Beach-cast seagrass wrack: A natural marine resource improving the establishment of dune plant communities under a changing climate.

Seagrass wrack plays multiple ecological roles in coastal habitats but is often removed from beaches and used for economical processing, neglecting its potential role in sustaining dune plant establishment under changing climate scenarios. Rainwater shortage is a major stress for seedlings and reduced precipitations are expected in some coastal areas. We investigated in mesocosm how wrack influenced seedling performance of Cakile maritima, Thinopyrum junceum, and Calamagrostis arenaria under current and reduced precipitation. We also assessed wrack water holding capacity and leachate chemical/physical properties. Wrack stimulated seedling growth while reduced precipitation decreased root development. Wrack mitigated the effects of reduced precipitation on T. junceum and C. arenaria biomass. Wrack retained water up to five-fold its weight, increased water pH, conductivity, and nutrient content. Wrack promotes dune colonization by vegetation even under rainwater shortage. Thus, the maintenance of this natural resource on beaches is critical for improving dune resilience against climate changes.

Innovative Bioplasticizers from Residual Cynara cardunculus L. Biomass-Derived Levulinic Acid and Their Environmental Impact Assessment by LCA Methodology.

This work is focused on the application of Life Cycle Assessment (LCA) methodology for the quantification of the potential environmental impacts associated with the obtainment of levulinic acid from residual Cynara cardunculus L. biomass and its subsequent valorization in innovative bioplasticizers for tuning the properties as well as the processability of biopolymers. This potentially allows the production of fully biobased and biodegradable bioplastic formulations, thus addressing the issues related to the fossil origin and nonbiodegradability of conventional additives, such as phthalates. Steam explosion pretreatment was applied to the epigean residue of C. cardunculus L. followed by a microwave-assisted acid-catalyzed hydrolysis. After purification, the as-obtained levulinic acid was used to synthesize different ketal-diester derivatives through a three-step selective synthesis. The levulinic acid-base additives demonstrated remarkable plasticizing efficiency when added to biobased plastics. The LCA results were used in conjunction with those from the experimental activities to find the optimal compromise between environmental impacts and mechanical and thermal properties, induced by the bioadditives in poly(3-hydroxybutyrate), PHB biopolymer.

Conversion of the hydrochar recovered after levulinic acid production into activated carbon adsorbents.

Levulinic acid production by acid-catalyzed hydrothermal conversion of (ligno)cellulosic biomass generates significant amounts of carbonaceous hydrochar, which is currently considered a final waste. In this work, the hydrochar recovered after the levulinic acid production, was subjected to cascade pyrolysis and chemical activation treatments (by H3PO4 or KOH), to synthesize activated carbons. The pyrolysis post-treatment was already effective in improving the surface properties of the raw hydrochar (Specific Surface Area: 388 m2/g, VP: 0.22 cm3/g, VMESO: 0.07 cm3/g, VMICRO: 0.14 cm3/g), by removing volatile compounds. KOH activation resulted as the most appropriate for further improving the surface properties of the pyrolyzed hydrochar, showing the best surface properties (Specific Surface Area: 1421 m2/g, VP: 0.63 cm3/g, VMESO: 0.10 cm3/g, VMICRO: 0.52 cm3/g), which synergistically makes it a promising system towards adsorption of CO2 (∼90 mg/g) and methylene blue (∼248 mg/g). In addition, promising surface properties can be achieved after direct chemical activation of the raw hazelnut shells, preferably by H3PO4 (Specific Surface Area: 1918 m2/g, VP: 1.34 cm3/g, VMESO: 0.82 cm3/g, VMICRO: 0.50 cm3/g), but this choice is not the smartest, as it does not allow the valorization of the cellulose fraction to levulinic acid. Our approach paves the way for possible uses of these hydrochars originating from the levulinic acid chain for new environmental applications, thus smartly closing the biorefinery loop of the hazelnut shells.

