignin present in the TeOM. Yet, the main microbial genomes involved in TeOM degradation were not known. Here, we characterize 51 population genomes (PGs) representing some of the most abundant microbes in the Amazon River deriving from 106 metagenomes. The 51 reconstructed PGs are among the most abundant microbes in the Amazon River, and 53% of them are not able to degrade TeOM. Among the PGs capable of degrading TeOM, 20% were exclusively cellulolytic, while the others could also oxidize lignin. The transport and consumption of lignin oxidation byproducts seemed to be decoupled from the oxidation process, being apparently performed by different groups of microorganisms. Altogether, based on our findings, we suggest a new priming effect model that explains the quick turnover of TeOM as a product of the microbial consumption of lignin-derived aromatic compounds produced by lignin oxidation, reducing the inhibition of cellulose degradation and ensuring structural carbon and energy for cell growth. By connecting the genomic features of abundant microbes in the Amazon River with the degradation of recalcitrant TeOM, we contribute to increase our understanding of the rapid consumption of recalcitrant compounds in this ecosystem.