Fractionnation of AgroResources and Environment

Lignocellulosic biomass (LB) is an abundant and renewable resource from plants mainly composed of polysaccharides (cellulose and hemicelluloses) and an aromatic polymer (lignin). LB has a high potential as an alternative to fossil resources to produce second-generation biofuels and biosourced chemicals and materials without compromising global food security. One of the major limitations to LB valorisation is its recalcitrance to enzymatic hydrolysis caused by the heterogeneous multi-scale structure of plant cell walls. Factors affecting LB recalcitrance are strongly interconnected and difficult to dissociate. They can be divided into structural factors (cellulose specific surface area, cellulose crystallinity, degree of polymerization, pore size and volume) and chemical factors (composition and content in lignin, hemicelluloses, acetyl groups). Goal of this review is to propose an up-to-date survey of the relative impact of chemical and structural factors on biomass recalcitrance and of the most advanced techniques to evaluate these factors. Also, recent spectral and water-related measurements accurately predicting hydrolysis are presented. Overall, combination of relevant factors and specific measurements gathering simultaneously structural and chemical information should help to develop robust and efficient LB conversion processes into bioproducts.

Biorefining of lignocellulosic biomass has become one of the most valuable alternatives for the production of multi-products such as biofuels. Pretreatment is a prerequisite to increase the enzymatic conversion of the recalcitrant lignocellulose. However, there is still considerable debate regarding the key features of biomass impacting the cellulase accessibility. In this study, we evaluate the structural and chemical features of three different representative biomasses (Miscanthus × giganteus, poplar and wheat straw), before and after steam explosion pretreatment at increasing severities, by monitoring chemical analysis, SEM, FTIR and 2D NMR. Regardless the biomass type, combined steam explosion pretreatment with dilute sulfuric acid impregnation resulted in significant improvement of the cellulose conversion. Chemical analyses revealed that the pretreatment selectively degraded the hemicellulosic fraction and associated cross-linking ferulic acids. As a result, the pretreated residues contained mostly cellulosic glucose and lignin. In addition, the pretreatment directly affected the cellulose crystallinity but these variations were dependent upon the biomass type. Important chemical modifications also occurred in lignin since the β-O-4′ aryl-ether linkages were found to be homolytically cleaved, followed by some recoupling/recondensation to β-β′ and β-5′ linkages, regardless the biomass type. Finally, 2D NMR analysis of the whole biomass showed that the pretreatment preferentially degraded the syringyl-type lignin fractions in miscanthus and wheat straw while it was not affected in the pretreated poplar samples. Our findings provide an enhanced understanding of parameters impacting biomass recalcitrance, which can be easily generalized to both woody and non-woody biomass species. Results indeed suggest that the hemicellulose removal accompanied by the significant reduction in the cross-linking phenolic acids and the redistribution of lignin are strongly correlated with the enzymatic saccharification, by loosening the cell wall structure thus allowing easier cellulase accessibility. By contrast, we have shown that the changes in the syringyl/guaiacyl ratio and the cellulose crystallinity do not seem to be relevant factors in assessing the enzymatic digestibility. Some biomass type-dependent and easily measurable FTIR factors are highly correlated to saccharification.

Land-use practices aiming at increasing agro-ecosystem sustainability, e.g. no-till systems and use of temporary grasslands, have been developed in cropping areas, but their environmental benefits could be counterbalanced by increased N2O emissions produced, in particular during denitrification. Modelling denitrification in this context is thus of major importance. However, to what extent can changes in denitrification be predicted by representing the denitrifying community as a black box, i.e. without an adequate representation of the biological characteristics (abundance and composition) of this community, remains unclear. We analysed the effect of changes in land uses on denitrifiers for two different agricultural systems: (i) crop/grassland conversion and (ii) cessation/application of tillage. We surveyed potential denitrification (PD), the abundance and genetic structure of denitrifiers (nitrite reducers), and soil environmental conditions. N2O emissions were also measured during periods of several days on control plots. Time-integrated N2O emissions and PD were well correlated among all control plots. Changes in PD were partly due to changes in denitrifier abundance but were not related to changes in the structure of the denitrifier community. Using multiple regression analysis, we showed that changes in PD were more related to changes in soil environmental conditions than in denitrifier abundance. Soil organic carbon explained 81% of the variance observed for PD at the crop/temporary grassland site, whereas soil organic carbon, water-filled pore space and nitrate explained 92% of PD variance at the till/no-till site, without any residual effect of denitrifier abundance. Soil environmental conditions influenced PD by modifying the specific activity of denitrifiers, and to a lesser extent by promoting a build-up of denitrifiers. Our results show that an accurate simulation of carbon, oxygen and nitrate availability to denitrifiers is more important than an accurate simulation of denitrifier abundance and community structure to adequately understand and predict changes in PD in response to land-use changes.

