Algae from Cr-containing infiltrate bioremediation for valorised chemical production - Seasonal availability, composition, and screening studies on hydrothermal conversion.

Integrating bioremediation of toxic wastewater with value-added production is increasing interest, but - due to some essential problems - it is hardly applied in industrial practice. The aim of the study was an annual observation of the taxonomic and biochemical composition of various Cr-resistant algal communities grown in the existing Cr-containing infiltrate treatment system, selection of the most suitable algal biomass for infiltrates bioremediation and chromium-loaded algae conversion under mild subcritical conditions. Considering continuous availability and relatively constant chemical composition, Cladophora sp. was selected for utilisation in the chromium bioremediation system, simultaneously as a waste biomass source suitable for hydrothermal conversion. Screening studies conducted in a continuous pilot plant confirmed the possibility of selective extraction of saccharides and their separation from the metals remaining in the solid residual. The negligible concentration of metals in the obtained sugar-rich aqueous phase is essential for its further use in biotechnological processes.

Solid Foam Ru/C Catalysts for Sugar Hydrogenation to Sugar Alcohols-Preparation, Characterization, Activity, and Selectivity.

Sugar alcohols are obtained by hydrogenation of sugars in the presence of ruthenium catalysts. The research effort was focused on the development of solid foam catalysts based on ruthenium nanoparticles supported on active carbon. This catalyst was used in kinetic experiments on the hydrogenation of l-arabinose and d-galactose at three temperatures (90, 100, and 120 °C) and two hydrogen pressures (20 and 40 bar). Kinetic experiments were carried out with binary sugar mixtures at different d-galactose-to-l-arabinose molar ratios to study the interactions of these sugars in the presence of the prepared solid foam catalyst. The solid foam catalyst preparation comprised the following steps: cutting of the open-cell foam aluminum pieces, anodic oxidation pretreatment, carbon coating, acid pretreatment, ruthenium incorporation, and ex situ reduction. The carbon coating method comprised the polymerization of furfuryl alcohol, followed by a pyrolysis process and activation with oxygen. Incorporation of ruthenium on the carbon-coated foam was done by incipient wetness impregnation (IWI), using ruthenium(III) nitrosyl nitrate as the precursor. By applying IWI, it was possible to prepare an active catalyst with a ruthenium load of 1.12 wt %, which gave a high conversion of the sugars to the corresponding sugar alcohols. The catalysts were characterized by SEM, HR-TEM, TPR, and ICP-OES to interpret the catalyst behavior in terms of activity, durability, and critical parameters for the catalyst preparation. Extensive kinetic experiments were carried out in an isothermal laboratory-scale semibatch reactor to which gaseous hydrogen was constantly added. High selectivities toward the sugar alcohols, arabitol and galactitol, exceeding 98% were obtained for both sugars, and the sugar conversions were within the range of 53-97%, depending on temperature. The temperature effect on the reaction rate was very strong, while the effect of hydrogen pressure was minor. Regarding the sugar mixtures, in general, l-arabinose presented a higher reaction rate, and an acceleration of the hydrogenation process was observed for both sugars as the ratio of d-galactose to l-arabinose increased, evidently because of competitive interactions on the catalyst surface.

Intraocular toxicity caused by MEROCTANE perfluorocarbon liquid.

Serious intraocular toxicity cases have been reported worldwide after the use of different perfluorocarbon liquids. The current study reports for the first-time the clinical pictures of cases of acute intraocular toxicity caused by MEROCTANE, a perfluoro-octane commercialized by a Turkish company and distributed in many countries. A series of 18 cases from Chile and Spain was retrospectively analysed. To evaluate the impurity profile, a suspicious MEROCTANE sample (lot OCT.01.2013) was analysed by gas chromatography mass spectrometry and compared with a non-suspicious sample of the same commercial perfluoro-octane (lot OCT 722011). Cytotoxicity was tested following a direct-contact method, taking into consideration the high volatility and hydrophobicity of perfluoro-octane and following the ISO 10993 guideline. Cytotoxicity test showed clear cytotoxic effects of the analysed batch (less than 9% of cell viability). Moreover, chemical analysis demonstrated the presence of many contaminants, some highly toxic (acids and alcohols). Perfluorocarbon liquids are useful tools for intraocular surgery but companies and Agencies of Medical Devices must implement measures that guarantee the safety of these products based on both chemical and cytotoxicity analysis for every batch. Medical staff should be encouraged to report any suspected case to their respective National Agencies.

Chemical compounds causing severe acute toxicity in heavy liquids used for intraocular surgery.

