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In order to understand the cutaneous water loss in the desert-adapted and venomous lizard Heloderma suspectum, the microscopic structure and lipid composition of epidermal molts have been examined using microscopic, spectroscopic and chemical analysis techniques. The molt is formed by a variably thick, superficial beta-layer, an extensive mesos-region and few alpha-cells in its lowermost layers. The beta-layer contains most corneous beta proteins while the mesos-region is much richer in lipids. The proteins in the mesos-region are more unstructured than those located in the beta-layer. Most interestingly, among other lipids, high contents of cholesteryl-β-glucoside and cholesteryl sulfate were detected, molecules absent or present in traces in other species of squamates. These cholesterol derivatives may be involved in the stabilization and compaction of the mesos-region, but present a limited permeability to water movements. The modest resistance to cutaneous water-loss of this species is compensated by adopting other physiological strategies to limit thermal damage and water transpiration as previous eco-physiological studies have indicated. The increase of steroid derivatives may also be implicated in the heat shock response, influencing the relative behavior in this desert-adapted lizard.

Background: Information about the adherence to scientific societies guidelines in the ‘real-world’ therapeutic management of oncological patients are lacking. This multicenter, prospective survey was aimed to improve the knowledge relative to 2017-2018 recommendations of the Italian Association of Medical Oncology (AIOM). Patients and methods: Treatment-naive adult patients with pancreatic adenocarcinoma were enrolled. Group A received adjuvant therapy, group B received primary chemotherapy, and group C had metastatic disease. The results on patients accrued until 31 October 2019 with a mature follow-up were presented. Results: Since July 2017, 833 eligible patients of 923 (90%) were enrolled in 44 Italian centers. The median age was 69 years (range 36-89 years; 24% >75 years); 48% were female; 93% had Eastern Cooperative Oncology Group (ECOG) performance status (PS) score of 0 or 1; group A: 16%, group B: 30%; group C: 54%; 72% Nord, 13% Center, 15% South. In group A, guidelines adherence was 68% [95% confidence interval (CI) 59% to 76%]; 53% of patients received gemcitabine and 15% gemcitabine þ capecitabine; median CA19.9 was 29 (range 0-7300; not reported 15%); median survival was 36.4 months (95% CI 27.5-47.3 months). In group B, guidelines adherence was 96% (95% CI 92% to 98%); 55% of patients received nab-paclitaxel þ gemcitabine, 27% FOLFIRINOX, 12% gemcitabine, and 3% clinical trial; median CA19.9 was 337 (range 0-20220; not reported 9%); median survival was 18.1 months (95% CI 15.6-19.9 months). In group C, guidelines adherence was 96% (95% CI 94% to 98%); 71% of patients received nabpaclitaxel þ gemcitabine, 16% gemcitabine, 8% FOLFIRINOX, and 4% clinical trial; liver and lung metastases were reported in 76% and 23% of patients, respectively; median CA19.9 value was 760 (range 0-1374500; not reported 9%); median survival was 10.0 months (95% CI 9.1-11.1 months). Conclusions: The GARIBALDI survey shows a very high rate of adherence to guidelines and survival outcome in line with the literature. CA19.9 testing should be enhanced; nutritional and psychological counseling represent an unmet need. Enrollment to assess adherence to updated AIOM guidelines is ongoing.

Two novel protocols for the chemical valorization of polyhydroxybutyrate (PHB) were developed, aiming at the production of two bio-based molecules: methyl 3-hydroxybutyrate (MHB) and methyl 3-methoxybutyrate (MMB). Optimized reaction conditions were applied to pure PHB and PHB inclusions inside bacterial cells as starting materials. MHB was synthesized through a single-step catalytic methanolysis, while MMB was synthesized through a three-step process: thermolytic distillation to give crotonic acid (CA), esterification to give methyl crotonate (MC), and oxa-Michael addition of MeOH. The obtained MHB and MMB were tested as solvents for the recovery of PHB itself both from freeze-dried single strain cultures (SSC) and mixed microbial cultures (MMC) with low to medium contents of PHB (22-57 wt %). High PHB recovery was achieved: up to 96 ± 1% through MHB and up to 98 ± 1% through MMB. Extraction from MMC slurry (with a PHB content of 39% on dry weight) was also performed, recovering 77 ± 2% using MHB and 92 ± 2% using MMB. High purities and excellent molecular weights and polydispersity indexes of extracted PHB were obtained with both MHB and MMB. Solubility in water, octanol/water partition coefficients (log Kow), and aerobic ready biodegradability of both solvents were also evaluated.