Three new organic compounds primarily based on 8-hydroxyquinoline have been successfully synthesized and characterized via different spectroscopic methods (FTIR, 1H, and 13C NMR). The synthesized compounds, namely 5-propoxymethyl-8-hydroxyquinoline (PMHQ), 5-methoxymethyl-8-hydroxyquinoline (MMHQ) and 5-hydroxymethyl-8-hydroxyquinoline (HMHQ), were evaluated as corrosion inhibitors for carbon steel in 1 M HCl solution using electrochemical impedance spectroscopy, potentiodynamic polarization and weight loss measurements at 298 K. Electrochemical measurements confirmed that the newly synthesized 5-alkoxymethyl-8-hydroxyquinoline derivatives are mixed type corrosion inhibitors and confirmed maximum protection efficiencies of 94, 89 and 81% for PMHQ, MMHQ, and HMHQ, respectively, at the optimum concentration of 10-3 M. The EIS spectra confirmed a slightly depressed semi-circle profile with a single time constant in Bode diagrams for the three organic compounds over the whole concentration and temperature ranges studied. The adsorption of PMHQ, MMHQ, and HMHQ on the carbon steel surface followed the Langmuir adsorption isotherm. In addition, the kinetic and thermodynamic parameters for carbon steel corrosion and inhibitor adsorption, respectively, were determined and discussed. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) analyses supported the formation of a protective film on carbon steel in the presence of PMHQ, MMHQ, and HMHQ. Density functional theory calculations (DFT) showed that the effectiveness of the inhibitive actions of the studied compounds correlates well with their electron donating ability, whilst Monte Carlo simulations revealed that the extent and favourability of adsorption of inhibitor molecules on the carbon steel surface establish their corrosion inhibition performances.

The brown-midrib mutants of maize have a reddish-brown pigmentation of the leaf midrib and stalk pith, associated with lignified tissues. These mutants progressively became models for lignification genetics and biochemical studies in maize and grasses. Comparisons at silage maturity of bm1, bm2, bm3, bm4 plants highlighted their reduced lignin, but also illustrated the biochemical specificities of each mutant in p-coumarate, ferulate ester and etherified ferulate content, or syringyl/guaiacyl monomer ratio after thioacidolysis. Based on the current knowledge of the lignin pathway, and based on presently developed data and discussions, C3H and CCoAOMT activities are probably major hubs in controlling cell-wall lignification (and digestibility). It is also likely that ferulates arise via the CCoAOMT pathway.

Allergen immunotherapy (AIT) is a proven therapeutic option for the treatment of allergic rhinitis and/or asthma. Many guidelines or national practice guidelines have been produced but the evidence-based method varies, many are complex and none propose care pathways. This paper reviews care pathways for AIT using strict criteria and provides simple recommendations that can be used by all stakeholders including healthcare professionals. The decision to prescribe AIT for the patient should be individualized and based on the relevance of the allergens, the persistence of symptoms despite appropriate medications according to guidelines as well as the availability of good-quality and efficacious extracts. Allergen extracts cannot be regarded as generics. Immunotherapy is selected by specialists for stratified patients. There are no currently available validated biomarkers that can predict AIT success. In adolescents and adults, AIT should be reserved for patients with moderate/severe rhinitis or for those with moderate asthma who, despite appropriate pharmacotherapy and adherence, continue to exhibit exacerbations that appear to be related to allergen exposure, except in some specific cases. Immunotherapy may be even more advantageous in patients with multimorbidity. In children, AIT may prevent asthma onset in patients with rhinitis. mHealth tools are promising for the stratification and follow-up of patients.

