A biorefinery scheme for residual biomass using autohydrolysis and organosolv stages for oligomers and bioethanol production

Energy & Fuels

DOI: 10.1021/acs.energyfuels.6b00277

Straw is one of the main lignocellulosic waste produced during cereal crop cultivation. The abundance of barley straw makes it a good candidate for bioethanol production. This work deals with barley straw pretreatment by means of autohydrolysis in order to get xylooligosaccharides in the liquid phase, followed by an organosolv treatment using ethanol to increase the solid phase enzymatic susceptibility. Up to 17.4 g oligomers/L were obtained in the hydrothermal stage, in which practically all the cellulose and lignin remained in the solid phase. The solid phase from the hydrothermal-delignification was subjected to an experimental design in order to study the effect of pretreatment conditions in the bioethanol production, with values of solids concentrations in the range 7.7 to 20 weight % and values of enzyme loading in the range 14 FPU/g to 6 FPU/g. In the experiments carried out at a liquid to solid ratio = 4 g/g it is possible to obtain 31.6 g ethanol/L in just 9 h (corresponding to 100% ethanol conversion), with optimum results of 44.5 g ethanol/L in 46 h (90-93% glucose to ethanol conversion) and with a maximum concentration of 48.7 g ethanol/L in 89 h (79% conversion). The combination of a hydrothermal pretreatment (under conditions that lead to the recovery of high amounts of hemicellulosic by-products), followed by an organosolv treatment under mild conditions turns out to be suitable for second generation bioethanol production, applying a high solids loading, by means of fed-batch simultaneous saccharification and fermentation.

Characterization of virgin olive oils produced with autochthonous Galician varieties

Food Chemistry 212 ( 2016) 162–171

http://dx.doi.org/10.1016/j.foodchem.2016.05.135

The interest of Galician oil producers (NW Spain) in recovering the ancient autochthonous olive varieties Brava and Mansa has increased substantially in recent years. Virgin olive oils produced by co-crushing both varieties in two different proportions, reflecting the usual and most common practice adopted in this region, have gradually emerged for the production of virgin olive oils. Herein, the sensory and chemical characteristics of such oils were characterized by quality and genuineness-related parameters. The results of chemical analysis are discussed in terms of their effective contribution to the sensory profile, which suggests useful recommendations for olive oil producers to improve the quality of oils. Antioxidant compounds, together with aromas and coloured pigments were determined, and their contribution in determining the functional value and the sensory properties of oils was investigated. In general, given the high levels of phenolic compounds (ranging between 254 and 375 mg/kg oil), tocopherols (about 165 mg/kg oil) and carotenoids (10–12 mg/kg oil); these are oils with long stability, especially under dark storage conditions, because stability is reinforced with the contribution of chlorophylls (15–22 mg/kg oil). A major content of phenolic compounds, as well as a predominance of trans-2-hexen-1-al within odor-active compounds (from 897 to 1645 μg/kg oil), responsible for bitter sensory notes. This characterization allows to developing new antioxidant-rich and flavour-rich VOOs, when co-crushing with a higher proportion of Brava olives, satisfying the consumers’ demand in having access to more healthy dishes and peculiar sensory attributes.

Foto de Grupo - Septiembre de 2016

Investigadores del CIA en Vigo

Promoting sustainability in the mussel industry: mussel shell recycling to fight fluoride pollution

Journal of Cleaner Production, 131 (2016) 485–490

http://dx.doi.org/10.1016/j.jclepro.2016.04.154

Taking into account a background situation where some industrial activities greatly influence fluoride pollution, while other industries generate by-products that could be effective as fluoride bio-sorbents, and bearing in mind sustainability and environmental concern, batch-type experiments were performed to study fluoride sorption/desorption on individual (un-amended) and mussel shell-amended soils and materials. Specifically, the research focused on a forest soil, a vineyard soil, pyritic material, granitic material, and ground mussel shell, as well as on both soils and the pyritic and granitic materials amended with mussel shell. The main findings of the research indicate that the shell amendment clearly increased fluoride sorption in the pyritic material (reaching more than 90%), showing no effect as regards fluoride desorption from this material. The amendment caused a slight increase in fluoride sorption on forest soil, as well as a slight decrease in fluoride desorption from it. The un-amended vineyard soil and the un-amended granitic material had lower fluoride-retention capacity than the forest soil and pyritic material, and it did not change after amending with mussel shell. The mussel shell by itself showed the lowest fluoride-retention potential among the tested materials. As a conclusion, and focusing on applicability, these results can be useful to program the correct use of mussel shell amendment on soils and even on degraded environments with the aim of increasing fluoride retention or removal, thus decreasing risk of environmental pollution due to excessive fluoride concentrations in solid and/or liquid media, also facilitating recycling, sustainability and cleaner production in the mussel shell industry.

