M. Gonçalves

Phase equilibria of CO2 + dl-α-tocopherol at temperatures from 292 K to 333 K and pressures up to 26 MPa

Abstract Phase equilibria for the system carbon dioxide + dl-α-tocopherol were studied, at temperatures from 292 K to 333 K and pressures up to 26 MPa. Pressure-composition isotherms were measured for the liquid and vapour phases in equilibrium, using the analytical method, from 9 MPa to 26 MPa, and at five temperatures between 298 K and 333 K. The projection of the liquid-liquid-vapour three phase equilibrium surface on the pressure-temperature plane has been followed from 292 K up to the critical end point, close to the critical temperature of CO2. The results were modelled using the Peng-Robinson equation of state and the composition-dependent mixing rules of Panagiotopoulos and Reid. Good agreement with experimental results was obtained.

Distinct Domestication Trajectories in Top-Fermenting Beer Yeasts and Wine Yeasts

Beer is one of the oldest alcoholic beverages and isxa0produced by the fermentation of sugars derived from starches present in cereal grains. Contrary to lager beers, made by bottom-fermenting strains of Saccharomyces pastorianus, a hybrid yeast, ale beers are closer to the ancient beer type and are fermented by S.xa0cerevisiae, a top-fermenting yeast. Here, we use population genomics to investigate (1) the closest relatives of top-fermenting beer yeasts; (2) whether top-fermenting yeasts represent an independent domestication event separate from those already described; (3) whether single orxa0multiple beer yeast domestication events can be inferred; and (4) whether top-fermenting yeasts represent non-recombinant or recombinant lineages. Our results revealed that top-fermenting beer yeasts are polyphyletic, with a main clade composed of at least three subgroups, dominantly represented by the German, British, and wheat beer strains. Other beer strains were phylogenetically close to sake, wine, or bread yeasts. We detected genetic signatures of beer yeast domestication by investigating genes previously linked toxa0brewing and using genome-wide scans. We propose that the emergence of the main clade of beer yeasts is related with a domestication event distinct from the previously known cases of wine and sake yeast domestication. The nucleotide diversity of the main beer clade more than doubled that of wine yeasts, which might be a consequencexa0of fundamental differences in the modes of beerxa0and wine yeast domestication. The higher diversity of beer strains could be due to the more intense and different selection regimes associated to brewing.

On the application of supercritical fluid extraction to the deacidification of olive oils

A recent suggestion on the applicability of supercritical fluid extraction to the deacidification of olive oils of high acid content was based on solubility data in clear disagreement with the results of other authors. In this work, we measured the solubilities of substances chosen for their importance in that extraction process, namely pure glycerol trioleate, the most abundant triglyceride in olive oil, and of a husk oil with a high acid content. Our results agree well with some of the previous reports on this subject. These seem to be a trustworthy data base, but more results are needed for a definite conclusion about the technical feasibility of the process.

Physico-chemical properties of chars obtained in the co-pyrolysis of waste mixtures

The present work aims to perform a multistep upgrading of chars obtained in the co-pyrolysis of PE, PP and PS plastic wastes, pine biomass and used tires. The quality of the upgraded chars was evaluated by measuring some of their physico-chemical properties in order to assess their valorisation as adsorbents precursors. The crude chars were submitted to a sequential solvent extraction with organic solvents of increasing polarity (hexane, mixture 1:1 v/v hexane:acetone and acetone) followed by an acidic demineralization procedure with 1M HCl solution. The results obtained showed that the upgrading treatment allow the recovery of 63-81% of the pyrolysis oils trapped in the crude chars and a reduction in the chars ash content in the range of 64-86%. The textural and adsorption properties of the upgraded chars were evaluated and the results indicate that the chars are mainly mesoporous and macroporous materials, with adsorption capacities in the range of 3.59-22.2 mg/g for the methylene blue dye. The upgrading treatment allowed to obtain carbonaceous materials with quality to be reused as adsorbents or as precursors for activated carbon.