Perfluorocarbon liquids (PFCLs) have been considered safe for intraocular manipulation of the retina, but since 2013 many cases of acute eye toxicity cousing blindness have been reported in various countries when using various commercial PFCLs. All these PFCLs were CE marked (Conformité Européenne), which meant they had been subjected to evaluation complying with the International Organization for Standardization (ISO) guidelines. These dramatic events raised questions about the safety of PFCLs and the validity of some cytotoxicity tests performed under ISO guidelines. Samples from toxic batches were analyzed by gas chromatography-mass spectrometry combined with Raman and infrared spectrometry. Perfluorooctanoic acid, dodecafluoro-1-heptanol, ethylbenzene and tributyltin bromide were identified and evaluated by a direct contact cytotoxicity test using ARPE-19 cell line, patented by our group (EP 3467118 A1). Perfluorooctanoic acid at a concentration of >0.06 mM and tributyltin bromide at a concentration of ≥0.016 mM were shown to be toxic, whereas the concentration found in the toxic samples reached 0.48 mM, and 0.111 mM, respectively. These finding emphasized the idea that determination of partially fluorinated compounds are not enough to guarantee the safety of these medical devices.

Production of molecular weight fractionated hemicelluloses hydrolyzates from spent coffee grounds combining hydrothermal extraction and a multistep ultrafiltration/diafiltration.

Spent coffee grounds are a huge residual stream from instant coffee makers. The production of spent coffee oil and molecular weight fractionated hemicellulose hydrolysates via supercritical CO2 and a hydrothermal treatment followed by concentration, separation, and purification through cascade ultrafiltration/diafiltration (30-10-5 kDa) was studied. Hemicelluloses extraction yield reached 3.49 g/100 g of dry defatted spent coffee after 40 min at 160 °C. The ultrafiltration system allowed concentrating up to 5-fold certain groups of hemicellulose, being most of them retained in the first membrane. Hemicellulose concentration and molecular weight of the feed exerted a great influence on the mass transfer through the membrane due to the formation of aggregates. However, purification through diafiltration allowed both to decrease by-products retentions from 45.6% to 8.7%, increasing the molecular weight of each fraction. Six hemicellulose products were obtained with purities between 83.7 and 97.8 wt% and weight-average molecular weights between 1641 and 49,733 Da.

Hydrothermal extraction of hemicellulose: from lab to pilot scale.

A flow-through reactor for hemicelluloses extraction with hot pressurized water was scaled with a factor of 73. System performance was evaluated by comparing the temperature profile, extraction yield and kinetics of the two systems, performing experiments at 160 and 170°C, 11barg for 90min, using catalpa wood as raw material. Hemicellulose yields were 33.9% and 38.8% (lab scale 160°C and 170°C) and 35.7% and 41.7% (pilot scale 160°C and 170°C). The pilot reactor was upgraded by designing a manifold system capable to provide samples with different liquid residence time during the same experiment. Tests at 140, 150, 160 and 170°C were carried for 90min. Increasing yields (9.3-40.6%) and decreasing molecular weights (4078-1417Da) were obtained at increasing the temperature. Biomass/water ratio of 1/27 gave total average concentration of xylose of 0.4g/L (140°C) to 1.8g/L (170°C).

Hydrothermal fractionation of woody biomass: Lignin effect on sugars recovery.

Subcritical water was employed to fractionate woody biomass into carbohydrates and lignin. Nine urban trees species (hardwood and softwood) from Spain were studied. The experiments were carried out in a semi-continuous reactor at 250 °C for 64 min. The hemicellulose and cellulose recovery yields were between 30%wt. and 80%wt. while the lignin content in the solid product ranged between 32%wt. and 92%wt. It was observed that an increment of solubilized lignin disfavored the hydrolysis of hemicelluloses. It was determined that the maximum extraction of hemicellulose was achieved at 20 min of solid reaction time while the extraction of celluloses not exhibited a maximum value. The hydrolysis of hemicellulose and cellulose would be governed by the hydrolysis kinetic and the polymers accessibility. In addition, the extraction of hemicellulose was negatively affected by the lignin content in the raw material while cellulose hydrolysis was not affected by this parameter.

Simulation and flavor compound analysis of dealcoholized beer via one-step vacuum distillation.

The coupled operation of vacuum distillation process to produce alcohol free beer at laboratory scale and Aspen HYSYS simulation software was studied to define the chemical changes during the dealcoholization process in the aroma profiles of 2 different lager beers. At the lab-scale process, 2 different parameters were chosen to dealcoholize beer samples, 102mbar at 50°C and 200mbar at 67°C. Samples taken at different steps of the process were analyzed by HS-SPME-GC-MS focusing on the concentration of 7 flavor compounds, 5 alcohols and 2 esters. For simulation process, the EoS parameters of the Wilson-2 property package were adjusted to the experimental data and one more pressure was tested (60mbar). Simulation methods represent a viable alternative to predict results of the volatile compound composition of a final dealcoholized beer.