A novel thermolytic distillation process was developed to depolymerize polyhydroxybutyrate (PHB) for the selective production of crotonic acid. The conditions adopted (170 °C, 150 mbar) were applied to pure PHB and PHB-enriched bacteria containing 60 and 30% of PHB, giving a recovery of crotonic acid of 92, 78 and 58%, respectively. The high efficiency of the developed process poses the basis for a drop-in production of bio-based crotonic acid, whose versatility as a platform chemical has been investigated through a photochemical approach. The photocatalytic addition (promoted by tetrabutylammonium decatungstate – TBADT) of aliphatic and aromatic aldehydes to crotonic acid took place under solar-simulated light irradiation. TBADT triggered the in situ formation of valuable acyl radicals from the corresponding aldehydes, thus inducing the desired hydroacylation via radical conjugate addition. Notably, the functionalization took place in a satisfactory yield quite independently of the adopted sample of crotonic acid (whether commercial or bio-based).

A novel hyphenated Pyrolysis-Anaerobic Digestion prototype (Py-AD) was tested in order to evaluate the potential of hybrid thermochemical biological process to produce methane from woody biomass. An auger intermediate pyrolyzer was directly coupled to two biological reactors optimized for the digestion of residual condensable compounds and gas produced by pyrolysis of softwood. The Py-AD was monitored for 16 months and a detailed chemical analysis of the main fractions, gas (pyrobiogas), biochar, aqueous phase and pyrolytic lignin was performed under regime conditions. The results from Py-AD and those from experiments with bench-scale pyrolysis and fermentation reactors analysis provided information on the overall performance of the Py-AD and mass and energy balance based on chemical oxygen demand. Py-AD allowed to obtain, with acceptable volumetric productivity, a pyrobiogas with a composition approaching that of biogas (47 %v/v CH4 and 45 %v/v CO2). Pyrobiogas yield was about half of the theoretical value calculated from gas and liquid fractions. A preliminary technical evaluation of the process confirmed the feasibility of Py-AD and its value to produce carbon negative fuels with simple equipment and low waste generation. Important key constraints of the process were also evidenced in the study.

An overview of the main polyhydroxyalkanoates (PHA) recovery methods is here reported, by considering the kind of PHA-producing bacteria (single bacterial strains or mixed microbial cultures) and the chemico-physical characteristics of the extracted polymer (molecular weight and polydispersity index). Several recovery approaches are presented and categorized in two main strategies: PHA recovery with solvents (halogenated solvents, alkanes, alcohols, esters, carbonates and ketones) and PHA recovery by cellular lysis (with oxidants, acid and alkaline compounds, surfactants and enzymes). Comparative evaluations based on the recovery, purity and molecular weight of the recovered polymers as well as on the potential sustainability of the different approaches are here presented.

In order to deal with hydrothermal liquefaction wastewater (HTWW), a new anaerobic-aerobic continuous process was developed. The process, which included a sequence of Up-Flow Anaerobic Sludge Blanket (UASB) and downstream aerobic Continuously Stirred Tank Reactor (CSTR), was tested on the HTWW obtained from Waste to Fuel® demo plant developed by ENI s.p.a. [ 1 ]. Performance of the system was evaluated in term of methane yield and chemical oxygen demand (COD) abatement capability. Detailed fate of organic compounds was evaluated through different analytical techniques, highlighting main issues and potential of HTWW biological treatment. The system was fed with neat HTWW (189 gCOD L−1) for 2.5 y, with variable organic loading rate (OLR) and minimal external inputs. UASB reactors converted most of HTWW organics into volatile fatty acids (VFA) and methane with concurrent precipitation of oily like insoluble, whereas aerobic CSTR removed VFA from anaerobic effluent. Under regime conditions (ORL equal to 0.5 gCOD L−1 d−1) COD decreased from 189 to 6.6 gCOD L-1, showing 97 % COD abatement with the coupled anaerobic-aerobic treatment. Such a COD abatement was obtained by means of multiple effects, namely biomethanation, precipitation of organic matter and aerobic oxidation of fermentation products (VFA produced in anaerobic digestion) and subsequent aerobic oxidation (in downstream aerobic reactor). These effects accounted for 43, 40 and 17 % of the total COD decrease, respectively. Inhibition phenomena were the key challenge for improving methane yields and system productivities. The overall results confirmed that valorization of HTWW is a feasible task, albeit rather challenging.

