Particulate Lignin Research Articles

Pickering emulsion via interfacial assembly of lignin particles and cationic surfactant: Formation of robust anchoring layer

Lignin, a byproduct of the paper and pulp industry, shows promise as stabilizers for emulsions, offering potential value-added applications to direct disposal. However, utilizing particulate lignin directly as stabilizers is challenging due to limited emulsion stability. In this study, co-stabilization of Pickering emulsions is investigated by combination of lignin particles and cationic surfactants (CTAB and DDAB), wherein lignin source and oil types are optimized with a focus on emulsion stability. A battery of characterization methods, including visual appearance, microstructure, droplet size, zeta potential, etc., is employed to evaluate emulsion stability. The findings reveal that kraft lignin nanospheres (LNS) are the optimal stabilizing particles. The incorporation of cationic surfactants via electrostatic adsorption enhances the stabilizing effect of LNS, and the use of DDAB is found to significantly enhance emulsion stability compared to CTAB, attributing to higher charge shielding capability of DDAB, as well as the formation of a more robust and compact nonpolar anchoring layer. The surfactant-assisted LNS can be used to stabilize a range of oil types, with tridecane as the optimal oil. This research presents a straightforward, efficient, and scalable approach for producing highly stable lignin-based Pickering emulsions, showing potential applications in recycling and value enhancement of waste lignin.

The role of earthquakes and storms in the fluvial export of terrestrial organic carbon along the eastern margin of the Tibetan plateau: A biomarker perspective

Driven by earthquakes and intense rainfall, steep tectonically active mountains are hotspots of terrestrial organic carbon mobilization from soils, rocks, and vegetation by landslides into rivers. Subsequent delivery and fluvial mobilization of organic carbon from different sources can impact atmospheric CO2 concentrations across a range of timescales. Extreme landslide triggering events can provide insight on processes and rates of carbon export. Here we used suspended sediment collected from 2005 to 2012 at the upper Min Jiang, a main tributary of the Yangtze River on the eastern margin of the Tibetan Plateau, to compare the erosion of terrestrial organic carbon before and after the 2008 Wenchuan earthquake and a storm-derived debris flow event in 2005. To constrain the source of riverine particulate organic carbon (POC), we quantified lignin phenols and n-alkanoic acids in the suspended sediments, catchment soils and landslide deposits. We found that riverine POC had higher inputs of less-degraded, discrete organic matter at high suspended sediment loads, while the source of POC seemed stochastic at low suspended sediment concentrations. The debris flow in 2005 mobilized a large amount of POC, resulting in an export of lignin within a single day equivalent to a normal year. In comparison, the 2008 Wenchuan earthquake increased the flux of POC and particulate lignin, albeit with limited impact on POC sources in comparison to seasonal variations. Our results highlight the important role of episodic events in the fluvial export of terrestrial carbon.

Runoff-driven export of terrigenous particulate organic matter from a small mountainous river: sources, fluxes and comparisons among different rivers

The land-to-ocean export and subsequent preservation of terrestrial particulate organic carbon (POC) in oceans represents a major carbon sink in the global carbon cycle. Small mountainous rivers (SMRs) are hotspots of this process; however, how the sources and fluxes of POC change during rain events in low-gradient SMRs and how they compare with those in steep SMRs are unknown. Here, we combined the bulk properties and lignin phenols to trace changes in POC sources and fluxes in a low-gradient SMR (stream gradient: 0.6%) in southeastern China. Our results were further compared with other SMRs to understand the geomorphological influences on the POC export from SMRs. The results indicated that POC sources changed from aquatic organisms and deep soils during low-flow periods to surface soils and plant debris during high-flow periods. The lignin concentration showed a significant positive relationship with the runoff, suggesting that hydrology played an important role in exporting terrigenous POC in low-gradient SMRs. We further estimated that approximately 22%, 56% and 79% of annual water, POC and particulate lignin were exported during high-flow periods, respectively. Furthermore, we found that with increasing water discharge, the magnitude of the lignin increase was greater in SMRs with smaller stream gradients. Our results suggest that the export of terrigenous POC from low-gradient SMRs is driven by hydrology and is more sensitive to rain events than that in steep SMRs.