State of the art on public risk assessment of combined human exposure to multiple chemical contaminants

Trends in Food Science & Technology, 55 (2016) 11–28

http://dx.doi.org/10.1016/j.tifs.2016.06.011

Concern about the effects on health of exposure of combined chemicals present in food, air or water are increasing nowadays. However, mechanism and effects of combined chemical contaminants are still poorly know.

This review deals with the variety of routes of these chemicals when enter the human body. The gaol is the development of a mechanism-based and quantitative framework for risk assessment to estimate the impact on human health and prevent exposure to multiple chemicals.

It has been shown that new studies should be developed taking into account cumulative effect of these substances and different tiers as external exposition, dietary exposition, lifestyle, age and economic factors. New techniques must also be implemented, mainly “omic” techniques, bioassay systems, mathematical modelling, quantitative structure-activity relationship models, and threshold of toxicological concern to develop databases. In conclusion, several programs should continuously be developed by different health agencies to have a better understanding of the effect of these substances and to develop a unified policy.

Kinetic modelling of mancozeb hydrolysis and photolysis to ethylenethiourea and other by-products in water

Water Research 102 (2016) 561–571

http://dx.doi.org/10.1016/j.watres.2016.07.006

The aim of this study was to propose kinetic models suitable for reproducing and predicting mancozeb (Mz) conversion to by-products as a function of the operational conditions. The main factors (pH, temperature and light) potentially affecting the mancozeb degradation in aqueous models were studied by a multifactorial screening design. In addition, the response surface methodology (RSM) was applied to evaluate the interactive effects of these factors on ethylenethiourea (ETU) formation. The response surface revealed that the best degradation conditions to minimize mancozeb conversion to ETU were low pH (2), low temperature (25 °C) and darkness. Under these conditions, the percentage of mancozeb remained in the solution at 72 h was approximately 10% of the initial concentration and the percentage of ETU conversion was 5.4%. However, according to the model, in surface waters under typical environmental conditions (pH 8, 25 °C and light) the percentage of mancozeb conversion to ETU would be about 17.5%. The proposed model provides a satisfactory interpretation of the experimental data obtained during the hydrolysis of mancozeb.

Valorization of biosorbent obtained from a forestry waste: Competitive adsorption, desorption and transport of Cd, Cu, Ni, Pb and Zn

Ecotoxicology and Environmental Safety, 131(2016) 118–126

http://dx.doi.org/10.1016/j.ecoenv.2016.05.007

Bark from Pinus pinaster is one of the most abundant forestry wastes in Europe, and among the proposed technologies for its reutilization, the removal of heavy metals from wastewater has been gaining increasing attention. In this work, we have studied the performance of pine bark for heavy metal biosorption on competitive systems. Pb, Cu, Ni, Zn and Cd sorption and desorption at equilibrium were studied in batch experiments, whereas transport was studied in column experiments. Batch experiments were performed adding simultaneously different concentrations (0.08–3.15 mM) of two or more metals in solution to pine bark samples. Column experiments were performed with 10 mM solutions of two metals or a 5 mM solution of the five metals. In general, the results under competitive conditions were different to those obtained in monoelemental experiments. The multi-metal batch experiments showed the adsorption sequence Pb≈Cu>Cd>Zn>Ni for lower metal doses, Pb>Cu>Cd>Zn>Ni for intermediate doses, and Pb>Cu>Cd≈Zn≈Ni for high metal doses. Desorption followed the sequence Pb<Cd<Cu<Zn<Ni for the lowest metal doses, and Pb<Cu<Zn<Cd<Ni for the highest ones. The bi-metal batch experiments indicated that Cu and Pb suffered the highest retention, with high capacity to displace Cd, Ni and Zn from adsorption sites on pine bark. The transport experiments produced comparable results to those obtained in the batch experiments, with pine bark retention capacity following the sequence Pb>Cu>Zn>Cd>Ni. The presence of a second metal affected the transport of all the elements studied except Pb, and confirmed the strong influence of Pb and Cu on the retention of the other metals. These results can help to appropriately design decontamination systems using this forestry waste.