Abstract Soil enzymes are central to ecosystem processes because they mediate numerous reactions that are essential in biogeochemical cycles. However, how soil enzyme activities will respond to global warming is uncertain. We reviewed the literature on mechanisms linking temperature effects on soil enzymes and microbial communities, and outlined a conceptual overview on how these changes may influence soil carbon fluxes in terrestrial ecosystems. At the enzyme scale, although temperature can have a positive effect on enzymatic catalytic power in the short term (i.e. via the instantaneous response of activity), this effect can be countered over time by enzyme inactivation and reduced substrate affinity. At the microbial scale, short‐term warming can increase enzymatic catalytic power via accelerated synthesis and microbial turnover, but shifts in microbial community composition and growth efficiency may mediate the effect of warming in the long term. Although increasing enzyme activities may accelerate labile carbon decomposition over months to years, our literature review highlights that this initial stage can be followed by the following phases: (a) a reduction in soil carbon loss, due to changing carbon use efficiency among communities or substrate depletion, which together can decrease microbial biomass and enzyme activity and (b) an acceleration of soil carbon loss, due to shifts in microbial community structure and greater allocation to oxidative enzymes for recalcitrant carbon degradation. Studies that bridge scales in time and space are required to assess whether there will be an attenuation or acceleration of soil carbon loss through changes in enzyme activities in the very long term. We conclude that soil enzymes determine the sensitivity of soil carbon to warming, but that the microbial community and enzymatic traits that mediate this effect change over time. Improving representation of enzymes in soil carbon models requires long‐term studies that characterize the response of wide‐ranging hydrolytic and oxidative enzymatic traits—catalytic power, kinetics, inactivation—and the microbial community responses that govern enzyme synthesis. Read the free Plain Language Summary for this article on the Journal blog.

Abstract In order to improve the properties of plasticized wheat starch (PWS) and to conserve its final biodegradability, PWS can be blended with biodegradable polyesters [polyesteramide, poly(ε‐caprolactone), poly(lactic acid), poly(butylene succinate adipate) and poly(butylene adipate terephthalate)] which exhibit variable polar characteristics. This paper is focused on the analysis of the compatibility of these blends which vary according to their formulation. To understand the lack of affinity between the different phases, interface adhesion has been investigated by contact angle measurements to obtain the work of adhesion. From these determinations a forecast approach has been developed to predict blend compatibility. Blend structures were obtained by scanning electron microscopy observations. Blends show either a dispersed structure or a co‐continuous morphology. Percolation thresholds (co‐continuity) and full continuity regions were determined thanks to a method based on solvent extraction. Finally, rheological investigations have been carried out on the different biodegradable polymers to understand better the blend structure formation during the process. Copyright © 2004 Society of Chemical Industry

Multilayer films based on plasticized wheat starch (PWS) and various biodegradable aliphatic polyesters have been prepared through flat film coextrusion and compression molding. Poly(lactic acid) (PLA), polyesteramide (PEA), poly(μ-caprolactone) (PCL), poly(butylene succinate adipate) (PBSA), and poly(hydroxybutyrate-co-valerate) (PHBV) were chosen as the outer layers of the stratified "polyester/PWS/polyester" film structure. The main goal of the polyester layers was to improve significantly the properties of PWS in terms of mechanical performance and moisture resistance. Since no specific compatibilizer or tie layer were added, the properties of subsequent films rely on the compatibility between the respective materials only. The effects of glycerol content in PWS, polyester type, and film composition on the mechanical properties and adhesion strength of multilayers were investigated. The conditions for optimal product performance were examined. The multilayer films may be suitable for applications in food packaging or disposable articles.