The chemical fingerprint of solubilized organic matter from eroded soils and sediments

Organic matter (OM) transfers between solid and water phases are critical components of OM cycling in surface waters as they contribute to compositional differences between dissolved OM (DOM) and particulate OM (POM). However, fractionation effects during such phase changes are not well-characterized, especially during the release of soluble OM from sediments and eroded soils. Agricultural practices alter the magnitude and timing of OM export and constitute a major source of sediment through soil erosion. This study assessed the elemental, biomolecular, and optical characteristics of DOM solubilized from sediments and soils in an agricultural watershed of northern California to trace compositional changes during OM flow from mobilized soils in streams. Relative to mineral-bound OM, solubilized DOM was nitrogen-poor (more than doubled C:N ratios) and depleted in amino acids and lignin (three- to six-fold decrease in carbon-normalized yields). Distinct fractionation patterns of individual amino acids and lignin phenols led to a more acidic pool of solubilized DOM that appeared substantially more degraded than its source POM, with decreased degradation index (DI) values and more than doubled molar contributions of non-protein amino acids and processing ratio (PR) values. Lignin composition also greatly differed in solubilized DOM compared to mineral-bound OM, with cinnamyl:vanillyl phenol ratios up to six-fold lower in solubilized lignin than in particulate lignin. Solubilized DOM generally resembled stream DOM more than its source POM and was chemically distinguishable from DOM leached from plants. Absorption coefficients and fluorescence peak intensities were strongly correlated with solubilized DOM concentrations and composition, while optical parameters established to characterize DOM origin and reactivity such as spectral slope, fluorescence index, and carbon-specific fluorescence intensities suggested unique compositional traits for solubilized DOM compared to stream DOM. This study therefore documented strong fractionation patterns during solubilization, linking eroded soil OM and stream DOM and highlighting a pathway that can account for compositional differences between DOM and POM in surface waters. A new amino acid parameter, the Solubilization Index (SI), was defined to capture the effects of solubilization processes on OM composition. SI values in solubilized DOM were up to an order of magnitude higher than in its source POM and were similar to SI values in stream DOM. Because the SI is based on empirical behaviors of individual amino acids, each tied to mechanistic interpretations, the SI is demonstrating a strong potential for mechanistic-driven research on the extent of phase changes in streamwater DOM.

Connecting tropical river DOM and POM to the landscape with lignin

Tropical rivers account for two thirds of global fluxes of terrigenous organic matter to the oceans, yet because of their remote locations relative to most industrialized countries, they are poorly studied compared to temperate and even Arctic rivers. Further, most tropical river research has focused on large rivers like the Amazon or Congo, yet more than half of organic matter fluxes from tropical rivers comes from much smaller rivers. This study focuses on two such rivers in the Luquillo Experimental Forest of Puerto Rico, namely the Rio Mameyes and Rio Icacos, and uses time-series measurements of lignin biomarkers to put them in context with much bigger tropical rivers in the literature. Although lignin concentrations and carbon-normalized yields offer some distinction between mountainous vs. floodplain tropical river reaches, compositional differences appear to offer greater potential, including S:V vs. C:V plots that may capture the poorly-studied influence of palm trees, and (Ad:Al)s vs. (Ad:Al)v plots that may reflect differences in underlying mineralogy and degradation in soils. Even though dissolved and particulate lignin ultimately come from the same vegetation sources, comparison of dissolved and particulate lignin parameters within the two Puerto Rican rivers indicate that the pathways by which they end up in the same parcel of river water are largely decoupled. Across several particulate lignin studies in tropical rivers, mineral composition and concentration appears to exert a strong control on particulate lignin compositions and concentrations. Finally, the time-series nature of this study allows for new ways of analyzing dissolved lignin endmember compositions and degradation within the catchment. Plots of dissolved lignin parameters vs. lignin concentration reveal both the composition of “fresh” DOM that is likely mobilized from organic-rich soil surface layers along with the extent and trajectory of degradation of that signature that is possible within the lower mineral layers of the soil. Establishing connectivity between river chemistry and catchment sources and processes in this manner is the only way to realize the full potential of river chemistry as a diagnostic tool for changing sources and processes within the catchment.

Removal of lignin from straw spent pulping liquor using synthetic cationic and biobased flocculants

Abstract The spent pulping liquor (SPL) obtained from straw processed by soda (alkaline) pulping contains dissolved non-sulfonated lignin. The lignin can be separated from SPL using acid or cationic flocculants which are potentially hazardous to the environment. In this study, the performance of the biobased protein flocculant hemoglobin (HEM) with and without added calcium chloride was compared with that of a high charge density synthetic cationic flocculant, poly (diallyldimethylammonium chlorides) (pDADMAC). Turbidity measurements gave overly broad concentration ranges for optimal lignin removal which may be related to the mechanism of flocculation which requires several major steps: Conversion of dissolved lignin to particulate lignin, formation of particulate lignin flocs, and subsequent sedimentation of these flocs. An optimal flocculant concentration or concentration range was estimated using the three methods: average Zeta potential corresponding to the lowest turbidity range; a novel method using the maximum percent pellet mass calculated using the dried masses of the pellet and supernatant after centrifugation; measurement of supernatant lignin using spectroscopy. HEM light absorption interfered with spectroscopic lignin determination, and a method for correcting the measurements was devised. This study shows that HEM is an effective flocculant for nonsulfonated lignin in SPL. The HEM-lignin complex is a potential high protein component of animal feed.

