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The use of biochar is an interesting alternative to control release of P in soil and efficient use by plants. In this study, a new-coated slow-release P was developed by coating triple superphosphate (TSP) using different biochars (BC) and carboxymethyl cellulose (CMC). This study employs an integrated lignocellulosic biorefinery methodology and circular bioeconomy concept, utilizing a cellulose derivative and biochar produced from macroalgal residues (BCA) and olive pomace (BCO). The study explores the impact of integrating these biochars into CMC matrix as coating materials. The findings demonstrated that the origin of biochar had an effect on the surface and mechanical attributes of the composites. Introducing biochar modified the mechanical proprieties, alongside an increase in the contact angle. However, the attrition of coated TSP seems to be high with high biochar content. An increase in water absorption was also observed with formulations containing more biochar. The release tests showed that the P release decreased up to 67 %, 78 % and 82 % within 30 days with CMC coatings in presence of BCO, BCV and BCA, respectively compared to 100 % with uncoated TSP fertilizer. However, no significant difference on P release was observed when varying the biochar content from 10 to 30 %., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025. Published by Elsevier B.V.)

Microbial bioremediation has emerged promisingly to improve crop tolerance to cadmium (Cd). Moreover, Cd tolerance and phosphate acquisition in plants positively correlated under P solubilizing bacteria inoculation, yet there is no evidence on specific mechanisms influencing Cd tolerance and plant P acquisition. The present study evaluates Cd tolerance in rock P-amended durum wheat in response to inoculation with P solubilizing bacteria (PSB) [three individual isolates Bacillus siamensis, Rahnella aceris, Bacillus cereus and their consortium (PSB Cs )] and consequently reveals key rhizosphere mechanisms involved in both Cd tolerance and P use efficiency. Results show that inoculation overall improved plant growth, rhizosphere parameters and nutrient uptake (P, N, K) under increasing Cd concentrations [8 (Cd 8 ) and 16 (Cd 16 ) ppm Cd 2+ ]. Under Cd 16 , Rahnella aceris induced the most significant plant responses in terms of biomass [shoots (31 %), roots (40 %), and spikes (92 %)], rhizosphere available P (234 %) and root inorganic P (109 %) compared to uninoculated plant. Microbial biomass P (MBP) and root acid phosphatases (APase) were 33-and 13-times higher, respectively, than in uninoculated plants. In addition, inoculation (particularly using PSB Cs ) significantly decreased Cd translocation factor (TF) (Cd 8 : -17 % and Cd 16 : -22 %) and Cd bioaccumulation factor (BAF) (Cd 8 : -6 % and Cd 16 : -40 %) concomitantly to enhanced root morphological traits and P contents in shoots and spikes. Furthermore, PSB inoculation under Cd constraint increased (rhizosphere available P / MBP) and (Root APase / Rhizosphere Apase) ratios that significantly (p < 0.05) correlate with plant P uptake in shoots and spikes. Increase in both ratios was concomitant to a significant decrease in TF and BAF of Cd exemplified by negatively significant correlations (r 2 =0.70 and r 2 =0.57, p < 0.05). This finding elucidates the key role of bacterial inoculation that presumably triggered Cd tolerance and aboveground P owing to increased (rhizosphere available P / MBP) and (Root / Rhizosphere APase) ratios in PSB-inoculated wheat., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Recently, Cellulose microfibers (CMF) have garnered significant attention due to their renewability, biodegradability, and unique properties such as high aspect ratio, low density, high strength, stiffness, and distinctive optical properties. These characteristics have been highlighted in publications worldwide. However, the structure of CMF is difficult to access with solvents, limiting its dissolution in common organic solvents. The synthesis of CMF-siloxane or CMF-silane hybrid materials from cellulose generally involves several reactions steps, and therefore catalysts. The allylation of CMF is catalyzed by the phase-transfer catalyst tetrabutylammonium bromide (TBAB), which enables the combination of CMF with allyl. This is followed by a hydrosilylation reaction catalyzed by Karstedt's catalyst, based on platinum (0), to combine the hydrophilic allylated CMF with hydride-terminated hydrophobic hydrosilane or hydrosiloxane. Environmentally friendly particleboards were developed using bio-based adhesives composed of corn-starch and Mimosa tannin (CSMT) mixtures. These mixtures included 4, 6, 8, and 10 wt% of CMF, allylated CMF and silylated CMF. The mechanical and physical properties of particleboards, such as modulus of elasticity (MOE), modulus of rupture (MOR), internal bond strength (IB), surface soundness (SS), water absorption (WA) and thickness swelling (TS) were determined., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The present work involves investigating an unexplored soft-chemical method for synthesizing nanostructured ZnO through biopolymer gelation. Our objective was to exploit (i) the difference in the gelation mechanism of four tested biopolymers, namely, alginate, chitosan, carboxymethylcellulose (CMC), and pectin and (ii) numerous experimental parameters that govern this process in order to allow the control of the growth of nanostructured ZnO, with a view to using the prepared oxides as photocatalysts for the oxidation of the Orange G dye. So, the effect of biopolymer's nature on the microstructural, morphological, and textural properties was examined by thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field-emission gun-scanning electron microscopy-high resolution (FEG-SEM) with energy-dispersive spectrometry (SEM-EDS), ultraviolet-visible (UV-vis) spectroscopy, and N 2 adsorption/desorption. As-prepared oxides were crystallized in a hexagonal wurtzite structure, with a clear difference in their morphologies. The sample prepared by using chitosan has a specific surface area of around 36.8 m 2 /g in the form of aggregated and agglomerated nanostructured minirods and thus shows the best photocatalytic performance with 99.3% degradation of the Orange G dye in 180 min., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Africa benefits from diverse biomasses that are rich in high-added value materials and precursors for energy, food, agricultural, cosmetic and medicinal applications. Many African countries are interested in valorizing biomasses to develop efficient and integrated biorefinery processes and their use for local and regional economic development. Thus, this report critically reviews the current status of African biomass richness, its diversity, and potential applications. Moreover, particular attention is given to bioenergy production, mainly by biological and thermochemical conversion processes. This also includes biomass valorization in agriculture, particularly for the production of plant-based biostimulants, which are a potential emerging agri-input sector worldwide. This study points out that even though several processes for biofuel, biogas, biofertilizer and biostimulant production have already been established in Africa, their development on a larger scale remains limited. This study also reports the different socioeconomic and political aspects of biomass applications, along with their challenges, opportunities, and future research perspectives, to promote concrete technologies transferable into an industrial level., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Until now, the solubilization capacities of insoluble mineral P by soil microorganisms have been screened in vitro with media containing NH4+ as a nitrogen source. This presence of NH4+ will lead to an acidification of the medium responsible for the solubilization of the insoluble P. However, besides proton release, the production of organic acids can play a very important role in the release of free P. This physiological mechanism can largely depend on the source of nitrogen (NH4+vs NO3-) assimilated by the bacteria but the influence of the N source on the production of organic acids has yet to be studied. Our aim was to investigate if the N source assimilated by bacteria and the soil characteristics such as the dominant N source (NH4+vs NO3-) and CaCO3 contents might influence the bacterial capacities to solubilize rock phosphate. To fill this objective, we screened the capacity of bacteria isolated from 3 soils to solubilize rock phosphate in vitro in presence of NH4+or NO3-. Then, we selected the most efficient bacterial strains to identify and quantify the release of organic anions into the medium. Among the two hundred and forty-three bacterial strains isolated from the 3 soils, nine and seven isolates were identified with the highest % rock phosphate-solubilization values with NH4+ or NO3- as the sole N-source. Only one strain was able to release free Pi with NH4+ or NO3- as the sole N-source. The most predominant organic acids released by almost all isolates were gluconic acid, lactic acid, glycolic acid, acetic acid, formic acid and pyruvic acid regardless the N-source. However, with NO3- as source of N, the highest concentrations on those acids were found together with the highest release of free Pi into the medium. Molecular analysis of 16S rRNA indicated that almost all strains belonged to Bacillus and Paenibacillus genera. The PCA analysis between soil properties and bacterial capacities to release organic acids and free Pi also revealed that soil factors such as CaCO3 and soil NO3- content positively influenced the release of organic acids by bacteria grown in vitro. Our results concluded that the bacterial rock phosphate-solubilization was intimately related to organic acids production which in turn seemed to be driven by the assimilation of NO3- by bacteria. Therefore, the N-source might be considered a key factor to take into consideration during the screening and selection of suitable strains involved in the P-solubilization., Competing Interests: The authors have declared that no competing interest exist., (Copyright: © 2023 Garcia-Sanchez et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Aims: Although phosphate solubilizing bacteria (PSB) have been globally reported to improve soil phosphorus (P) availability and plant growth, technical gaps such as the lack of an ideal screening approach, is yet to be addressed. The potential of non-halo-forming PSB remains underestimated because of the currently adopted screening protocols that exclusively consider halo-forming and PSB with high phosphorus solubilization (PS) capacities. Yet, caution should be taken to properly assess PSB with contrasting PS rates regardless of the presence or absence of the solubilization halo., Methods and Results: This study sought to examine the PS rate and plant growth promotion ability of 12 PSB categorized as high PSB (H-PSB), medium PSB (M-PSB), and low PSB (L-PSB) based on their PS rates of rock phosphate (RP). The non-halo-forming PSB Arthrobacter pascens was categorized as H-PSB, which might have been eliminated during the classical screening process. In addition, induction of organic acids and phosphatase activity in rhizosphere soils by H-, M-, and L-PSB was proportional to increased wheat P content by 143.22, 154.21, and 77.76 mg P g-1 compared to uninoculated plants (18.1 mg P g-1)., Conclusions: Isolates considered as M- and L-PSB could positively influence wheat above-ground physiology and root traits as high as H-PSB. In addition, non-halo-forming PSB revealed significant PS rates along with positive effects on plant growth as high as halo-forming PSB., (© The Author(s) 2022. Published by Oxford University Press on behalf of Applied Microbiology International.)