Phosphorus retention on forest and vineyard soil samples, mussel shell, pine-sawdust, and on pyritic, granitic and waste materials

Geoderma, 280 (2016) 8–13

http://dx.doi.org/10.1016/j.geoderma.2016.06.003

Focusing on P, we used batch-type experiments to study P retention on various materials: a forest soil sample, a vineyard soil sample, finely and coarsely ground mussel shell, pine-sawdust, pyritic material, granitic material, mussel shell calcination ash, slate processing fines, and three different mixtures that included three components: sewage sludge, mussel shell ash, and calcined mussel shell or pine wood ash. The pyritic material and the mussel shell ash showed the highest P retention capacity, reaching > 95%. The lowest P retention (< 60%) corresponded to the pine-sawdust and slate processing fines. Data fitted satisfactorily to the Freundlich model, unless in the case of pine-sawdust and slate fines; however, only forest and vineyard soil samples can be satisfactorily adjusted to the Langmuir model. These results could be useful to program appropriate management practices, especially when focusing on controlling P concentrations in different environmental compartments, as well as to correctly recycle the by-products and waste materials assayed.

Competitive and non-competitive cadmium, copper and lead sorption/desorption on wheat straw affecting sustainability in vineyards

Journal of Cleaner Production

http://dx.doi.org/10.1016/j.jclepro.2016.09.021

The novelty of this work lies on the consideration of wheat straw to retain Cu and other heavy metals in vineyards, in addition to its known potential to decrease erosion, thus facilitating the growth of new vine plants and contributing to sustainability in vineyard production. In this study we used batch-type experiments to investigate Cd, Cu and Pb competitive and non-competitive sorption/desorption on wheat straw. In non-competitive experiments, sorption sequence was Pb > Cd > Cu when the lowest molar concentrations (0.5 mmol L−1) were added, and Pb > Cu > Cd when the highest molar concentrations (6.0 mmol L−1) were added. Sorption curves indicated clearly higher sorption for Pb, lower initial sorption in the case of Cu, and certain trend to saturation of sorption sites for Cd. Data showed good adjustment to the Langmuir model just for Cd, whereas the Freundlich equation fitted well for all three metals. Desorption rates were low, in the order Pb < Cd < Cu. In the competitive experiment, the sorption sequence was Pb > Cu > Cd. The results indicate that competition clearly affected to Cd sorption, especially when the highest concentrations (6 mmol L−1) of the three heavy metals were added. The highest percentage of desorption in the competitive system corresponded to Cd, whereas Pb and Cu experienced clearly lower release. Comparing competitive and non-competitive experiments, Pb sorption was equivalent in the non-competitive and competitive trials, Cu sorption was slightly higher in the non-competitive than in the competitive experiment, and Cd sorption was clearly higher in the non-competitive trial. Percentage desorption decreased for Pb and for Cu in the competitive trial, whereas it was clearly higher for Cd in the competitive than in the non-competitive experiment. The overall results indicate that Pb, Cu and Cd can be retained by wheat straw (especially Cu and Pb), thus decreasing risks of pollution, which could be used to treat polluted waters, and could also give additional value to wheat straw mulching used to protect vineyards from erosion and Cu (and other heavy metals) pollution, thus contributing to sustainability in this productive sector.

Biological activities and novel applications of chalcones

Planta Daninha

http://dx.doi.org/10.1590/S0100-83582016340300022

This review provides information on the biological activities of chalcones (whether natural or synthetic derivatives) on different organisms, as well as an overview of the functions and possible new applications of these plant secondary metabolites on crop protection, as eco-friendly pesticides and weed control agents. Naturally occurring chalcones have been used in traditional medicine for many years; however, recent scientific advances have shown that these molecules have a broad range of biological activities in a variety of organisms. A review on the major sources of chalcones and the main molecular events involved in the modes of action of these natural products is achieved. Chalcones are molecules with a broad spectrum of biological activities, which are of great interest in agriculture to control weeds and unwanted pests.