In view of the potential application of pyrolysis-based biotechnologies, it is crucial to look for novel microorganisms able to convert pyrolysis-derived products, in particular bio-oil water-soluble constituent, into valuable compounds. For the first time, this paper proposed a survey on a collection of bacterial, yeast, and fungal strains with well-known industrial properties as well as new bacterial isolates in order to select microbes able to both tolerate bio-oil inhibitors and convert bio-oil into valuable products. This survey found that bio-oil aqueous phase (BOAP) obtained from intermediate pyrolysis could be metabolized as it is by fungal strains whereas several dilutions are needed to do not hamper cell viability of many tested yeast and bacterial isolates. To process BOAP into valuable products, the yeast Saccharomyces cerevisiae L13, selected as the most industrially relevant tested strain, was adopted to convert bio-oil aqueous fraction hydrolysate into ethanol without any detoxification step. The fermenting performances were much greater than those of the benchmark yeast strain and S. cerevisiae L13 proved to be a strong candidate for bioethanol production from BOAP hydrolysates. This study demonstrated that the search for microorganisms is a promising approach to the future development of pyrolysis oil-based biorefinery platforms.

An analytical procedure based on off-line analytical pyrolysis was utilized to study the bioaccumulation of polystyrene microspheres with different size (3 μm and 45 μm) by gills and digestive glands of Mytilus galloprovincialis exposed for 4 days at different concentrations of the polymer (3 μm: 0.015–1.5 μg L−1; 45 μm: 5−500 μg L−1). The mussel tissues were treated with 10 % KOH at 90 °C with good digestion efficiency (97 ± 1 %) and extracted with toluene. After evaporation the residue was pyrolysed at 500 °C with a resistively heated platinum filament. Pyrolysis products were trapped onto a charcoal cartridge, eluted with toluene and analysed by GC–MS under selected ion monitoring. Polystyrene concentrations were determined by the internal standard method from the peak areas of styrene. The procedure provided information on the effect of particle size, exposure level and tissue type on the bioaccumulation of polystyrene particles in terms of mass concentrations. Accumulation was observed in digestive glands, not in gills. The accumulation of larger particles in digestive glands increased with increasing concentrations of polystyrene in water and peaked at 14 ± 4 μg g−1. The reduction of lysosome membrane stability was observed for both particles size at a water concentration of 10,000 particles per litre, that corresponded to a lower mass concentration for the smaller particles. This study confirmed the capability of analytical pyrolysis to provide microplastic concentrations in terms of mass concentration in complex matrices.

The recycling of polyhydroxybutyrate (PHB) via depolymerization-polymerization is here proposed and assessed for the first time. Effective depolymerization of PHB to crotonic acid through a thermolytic distillation at mild conditions (170 °C and 150 mbar), and without the need of any catalyst, gives a crotonic acid-enriched condensate (94% yield and 98% selectivity towards trans-crotonic acid) that was used without any further purification as a substrate for producing renewed PHB with a culture of Cupriavidus necator. The yield of PHB (0.6 g PHB per g of crotonic acid), final PHB content (63%), and PHB-molecular weight (1.5 MDa) confirmed the technical feasibility of this tandem approach, with a 55% overall yield. A preliminary evaluation of the energy consumption of various depolymerization approaches indicated that the thermolytic distillation consumes 20–25% less energy than previously reported methods; the energy requirement for producing crotonic acid from PHBwaste with 50% moisture has a still acceptable energy demand (4 MJ/kgcrotonic acid), comparable to the energy required for obtaining fermentable sugars (4.4 MJ/kgsugar) to be used for feeding bacteria that accumulate PHB.