Isolation of Pure Lignin and Highly Digestible Cellulose from Defatted and Steam-Exploded Cynara cardunculus.

In this work, a three-step approach to isolate the main components of lignocellulosic cardoon, lignin and cellulose, was investigated. The raw defatted biomass, Cynara cardunculus, after steam explosion was subjected to a mild organosolv treatment to extract soluble lignin (L1). Then, enzymatic hydrolysis was performed to achieve decomposition of the saccharidic portion into monosaccharides and isolate residual lignin (L2). The fractionation conditions were optimized to obtain a lignin as less degraded as possible and to maximize the yield of enzymatic hydrolysis. Furthermore, the effect of the use of aqueous ammonia as an extraction catalyst on both fractions was studied. Each fraction was characterized by advanced techniques, such as elemental analysis and 31P nuclear magnetic resonance (NMR), 13C-1H two-dimensional (2D)-NMR, attenuated total reflectance-Fourier transform infrared (ATR-FTIR), and UV-vis spectroscopies for lignin and X-ray diffraction (XRD), Klason compositional analysis, elemental analysis, and ATR-FTIR spectroscopy for cellulose-rich fractions. The impact of the cellulose-rich fraction composition and crystallinity was also correlated to the efficiency of the hydrolysis step, performed using the enzymatic complex Cellic CTec3.

Plastic litter in coastal sand dunes: Degradation behavior and impact on native and non-native invasive plants.

Pollution associated to marine plastic litter is raising increasing concerns due to its potential harmful effects on human health, biota, and coastal ecosystems. However, limited information is available on the degradation behavior of plastics, especially biodegradable ones, in dune habitats. Moreover, the effects of plastics on dune plant growth and ability to withstand environmental stresses and invasion by non-native plants have been largely neglected. This is a particularly relevant issue since biological invasions are major threats to dune ecosystems. In this 18-month study, we examined the degradation behavior of two plastic bags, non-biodegradable (NBP) or biodegradable/compostable (BP), in the dune environment by visual observations and analytical techniques. Concomitantly, we investigated the individual and combined effects of bag type and sand burial (no burial vs. partial burial) on the performance of a native dune plant (Thinopyrum junceum) and an invasive plant (Carpobrotus sp.) and on their interaction. NBP did not show relevant degradation signs over the experimental period as expected. BP exhibited gradual surface modifications and changes in chemical functionality and were almost disintegrated after 18 months. Bags and burial reduced independently T. junceum survival and growth, and most plants died within 8 months of plastic exposure. Bags and burial did not affect Carpobrotus survival. However, burial decreased Carpobrotus growth while NBP increased it. Both plastics increased Carpobrotus competitive ability, and no T. junceum plants survived to co-occurrent Carpobrotus, BP, and burial. These findings indicate that removing all littered plastics from beach-dune systems not only is critical to reduce plastic pollution but also to prevent further spread of invasive species in coastal dunes.

Challenges and Opportunities in the Catalytic Synthesis of Diphenolic Acid and Evaluation of Its Application Potential.

Diphenolic acid, or 4,4-bis(4-hydroxyphenyl)pentanoic acid, represents one of the potentially most interesting bio-products obtainable from the levulinic acid supply-chain. It represents a valuable candidate for the replacement of bisphenol A, which is strongly questioned for its toxicological issues. Diphenolic acid synthesis involves the condensation reaction between phenol and levulinic acid and requires the presence of a Brønsted acid as a catalyst. In this review, the state of the art related to the catalytic issues of its synthesis have been critically discussed, with particular attention to the heterogeneous systems, the reference benchmark being represented by the homogeneous acids. The main opportunities in the field of heterogeneous catalysis are deeply discussed, as well as the bottlenecks to be overcome to facilitate diphenolic acid production on an industrial scale. The regioselectivity of the reaction is a critical point because only the p,p'-isomer is of industrial interest; thus, several strategies aiming at the improvement of the selectivity towards this isomer are considered. The future potential of adopting alkyl levulinates, instead of levulinic acid, as starting materials for the synthesis of new classes of biopolymers, such as new epoxy and phenolic resins and polycarbonates, is also briefly considered.