Foto de Grupo - Septiembre de 2016

Investigadores del CIA en Ourense

Feruloyl esterase production by Aspergillus terreus CECT 2808 and subsequent application to enzymatic hydrolysis

Enzyme and Microbial Technology, 91 (2016) 52–58

http://dx.doi.org/10.1016/j.enzmictec.2016.05.011

Ferulic acid esterases (FAE) were produced by Aspergillus terreus CECT 2808 from vine trimming shoots (VTS) and corn cob. Later, the fungal extracts thus obtained were used to enzymatically release ferulic acid (FA) from both substrates. Our findings showed a higher FAE activity in the enzymatic extracts produced on corn cob (0.070 ± 0.004 U/mL). Nevertheless, the enzymatic extracts produced on VTS demonstrated a better performance for FA release from both corn cob (2.05 ± 0.01 mg/g) and VTS (0.19 ± 0.003 mg/g). This result was probably because of the higher xylanase/FAE ratio determined in VTS extract. Therefore, an additional assay was carried out by supplementing corn cob extract with a commercial xylanase to test the influence of FAE/xylanase ratio in FA release. The results revealed the relevance of the FAE/xylanase ratio for an optimal FA release.

Carbon fractionation in a mine soil amended with compost and biochar and vegetated with Brassica juncea L

Journal of Geochemical Exploration

Volume 169, October 2016, Pages 137–143

http://dx.doi.org/10.1016/j.gexplo.2016.07.021

The aim of this study was to evaluate the effect of the application of compost and biochar as soil amendments and planting of Brassica juncea L. to improve soil carbon fractions in a copper mine soil. A greenhouse experiment was carried out for 3 months amending the mine soil with increasing proportions of compost and biochar mixture (20, 40, 80 and 100%) and planting Brassica juncea L. The results showed that the addition of amendments increased soil pH from 2.7 to 8.66, TC from undetectable levels to 149 g kg− 1, SOC from undetectable levels to 128 g kg− 1 and TN from undetectable levels to 11.13 g kg− 1. Organic amending also increased DOC (dissolved organic carbon) from undetectable levels to 25.56 g kg− 1, FOM (carbon in the free organic matter) from undetectable levels to 38.04 g kg− 1, FAP (carbon in fulvic acids removed with phosphoric acid) from undetectable levels to 15.57 g kg− 1, as well as increased the humification ratio, the humification index, the polymerisation rate and the organic carbon in the humified fractions (humic acids, fulvic acids and humin). Soils amended and vegetated with Brassica juncea showed lower values for FOM and FAP and higher values for humification ratio and polymerisation rate than the amended not-vegetated soils. Therefore, the combination of compost and biochar as soil amendment can be considered an efficient treatment to improve soil carbon fractions, making it suitable for a field scale application.

Lipid characteristics of dry-cured “Tocino” during the manufacturing process. Effects of salting intensity and ripening temperature

Journal of Food Composition and Analysis, 52 (2016) 33–43

http://dx.doi.org/10.1016/j.jfca.2016.07.005

The fatty acid composition, the lipid characteristics and the colour parameters of Tocino, a salted and ripened meat product made from subcutaneous backfat from pig, were studied throughout manufacturing of the product. The effects of the ripening temperature and of the duration of the salting process were also studied. Ripening process caused a significant (P < 0.001) decrease in the total and some individual polyunsaturated fatty acids (C18:2n-6, C18:3n-3, C20:2n-6, C20:3n-6, C20:4n-6, and C20:3n-3), particularly in the polar lipid fraction (total polyunsaturated fatty acids descended from 13.6 to 3.5% of total methyl esters). Increased ripening temperature (from 8 to 12 °C) and longer duration of salting (from 2 to 4 days) caused a significantly greater decrease in the content of polyunsaturated fatty acids. The nutritional and health index values indicated that Tocino is not a healthy product. During the ripening stage, Tocino underwent moderate lipolysis and very intense lipid oxidation (final values of 3.57–5.09 mg KOH/g of fat and 0.84–1.16 mg malondialdehyde/kg). Increasing the ripening temperature significantly increased (P < 0.001) both lipolysis and fat oxidation, while increasing the duration of salting only had a significant positive effect on oxidation processes. Longer ripening times led to a significant increase (P < 0.001) in the b* values (from 8.81 to 18.7–23.7) and significant decreases in the a* (from 7.10 to −3.31 – −4.04) and L* (from 81.5 to 66.4–70.2) values.