The current research work attempted to investigate, for the first time, the impact of biochar addition, on anaerobic digestion of olive mill wastewater with different initial chemical oxygen demand loads in batch cultures (10 g/L, 15 g/L, and 20 g/L). Methane yields were compared by applying one-way analysis of variance (ANOVA) followed by post-hoc Tukey's analysis. The results demonstrated that adding at 5 g/L biochar to olive mill wastewater with an initial chemical oxygen demand load of 20 g/L increased methane yield by 97.8% and mitigated volatile fatty acid accumulation compared to the control batch. According to the results of microbial community succession revealed by the Illumina amplicon sequencing, biochar supplementation significantly increased diversity of the microbial community and improved the abundance of potential genera involved in direct interspecies electron transfer, including Methanothrix and Methanosarcina . Consequently, biochar can be a promising alternative in terms of the recovery of metabolic activity during anaerobic digestion of olive mill wastewater at a large scale., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Abid, Karray, Kallel, Slim, Barakat, Mhiri, Chamkha and Sayadi.)

Rhizosphere microbes significantly enhance phosphorus (P) availability from a variety of unavailable P pools in agricultural soils. However, little is known about the contribution of root-associated microorganisms, notably P solubilizing bacteria (PSB), to enhance the use of polyphosphate (PolyP) fertilizers as well as the key mechanisms involved. This study assesses the ability of four PSB (Bacillus siamensis, Rahnella aceris, Pantoea hericii, Bacillus paramycoides) and their consortium (Cs) to enhance the release rate of available P from two types of PolyP ("PolyB" and "PolyC") with a focus on the key role of phosphatase enzyme activities and organic acids production. Wheat growth performance and P acquisition efficiency were evaluated in response to co-application of PSB and PolyP. Results showed that inoculation with PSB, notably Cs, significantly enhanced available P from PolyC, PolyB and tri-calcium P. Increased available P in response to inoculation with PSB significantly correlated with medium acidification, organic acids production (notably glycolic acid) and induced activities of acid phosphatase and pyrophosphatase. In planta, the co-application of PSB-PolyP improved wheat plant biomass, root growth and P acquisition, with best results obtained from Cs-PolyP co-application as compared to uninoculated and unfertilized plants. At seedling stage, the co-application of Cs-PolyP (PolyB and PolyC) enhanced root hairs length (125 % and 131 %), root length (26 % and 37 %) and root inorganic P (Pi) content (160 % and 182 %), respectively compared to uninoculated plants. Similarly, at tillering stage, plant biomass (35 % and 47 %), Pi content (43 % and 253 %), P translocation (215 % and 315 %) and soil phosphatases (213 % and 219 %) significantly improved under PolyB and PolyC application, respectively. Findings from this study demonstrate the key role of PSB to enhance the use of PolyP through production of organic acids and phosphatases, exhibiting differential traits patterns between the two PolyP. Improved wheat growth and root P acquisition in response to PSB-PolyP co-application can be attributed to induced rhizosphere processes leading to enhanced available P taken up by roots., (Copyright © 2022 Elsevier GmbH. All rights reserved.)