Abstract In this article, we describe an efficient physical electric‐field‐assisted method to study self‐assembly and orientation of cellulose nanocrystals. When applying an alternating voltage to a cellulose nanocrystals suspension deposited onto a thin gap of coplanar lithographically patterned metallic electrodes, a highly homogeneous orientation of cellulose nanocrystals is obtained. Parameters such as strength and frequency of the applied electric field and cellulose nanocrystals aspect ratios were studied to determine how they affect cellulose nanocrystals assembly and orientation. The prepared films were analyzed by atomic force microscopy, and the results suggest that the alignment of cellulose nanocrystals generated films is greatly influenced by the frequency and the strength of the applied electric field. The orientation of cellulose nanocrystals becomes more homogeneous with increasing electric field higher than 2000 V/cm with a frequency ranging between 10 4 and 10 6 Hz. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1430–1436, 2008

Novel nanocomposite coatings composed of cellulose nanocrystals (CNCs) and lignin (either synthetic or fractionated from spruce and corn stalks) were prepared without chemical modification or functionalization (via covalent attachment) of one of the two biopolymers. The spectroscopic properties of these coatings were investigated by UV-visible spectrophotometry and spectroscopic ellipsometry. When using the appropriate weight ratio of CNC/lignin (R), these nanocomposite systems exhibited high-performance optical properties, high transmittance in the visible spectrum, and high blocking in the UV spectrum. Atomic force microscopy analysis demonstrated that these coatings were smooth and homogeneous, with visible dispersed lignin nodules in a cellulosic matrix. It was also demonstrated that the introduction of nanoparticles into the medium increases the weight ratio and the CNC-specific surface area, which allows better dispersion of the lignin molecules throughout the solid film. Consequently, the larger molecular expansion of these aromatic polymers on the surface of the cellulosic nanoparticles dislocates the π-π aromatic aggregates, which increases the extinction coefficient and decreases the transmittance in the UV region. These nanocomposite coatings were optically transparent at visible wavelengths.

Abstract Agriculture is the main source of terrestrial N 2 O emissions, a potent greenhouse gas and the main cause of ozone depletion. The reduction of N 2 O into N 2 by microorganisms carrying the nitrous oxide reductase gene ( nosZ ) is the only known biological process eliminating this greenhouse gas. Recent studies showed that a previously unknown clade of N 2 O‐reducers ( nos Z II ) was related to the potential capacity of the soil to act as a N 2 O sink. However, little is known about how this group responds to different agricultural practices. Here, we investigated how N 2 O‐producers and N 2 O‐reducers were affected by agricultural practices across a range of cropping systems in order to evaluate the consequences for N 2 O emissions. The abundance of both ammonia‐oxidizers and denitrifiers was quantified by real‐time qPCR , and the diversity of nosZ clades was determined by 454 pyrosequencing. Denitrification and nitrification potential activities as well as in situ N 2 O emissions were also assessed. Overall, greatest differences in microbial activity, diversity, and abundance were observed between sites rather than between agricultural practices at each site. To better understand the contribution of abiotic and biotic factors to the in situ N 2 O emissions, we subdivided more than 59,000 field measurements into fractions from low to high rates. We found that the low N 2 O emission rates were mainly explained by variation in soil properties (up to 59%), while the high rates were explained by variation in abundance and diversity of microbial communities (up to 68%). Notably, the diversity of the nos Z II clade but not of the nos Z I clade was important to explain the variation of in situ N 2 O emissions. Altogether, these results lay the foundation for a better understanding of the response of N 2 O‐reducing bacteria to agricultural practices and how it may ultimately affect N 2 O emissions.

In previous works, we had shown that blending plasticised wheat starch (PWS) with biodegradable polyesters improves properties such as the water resistance. The present study was more specifically based on PWS/cellulose fibres composites. In addition, these multiphase systems (blends and composites) have been tested with respect to thermoforming applications. The composites shown an increase in modulus and strength, improved temperature stability and glass transition shifts. After sheet extrusion, each type of materials (blends and composites) was thermoformed. The ageing of the resulting thermoformed trays was tested in storage conditions from 4°C to ambient temperature, composites based-materials show reduced ageing compared to PWS.