Effect of high pressure treatment on the structural, mechanical and rheological properties of glucomannan gels

Food Hydrocolloids, 60 (2016) 437–444

http://dx.doi.org/10.1016/j.foodhyd.2016.04.015

The influence of high hydrostatic pressure (HHP) of 100 (C100), 200 (C200), 400 (C400) and 600 MPa (C600) on the structural, physicochemical, and thermo-rheological properties of aqueous glucomannan dispersions (AGD) was studied. Each AGD was prepared with a 5% concentration of deacetylated glucomannan (GM) at pH = 11 for use in the preparation of restructured fish products. The control (0 MPa) AGD (C0) exhibited a partially crystalline GM network with a glass transition temperature (Tg) of ∼75 °C. C0 gels at 25 °C were rigid, with high breaking force (BF), fracture constant (Kf) and complex modulus (G*) and low tanδ values due to the large number of physical junctions produced by complete deacetylation of the GM chains. This structural response was reflected in high water binding capacity (WBC) and colour (L*) and low cooking loss (CL). Specifically, 200 MPa reduced close packing ability in the crystalline regions, evidenced in the lower Tg∼65 °C and resulting in lower gel strength (S), Kf, G* and a higher viscous component (high tanδ), thus reducing the L* value. Conversely, 600 MPa increased the degree of cross-linking in C600, reinforcing the number and extent of crystalline regions, resulting in the broadening of the O–H stretching band in the FT-IR spectrum and producing a thermoset physical network with no glass transition region. Thus, C600 gel was firmer (higher G*) with greater S, and less flexible (lower strain amplitude-γmax). Consequently, depending on the textural properties desired in the final restructured fish product, the most appropriate pressure would be 200 MPa for softer final gels and 600 MPa for firmer and less deformable gels.

Combined alkali and hydrothermal pretreatments for oat straw valorization within a biorefinery concept

Bioresource Technology

http://dx.doi.org/10.1016/j.biortech.2016.08.077

The aim of this work was the evaluation of lime pretreatment combined or not with previous step of autohydrolysis for oat straw valorization. Under selected conditions of lime pretreatment, 96% of glucan and 77% of xylan were recovered and 42% of delignification was achieved. Xylose fermentation to ethanol by metabolic engineered Saccharomyces cerevisiae (MEC1133) strain improved the ethanol production by 22% achieving 41 g/L. Alternatively, first step of autohydrolysis (S0=4.22) allowed a high oligosaccharides recovery (68%) and subsequent lime pretreatment attained a 57% of delignification and 99% of glucan to glucose conversion. Oat straw processed by autohydrolysis and lime pretreatment reached the maximal ethanol concentration (50 g/L). Both strategies led to oat straw valorization into bioethanol, oligosaccharides and lignin indicating that these pretreatments are adequate as a first stage within an oat straw biorefinery.

Production and characterization of a novel distilled alcoholic beverage produced from blueberry (Vaccinium corymbosum L.)

Fruits, 2016, vol. 71(4), 215-220

http://dx.doi.org/10.1051/fruits/2016013

The cultivation of underutilized berries and the process production of high-value-added products, such as fruit-based spirits, could have a beneficial effect on the economy of disadvantaged rural mountain areas of Spain. However, production of a distilled alcoholic beverage from the blueberry has not been reported before. The pulp of blueberries var. Bluecrop was fermented with Saccharomyces cerevisiae IFI83, distilled by using a steam drag distillation system and the volatile compounds were determined by gas chromatography. In the distillate obtained, the mean concentrations of ethanol (45.3 mL 100 mL-1 distillate), volatile substances (317.1 g hL-1 absolute alcohol) and methanol (261.0 g hL-1 absolute alcohol) were in accordance with the specifications that the European Council (Regulation 110/2008) fixed for these compounds. In addition, the ratios [3-methyl-1-butanol/2-methyl-1-propanol] and [2-methyl-1-propanol/1-propanol] were 2.60 and 1.34, respectively, indicating that the distilled alcoholic beverage has a good organoleptic quality. The results suggest that blueberry can be successfully used for the production of a novel spirit with a good sensory quality that is safe for the consumers.