Bioreactors are commonly used apparatuses generally equipped with several built-in specifications for the investigation of biological treatment studies. Each bioreactor test may require different types of specialty such as heating, agitation, re-circulation and some further technologies like online sensoring. Even thought, there are many ready-to-use fabricated bioreactors available in the market with a cost usually over than 1000 €, it is often not possible to access those advanced (but inflexible) systems for many students, young-researchers or small-scale private R&D companies. In this work, a new low cost (≈100€) packed-bed anaerobic bioreactor was developed, and all methodological details including open-source coding and 3D design files are shared with informative descriptions. Some preliminary tests were conducted to verify the developed bioreactor system's credibility in terms of leak-tightness, accurate gas monitoring, temperature controlling, and mass balance (COD-eq) coverage, which all have shown a very promising performance.•A consistent model bioreactor that will be called as “tetrapod” was developed for anaerobic treatment of challenging substrates such as pyrolytic liquids.•Coarse biochar grains were used as an organic packing material to stimulate the microbial bioconversion by increasing the active surface area for the attached-growth anaerobic mixed microbial culture (MMC).•An open-source Arduino based digital gasometer was developed for online monitoring of biogas change in the lab-scale system. Arduino was also used as a digital controller for maintaining pulse-mode liquid recirculation of the bioreactor., Graphical abstract Image, graphical abstract

Dimethicone (poly(dimethylsiloxane), PDMS) and its copolymers bearing a poly(ethylene glycol) (PEG) side chain (PEG-12 dimethicone and PEG-8 dimethicone) are utilised as ingredients in personal care products. These materials along with bis-PEG-18 methyl ether dimethyl silane were analysed by Py-GC–MS. The pyrolysates of dimethicone was dominated by cyclic dimethyl siloxanes from D3 to over D10. Besides Dn, the pyrolysates of PEG-dimethicone were featured by the presence of linear dimethyl siloxanes Ln. Hydroxylated siloxanes were also tentatively identified. Pyrograms were also characterised by PEG oligomers with different terminal groups (hydroxyl, ethyl, ethenyl). The molecular structure of pyrolysis products from the combined structural units of PDMS and PEG could not be assigned. Internal standard calibration protocols using pyrolysis products of PEG-12 dimethicone (L6, L8, L9, and triethyleneglycol monoethyl ether) exhibited satisfactory linearity (R2 > 0.992) in the 0.75−58 μg range and repeatability (RSD < 15 %). Three samples of dried sewage sludge from a municipal water treatment plant were extracted with tetrahydrofuran and the extracts analysed by Py-GC–MS. The pyrograms were characterised by intense signals due to the lipid matrix (hydrocarbons, fatty acids, steranes, sterenes, sterols). Dn and Ln were identified indicative for the presence of siloxanes at levels around 60−290 μg gdw−1, while pyrolytic markers of PEG were not revealed. The recovery of PEG-12 dimethicone (17 μg) in spiked sample was 76 %. Galaxolide, galaxolide lactone and triclosan were identified in the pyrograms. The results of this study evidenced the potential of Py-GC–MS as a screening tool for the determination of cosmetic ingredients in sewage sludge.

Polyhydroxyalkanoates (PHA) are a key constituent of excess sludge produced by Aerobic Sewage Sludge Treatment plants. The accumulation of significant amount of PHA inside aerobic microbial cells occurs when a surplus of an easily degradable carbon source (e.g., volatile fatty acids, VFA) is found in combination with other nutrients limitation. Herein, hydrothermal treatment (HT) of PHA-containing sludge at 300 and 375 °C was demonstrated to be effective in converting most (>70% w/w) of the bacterial PHA stored inside microbial cells into alkene/CO2 gas mixtures. Simultaneously, most of non-PHA biomass was converted into water-soluble compounds (50% carbon yield) that were acidogenic fermented to produce volatile fatty acids, ideal substrate to feed aerobic bacteria and produce more PHA. According to results here presented, HT of excess sludge with moderate (13%) PHA content can produce about 50 kg of alkenes per tonne of suspended solids treated, with a significant reduction of sludge mass (80% reduction of wet sludge volume) and consequent disposal cost.