An innovative hybrid organic-inorganic material composed of alginate-brushite xerogel beads was successfully applied for the catalysis of the Knoevenagel condensation. The catalyst was derived from phosphated alginate xerogel microspheres formed from the ionotropic gelling effect of phosphated alginate. To this end, alginate was phosphated by the addition of diammonium hydrogen phosphate in a 1% w/w alginate gel. The phosphated alginate was subsequently precipitated by chelation of Ca 2+ cations, generating a phosphated alginate hydrogel microsphere, which was washed and dried, forming hybrid organic-inorganic xerogel beads as a crystalline phosphate-rich mineral fraction covered by alginate. X-ray diffraction analysis revealed that the crystalline inorganic matrix of the material was composed predominantly of brushite. SEM analysis revealed plate-like, ribbon-like, or needle-like morphologies in the hybrid alginate-brushite beads. The hybrid material was tested as a catalyst for Knoevenagel condensation, which was performed ″on-water″ under mild conditions with aromatic aldehydes and activated methylene compounds, giving high yields (up to 97%). The reaction rate and product yield increased together with the reaction temperature for all reagents. The recyclable solid catalyst was effective for three runs, revealing the potential of the innovative hybrid catalyst as an eco-friendly heterogeneous catalyst., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Well-organized zirconia (ZrO 2 ) nanoparticles forming mesoporous materials have been successfully synthesized via a facile micelle-templating method using cetyltrimethylammonium bromide as a structure-directing template to control the nucleation/growth process and porosity. The systematic use of such a surfactant in combination with a microwave-assisted solvothermal (cyclohexane/water) reaction enabled the control of pore size in a narrow-size distribution range (3-17 nm). The effect of solvent mixture ratio on the porosity of the synthesized oxide was determined, and the controlled growth of zirconia nanoparticles was confirmed by means of powder X-ray diffraction, small-angle X-ray scattering, transmission electron microscopy, selected area electron diffraction, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, and Fourier transform infrared spectroscopy as well as N 2 physisorption isotherm analysis. Then, the as-prepared nanostructured zirconia oxides were treated with sulfuric acid to have sulfated samples. The catalytic performances of these mesoporous zirconia nanoparticles and their sulfated samples were tested for levulinic acid (LA) esterification by ethanol, with quantitative conversions of LA to ethyl levulinate after 8 h of reaction., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The sustainability of the anaerobic digestion industry is closely related to proper digestate disposal. In this study, an innovative cascading biorefinery concept coupling anaerobic digestion and subsequent pyrolysis of the digestate was investigated with the aim of enhancing the energy recovery and improving the fertilizers from organic wastes. Continuous anaerobic co-digestion of quinoa residues with wastewater sludge (45/55% VS) exhibited good stability and a methane production of 219 NL CH 4 /kg VS. Subsequent pyrolysis of the solid digestate was carried out (at 500 °C, 1 h, and 10 °C/min), resulting in a products distribution of 40 wt% biochar, 36 wt% bio-oil, and 24 wt% syngas. The organic phase (OP) of bio-oil and syngas exhibited higher and lower heating values of 34 MJ/kg and 11.8 MJ/Nm 3 , respectively. The potential synergy of coupling biochar with liquid digestate (LD) for agronomic purposes was investigated. Interestingly, coupling LD (at 170 kg N/ha) with biochar (at 25 tons/ha) improved the growth of tomato plants up to 25% compared to LD application alone. In parallel, co-application of biochar with LD significantly increased the ammonia volatilization (by 64%) compared to LD application alone, although their simultaneous use did not impact the C and N mineralization rates., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Background: Increasing crop production to feed a growing population has driven the use of mineral fertilizers to ensure nutrients availability and fertility of agricultural soils. After nitrogen, phosphorus (P) is the second most important nutrient for plant growth and productivity. However, P availability in most agricultural soils is often limited because P strongly binds to soil particles and divalent cations forming insoluble P-complexes. Therefore, there is a constant need to sustainably improve soil P availability. This may include, among other strategies, the application of microbial resources specialized in P cycling, such as phosphate solubilizing bacteria (PSB). This P-mediating bacterial component can improve soil biological fertility and crop production, and should be integrated in well-established formulations to enhance availability and efficiency in use of P. This is of importance to P fertilization, including both organic and mineral P such as rock phosphate (RP) aiming to improve its agronomic efficiency within an integrated crop nutrition system where agronomic profitability of P and PSB can synergistically occur., Aim of Review: The purpose of this review is to discuss critically the important contribution of PSB to crop P nutrition in concert with P fertilizers, with a specific focus on RP. We also highlight the need for PSB bioformulations being a sustainable approach to enhance P fertilizer use efficiency and crop production., Key Scientific Concepts of Review: We first recognize the important contribution of PSB to sustain crop production, which requires a rational approach for both screening and evaluation of PSB enabling an accurate assessment of the bacterial effects both alone and in intertwined interaction with plant roots. Furthermore, we propose new research ideas about the development of microbial bioformulations based on PSB with a particular focus on strains exhibiting synergetic effects with RP., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2022 The Authors. Published by Elsevier B.V. on behalf of Cairo University.)

Microalgae are considered potential candidates in biorefinery processes, and due to their biochemical properties, they can be used in the production of biofuels such as biogas, as well as for bioremediation of liquid effluents. The objective of this review is to study the current status of microalgae anaerobic digestion and agricultural uses (as bio-stimulants and biofertilizers), starting from microalgae cultivation. Indeed, the efficiency of these processes necessarily depends on the evaluation of different biotic and abiotic factors that affect the growth of microalgae. However, the adaptation and the optimization of process parameters on a large scale is also limited by energy and economic constraints. Moreover, the integration of biogas production processes with microalgae cultivation allows a nutrients and CO 2 virtuous loop, thus promoting the sustainability of the process. Finally, this paper provides a general overview of biogas and biofertilizers production combination, as well as the related challenges and recommended future research perspectives to complement the gap in the literature., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Apretreatment step forlignocelluloses is responsible to alter the complex structure which allows enhancingenzymatic accessibility and bioconversion of the materials.However, there is a gap on the methods to characterize physicalevolutions of the material throughout its pretreatment.The aim of this study is to evaluate the physical changes in rice straw (RS)pretreated with alkaline followed by grinding to produce biopowders.A hydro-textural approach was applied to evaluate the physical changes of RS pretreated byimpregnation and soaking in NaOH.The results indicated that the volume deformation increased by 110%, whilethe energy consumptiondecreased by 11.3% compared to unpretreated RS.Moreover, the cellulose content and glucose were 66.8 and 212 mg/gRS obtained by RSsoaking. Thealkaline-mechanicalpretreatment was shown asan effective process to providehigh glucosereadily converted to bioethanol.Additionally, the hydro-textural approach can be considered an alternative method for biomass structural characterization., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The growth of the human population is causing an exponential increase in the need for food. Fertilizers are one of the most important elements to meet this increased demand and to ensure global food security. Many enhanced efficiency fertilizers, such as controlled-release fertilizers (CRFs) have been developed. Although these fertilizers offer many advantages over prior generations, their high cost of production as well as unfavorable effects on the environment and soil quality have limited their use. To mitigate these issues, CRFs based on biopolymers (CRF@BB) represent a new generation of fertilizers produced by coating the granules with biopolymers. In addition to controlling the nutrient release rate, these products also enhance the soil quality and they reduce the negative effects associated with conventional fertilizers. This review summarizes the recent advances in biopolymers and derived biopolymers used in the area of CRF@BB, the coating technologies, and the parameters governing the release behavior through organic coating materials, as well as the effect of coated CRFs on the soil and plants growth., (Copyright © 2020. Published by Elsevier B.V.)