Phenolic matter from deadwood can impact forest soil properties

Deadwood is a key factor in forest ecosystems, yet how it influences forest soil properties is uncertain. We hypothesized that changes in soil properties induced by deadwood mainly depend on the amount of released phenolic matter. Consequently we expected softwood- and hardwood-related deadwood effects on soil to be explained by unequal enrichment of phenolic substances. We measured differences in the quantity and composition of soil organic matter (SOM), pH, nutrient concentrations, and enzymatic activity between paired control and treatment points influenced by deadwood of silver fir (Abies alba Mill.) and European beech (Fagus sylvatica L.), and checked for correlations with total C and phenolic matter; the latter was quantified as aromaticity of water-extractable organic C through specific UV absorbance at 280nm. Near fir deadwood, aromaticity and effective cation exchange capacity (CEC) increased while pH decreased. In comparison, concentrations of water-extractable organic C, effective CEC, exchangeable Ca2+ and Mg2+, base saturation, and available molybdenum-reactive P increased near beech deadwood while exchangeable Al3+ decreased. For fir deadwood, soil properties strongly correlated almost exclusively with total C. For beech deadwood, numerous strong correlations with aromaticity indicated that extractable phenolics influenced soil properties. These differences in correlations imply that deadwood affects soil through the composition of added phenolic matter, which would stem from differing decay processes and organisms. Decayed, particulate lignin from brown-rot in fir deadwood as opposed to oxidized, dissolved lignin from white-rot in beech deadwood would account for our observations.

Detection of the Sensitive Inflowing River Indicators Related to Non-Point Source Organic Pollution: A Case Study of Taihu Lake

Organic matter transport from watershed soil into an aquatic ecosystem plays a key role in the fate of contaminants and lake eutrophication. Special emphasis is needed to understand whether sensitive river indicators can reflect watershed non-point source organic carbon (OC) pollution, in which the accurate assessment of non-point source (NPS) pollution is crucial. This study selected a sub-basin within the Taihu basin, China, as the study site, a typical rural-urban fringe region undergoing rapid urbanization where soil organic carbon (SOC) loss would likely take place due to the integration of agriculture NPS and impervious surface NPS. The seasonal tendency of NPS soil organic carbon (SOC) loads were evaluated by using the integration of SEDD and PLOAD models, which consider the sediment adsorption fraction loads (Sed-OC) and runoff dissolved fraction loads (Dis-OC) together. And then the sensitive water indicators for OC loads were determined by measurements of inflowing river properties and stepwise regression analysis. The results showed that active dissolved carbon fraction loads were the dominant contributors to the total organic carbon loads (Tot-OC) and that Sed-OC loads have more spatial variation. With respect to sensitive river properties, the lignin owned the greatest correlation degree with different OC fraction loads, in which the correlation coefficient between particulate lignin and Sed-OC loads reached 0.782, which is the greatest among the different indicators. In addition, the colored dissolved organic matter (CDOM) was also correlated with Dis-OC loads. However, the particulate organic carbon (POC) was not well related to OC loads. The findings of this study are useful for better understanding the nutrient migration from watershed soil into aquatic ecosystem controlled by watershed NPS pollution.

Importance of Oceanian small mountainous rivers (SMRs) in global land-to-ocean output of lignin and modern biospheric carbon.

The land-to-ocean export of particulate organic carbon (POC) connects carbon flow from the atmosphere through land to the ocean, of which the contemporary fraction that reaches the deep sea for burial may effectively affect atmospheric CO2. In this regard, small mountainous rivers (SMRs) in Oceania, a global erosion hotspot driven by torrential typhoon rain and active earthquakes are potentially important. Here we measured typhoon lignin discharges for Taiwan SMRs. We found that the particulate lignin export in 96 hours by a single SMR amounting to ~20% of the annual export by Mississippi River. The yearly particulate lignin discharge from Taiwan Island (35,980 km2) is governed by the frequency and magnitude of typhoon; thus, the historical lignin export ranged widely from 1.5 to 99.7 Gg yr−1, which resulted in a 10–100 times higher areal yield relative to non-Oceanian rivers. The lignin-derived modern POC output from Oceania region is 37 ± 21 Tg C yr−1, account for approximately 20% of the annual modern POC export from global rivers. Coupled with the hyperpycnal pathway, the forested watersheds of SMRs in Oceania may serve as a giant factory to rapidly produce and efficiently convey modern POC into deep sea for sequestration.