Volatile fatty acids (VFAs) are ideal substrates for mixed microbial cultures to synthesize polyhydroxyalkanoates. Therefore, VFA pertraction from anaerobic diluted fermentation broths to slightly alkaline aerobic medium becomes a crucial step to develop a closed loop concept in which VFAs are used for polyhydroxyalkanoate production. New liquid membranes (LMs) based on lipophilic amines and biodiesel were proposed for this purpose. The performance of each LM was tested through a VFA distribution coefficient test and pertraction kinetic experiments. The transfer of VFAs from LM to receiving solution was the main limiting step of the process, with flux rates of 0.001–0.04 cm3 cm−2 h−1 (best LM with 10 wt% of trioctylamine). The biocompatibility of trioctylamine -biodiesel LM towards anaerobic bacteria was confirmed through a 15-d acidogenic fermentation test. Trioctylamine-biodiesel LM was finally tested in a specifically designed continuous pertraction module, where VFA transfer rates of 1–3 h−1 were achieved.

A transdisciplinary approach that integrates thermochemical conversions and biological transformations for valorizing C-content and chemical energy of anaerobically digested sewage sludge and producing biopolymers (polyhydroxyalkanoates, PHA) and drop-in chemicals (crotonic acid) has been presented here. Hydrothermal carbonization has increased by 10-times the soluble COD of sewage sludge, allowing it to split 44-54% of its COD into an aqueous phase (HTCap) enriched in small fermentable organic molecules; the coupling of acidogenic fermentation and aerobic fermentation converted these substrates first into volatile fatty acids (20% of CODHTCap) and then into PHA (about 20% of CODVFA). The extraction of microbial biomass with dimethyl carbonate (DMC) allowed high quality PHA to be produced, with a high molecular weight (0.9 MDa) and a percentage of medium chain monomers (hydroxyvalerate and hydrohexanoate) close to 12%. The postextraction microbial biomass, still containing a relevant portion of "unextractable" PHA, was last treated at 300 °C to selectively convert the PHA-backbone into crotonic acid with a 42% yield on PHA content basis.

A “cradle-to-grave” life cycle assessment is performed to identify the environmental issues of polyhydroxyalkanoates (PHAs) produced through a hybrid thermochemical-biological process using anaerobically digested sewage sludge (ADSS) as feedstock. The assessment includes a measure of the energy performance of the process. The system boundary includes: (i) Sludge pyrolysis followed by volatile fatty acids (VFAs) production; (ii) PHAs-enriched biomass production using a mixed microbial culture (MMC); (iii) PHAs extraction with dimethyl carbonate; and iv) PHAs end-of-life. Three scenarios differing in the use of the syngas produced by both pyrolysis and biochar gasification, and two more scenarios differing only in the external energy sources were evaluated. Results show a trade-off between environmental impacts at global scale, such as climate change and resources depletion, and those having an effect at the local/regional scale, such as acidification, eutrophication, and toxicity. Process configurations based only on the sludge-to-PHAs route require an external energy supply, which determines the highest impacts with respect to climate change, resources depletion, and water depletion. On the contrary, process configurations also integrating the sludge-to-energy route for self-sustainment imply more onsite sludge processing and combustion; this results in the highest values of eutrophication, ecotoxicity, and human toxicity. There is not a categorical winner among the investigated configurations; however, the use of a selected mix of external renewable sources while using sludge to produce PHAs only seems the best compromise. The results are comparable to those of both other PHAs production processes found in the literature and various fossil-based and bio-based polymers, in terms of both non-biogenic GHG emissions and energy demand. Further process advancements and technology improvement in high impact stages are required to make this PHAs production process a competitive candidate for the production of biopolymers on a wide scale.

This study proposes FTIR spectroscopy in the far-infrared region (FarIR) as an alternative method for the characterisation of natural resins. To this purpose, standards of natural resins belonging to four different categories (sesquiterpenic, i.e. elemi, shellac; diterpenic, i.e. colophony, Venice turpentine; diterpenic with polymerised components, i.e. copal, sandarac; triterpenic, i.e. mastic and dammar) used as paint varnishes have been analysed by FarIR spectroscopy in ATR mode. Discrimination between spectral data and repeatability of measurements have been magnified and verified using principal component analysis, in order to verify the effectiveness of the method in distinguishing the four resin categories. The same samples were analysed in the MidIR range, but the spectral differences between the different categories were not evident. Moreover, the method has been tested on historical samples from the painting "La Battaglia di Cialdiran" (sixteenth century) and from a gilded leather (seventeenth century). In the first case, FarIR spectroscopy allowed confirmation of the results obtained by analytical pyrolysis. In the latter, FarIR spectroscopy proved successfully, effective in the identification of the superficial resin layer that could not be detected with the bulk chromatographic analyses.