Sustainable Valorisation and Efficient Downstream Processing of Giant Reed by High-Pressure Carbon Dioxide Pretreatment.

This work investigated the catalytic high-pressure CO2 pretreatment of giant reed. CO2 is a renewable resource; its use does not generate chemical wastes and it can be easily removed and recycled. The effect of the addition of low concentrations of FeCl3 (0.16 wt %) and PEG 400 (1.0 wt %) on the hemicellulose hydrolysis to xylose and xylo-oligosaccharides (XOS) is reported for the first time. Under the optimised pretreatment conditions, the xylan conversion of 82 mol % and xylose and XOS yields of 43 and 20 mol % were achieved, respectively. The solid residues obtained from different pretreatments were used as the substrate for the enzymatic hydrolysis to give glucose. The total glucose yield achieved under the optimised two-step process was 67.8 mol % with respect to the glucan units in the biomass. The results demonstrated that PEG-assisted FeCl3 -catalysed scCO2 pretreatment can produce xylose- or XOS-rich hydrolysates and improve the enzymatic hydrolysis of biomass.

Hydrothermal carbonization of digested sewage sludge: The fate of heavy metals, PAHs, PCBs, dioxins and pesticides.

Hydrothermal carbonization (HTC) is emerging as a promising technology for the management of sewage sludge. The fate of phytosanitary products, Polycyclic aromatic hydrocarbons (PAHs) and PCBs (Polychlorinated biphenyls) after HTC, as well as the formation of dioxins and furans, is still unclear. Moreover, only little information is available on the distribution of heavy metals and major nutrients between the hydrochars and the process water. Here, we aim to contribute to fill these gaps. HTC of sewage sludge from six different wastewater treatment plants has been carried out at 220 °C for 85 min. Feedstock, hydrochars and spent liquor have been then characterized and discussed. HTC is here proven to be a suitable technology for the immobilization of both heavy hydrocarbons and heavy metals, with the exception arsenic, which was also found in the spent liquor at a significant proportion (∼15-∼50%). DDD, DDT, DDE were detected in all sludge samples and their content was reduced by nearly one order of magnitude after the process. HTC is here proven to not be responsible at an appreciable extent of PCBs enrichment of the processed solids. Moreover, the sum of PCDDs and PCDFs in hydrochars never exceeded 20 ng kg-1 s.s. The results obtained encourage further developing of HTC, with the aim to improve the sustainability of sewage sludge management. Additional studies on the environmental impact of hydrochar when used as alternative fuel, as well as soil amendment, could lead to the overcoming of the issues which still hinder these applications.

Integrated Cascade Process for the Catalytic Conversion of 5-Hydroxymethylfurfural to Furanic and TetrahydrofuranicDiethers as Potential Biofuels.

The depletion of fossil resources is driving the research towards alternative renewable ones. Under this perspective, 5-hydroxymethylfurfural (HMF) represents a key molecule deriving from biomass characterized by remarkable potential as platform chemical. In this work, for the first time, the hydrogenation of HMF in ethanol was selectively addressed towards 2,5-bis(hydroxymethyl)furan (BHMF) or 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) by properly tuning the reaction conditions in the presence of the same commercial catalyst (Ru/C), reaching the highest yields of 80 and 93 mol%, respectively. These diols represent not only interesting monomers but strategic precursors for two scarcely investigated ethoxylated biofuels, 2,5-bis(ethoxymethyl)furan (BEMF) and 2,5-bis(ethoxymethyl)tetrahydrofuran (BEMTHF). Therefore, the etherification with ethanol of pure BHMF and BHMTHF and of crude BHMF, as obtained from hydrogenation step, substrates scarcely investigated in the literature, was performed with several commercial heterogeneous acid catalysts. Among them, the zeolite HZSM-5 (Si/Al=25) was the most promising system, achieving the highest BEMF yield of 74 mol%. In particular, for the first time, the synthesis of the fully hydrogenated diether BEMTHF was thoroughly studied, and a novel cascade process for the tailored conversion of HMF to the diethyl ethers BEMF and BEMTHF was proposed.