Temporal variability of particulate organic carbon in the lower Changjiang (Yangtze River) in the post‐Three Gorges Dam period: Links to anthropogenic and climate impacts

AbstractSuspended particles from the lower Changjiang were collected monthly from 2003 to 2011, which corresponds to the three construction periods of the Three Gorges Dam. Organic carbon (%OC), organic carbon to total nitrogen molar ratio, stable carbon isotope, and terrestrial biomarkers were examined. Rating curve studies were applied for the temporal trend analysis. The composition of particulate lignin phenols exhibited clear annual and periodic variations but only minor seasonal changes. Lignin phenol ratios (vanillyl/syringyl and cinnamyl/vanillyl) indicated that the terrigenous organic matter (OM) was primarily composed of woody and nonwoody tissue derived from angiosperm plants. The low‐lignin phenol yields (Λ8) in combination with higher acid to aldehyde ratios reflected a substantial contribution from soil OM to the particle samples or modifications during river transport. The temporal shift of the lignin phenol vegetation index with the sediment load during the flood seasons revealed particulate organic matter (POM) erosion from soils and the impact of hydrodynamic processes. The dam operations affected the seasonal variability of terrigenous OM fluxes, although the covariation of lignin and sediment loads with discharged water implies that unseasonal extreme conditions and climate change most likely had larger influences, because decreases in the sediment load and lignin flux alter the structure and composition of particulate OM (POM) on interannual time scales, indicating that they may be driven by climate variability. The modification of the composition and structure of POM will have significant impacts on regional carbon cycles and marine ecosystems.

Temporal variation in river nutrient and dissolved lignin phenol concentrations and the impact of storm events on nutrient loading to Hood Canal, Washington, USA

Rapid rainfall events can be responsible for a large proportion of annual nutrient and carbon loading from a watershed. The bioavailability of organic matter during these rapid loading events increases, suggesting that storms play a relevant role in the mobilization of potentially labile terrestrial carbon. A high correlation between river discharge rates and dissolved and particulate nutrient and carbon concentrations during autumn and winter storms was observed in several temperate Pacific Northwest rivers. Dissolved and particulate lignin concentrations also increased with river discharge; for example, in October 2009 dissolved lignin concentrations increased roughly 240% with a 200% increase in river discharge. During these storms a unique phenolic composition was observed for dissolved lignin that was rapidly mobilized from surface soils relative to the base flow of dissolved lignin. The observed increase in Ad/Al ratios with discharge indicates that rapidly mobilized dissolved lignin is more degraded than the base flow of dissolved lignin. Similarly, a marked increase in C/V ratios and decrease in the S/V ratio of dissolved lignin phenols with increasing river discharge was observed. These results may indicate a difference in source between mobilized and base flow pools, or, more likely, preferential degradation and mobilization/retention of specific lignin phenols. The cumulative results from this year-long data set indicate that a shallow nutrient-rich pool of particulate and dissolved organic matter accumulates in watersheds during periods of soil-saturation deficiency (summer). Autumn and winter storms mobilize this pool of accumulated nutrients from surface soils, which is exhausted with successive winter storms.

Inhibition of cellulase, xylanase and β-glucosidase activities by softwood lignin preparations

The conversion of lignocellulosic biomass to fuel ethanol typically involves a disruptive pretreatment process followed by enzyme-catalyzed hydrolysis of the cellulose and hemicellulose components to fermentable sugars. Attempts to improve process economics include protein engineering of cellulases, xylanases and related hydrolases to improve their specific activity or stability. However, it is recognized that enzyme performance is reduced during lignocellulose hydrolysis by interaction with lignin or lignin-carbohydrate complex (LCC), so the selection or engineering of enzymes with reduced lignin interaction offers an alternative means of enzyme improvement. This study examines the inhibition of seven cellulase preparations, three xylanase preparations and a beta-glucosidase preparation by two purified, particulate lignin preparations derived from softwood using an organosolv pretreatment process followed by enzymatic hydrolysis. The two lignin preparations had similar particle sizes and surface areas but differed significantly in other physical properties and in their chemical compositions determined by a 2D correlation HSQC NMR technique and quantitative 13C NMR spectroscopy. The various cellulases differed by up to 3.5-fold in their inhibition by lignin, while the xylanases showed less variability (< or = 1.7-fold). Of all the enzymes tested, beta-glucosidase was least affected by lignin.