After press separation of the liquid and solid digestate from an agricultural biogas plant, pyrolysis of solid anaerobic digestate was carried out (i.e., at 500 °C, 1h, and 10 °C/min) to produce biochar (37.6 wt%), bio-oil (33.7 wt%) and syngas (29.3 wt%). The organic phase of bio-oil and syngas exhibited high and low heating values of 28.4 MJ/kg and 12.9 MJ/Nm 3 , respectively. Then, the synergy of coupling biochar with liquid digestate for agronomic purposes was investigated by leaching experiment and growth plant tests on wheat. Leaching experiments using combination of liquid digestate (170 kg N/ha) and biochar demonstrated that biochar addition increases the cumulative leaching of all nutrients, except nitrate, that have a significant decrease of 82% and 91%, respectively at 50 and 100 t/ha, compared to soil treated only with liquid digestate. The co-application of biochar with liquid digestate on growth wheat plant tests demonstrated that biochar application at 50 t/ha did not exhibit a negative impact on the relative seed germination and improved aerial dry biomass production (up to 27.5%) compared to soil with only liquid digestate addition., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

This study aimed to produce activated biochars (BCs) from Moroccan algae residue (AG) and olive pomace (OP) using mechanochemical activation with NaOH and ball milling (BM) for treating artificial textile wastewater containing methylene blue (MeB). The produced OP-activated BC by BM showed the highest absolute value of ζ-potential (-59.7 mV) and high removal efficiency of MeB compared to other activated BCs. The nonlinear pseudo-first-order kinetic model was the most suitable model to describe the kinetics of adsorption of MeB onto biochars produced from AG and the NaOH-activated BC from OP, whereas the nonlinear pseudo-second-order kinetic model suits the OP raw biochar and BM-activated BC. The nonlinear Langmuir isotherm model was the most suitable model for describing MeB adsorption onto BCs, compared to the nonlinear Freundlich isotherm model. The maximum adsorption capacities of AG-activated BCs with NaOH and BM were 13.1 and 9.1 mg/g, respectively, while those of OP-activated BCs were 2.6 and 31.8 mg/g, respectively. The thermodynamic study indicates the spontaneous and endothermic nature of the adsorption process of most activated BCs. In addition, Δ S ° values indicate the increase of randomness at the solid-liquid interface during MeB sorption onto BC., Competing Interests: The authors declare no competing financial interest., (© 2020 The Authors. Published by American Chemical Society.)

This study aims at investigating how organic waste co-digestion coupled with alkaline pretreatment can impact the methane production and agronomic value of produced digestates. For this purpose, sludge alone and mixed with olive pomace or macroalgal residues were subjected to anaerobic digestion with and without alkaline pretreatment. In addition, co-digestion of pretreated sludge with raw substrates was also carried out and compared to the whole mixture pretreatment. KOH pretreatment enhanced methane production by 39%, 15% and 49% from sludge, sludge mixed with olive pomace and sludge mixed with macroalgal residues, respectively. The digestates were characterised according to their physico-chemical and agronomic properties. They were then applied as biofertilizers for tomato growth during the first vegetative stage (28 days of culture). Concentrations in chlorophyll a and carotenoids in tomato plants, following sludge digestate addition, rose by 46% and 41% respectively. Sludge digestate enhanced tomato plant dry weight by 87%, while its nitrogen content increased by 90%. The impact of nitrogen and phosphorus contents in the digestate was strongest on tomato plant dry weight, thus explaining the efficiency of sludge digestate relative to other types of digestate. However, when methane production is considered, the combination of pre-treatment with co-digestion of macroalgal residues and sludge appears most beneficial for maximizing energy recovery and for biofertilizer generation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Nanocrystalline titania was synthesized by a simple, innovative and eco-friendly gelation method by using biopolymers (polysaccharides). The effect of the gelling agent, such as carboxymethylcellulose (CMC) or alginate (Alg), and the drying routes (conventional drying at room temperature, or freeze-drying) on the properties and photocatalytic performances of nanostructured TiO 2 was examined. The crystallographic structures, and textural and morphological characteristics were investigated by thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy with energy dispersive spectrometry (ESEM-FEG-EDS), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (DRS) and N 2 adsorption/desorption isotherms. The as-synthesized samples were fully crystallized and appeared to be highly phase-pure anatase or mixed titania polymorphs, and have a quasi-spherical shape with a particle size ranging from 10.34 to 18.07 nm. Phase-pure anatase was obtained by using alginate as the gelling agent, whereas CMC's gelation promotes mixed structures. The presence of rutile phase results in a lower bandgap value of 3.04 eV corresponding to 408 nm. Thus, the material absorption wavelength shifts slightly from the UV (190-380 nm) to visible region (380-750 nm). The drying process also affects TiO 2 properties. The lyophilization route improves the oxide's specific surface area, and also its photocatalytic properties verified during Orange G dye photodegradation study., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The aim of this paper is to investigate the impact of pretreating macroalgal residue (MAR) from agar-agar extraction and its co-digestion with sewage sludge on methane production and the agronomic quality of the digestates produced. First, different pretreatments were assessed on BMP tests. Among milling technologies used, knife milling with a 4 mm-screen improved methane production by 25%. The MAR was then knife milled before alkaline, acid and thermal pretreatment. KOH pretreatment (5% TS basis, 25 °C for 2 days) led to the highest methane improvement. It was applied to semi-continuous anaerobic digestion and methane production achieved 237 Nml/gVS which was 20% higher than the control (198 Nml/gVS). In comparison to MAR mono-digestion, co-digestion with thickened activated sludge produced less methane (184 Nml/gVS) but reduced H 2 S emission by 91%. None of the digestates was toxic for the germination or growth of wheat and tomato plants. Particularly, co-digestion had the highest impact on tomato plant dry weight (+94% compared to soil alone) mainly due to the phosphorous brought by sludge. However, the impact of alkaline pretreatment on plant growth was not significant., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

This study aims to investigate the effects of microwaves, ultrasonic and alkaline pretreatments on olive pomace properties and its biomethane potential. Alkaline pretreatment was found to reduce lipid and fiber contents (especially lignin) and to increase soluble matter. The alkali pretreatment at a dose of 8% (w/w TS) under 25 °C and for 1 day removed 96% of initial lipids from the solid olive pomace. Unlike NaOH addition, mild microwaves and ultrasonic pretreatments had no impact on lignin. However, in the case of long microwaves pretreatment (450 W-10 min), cellulose and lignin contents were reduced by 50% and 26% respectively. Similarly, the combination of ultrasonic and alkali reagent showed a positive effect on fiber degradation and lipid solubilization as well as a positive impact on methane production. Statistical analysis highlighted the correlation between NaOH dose, solubilization and methane production. The alkaline pretreatment at ambient temperature appeared the most energetically efficient., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The main objective of this work was to study the possibility of using polysaccharides and lignin as a coating material for water-soluble triple superphosphate (TSP) granular fertilizers. In this study, composites based on three polysaccharides (sodium alginate (alginic acid sodium salt): AL, kappa-carrageenan: CR and carboxymethyl cellulose sodium salt: CM) and lignin (LG) were prepared. The lignin used was extracted from olive pomace (OP) biomass using the alkali method. The morphological, mechanical, and surface properties as well as the thermal behavior of the coatings were characterized and compared. Their morphology and thickness revealed by scanning electron microscopy (SEM) showed good adhesion between the fertilizer and coating materials. The results showed that the lignin-carrageenan formulation (LGCR) exhibited the highest water absorbency and elastic modulus. Release tests showed the effect of the TSP/biopolymer mass ratio and that the slowest P release was obtained with the LGCR@TSP formulation composite within 3 day. In addition, 59.5% and 72.5% of P was released after 3 days with the TSP/biopolymer mass ratios of 5/1 and 15/1, respectively, compared to 100% P release with the uncoated TSP., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The conversion of poplar wood biomass to highly value-added chemicals and molecular building blocks was achieved by using the dispersed mixed oxide Zn 3 V 2 O 8 (ZVO) in water under 100 kPa of 10% O 2 /N 2 at 160, 180, and 200 °C for 4 h. This nanostructured mixed oxide was prepared via the precipitation process and then characterized by several techniques. The results showed that this mixed oxide has interesting catalytic properties and is a versatile catalyst for biomass delignification and lignin and hemicellulose depolymerization. ZVO exhibited high activity on poplar biomass delignification and fractionation (degree of delignification > 97%) and lignin and holocellulose conversion with high yield into aromatic and furan compounds (80 mg/g initial wood at 200 °C), with high selectivities for 5-hydroxymethylfurfural (HMF) (25 mg/g of initial wood), vanillin, and syringaldehyde., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