Toxicity of char residues produced in the co-pyrolysis of different wastes.

Char residues produced in the co-pyrolysis of different wastes (plastics, pine biomass and used tyres) were characterized using chemical and toxicity assays. One part of the solid chars was submitted to extraction with dichloromethane (DCM) in order to reduce the toxicity of the char residues by removing organic contaminants. The different volatility fractions present in the extracted char (Char A) and in the raw char (Char B) were determined by progressive weight loss combustion. A selected group of heavy metals (Cd, Pb, Zn, Cu, Hg and As) was determined in both chars. The chars were subjected to the leaching test ISO/TS 21268 - 2, 2007 and the resulting eluates were further characterized by determining a group of inorganic parameters (pH, conductivity, Cd, Pb, Zn, Cu, Hg and As contents) and the concentrations of several organic contaminants (volatile aromatic hydrocarbons and alkyl phenols). An ecotoxicological characterization was also performed by using the bio-indicator Vibrio fischeri. The chemical and ecotoxicological results were analyzed according to the Council Decision 2003/33/CE and the criteria on the evaluation methods of waste ecotoxicity (CEMWE). The results obtained in this work indicated that the extraction with DCM is an effective method for the removal of organic contaminants of high to medium volatility from pyrolysis solid residues, thus decreasing their toxicity potential. Zn can be leached from the chars even after the DCM extraction treatment and can contribute to the ecotoxicity of the eluates obtained from chars. Both chars (treated and non treated with DCM) were classified as hazardous and ecotoxic wastes.

Determination of alkylphenols in eluates from pyrolysis solid residues using dispersive liquid–liquid microextraction

Dispersive liquid-liquid microextraction (DLLME) coupled with gas chromatography-mass spectrometry (GC-MS) was applied for the determination of 11 alkylphenols in eluates of chars produced in the co-pyrolysis of different wastes. The optimized DLLME procedure, 4 mL of sample solution, 15 microL of trichloroethylene as extraction solvent, 1 mL of acetone as dispersion solvent and addition of 15% (w/v) of NaCl, was validated. Under the optimum conditions, the enrichment factors were in the range of 82-180. Calibration curves were constructed for each analyte in pure water in the concentration range of 0.5-8 microg/L with correlation coefficients higher than 0.999. The limits of detection were between 0.07 and 0.17 microg/L. The repeatability of the method was evaluated using water samples fortified with the analyte mixture at two concentration levels: the relative standard deviation (RSD) values were between 3.7% and 8.0% for a concentration of 0.5 microg/L, and between 4.2% and 6.4% for a concentration of 3 microg/L. The recoveries of the analytes evaluated by fortification of real eluate samples were in the range of 67.9-97.9% for eluate 1 (obtained from a decontaminated char) and in the range of 61.9-101.4% for eluate 2 (obtained from the untreated char). o-Methylphenol presented low recoveries for both eluates showing a possible matrix effect. The results obtained show that this method is adequate for the determination of alkylphenols in environmental aqueous samples and presents itself as a fast and inexpensive technique, using minor amounts of organic solvents.

Determination of aromatic compounds in eluates of pyrolysis solid residues using HS-GC–MS and DLLME–GC–MS

