A specific H2/CO2 consumption molar ratio of 3 as a signature for the chain elongation of carboxylates from brewer's spent grain acidogenesis.

Brewer's spent grain (BSG) is an undervalorized organic feedstock residue composed of fermentable macromolecules, such as proteins, starch, and residual soluble carbohydrates. It also contains at least 50% (as dry weight) of lignocellulose. Methane-arrested anaerobic digestion is one of the promising microbial technologies to valorize such complex organic feedstock into value-added metabolic intermediates, such as ethanol, H2, and short-chain carboxylates (SCC). Under specific fermentation conditions, these intermediates can be microbially transformed into medium-chain carboxylates through a chain elongation pathway. Medium-chain carboxylates are of great interest as they can be used as bio-based pesticides, food additives, or components of drug formulations. They can also be easily upgraded by classical organic chemistry into bio-based fuels and chemicals. This study investigates the production potential of medium-chain carboxylates driven by a mixed microbial culture in the presence of BSG as an organic substrate. Because the conversion of complex organic feedstock to medium-chain carboxylates is limited by the electron donor content, we assessed the supplementation of H2 in the headspace to improve the chain elongation yield and increase the production of medium-chain carboxylates. The supply of CO2 as a carbon source was tested as well. The additions of H2 alone, CO2 alone, and both H2 and CO2 were compared. The exogenous supply of H2 alone allowed CO2 produced during acidogenesis to be consumed and nearly doubled the medium-chain carboxylate production yield. The exogenous supply of CO2 alone inhibited the whole fermentation. The supplementation of both H2 and CO2 allowed a second elongation phase when the organic feedstock was exhausted, which increased the medium-chain carboxylate production by 285% compared to the N2 reference condition. Carbon- and electron-equivalent balances, and the stoichiometric ratio of 3 observed for the consumed H2/CO2, suggest an H2- and CO2-driven second elongation phase, converting SCC to medium-chain carboxylates without an organic electron donor. The thermodynamic assessment confirmed the feasibility of such elongation.

Improved sugar yields from biomass sorghum feedstocks: comparing low-lignin mutants and pretreatment chemistries.

BACKGROUND: For biofuel production processes to be economically efficient, it is essential to maximize the production of monomeric carbohydrates from the structural carbohydrates of feedstocks. One strategy for maximizing carbohydrate production is to identify less recalcitrant feedstock cultivars by performing some type of experimental screening on a large and diverse set of candidate materials, or by identifying genetic modifications (random or directed mutations or transgenic plants) that provide decreased recalcitrance. Economic efficiency can also be increased using additional pretreatment processes such as deacetylation, which uses dilute NaOH to remove the acetyl groups of hemicellulose prior to dilute acid pretreatment. In this work, we used a laboratory-scale screening tool that mimics relevant thermochemical pretreatment conditions to compare the total sugar yield of three near-isogenic brown midrib (bmr) mutant lines and the wild-type (WT) sorghum cultivar. We then compared results obtained from the laboratory-scale screening pretreatment assay to a large-scale pretreatment system. RESULTS: After pretreatment and enzymatic hydrolysis, the bmr mutants had higher total sugar yields than the WT sorghum cultivar. Increased pretreatment temperatures increased reactivity for all sorghum samples reducing the differences observed at lower reaction temperatures. Deacetylation prior to dilute acid pretreatment increased the total sugar yield for all four sorghum samples, and reduced the differences in total sugar yields among them, but solubilized a sizable fraction of the non-structural carbohydrates. The general trends of increased total sugar yield in the bmr mutant compared to the WT seen at the laboratory scale were observed at the large-scale system. However, in the larger reactor system, the measured total sugar yields were lower and the difference in total sugar yield between the WT and bmr sorghum was larger. CONCLUSIONS: Sorghum bmr mutants, which have a reduced lignin content showed higher total sugar yields than the WT cultivar after dilute acid pretreatment and enzymatic hydrolysis. Deacetylation prior to dilute acid pretreatment increased the total sugar yield for all four sorghum samples. However, since deacetylation also solubilizes a large fraction of the non-structural carbohydrates, the ability to derive value from these solubilized sugars will depend greatly on the proposed conversion process.