Additive manufacturing or 3D printing has the potential to displace some of the current manufacturing techniques and is particularly attractive if local renewable waste resources can be used. In this study, rice husk, and wood powders were compounded in polylactic acid (PLA) by twin screw extrusion to produce filaments for fused-deposition modeling 3D printing. The biomasses were characterized in terms of physical features (e.g., particle size, density) and chemical compositions (e.g., solid state nuclear magnetic resonance, ash content). The two biomasses were found to have a different impact on the rheological behavior of the compounds and the extrusion process overall stability. When comparing the complex viscosity of neat PLA to the biomass/PLA compounds, the integration of wood powder increased the complex viscosity of the compound, whereas the integration of rice husk powder decreased it. This significant difference in rheological behavior was attributed to the higher specific surface area (and chemical reactivity) of the rice husk particles and the presence of silica in rice husks compared to the wood powder. Color variations were also observed. Despite the biomass filler and rheological behavior differences, the mechanical properties of the 3D printed samples were similar and predominantly affected by the printing direction., (Copyright © 2019 Le Guen, Hill, Smith, Theobald, Gaugler, Barakat and Mayer-Laigle.)

Biogas plants for waste treatment valorization are presently experiencing rapid development, especially in the agricultural sector, where large amounts of digestate are being generated. In this study, we investigated the effect of vibro-ball milling (VBM) for 5 and 30 min at a frequency of 20 s -1 ) on the physicochemical composition and enzymatic hydrolysis (30 U g -1 total solids (TS) of cellulase and endo-1,4-xylanase from Trichoderma longibrachiatum ) of dry and wet solid digestates from an agricultural biogas plant. We found that VBM of dry solid digestate improved the physical parameters as both the particle size and the crystallinity index (from 27% to 75%) were reduced. By contrast, VBM of wet solid digestate had a minimal effect on the physicochemical parameters. The best results in terms of cellulose and hemicelluloses hydrolysis were noted for 30 min of VBM of dry solid digestate, with hydrolysis yields of 64% and 85% for hemicelluloses and cellulose, respectively. For the condition of 30 min of VBM, bioethanol and methane production on the dry solid separated digestate was investigated. Bioethanol fermentation by simultaneous saccharification and fermentation resulted in an ethanol yield of 98 g eth kg -1 TS (corresponding to 90% of the theoretical value) versus 19 g eth kg -1 TS for raw solid digestate. Finally, in terms of methane potential, VBM for 30 min lead to an increase of the methane potential of 31% compared to untreated solid digestate., Competing Interests: The authors declare no conflict of interest.

Solid-state fermentation is a potential technology for developing lignocellulosic biomass-based biorefineries. This work dealt with solid-state fermentation for carboxylates production from corn stover, as building blocks for a lignocellulosic feedstock-based biorefinery. The effect of extrusion pretreatment, together with the action of a microbial consortia and hydrolytic enzymes as biotic triggers, was investigated on corn stover conversion, microbial metabolic pathways, and populations. The extrusion caused changes in the physical and morphological characteristics, without altering the biochemical composition of the corn stover. Extrusion also led to remarkable differences in the composition of the indigenous microbial population of the substrate. Consequently, it affected the structure of community developed after fermentation and the substrate conversion yield, which increased by 118% (from 23 ± 4 gCOD/kgVSi obtained with raw substrate to 51 ± 1 gCOD/kgVSi with extruded corn stover) with regard to self-fermentation experiments. The use of activated sludge as inoculum further increased the total substrate conversion into carboxylates, up to 60 ± 2 gCOD/kgVSi, and shaped the microbial communities (mainly composed of bacteria from the Clostridia and Bacteroidia classes) with subsequent homogenization of the fermentation pathways. The addition of hydrolytic enzymes into the reactors further increased the corn stover conversion, leading to a maximum yield of 142 ± 1 gCOD/kgVSi. Thus, extrusion pretreatment combined with the use of an inoculum and enzyme addition increased by 506% corn stover conversion into carboxylates. Beside biomass pretreatment, the results of this study indicated that biotic factor greatly impacted solid-state fermentation by shaping the microbial communities and related metabolic pathways.

This experimental work aims at investigating the effects of milling; sieving; and electrostatic separation on the biochemical methane potential of two olive pomaces from traditional olive oil extraction (M) and from a three-phase system (T). Sieving proved to be efficient for increasing the soluble chemical oxygen demand in the smallest fractions of the sieve of both M (62%) and T (78%) samples. The positive fraction following electrostatic separation also enhanced chemical oxygen demand (COD) solubilisation by 94%, in comparison to sample T milled at 4 mm. Sieve fractions with a size greater than 0.9 mm contained 33% and 47% less lipids for the M and T biomasses; respectively. Dry fractionation modified sample properties as well as lipid and fiber distribution. Concomitantly; milling increased the accessibility and facilitated the release of organic matter. The energy balance was positive after knife milling and sieving; while ball milling and ultrafine milling proved to be inefficient.

The aim of this study was to explore the efficiency of a mechano-enzymatic deconstruction of two macroalgae species for sugars and bioethanol production, by using a new enzymatic cocktail (Haliatase) and two types of milling modes (vibro-ball: VBM and centrifugal milling: CM). By increasing the enzymatic concentration from 3.4 to 30 g/L, the total sugars released after 72 h of hydrolysis increased (from 6.7 to 13.1 g/100 g TS and from 7.95 to 10.8 g/100 g TS for the green algae U. lactuca and the red algae G. sesquipedale , respectively). Conversely, total sugars released from G. sesquipedale increased (up to 126% and 129% after VBM and CM, respectively). The best bioethanol yield (6 g eth /100 g TS) was reached after 72 h of fermentation of U. lactuca and no increase was obtained after centrifugal milling. The latter led to an enhancement of the ethanol yield of G. sesquipedale (from 2 to 4 g/100 g TS)., Competing Interests: The authors declare no conflict of interest