Germination tests were performed in order to assess biochar quality. Biochars were obtained from corn stalk pellets using two pyrolysis reactors and five different combinations of residential time and temperature. The five biochars were employed at diverse concentrations to perform germination tests of garden cress (Lepidium sativum L.) and perennial ryegrass (Lolium perenne L.) in soil-less Petri dishes bioassay. In general, the higher is pyrolysis temperature the higher is carbonization rate; the pH values range from 8 to 11 while EC values range from 16,2 to 4860 microS.cm-1, both rising with increasing biochars in the suspension. Concerning germination tests, at lower concentrations no significant differences arise from the thesis otherwise, the highest concentration seems to determine a decrease in the number of germinated seeds and a weak grow of sprouts.

Lipid extraction is a critical step in the development of biofuels from microalgae. The use of toxic and polluting organic solvents should be reduced and the sustainability of the extraction procedures improved in order to develop an industrial extraction procedure. This could be done by reducing solvent amounts, avoiding use of harmful solvents, or eliminating the solvent at all. Here we describe two new processes to extract hydrocarbons from dried and water-suspended samples of the microalga Botryococcus braunii. The first one is a solvent-based procedure with switchable polarity solvents (SPS), a special class of green solvents easily convertible from a non-ionic form, with a high affinity towards non-polar compounds as B. braunii hydrocarbons, into an ionic salt after the addition of CO2, useful to recover hydrocarbons. The two SPS chosen for the study, based on equimolar mixtures of 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and an alcohol (DBU/octanol and DBU/ethanol), were tested for the extraction efficiency of lipids from freeze-dried B. braunii samples and compared with volatile organic solvents extraction. The DBU/octanol system was further evaluated for the extraction of hydrocarbons directly from algal culture samples. DBU/octanol exhibited the highest yields of extracted hydrocarbons from both freeze-dried and liquid algal samples (16 and 8.2%, respectively, against 7.8 and 5.6% with traditional organic solvents). The second procedure here proposed is the thermochemical conversion of algal biomass by using pyrolysis; this process allowed to obtain three valuable fractions, exploitable for energy purpose, fuel production, and soil carbon storage: a volatile fraction (37% on dry biomass weight), a solid fraction called biochar (38%) and, above all, a liquid fraction named bio-oil (25%), almost entirely composed by hydrocarbon-like material, thus directly usable as fuel.

Lignin, the most abundant aromatic biopolymer on Earth, is extremely recalcitrant to degradation. Therefore, the presence of lignin in the biomass constrains and challenges the improvement of bioconversion techniques. This paper presents a preliminary life cycle assessment of an innovative combination of technologies to convert high ligno-cellulosic biomass into useful products, primary energy and fuels. The experimental process exploits residual biomasses with high ligno-cellulosic content for the production of biogas and consists on the combined use of thermo-chemical (pyrolysis) and biological (anaerobic digestion) pathways and would allow for a wider range of exploitable residual biomasses, higher yields, product diversification and other advantages for agro-energy industries and the environment. Residual biomass energy sources – such as manure and corn “stover” (cobs, leaves, etc.) or other by-products of farming or other activities – represent a low cost feedstock source that can be used for energy production. Moreover, the employment of residual biomass might be less controversial than those of harvested biomass, which raise environmental concerns or issues related to competition with food needs. These concerns and issues have resulted in growing interests in alternative, non-edible biomass resources. Corn stover, typically composed of 35−40% cellulose, 20−25% hemicellulose, and 15−20% lignin, is very abundant agricultural residue but its raw substrate is recalcitrant to bioconversion and this represents the major obstacle to its cost-effective exploitation. The experimental processing of corn stover through a pyrolytic pre-treatment provides a digestible feed for anaerobic bacteria producing biogas. The process provides also some valuable co-products, such as biochar and digestate which can be used as soil fertilizers. The experimentation has been conducted at a laboratory scale and is divided into three steps: 1) drying of corn stover; 2) pyrolysis of the corn stover, with the production of bio-oil, gas and biochar and 3) anaerobic digestion of bio-oil and gas, with the production of methane, CO2, digestate. The functional unit was defined as 10 t of dried corn stover, the system boundaries include the three above-mentioned steps. This first assessment has focused on the energy and carbon balance of the process. Calculations have been conducted with experimental data, when available, and with data from literature, always assuming a conservative approach, in particular regarding the amount of bio-oil obtainable from the pyrolysis of corn stover, pyrolysis energy consumption, heating requirements, methane yield. Results show a ratio between spent and produced energy always higher than 1, with a mean value of 2.6 ± 1.3. The pyrolytic pre-treatment allows for an 2.5 fold increase of the carbon available for bio-methanation. As for the C balance, apart from the avoided emissions due to fossil fuels replacement, a relevant contribution is given by biochar, which appears able to store C in soils and is widely studied for this property. Results have been compared to the conventional anaerobic digestion of corn stover.