The effect of physical form of orchardgrass hay on the passage of particulate matter through the rumen of sheep.

Four Texel wethers (60 to 64 kg) fitted with ruminal and duodenal cannulas were used to study the kinetics of particulate matter in the rumen and the series of processes involved in their selection and passage. They were fed, in eight equal meals, 1,200 g of a mixture of a chopped orchardgrass hay and ground (8-mm screen) and pelleted orchardgrass hay in 90/10, 50/50, 30/70, or 10/90 ratios, according to a 4 x 4 Latin square design. The particle size distributions in feed, chewed feed, and ruminal, reticular, and duodenal digesta were determined by a wet-sieving procedure. Indigestible lignin was used as an internal marker to trace the passage of particles through the rumen. Digesta flow measurement was performed using the double-marker technique. We used a three-pool model, which partitions particles through the large, medium, and small particle pools, to determine the passage of lignin through those pools. Particle pool sizes and rumen and pool mean retention times (MRT) of lignin and of the rumen MRT of an ideal marker introduced separately in each pool were corrected for the "filter bed" effect. Grinding and pelleting of hay decreased the MRT of the indigestible lignin pool in the rumen. Particle MRT decreased and then reached a plateau with increased proportion of ground/pelleted hay in the diet. The diet with a ratio of 50/50 of chopped and ground/pelleted hay was the most favorable for the exit of particles from the rumen because of both a higher outflow rate from the rumen of particles eligible to exit and a sufficient comminution rate of larger particles to supply particles that were able to pass. For all diets, the large-particle comminution rate was always higher than the small-particle outflow rate, indicating that comminution was not the limiting step for passage. These results were the consequence of the curvilinear and opposite evolutions of both the particulate lignin pool in, and outflow from, the rumen. Those results contribute to an improved explanation of the mechanisms involved in the outflow of particles from the rumen.

Terrestrial plant biopolymers in marine sediments

The vascular land plant biopolymers lignin and cutin were surveyed in the surface sediments of coastal and open ocean waters by controlled alkaline CuO oxidation/reaction. Two contrasting oceanic regimes were studied: the northwest Mediterranean (NWM) Sea, which receives significant particulate terrigenous debris through riverine discharge; and the northeast Atlantic (NEA) Ocean, with poorly characterised terrestrial carbon inputs. In the NWM products of lignin and cutin co-occurred at all stations, elevated levels (ca. 0.5–3.0 mg lignin phenols/100 mg organic carbon; ca. 0.01–0.09 mg cutin acids/100 mg organic carbon) were observed for near-shore deltaic and shelf sediments. The influence of terrestrial land plant inputs extended across the shelf and through the slope to the abyssal plain, providing molecular evidence for advective offshore transfer of terrestrial carbon. Mass balance estimates for the basin suggest riverine inputs account for the majority of surface sedimentary lignin/cutin, most of which (>90%) is deposited on the shelf. Products of CuO oxidation of lignin and cutin were also detected in NEA surface sediments, at levels comparable to those observed for the NWM continental slope, and were detectable at low concentrations ( ca. 0.5 μg g −1 in the sediments of the abyssal plains (>4,000 m depth). While atmospheric deposition of lignin/cutin-derived material cannot be discounted in this open ocean system, lateral advective transfer of enriched shelf sediments is inferred as a possible transport process. A progressive enrichment in cutin-derived material relative to lignin was observed offshore, with evidence of an increase in the degree of oxidative alteration of lignin residues. To account for these observations, preferential offshore transport of finer and more degraded material is proposed. Nonspecific oxidation products dominated the gas chromatograms of NEA sediments, which appear to originate from marine sources of sedimentary organic carbon. Preliminary mass balance calculations applied to the global ocean margin suggest riverine sources of both particulate lignin and cutin are important and that most (>95%) deposition of recognisable land plant biopolymers occurs in shelf seas.

The composition of lignin in estuarine suspended particulates and the distribution of particulate lignin in estuaries as determined by capillary gas chromatography of cupric oxide oxidation products

The contribution of lignin to the estuarine suspended particulate fraction is described in terms of its distribution over a spring tide and a neap tide in the Tamar Estuary, Southwest England and the Mersey Estuary, Northwest England. Suspended particulate samples are treated with CuONaOH at 170°C to yield simple, lignin-derived phenolic compounds, which are separated, derived and quantified by capillary gas chromatography with flame ionization detection (GC-FID). Estuarine distributions of particulate lignin are described and the sources and compositional changes of the lignin identified. Comparison of the lignin concentrations in the suspended material with those in the underlying sediment reveals that lignin is preferentially enriched in the suspended material.