Red algae is widely available around the world and its exploitation for the production of agar products has become an important industry in recent years. The industrial processing of red algae generates a large quantity of solid fibrous wastes, which constitutes a source of serious environmental problems. In the present work, the utilization of red algae waste as raw material to produce high-quality cellulose nanocrystals (CNC) has been investigated, and the ability of the as-isolated CNC to reinforce polymer has been studied. Red algae waste was chemically treated via alkali, bleaching and acid hydrolysis treatments, in order to obtain pure cellulose microfibers and CNC. The raw waste and the as-extracted cellulosic materials were successively characterized at different stages of treatments using serval analysis techniques. It was found that needle-like shaped CNC were successfully isolated at nanometric scale with diameters and lengths ranged from 5.2±2.9 to 9.1±3.1nm, and from 285.4±36.5 to 315.7±30.3nm, respectively, and the crystallinity index ranged from 81 to 87%, depending on the hydrolysis time (30, 40 and 80min). The as-extracted CNC were used as nanofillers for the production of polyvinyl alcohol (PVA)-based nanocomposite films with improved thermal and tensile properties, as well as optical transparency. It is shown that the addition of 8wt% CNC into the PVA matrix increased the Young's modulus by 215%, the tensile strength by 150%, and the toughness by 45%. Additionally, the nanocomposite films maintained the same transparency level of the neat PVA film (transmittance of ∼90% in the visible region), suggesting that the CNC were dispersed at the nanoscale., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Hydrothermal pretreatment of five lignocellulosic substrates (i.e. wheat straw, rice straw, biomass sorghum, corn stover and Douglas fir bark) were conducted in the presence of CO 2 as a catalyst. To maximize disintegration and conversion into bioenergy (methane and hydrogen), pretreatment temperatures and subsequent pressures varied with a range of 26-175 °C, and 25-102 bars, respectively. Among lignin, cellulose and hemicelluloses, hydrothermal pretreatment caused the highest reduction (23-42%) in hemicelluloses while delignification was limited to only 0-12%. These reductions in structural integrity resulted in 20-30% faster hydrolysis rates during anaerobic digestion for the pretreated substrates of straws, sorghum, and corn stover while Douglas fir bark yielded 172% faster hydrolysis/digestion due to its highly refractory nature in the control. Furans and phenolic compounds formed in the pretreated hydrolyzates were below the inhibitory levels for methane and hydrogen production which had a range of 98-340 ml CH 4 /g volatile solids (VS) and 5-26 ml H 2 /g VS, respectively. Results indicated that hydrothermal pretreatment is able to accelerate the rate of biodegradation without generating high levels of inhibitory compounds while showing no discernible effect on ultimate biodegradation., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Innovative dry chemo- and chemo-mechanical pretreatments form an interesting approach for modifying the native physico-chemical composition of lignocellulose facilitating its microbial conversion to carboxylates. Here, the impact of four dry-pretreatment conditions on the microbial transformation of wheat straw was assessed: milling to 2mm and 100µm, and NaOH chemical impregnation at high substrate concentrations combined with milling at 2mm and 100µm. Pretreatment effect was assessed in the light of substrate structure and composition, its impact on the acidogenic potential and the major enzyme activities of a rumen-derived microbial consortium RWS. Chemo-mechanical pretreatment strongly modified the substrate macroporosity. The highest carboxylate production rate was reached after dry chemo-mechanical treatment with NaOH at 100µm. A positive impact of the dry chemo-mechanical treatment on xylanase activity was observed also. These results underline that increasing substrate macroporosity by dry chemo-mechanical pretreatment had a positive impact on the microbial acidogenic potential., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Novel synthesis strategy of eco-friendly bio-nanocomposite films have been exploited using cellulose nanocrystals (CNC) and polyvinyl alcohol/carboxymethyl cellulose (PVA/CMC) blend matrix as a potential in food packaging application. The CNC were extracted from sugarcane bagasse using sulfuric acid hydrolysis, and they were successfully characterized regarding their morphology, size, crystallinity and thermal stability. Thereafter, PVA/CMC-CNC bio-nanocomposite films, at various CNC contents (0.5-10wt%), were fabricated by the solvent casting method, and their properties were investigated. It was found that the addition of 5wt% CNC within a PVA/CMC increased the tensile modulus and strength by 141% and 83% respectively, and the water vapor permeability was reduced by 87%. Additionally, the bio-nanocomposites maintained the same transparency level of the PVA/CMC blend film (transmittance of ∼90% in the visible region), suggesting that the CNC were dispersed at the nanoscale. In these bio-nanocomposites, the adhesion properties and the large number of functional groups that are present in the CNC's surface and the macromolecular chains of the PVA/CMC blend are exploited to improve the interfacial interactions between the CNC and the blend. Consequently, these eco-friendly structured bio-nanocomposites with superior properties are expected to be useful in food packaging applications., (Copyright © 2016. Published by Elsevier B.V.)

We have investigated the effect of non-thermal atmospheric plasma (NTAP) on the structure of microcrystalline cellulose. In particular, by means of different characterization methods, we demonstrate that NTAP promotes the partial cleavage of the β-1,4 glycosidic bond of cellulose leading to the release of short-chain cellodextrins that are reassembled in situ, preferentially at the C6 position, to form branched glucans with either a glucosyl or anhydroglucosyl terminal residue. The ramification of cellulosic chain induced by NTAP yields branched glucans that are soluble in DMSO or in water, thus opening a straightforward access to processable glucans from cellulose. Importantly, the absence of solvent and catalyst considerably facilitates downstream processing as compared to (bio)catalytic processes which typically occur in diluted conditions., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Cellulosic pulps have been successfully isolated from wheat straw through a Lewis acids organosolv treatment. The use of Lewis acids with different hardness produced pulps with different delignification degrees. The cellulosic residue was characterised by chemical composition, X-ray diffraction, FT-IR spectroscopy, N2 physisorption, scanning electron microscopy and potential for anaerobic digestibility. Surface area and pore volume increased with the hardness of the Lewis acid, in correspondence with the decrease of the amount of lignin and hemicellulose in the pulp. The non linearity of the correlation between porosity and composition suggests that an agglomeration of cellulose fibrils occurs in the early stages of pulping. All organosolv pulps presented a significantly higher methane potential than the parent straw. A methane evolution of 295Ncm(3)/g OM was reached by a moderate improvement of the accessibility of the native straw., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Novel functional hybrid nanofillers composed of cellulose nanocrystals (CNC) and graphene oxide nanosheets (GON), at different weight ratios (2:1, 1:1 and 1:2), were successfully prepared and characterized, and their synergistic effect in enhancing the properties of poly(vinyl alcohol) (PVA) nanocomposites was investigated. Due to the synergistic reinforcement, it was found that the Young's modulus, tensile strength and toughness of the PVA nanocomposite containing 5 wt% hybrid nanofiller (1:2) were significantly improved by 320%, 124% and 159%, respectively; and the elongation at break basically remained compared to the neat PVA matrix. In addition, the glass and melting temperatures as well as the moisture sorption of nanocomposites were also enhanced. This synergistic effect improved the dispersion homogeneity by avoiding the agglomeration phenomenon of nanofillers within the polymer matrix, resulting in nanocomposites with largely enhanced properties compared to those prepared from single nanofiller (CNC or GON). The preparation of these hybrid nanofillers and their incorporation into a polymer provided a novel method for the development of novel multifunctional nanocomposites based on the combination of existing nanomaterials., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Ball milling of cellulose in the presence of a catalytic amount of H2SO4 was found to be a promising pre-treatment process to produce butyl glycosides in high yields. Conversely to the case of water, n-butanol has only a slight effect on the recrystallization of ball-milled cellulose. As a result, thorough depolymerization of cellulose prior the glycosylation step is no longer required, which is a pivotal aspect with respect to energy consumption. This process was successfully transposed to wheat straw from which butyl glycosides and xylosides were produced in good yields. Butyl glycosides and xylosides are important chemicals as they can be used as hydrotropes but also as intermediates in the production of valuable amphiphilic alkyl glycosides., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This study was aimed to develop bio-nanocomposite films of carboxymethyl cellulose (CMC)/starch (ST) polysaccharide matrix reinforced with cellulose nanocrystals (CNC) using the solution casting method. The CNC were extracted at the nanometric scale from sugarcane bagasse via sulfuric acid hydrolysis and used as reinforcing phase to produce CMC/ST-CNC bio-nanocomposite films at different CNC loading levels (0.5-5.0 wt%). Steady shear viscosity and dynamic viscoelastic measurements of film-forming solution (FFS) of neat CMC, CMC/ST blend and CMC/ST-CNC bio-nanocomposites were evaluated. Viscosity measurements revealed that a transition from Newtonian behavior to shear thinning occurred when CNC were added. The dynamic tests confirmed that all FFS have a viscoelastic behavior with an entanglement network structure, induced by the hydrogen bonding. In regard to the cast film quality, the rheological data showed that all FFS were suitable for casting of films at ambient temperature. The effect of CNC addition on the optical transparency, water vapor permeability (WVP) and tensile properties of bio-nanocomposite films was studied. It was found that bio-nanocomposite films remain transparent due to CNC dispersion at the nanoscale. The WVP was significantly reduced and the elastic modulus and tensile strength were increased gradually with the addition of CNC. Herein, the steps to form new eco-friendly bio-nanocomposite films were described by taking advantage of the combination of CMC, ST and CNC. The as-produced films exhibited good optical transparency, reduced WVP and enhanced tensile properties, which are the main properties required for packaging applications., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