Plant fibers are one of the most important renewable resources, used as raw material in the paper industry, and for various textiles and for composites. Fibers are structural components in timber and an energy-rich component of fuel-wood. For the plant itself, fibers are important in establishing plant architecture, as a source of mechanical support, in defence from herbivory, and in some cases as elements with contractile properties, resembling those of muscles. In addition, fibers may store ergastic carbon resources and water. Here, we review various aspects of fiber development such as initiation, elongation, cell wall formation and multinuclearity, discuss open questions and propose directions for further research. Most of the recent progress in fiber formation biology, especially in cell wall structure and chemistry, emerged from studies of only a few model plants including flax, Populus spp., Eucalyptus spp., Arabidopsis thaliana and hemp. Considering the enormous importance of fibers to humanity, it is surprising how little is known about the biology of fiber formation.

Microscopic and chemical changes of hemp bast fibers were studied during the maturation from vegetative to grain maturity stages at both apical and basal regions of the stems. The content of protein was the main factor related to fiber maturation, whereas increased proportions of mannose and glucose and decreasing levels of galactose were also highly significant. Enhanced glucose deposition in apical fibers could be related to the gradual thickening of the fibers, whereas in basal regions the thickness of the fibers nearly reached the maximum at vegetative stages. In contrast, the extent of lignification remained close to 3-4% during plant growth. Hemp fiber lignins were rich in guaiacyl units and would be rather condensed in nature. In addition, the proportion of p-hydroxyphenyl units displayed a constant decline during maturation. A progressive chemical fractionation of hemp fibers provided further insights to the occurrence and nature of noncellulosic polysaccharides. Notably, these data pointed out that maturation is accompanied by a significant increase in water- and alkali-soluble components containing glucose- and mannose-related polymers and a decrease in arabinose and galactose components disrupted by diluted hydrochloric acid. Taken together, chemical features of the noncellulosic components suggest that the architecture of hemp fibers differs slightly from that of the more widely studied flax fibers.

Hardwood trees are able to reorient their axes owing to tension wood differentiation. Tension wood is characterised by important ultrastructural modifications, such as the occurrence in a number of species, of an extra secondary wall layer, named gelatinous layer or G-layer, mainly constituted of cellulose microfibrils oriented nearly parallel to the fibre axis. This G-layer appears directly involved in the definition of tension wood mechanical properties. This review gathers the data available in the literature about lignification during tension wood formation. Potential roles for lignin in tension wood formation are inferred from biochemical, anatomical and mechanical studies, from the hypotheses proposed to describe tension wood function and from data coming from new research areas such as functional genomics.

This paper opens onto a general discussion on the development of new polymeric materials obtained from lignin blends. The aim is (i) to look for good polymer candidates to obtain a good compatibility with lignins (that is among semi polar polymers), and (ii) to look for good lignin candidates to obtain a good compatibility with polymers showing extreme behaviours (very polar, e.g. starch, or apolar, e.g. polypropylene). The compatibility is simply assessed through the blend morphology, as studied by visible microscopy. The morphology of the blends obtained from semi polar polymers is very sensitive to the variation of the solubility parameters. In a low range of polymer solubility parameters (delta delta = 1 cal cm(-3)), both heterogeneous and homogeneous systems are obtained. These blends could be easily improved by a careful choice in the polymer structure (particularly in the family of biodegradable polyesters); it could be possible also to take advantage of lignin variability to improve the compatibility. Only low molecular weight lignins are compatible with apolar and very polar matrixes. These compounds induce interesting specific properties, and original methods have to be looked for in order to improve their production.