In questo lavoro vengono illustrati i risultati preliminari relativi ad una sperimentazione condotta su scala di laboratorio al fine d'integrare la frazione lignocellulosica di biomassa nella filiera di produzione del biogas. Lo studio mostra come l'utilizzo combinato di tecniche termochimiche e biochimiche sia in grado di estendere la gamma delle biomasse originarie da cui ottenere biogas, con maggiori rese, una diversificazione di prodotto e altri numerosi vantaggi per l'industria delle agro-energie e l'ambiente. In particolare viene presentato un procedimento di trasformazione di stocchi di mais che prevede un pretrattamento di tipo pirolitico mirato alla creazione di un substrato biodigeribile e successiva produzione di biogas. I risultati preliminari mostrano un rapporto tra energia consumata ed energia prodotta compreso tra 2 nel caso peggiore e 3 nel caso migliore. I risultati mostrano anche come il pretrattamento pirolitico renda disponibile per il processo di biometanazione una quantità di carbonio pari ad almeno 2,5 volte quella ottenibile da un processo privo del pretrattamento. Il processo sperimentato permette di diversificare i sottoprodotti attraverso la produzione di biochar. Il biochar ottenuto è oggetto di un particolare approfondimento che mostra la capacità di riduzione delle emissioni di gas serra e il potenziale uso come ammendante in agricoltura.

The scope of this study was to evaluate the importance of cytotype and cutting system on the pyrolytic production of semi/volatile compounds that ultimately ends up into bio-oil. The approach was based on the analysis of pyrolysis products by a microscale pyrolysis apparatus. An upland (trailblazer) and a lowland cytotype (Alamo) under one- (winter) or two-cut (summer plus winter re-growth) systems were compared. Pyrolysis experiments were conducted by means of a platinum filament analytical pyrolyser at 700 °C and evolved products were analysed by GC-MS and quantified by internal calibration. Yields (by weight relative to pyrolysed biomass amount) were determined on a suite of pyrolysis products representative of chemical families, namely organic acids, aldehydes, lignin phenols and C5-C6 cyclic carbohydrate derivatives.

Vantaggi della pirolisi in colture da biomassa

Background Cyclosporin A is a powerful immunosuppressive drug with considerable impact on transplants and is able to modify extracellular matrix (ECM) composition. It has recently been demonstrated that cyclosporin A stimulates the production of the cytokine family. Cytokines such as interleukin, transforming growth factor β 1 , and bone morphogenetic protein induce the deposition of glycosaminoglycans (GAGs), proteoglycans, and collagen fibers in the connective ECM. ECM composition is very important for normal tissue development and function. In this work, we examine the effects caused by cyclosporin A on cultures of normal human palate fibroblasts in order to evaluate interleukin, transforming growth factor β II, and bone morphogenetic protein II membrane receptor induction and extracellular GAG changes such as hyaluronic acid, heparin sulfate, and chondroitin sulfate. Methods Palate fibroblasts were maintained for 24 h in serum-free 199 medium containing 5 μg/mL 3 H glucosamine hydrochloride. After this time, TGF II and BMP II receptors were determined by microarray analysis and GAG classes by the biochemical method. Results The results show that TGFβ 1 II and BMP II membrane receptors are significantly inhibited in cyclosporin A-treated cultures as compared to controls, whereas IL-1R2 membrane receptors are stimulated. The behavior of total intra- and extracellular GAGs is significantly increased in cyclosporin A-treated cultures, whereas the ratio between non-sulfated/sulfated GAGs decreases ( p ≤0.01) vis-a-vis controls. Conclusions Because they form a highly complicated macromolecular network in the ECM, which provides an indication of cell function and gene expression and modulates growth factor activities, GAG changes are related to modification of ECM functions. Our data show that cyclosporin A causes biochemical changes to ECM through alterations in cytokines and respective membrane receptor linkages.