License to mill: Proteins were continuously extracted from polysaccharides, lignin, and polyphenol by combining ultrafine milling with electrostatic separation. Such a fractionation process does not involve any solvent, catalyst, or external source of heating. In addition, this dry process is compatible with downstream enzymatic reactions, thus opening an attractive route for producing valuable chemicals from biomass., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Background: Today, most of pretreatments used to convert biomass into biofuels are based on expensive chemical processes that not only do not keep the major components intact after separation, but also consume water and generate many effluents. However, dry fractionation technologies are an important step for future biomass biorefineries since they do not require chemicals and do not generate wastewater. Therefore, the aim of the present study was to evaluate the feasibility of using milling combined with an electrostatic fractionation (ES) of wheat straw (WS) as a way to separate fractions that are enriched in cellulose and more enzymatically accessible, from recalcitrant tissues enriched in lignin-hemicelluloses, in order to produce biofuels., Results: After milling, WS particles are introduced into a tribo-electrostatic separator, where they are positively or negatively charged by tribo-electricity. Then they are introduced into a separation cell comprising two electrodes (+ and -). The negative electrode attracts the positively charged particles and the positive electrode attracts the negatively charged particles. Results show that amorphous cellulose rich particles were clearly more abundant in positively charged fractions (F+), and loose crystalline cellulose, lignin-xylan and ash-containing material were more abundant in negatively charged fractions (F-). Indeed, positively charged fractions (F+) are more accessible upon enzymatic hydrolysis, which resulted, for example, in sugars yield of 43.5% glucose (254 gKg(-1)) for F2B + compared to 25.2% (103 gKg(-1)) for F2A-, and 26.3% (130 gKg(-1)) for unfractionated WS F0, respectively., Conclusions: The combination strategy of milling and ES fractionation could improve the economic feasibility by low energy consumption (10.5 WhKg(-1)) and it produces reactive lignocelluloses particles with different physicochemical structures, which can be converted easily into biofuels and biomaterials without generating toxic effluents.

In this report new hybrid materials based on brushite-alginate and monetite-alginate were prepared by self-assembling alginate chains and phosphate source ions via a gelation process with calcium ions. The alginate served as nanoreactor for nucleation and growth of brushite or/and monetite due to its gelling and swelling properties. The alginate gel framework, the crystalline phase and morphology of formed hybrid biomaterials were shown to be strongly dependent upon the concentration of the phosphate precursors. These materials were characterized by thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive x-ray analysis (EDX)., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The use of lignocellulosic residues such as sunflower stalks (SS) for the production of bioenergy such as methane is a promising alternative to fossil fuels. However, their recalcitrant structure justifies the use of pretreatment to enhance the accessibility of holocelluloses and their further conversion into methane. First, different conditions of alkaline pretreatment (i.e. duration and NaOH concentration (g/100 g TS) at a fixed temperature of 55 degrees C) were tested to enhance the methane potential of the stalks of the Serin sunflower (193 mL of methane per gram of volatile solids (VS)). The greatest improvement to the methane potential (262 mL CH4 g(-1) VS) was observed at 55 degrees C, 24 h, 4 g NaOH/100 g TS. Fourier Transform Infrared spectra highlighted an accumulation of lignin in the digestate and the degradation of holocelluloses during the anaerobic process, both for pretreated and untreated SS. In a second stage, this optimum condition for alkaline pretreatment (55 degrees C, 24 h, 4 g NaOH/100 g TS) was applied to the stalks of three other varieties of sunflower. Alkaline pretreatment was effective in the delignification of the stalks of the different sunflower varieties, with lignin reduction varying from 23.3% to 36.3% VS. This reduction of lignin was concomitant with the enhancement of methane potential as compared to that of raw SS, with an increase ranging from 29% to 44% for the different SS.

The use of lignocellulosic biomass is promising for biofuels and materials and new technologies for the conversion need to be developed. However, the inherent properties of native lignocellulosic materials make them resistant to enzymatic and chemical degradation. Lignocellulosic biomass requires being pretreated to change the physical and chemical properties of lignocellulosic matrix in order to increase cell wall polymers accessibility and bioavailability. Mechanical size reduction may be chemical free intensive operation thanks to decreasing particles size and cellulose crystallinity, and increasing accessible surface area. Changes in these parameters improve the digestibility and the bioconversion of lignocellulosic biomass. However, mechanical size reduction requires cost-effective approaches from an energy input point of view. Therefore, the energy consumption in relation to physicochemical properties of lignocellulosic biomass was discussed. Even more, chemical treatments combined with physicochemical size reduction approaches are proposed to reduce energy consumption in this review., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Because of their rich composition in carbohydrates, lignocellulosic residues represent an interesting source of biomass to produce biohydrogen by dark fermentation. Nevertheless, pretreatments should be applied to enhance the solubilization of holocelluloses and increase their further conversion into biohydrogen. The aim of this study was to investigate the effect of thermo-alkaline pretreatment alone and combined with enzymatic hydrolysis to enhance biohydrogen production from sunflower stalks. A low increase of hydrogen potentials from 2.3 ± 0.9 to 4.4 ± 2.6 and 20.6 ± 5.6 mL of H2 g(-1) of volatile solids (VS) was observed with raw sunflower stalks and after thermo-alkaline pretreatment at 55 °C, 24 h, and 4% NaOH and 170 °C, 1 h, and 4% NaOH, respectively. Enzymatic pretreatment alone showed an enhancement of the biohydrogen yields to 30.4 mL of H2 g(-1) of initial VS, whereas it led to 49 and 59.5 mL of H2 g(-1) of initial VS when combined with alkaline pretreatment at 55 and 170 °C, respectively. Interestingly, a diauxic effect was observed with sequential consumption of sugars by the mixed cultures during dark fermentation. Glucose was first consumed, and once glucose was completely exhausted, xylose was used by the microorganisms, mainly related to Clostridium species.