Loss of Gravitropism in Farnesene-Treated Arabidopsis Is Due to Microtubule Malformations Related to Hormonal and ROS Unbalance

PLOS ONE

http://journals.plos.org/

Mode of action of farnesene, a volatile sesquiterpene commonly found in the essential oils of several plants, was deeply studied on the model species Arabidopsis thaliana. The effects of farnesene on the Arabidopsis root morphology were evaluated by different microscopic techniques. As well, microtubules immunolabeling, phytohormone measurements and ROS staining helped us to elucidate the single or multi-modes of action of this sesquiterpene on plant metabolism. Farnesene-treated roots showed a strong growth inhibition and marked modifications on morphology, important tissue alterations, cellular damages and anisotropic growth. Left-handed growth of farnesene-treated roots, reverted by taxol (a known microtubule stabilizer), was related to microtubule condensation and disorganization. As well, the inhibition of primary root growth, lateral root number, lateral root length, and both root hairs length and density could be explained by the strong increment in ethylene production and auxin content detected in farnesene-treated seedlings. Microtubule alteration and hormonal unbalance appear as important components in the mode of action of farnesene and confirm the strong phytotoxic potential of this sesquiterpene.

Carbohydrate Polymers, 146 (2016) 20–25

http://dx.doi.org/10.1016/j.carbpol.2016.03.049

Eucalyptus globulus wood samples were treated with hot, compressed water to separate hemicelluloses (as soluble saccharides) from a solid phase mainly made up of cellulose and lignin. The liquid phase was dehydrated, and the resulting solids (containing pentoses as well as poly- and oligo- saccharides made up of pentoses) were dissolved and reacted in media containing an Acidic Ionic Liquid (1-butyl-3-methylimidazolium hydrogen sulfate) and a co-solvent (dioxane). The effects of the reaction time on the product distribution were studied at temperatures in the range 120–170 °C for reaction times up to 8 h, and operational conditions leading to 59.1% conversion of the potential substrates (including pentoses and pentose structural units in oligo- and poly- saccharides) into furfural were identified.

Lithological and land-use based assessment of heavy metal pollution in soils surrounding a cement plant in SW Europe

Science of The Total Environment 562, 2016, 179–190

http://dx.doi.org/10.1016/j.scitotenv.2016.03.198

We study the influence of phasing out a cement plant on the heavy metal (Hg, Pb and Cr) content in the surrounding soils, taking into account factors often neglected, such as contributions due to local lithology or land use. The range of total Hg was 10–144 µg kg− 1, reaching up to 41 and 145 mg kg− 1 for total contents of Pb and Cr, respectively. Forest soils showed higher concentration of Hg than prairie soils, indicating the importance of land use on the accumulation of volatile heavy metals in soils. In forest soils, total Hg showed a trend to decrease with soil depth, whereas in prairie soils the vertical pattern of heavy metal concentrations was quite homogeneous. In most cases, the distance to the cement plant was not a factor of influence in the soils content of the analyzed heavy metals. Total Pb and Cr contents in soils nearby the cement plant were quite similar to those found in the local lithology, resulting in enrichment factor values (EF's) below 2. This suggests that soil parent material is the main source of these heavy metals in the studied soils, while the contribution of the cement plant to Pb and Cr soil pollution was almost negligible. On the contrary, the soils surrounding the cement plant accumulate a significant amount of Hg, compared to the underlying lithology. This was especially noticeable in forest soils, where Hg EF achieved values up to 36. These results are of relevance, bearing in mind that Hg accumulation in soils may be an issue of environmental concern, particularly in prairie soils, where temporal flooding can favor Hg transformation to highly toxic methyl-Hg. In addition, the concurrence of acid soils and total-Cr concentrations in the range of those considered phytotoxic should be also stressed.