A method for the determination of 15 aromatic hydrocarbons in eluates from solid residues produced during the co-pyrolysis of plastics and pine biomass was developed. In a first step, several sampling techniques (headspace solid phase microextraction (HS-SPME), static headspace sampling (HS), and dispersive liquid-liquid microextraction (DLLME) were compared in order to evaluate their sensitivity towards these analytes. HS-SPME and HS sampling had the better performance, but DLLME was itself as a technique able to extract volatiles with a significant enrichment factor. HS sampling coupled with GC-MS was chosen for method validation for the analytes tested. Calibration curves were constructed for each analyte with correlation coefficients higher than 0.999. The limits of detection were in the range of 0.66-37.85 ng/L. The precision of the HS method was evaluated and good repeatability was achieved with relative standard deviations of 4.8-13.2%. The recoveries of the analytes were evaluated by analysing fortified real eluate samples and were in the range of 60.6-113.9%. The validated method was applied in real eluate samples. Benzene, toluene, ethylbenzene and xylenes (BTEX) were the compounds in higher concentrations. The DLLME technique coupled with GC-MS was used to investigate the presence of less volatile contaminants in eluate samples. This analysis revealed the presence of significant amounts of alkyl phenols and other aromatic compounds with appreciable water solubility.

Removal of lead (Pb2+) from aqueous medium by using chars from co-pyrolysis

The effectiveness of chars from the co-pyrolysis of pine, used tires and plastic wastes for the removal of lead (Pb(2+)) from aqueous medium, was investigated. The chars were predominantly of macroporous nature, but the introduction of tires in the pyrolysis feedstock enhanced their mesoporous content as well as surface area. Pb(2+) sorption with the chars was a slow and unstable process in which sorption-desorption seems to be competing. The highest Pb(2+) removal (88%) was attained by the char resulting from the pyrolysis of a mixture composed by equal mass ratios of used tires and plastics, at 48 h of contact time. This char was also the one with the overall better performance for Pb(2+) sorption, achieving almost 100% of Pb(2+) removal on the study of the effect of adsorbent dose. Mixing the three raw materials for pyrolysis had no advantage for the resulting char concerning the removal efficiency of Pb(2+). The sorption mechanisms varied according to the pyrolysis feedstock: in chars from feedstock with pine, chemisorption involving complexation with oxygenated surface functional groups followed by cation exchange was the presumable mechanism. In tire rubber derived chars, cation exchange with Ca(2+), K(+), and Zn(2+) played the major role on Pb(2+) sorption.

Characterization of chars produced in the co-pyrolysis of different wastes: decontamination study.

The present work is devoted to the study of the decontamination of chars obtained in the co-pyrolysis of plastics, biomass and tyre wastes. The chars were extracted with several organic solvents of different polarities either individually or in sequence. The ability of each selected extractant to remove toxic pollutants was evaluated by comparing the extraction yields and by characterizing the crude extracts with a combination of chemical analysis and toxicity bioassays. Also, the mineral composition of the treated and non-treated chars was assessed. The results obtained in this study indicate that hexane is the more efficient extraction solvent to be used in the organic decontamination of chars obtained in the co-pyrolysis of plastics, tyres and biomass. A sequential extraction with solvents of increasing polarity can provide a better decontamination of the raw pyrolysis char than any individual extraction. The compounds removed from the char during the decontamination process are mainly aliphatic hydrocarbons and aromatic hydrocarbons, therefore a material that may be upgraded to be used as a fuel and/or as raw material for the organic chemical industry.

Leaching behaviour and ecotoxicity evaluation of chars from the pyrolysis of forestry biomass and polymeric materials

The main objective of this study was to assess the environmental risk of chars derived from the pyrolysis of mixtures of pine, plastics, and scrap tires, by studying their leaching potential and ecotoxicity. Relationships between chemical composition and ecotoxicity were established to identify contaminants responsible for toxicity. Since metallic contaminants were the focus of the present study, an EDTA washing step was applied to the chars to selectively remove metals that can be responsible for the observed toxicity. The results indicated that the introduction of biomass to the pyrolysis feedstock enhanced the acidity of chars and promote the mobilisation of inorganic compounds. Chars resulting from the pyrolysis of blends of pine and plastics did not produce ecotoxic eluates. A relationship between zinc concentrations in eluates and their ecotoxicity was found for chars obtained from mixtures with tires. A significant reduction in ecotoxicity was found when the chars were treated with EDTA, which was due to a significant reduction in zinc in chars after EDTA washing.