BACKGROUND: Besides classical utilization of wood and paper, lignocellulosic biomass has become increasingly important with regard to biorefinery, biofuel production and novel biomaterials. For these new applications the macromolecular assembly of cell walls is of utmost importance and therefore further insights into the arrangement of the molecules on the nanolevel have to be gained. Cell wall recalcitrance against enzymatic degradation is one of the key issues, since an efficient degradation of lignocellulosic plant material is probably the most crucial step in plant conversion to energy. A limiting factor for in-depth analysis is that high resolution characterization techniques provide structural but hardly chemical information (e.g. Transmission Electron Microscopy (TEM), Atomic Force Microscopy (AFM)), while chemical characterization leads to a disassembly of the cell wall components or does not reach the required nanoscale resolution (Fourier Tranform Infrared Spectroscopy (FT-IR), Raman Spectroscopy). RESULTS: Here we use for the first time Scanning Near-Field Optical Microscopy (SNOM in reflection mode) on secondary plant cell walls and reveal a segmented circumferential nanostructure. This pattern in the 100 nm range was found in the secondary cell walls of a softwood (spruce), a hardwood (beech) and a grass (bamboo) and is thus concluded to be consistent among various plant species. As the nanostructural pattern is not visible in classical AFM height and phase images it is proven that the contrast is not due to changes in surfaces topography, but due to differences in the molecular structure. CONCLUSIONS: Comparative analysis of model substances of casted cellulose nanocrystals and spin coated lignin indicate, that the SNOM signal is clearly influenced by changes in lignin distribution or composition. Therefore and based on the known interaction of lignin and visible light (e.g. fluorescence and resonance effects), we assume the elucidated nanoscale structure to reflect variations in lignification within the secondary cell wall.

Abstract Simulation models are extensively used to predict agricultural productivity and greenhouse gas emissions. However, the uncertainties of (reduced) model ensemble simulations have not been assessed systematically for variables affecting food security and climate change mitigation, within multi‐species agricultural contexts. We report an international model comparison and benchmarking exercise, showing the potential of multi‐model ensembles to predict productivity and nitrous oxide (N 2 O) emissions for wheat, maize, rice and temperate grasslands. Using a multi‐stage modelling protocol, from blind simulations (stage 1) to partial (stages 2–4) and full calibration (stage 5), 24 process‐based biogeochemical models were assessed individually or as an ensemble against long‐term experimental data from four temperate grassland and five arable crop rotation sites spanning four continents. Comparisons were performed by reference to the experimental uncertainties of observed yields and N 2 O emissions. Results showed that across sites and crop/grassland types, 23%–40% of the uncalibrated individual models were within two standard deviations ( SD ) of observed yields, while 42 (rice) to 96% (grasslands) of the models were within 1 SD of observed N 2 O emissions. At stage 1, ensembles formed by the three lowest prediction model errors predicted both yields and N 2 O emissions within experimental uncertainties for 44% and 33% of the crop and grassland growth cycles, respectively. Partial model calibration (stages 2–4) markedly reduced prediction errors of the full model ensemble E‐median for crop grain yields (from 36% at stage 1 down to 4% on average) and grassland productivity (from 44% to 27%) and to a lesser and more variable extent for N 2 O emissions. Yield‐scaled N 2 O emissions (N 2 O emissions divided by crop yields) were ranked accurately by three‐model ensembles across crop species and field sites. The potential of using process‐based model ensembles to predict jointly productivity and N 2 O emissions at field scale is discussed.

Abstract A renewable bisepoxide, SYR‐EPO, was prepared from syringaresinol, a naturally occurring bisphenol deriving from sinapic acid, by using a chemo‐enzymatic synthetic pathway. Estrogenic activity tests revealed no endocrine disruption for syringaresinol. Its glycidylation afforded SYR‐EPO with excellent yield and purity. This biobased, safe epoxy precursor was then cured with conventional and renewable diamines for the preparation of epoxy‐amine resins. The resulting thermosets were thermally and mechanically characterized. Thermal analyses of these new resins showed excellent thermal stabilities ( T d5 % =279–309 °C) and T g ranging from 73 to 126 °C, almost reaching the properties of those obtained with the diglycidylether of bisphenol A (DGEBA), extensively used in the polymer industry ( T d5 % =319 °C and T g =150 °C for DGEBA/isophorone diamine resins). Degradation studies in NaOH and HCl aqueous solutions also highlighted the robustness of the syringaresinol‐based resins, similar to bisphenol A (BPA). All these results undoubtedly confirmed the potential of syringaresinol as a greener and safer substitute for BPA.