We characterized the overall early effect of chronic ochratoxin A (OTA) treatment on rat liver, analyzing different aspects related to: (i) fibrosis, by measuring collagen content and turnover, and alpha-smooth muscle actin (alpha SMA); (ii) oxidative stress and stress response, by analyzing protein carbonylation, superoxide dismutase (SOD) and heat shock protein (HSP70) gene expression; (iii) the possible tumor promoter effect, evaluating cadherin and connexin (CX) mRNA levels. Light microscopy analysis showed no histological differences in OTA-treated and control (CT) rats. Collagen content, determined by computer analysis of Sirius red-stained liver sections, was similar in both groups. In liver homogenates COL-I, COL-III, TIMP-I and TGF-beta 1 mRNA levels and aSMA were unaffected by OTA. Matrix metalloproteinase (MMP)-1, MMP-2 and MMP-9 protein levels were also similar in the two groups. Protein carbonylation, a marker of severe oxidative stress, was not evident in the homogenates of OTA-treated livers; superoxide dismutase (SOD) mRNA tended to be lower and HSP70 was strongly down-regulated. OTA reduced E-cadherin and DSC-2 transcription, and down-regulated liver CX26, CX32 and CX43. In conclusion, these in vivo results show that OTA-induced liver injury involves a reduction in the ability to counterbalance oxidative stress, maybe leading to altered gap junction intercellular communication and loss of cell adhesion and polarity. This suggests that mild oxidative damage might be a key factor, in combination with other cytotoxic effects, in triggering the promotion of liver tumors after exposure to OTA. (c) 2006 Elsevier Ireland Ltd. All rights reserved.

Objective We aimed to characterize the fibroblast phenotype of patients by analyzing gene and protein expression of cleft lip and/or cleft palate fibroblasts in relation to collagen turnover and extracellular matrix remodeling. Patients Human palatal fibroblasts were obtained from three healthy subjects without cleft lip and/or cleft palate and from three subjects with nonsyndromic cleft lip and/or cleft palate. Collagen turnover–related gene and protein expression were analyzed by real-time polymerase chain reaction, Western and dot blots, and sodium dodecyl sulfate zymography. Results Cleft lip and/or cleft palate fibroblasts, compared with controls, displayed a down-regulation of collagens type I and III messenger RNA ( p < .0001 and p < .001, respectively) but an opposite tendency to increase protein levels. Cleft lip and/or cleft palate cells had higher lysyl hydroxylase-2b messenger RNA levels expressed in relation to collagen type I messenger RNA, down-regulated matrix metalloproteinase-1, tissue inhibitor of matrix metalloproteinase-1, and Secreted Protein Acidic and Rich in Cysteine messenger RNA ( p < .0001 and p < .01, respectively). Pro–matrix metalloproteinase-1 tended to decrease, and pro–matrix metalloproteinase-2 and -9 were down-regulated ( p < .01, p < .05, respectively), as was Secreted Protein Acidic and Rich in Cysteine protein expression ( p < .05). Conclusions Our results suggest that the cleft lip and/or cleft palate fibroblast phenotype is characterized by a tendency toward interstitial collagen deposition due to posttranslational modifications, such as decreased collagen degradation by matrix metalloproteinases and increased collagen cross-links. These findings may contribute to the knowledge of the cleft lip and/or cleft palate fibroblast phenotype and may be useful to the surgeon when considering the potential wound contraction and subsequent undesired scarring in cleft lip and/or cleft palate ocurring after the surgical closure of a cleft palate.