Biochemical methane potential prediction of plant biomasses: Comparing chemical composition versus near infrared methods and linear versus non-linear models.

The reliability of different models to predict the biochemical methane potential (BMP) of various plant biomasses using a multispecies dataset was compared. The most reliable prediction models of the BMP were those based on the near infrared (NIR) spectrum compared to those based on the chemical composition. The NIR predictions of local (specific regression and non-linear) models were able to estimate quantitatively, rapidly, cheaply and easily the BMP. Such a model could be further used for biomethanation plant management and optimization. The predictions of non-linear models were more reliable compared to those of linear models. The presentation form (green-dried, silage-dried and silage-wet form) of biomasses to the NIR spectrometer did not influence the performances of the NIR prediction models. The accuracy of the BMP method should be improved to enhance further the BMP prediction models.

Structural carbohydrates in a plant biomass: correlations between the detergent fiber and dietary fiber methods.

We compared the detergent fiber and dietary fiber methods to analyze the cellulose and hemicellulose contents of commelinid and non-commelinid magnoliophyta biomass. A good linear correlation was found between both methods. Compared to the more accurate dietary fiber method, the detergent fiber method overestimates the content of cellulose, whereas the detergent fiber method, as compared to the dietary fiber method, overestimates and underestimates the hemicellulose content in commelinid and non-commelinid magnoliophyta biomass, respectively. Because of the good linear correlations, conversion factors were determined to predict the cellulose, hemicellulose, and xylan contents to be expected from the dietary fiber method, on the basis of analyses made by the faster, cheaper, and more commonly practiced detergent fiber method. Nevertheless, the dietary fiber method offers the advantage of providing the detailed composition of the hemicelluloses (xylan, arabinan, hemicellulosic glucan, galactan, and mannan), and that is of interest for biorefining purposes.

Chemical characteristics and biofuels potentials of various plant biomasses: influence of the harvesting date.

BACKGROUND: An optimal valorization of plant biomasses to produce biofuels requires a good knowledge of the available contents and molecular composition of the main chemical components, which changes with the harvesting date. Therefore, we assessed the influence of harvesting date on the chemical characteristics of various energy crops in the context of their conversion to biofuels. RESULTS: We showed that the biomass chemical composition, enzymatic digestible organic matter, bioethanol and thermal energy production potential for each species are impacted by the harvesting date. The proportion of enzymatically digestible organic matter decreases as the harvesting date is delayed. This is related to the increase in cellulose and lignin contents. The suitability of the biomasses for bioethanol production increases with harvest stage, as the total carbohydrates content increases. The suitability of the biomasses as a source of thermal energy increases according to the harvesting date as the proportion of organic matter increases and the content of mineral compounds decreases. For all investigated energy conversions, the best harvesting period is autumn, because the significantly higher crop dry matter yield largely compensates for the sometimes slightly less favorable chemical characteristics. CONCLUSION: While the biomass composition of energy crops changes with harvest stage, the dry biomass yield per unit area is the main factor that controls the total amount of chemical components, digestible organic matter, bioethanol and thermal energy that can be expected to be harvested per unit area. The biomass compositions presented in this paper are essential to investigate their suitability for bioenergy conversion.

Optimisation of a semiochemical slow-release alginate formulation attractive towards Aphidius ervi Haliday parasitoids.

BACKGROUND: Optimisation of alginate formulations is described in order to develop semiochemical (E-ß-farnesene and E-ß-caryophyllene) slow-release devices in biological control approaches by attracting predators and parasitoids of aphids. Various formulation criteria were optimised with respect to semiochemical encapsulation capacity. Moreover, the optimised formulation was characterised by texturometry and confocal microscopy. The slow-release rates of semiochemicals were calculated in laboratory controlled conditions. The attractiveness of semiochemical formulations towards Aphidius ervi was demonstrated by olfactometry. RESULTS: Two major parameters were highlighted in encapsulation optimisation: the type of alginate (Sigma L) and the type of crosslinker ion (Ca(2+)). Other formulation parameters were optimised: ionic strength (0.5 M), Ca(2+) (0.2 M) and alginate (1.5%) concentrations and the maturation time of beads in CaCl(2) solution (48 h). After physical characterisation of beads, semiochemical slow-release measurements showed that alginate formulations were efficient sesquiterpene releasers, with 503 µg of E-ß-farnesene and 1791 µg of E-ß-caryophyllene totally released in 35 days. The efficiency of semiochemical alginate beads as attractants for female parasitoids was demonstrated, with high percentages of attraction for semiochemical odours (88 and 90% for E-ß-farnesene and E-ß-caryophyllene respectively) and significant statistical results. CONCLUSION: Semiochemical alginate beads can be considered as efficient slow-release systems in biological control. These formulations could be very useful to attract aphid parasitoids on crop fields.