In an integrated biorefinery concept, biological hydrogen and methane production from lignocellulosic substrates appears to be one of the most promising alternatives to produce energy from renewable sources. However, lignocellulosic substrates present compositional and structural features that can limit their conversion into biohydrogen and methane. In this study, biohydrogen and methane potentials of 20 lignocellulosic residues were evaluated. Compositional (lignin, cellulose, hemicelluloses, total uronic acids, proteins, and soluble sugars) as well as structural features (crystallinity) were determined for each substrate. Two predictive partial least square (PLS) models were built to determine which compositional and structural parameters affected biohydrogen or methane production from lignocellulosic substrates, among proteins, total uronic acids, soluble sugars, crystalline cellulose, amorphous holocelluloses, and lignin. Only soluble sugars had a significant positive effect on biohydrogen production. Besides, methane potentials correlated negatively to the lignin contents and, to a lower extent, crystalline cellulose showed also a negative impact, whereas soluble sugars, proteins, and amorphous hemicelluloses showed a positive impact. These findings will help to develop further pretreatment strategies for enhancing both biohydrogen and methane production.

Hydrolysates resulting from the lignocellulosic biomass pretreatment in bioethanol production may be used to produce biogas. Such hydrolysates are rich in xylose but also contain lignin polymers or oligomers as well as phenolic and furan compounds, such as syringaldehyde, vanillin, HMF, furfural. The aim of this study was to investigate the impact of these byproducts on biomethane production from xylose. The anaerobic digestion of the byproducts alone was also investigated. No inhibition of the anaerobic digestion of xylose was observed and methane was obtained from furans: 430 mL CH(4)/g of furfural and 450 mL CH(4)/g of HMF; from phenolic compounds: 453 mL CH(4)/g of syringaldehyde and 105 mL CH(4)/g of vanillin; and, to a lesser extent, from lignin polymers: from 14 to 46 mL CH(4)/g MV. The use of different natural polymers (lignosulfonates, organosolv and kraft lignins) and synthetic dehydrogenative polymers showed that higher S/G ratios and lower molecular weights in lignin polymers led to greater methane production., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Endo-beta-1,4-xylanases (EC 3.2.1.8) are the main enzymes involved in the hydrolysis of xylans, the most abundant hemicelluloses in plant biomass. However, the development of efficient endoxylanases for use in biorefinery processes is currently hampered by insufficient knowledge regarding the impact of the cell wall network organization on the action of the enzyme at the supramolecular level. The action pattern of a GH11 endoxylanase from Thermobacillus xylanilyticus (Tx-xyl) was investigated by means of in vitro reconstituted model systems which can mimic certain cell wall structures. The action of Tx-xyl was evaluated on polymer assemblies displaying increasing complexity using delignified glucuronoarabinoxylan (GAX), then GAX-DHP model complexes obtained by oxidative polymerization of coniferyl alcohol into dehydrogenation polymers (DHP: lignin model compounds) in the presence of GAX. At a high concentration of GAX, interchain associations are formed leading to high molecular weight aggregates. These structures did not appear to affect the action of endoxylanase, which induces disaggregation of the self-aggregates along with polymer depolymerization. To mimic lignin-carbohydrate interactions, two different GAX-DHP nanocomposites were prepared and incubated with endoxylanase. In both cases, free GAX was hydrolyzed, while the GAX-DHP complexes appeared to be resistant. In the case of the noncovalently linked GAX-DHP(ZL) complexes, enzyme action favored a decrease in particle size, owing to the removal of their relatively exposed carbohydrate chains, whereas the complex supramolecular organization of the covalently linked GAX-DHP(ZT) complexes severely hampers the enzyme's access to carbohydrate. Overall, these results establish the negative impact of DHP on the endoxylanase action and provide new knowledge regarding the limitations of the enzyme action in the lignocellulose bioconversion processes.

The supramolecular organization of particles composed of heteroxylans (HX) and synthetic lignin (dehydrogenation polymer, DHPs) was studied by light scattering (LS), atomic force microscopy (AFM), and fluorescent probes. Results from static and quasi-elastic light scattering indicate a dense core surrounded by a soft corona. Such organization is also supported by AFM images of the particles that display Gaussian height profiles when a low tapping force is applied, whereas the shape of the profile obtained at a higher mechanical solicitation is irregular and sharp due to deformation of the particles resulting from the tip indentation. This suggests a difference in mechanical behavior between the inner and outer parts of the particles. The formation of local chemical heterogeneities was demonstrated by use of two fluorescent polarity probes (pyrene and methyl-amino-pyrene) to be induced by the core-corona organization.

In plant cell walls, lignin polymerization occurs in concentrated polysaccharide gel. The effect of high polysaccharide concentrations on the structure of lignin-like polymers (DHPs=dehydrogenation polymers), were investigated by running lignification-like polymerization under three reaction conditions in which the concentrations of all reactants (xylan/coniferyl alcohol (CA)/oxidising system) were gradually increased. Control experiments were also run in similar conditions but without polysaccharides. DHPs showed increased solubility with increased concentrations of reactants in the presence of xylans but were mostly insoluble in buffer control experiments. The structures of DHPs were characterized by thioacidolysis and size exclusion chromatography (SEC). Results indicated that the frequency of beta-alkyl aryl ether bonds and DHP molecular weight increased with increasing concentration of the reaction mixture in the presence of xylans whereas those of control DHPs decreased slightly under the same conditions. This emphasizes the role of the pre-existing polysaccharide gel and high concentrations existing in the cell wall during construction of the lignin polymer.

The mechanism of lignin carbohydrate complex formation by addition of polysaccharides on quinone methide (QM) generated during lignin polymerisation was investigated using a model approach. Dehydrogenation polymers (DHPs, lignin model compounds) were synthesized from coniferyl alcohol in the presence of a glucuronoarabinoxylan (GAX) extracted from oat spelts, by Zutropfverfahren (ZT) and Zulaufverfahren (ZL) methods. The methods ZT and ZL differed in their distribution of QM over the reaction period but generated roughly the same QM amount. Steric exclusion chromatography of the ZT and ZL reaction products showed that only the ZT reaction produced high molar mass compounds. Covalent linkages in the ZT reaction involving ether bonds between GAX moiety and alpha carbon of the lignin monomer were confirmed by (13)C NMR and xylanase-based fractionation. The underlying phenomena were further investigated by examining the interactions between GAX and DHP in sorption experiments. GAX and DHPs were shown to interact to form hydrophobic aggregates. In the ZT process, slow addition permitted polymer reorganisation which led to dehydration around the lignin-like growing chains thereby limiting the addition of water on the quinone methide formed during polymerisation and thus favoured lignin-carbohydrate complex (LCC) formation.