Composition of structural carbohydrates in biomass: precision of a liquid chromatography method using a neutral detergent extraction and a charged aerosol detector.

We adapted and optimized a method to quantify the cellulose, hemicellulose, xylan, arabinan, mannan, galactan contents in lignocellulosic biomass. This method is based on a neutral detergent extraction (NDE) of the interfering biomass components, followed by a sulfuric acid hydrolysis (SAH) of the structural polysaccharides, and a liquid chromatography with charged aerosol detection (LC-CAD) to analyze the released monosaccharides. The first step of this NDE-SAH-LC-CAD method aims at removing all compounds that interfere with the subsequent sulphuric acid hydrolysis or with the subsequent chromatographic quantification of the cellulosic and hemicellulosic monosaccharides. This step includes starch hydrolysis with an analytical thermostable α-amylase followed by an extraction of soluble compounds by a Van Soest neutral detergent solution (NDE). The aim of this paper was to assess the precision of this method when choosing fiber sorghum (Sorghum bicolor (L.) Moench), tall fescue (Festuca arundinacea Schreb.) and fiber hemp (Cannabis sativa L.) as representative lignocellulosic biomass. The cellulose content of fiber sorghum, tall fescue and fiber hemp determined by the NDE-SAH-LC-CAD method were 28.7 ± 1.0, 29.7 ± 1.0 and 43.6 ± 1.2g/100g dry matter, respectively, and their hemicellulose content were 18.6 ± 0.5, 16.5 ± 0.5 and 14.5 ± 0.2g/100g dry matter, respectively. Cellulose, mannan and galactan contents were higher in fiber hemp (dicotyledon) as compared to tall fescue and fiber sorghum (monocotyledons). The xylan, arabinan and total hemicellulose contents were higher in tall fescue and fiber sorghum as compared to fiber hemp. The precision of the NDE-SAH-LC-CAD method was better for polysaccharide concentration levels above 1g/100g dry matter. Galactan analysis offered a lower precision, due to a lower CAD response intensity to galactose as compared to the other monosaccharides. The dispersions of the results (expanded uncertainty) of the NDE-SAH-LC-CAD method were smaller as compared to the Van Soest (VS) method. In addition, the NDE-SAH-LC-CAD method was able to provide additional information on the composition of the hemicellulose (xylan, arabinan, mannan and galactan content) that is not provided by the Van Soest method. The NDE-SAH-LC-CAD method offers also the advantage of a better specificity for hemicellulose and cellulose, as compared to the NREL and Uppsala methods.

Fast gas chromatography characterisation of purified semiochemicals from essential oils of Matricaria chamomilla L. (Asteraceae) and Nepeta cataria L. (Lamiaceae).

The chemical composition of Matricaria chamomilla L. and Nepeta cataria L. essential oils was determined by GC-MS on an apolar stationary phase by comparison of the characteristic fragmentation patterns with those of the Wiley 275L database. The GC-MS chromatograms were compared with those obtained by fast GC equipped with a direct resistively heated column (Ultra Fast Module 5% phenyl, 5 mx 0.1 mm, 0.1 microm film thickness). Analytical conditions were optimised to reach a good peak resolution (split ratio=1:100), with analysis time lower than 5 min versus 35-45 min required by conventional GC-MS. The fast chromatographic method was completely validated for the analysis of mono- and sesquiterpene compounds. Essential oils were then fractionated by column chromatography packed with silica gel. Three main fractions with high degree of purity in E-beta-farnesene were isolated from the oil of M. chamomilla. One fraction enriched in (Z,E)-nepetalactone and one enriched in beta-caryophyllene were obtained from the oil of N. cataria. These semiochemical compounds could act as attractants of aphid's predators and parasitoids.