Integrated cascade biorefinery processes for the production of single cell oil by Lipomyces starkeyi from Arundo donax L. hydrolysates.

Giant reed (Arundo donax L.) is a promising source of carbohydrates that can be converted into single cell oil (SCO) by oleaginous yeasts. Microbial conversion of both hemicellulose and cellulose fractions represents the key step for increasing the economic sustainability for SCO production. Lipomyces starkeyi DSM 70,296 was cultivated in two xylose-rich hydrolysates, obtained by the microwave-assisted hydrolysis of hemicellulose catalysed by FeCl3 or Amberlyst-70, and in two glucose-rich hydrolysates obtained by the enzymatic hydrolysis of cellulose. L. starkeyi grew on both undetoxified and partially-detoxified hydrolysates, achieving the lipid content of 30 wt% and yield values in the range 15-24 wt%. For both integrated cascade processes the final production of about 8 g SCO from 100 g biomass was achieved. SCO production through integrated hydrolysis cascade processes represents a promising solution for the effective exploitation of lignocellulosic feedstock from perennial grasses towards new generation biodiesel and other valuable bio-based products.

From paper mill waste to single cell oil: Enzymatic hydrolysis to sugars and their fermentation into microbial oil by the yeast Lipomyces starkeyi.

Single cell oil (SCO) represents an outstanding alternative to both fossil sources and vegetable oils from food crops waste. In this work, an innovative two-step process for the conversion of cellulosic paper mill waste into SCO was proposed and optimised. Hydrolysates containing glucose and xylose were produced by enzymatic hydrolysis of the untreated waste. Under the optimised reaction conditions (Cellic® CTec2 25 FPU/g glucan, 48 h, biomass loading 20 g/L), glucose and xylose yields of 95 mol% were reached. The undetoxified hydrolysate was adopted as substrate for a batch-mode fermentation by the oleaginous yeast Lipomyces starkeyi. Lipid yield, content for single cell, production and maximum oil productivity were 20.2 wt%, 37 wt%, 3.7 g/L and 2.0 g/L/d respectively. This new generation oil, obtained from a negative value industrial waste, represents a promising platform chemical for the production of biodiesel, biosurfactants, animal feed and biobased plastics.

Optimisation of glucose and levulinic acid production from the cellulose fraction of giant reed (Arundo donax L.) performed in the presence of ferric chloride under microwave heating.

A two-step exploitation of the giant reed cellulose to glucose and levulinic acid, after the complete removal of the hemicellulose fraction, was investigated using FeCl3 as catalyst. In the first step, the microwave-assisted hydrolysis of cellulose to glucose was optimised by response surface methodology analysis, considering the effect of temperature, reaction time and catalyst amount. Under the optimised reaction conditions, the glucose yield was 39.9 mol%. The cellulose-rich residue was also converted by enzymatic hydrolysis, achieving the glucose yield of 39.8 mol%. The exhausted residue deriving from the chemical hydrolysis was further converted to levulinic acid by microwave treatment at harsher reaction conditions. The maximum levulinic acid yield was 64.3 mol%. On the whole, this cascade approach ensured an extensive and sustainable exploitation of the C6 carbohydrates to glucose and levulinic acid, corresponding to about 70 mol% of glucan converted to these valuable bioproducts in the two steps.

Microwave-assisted cascade exploitation of giant reed (Arundo donax L.) to xylose and levulinic acid catalysed by ferric chloride.

The present work aimed to investigate and optimize the selective exploitation of hemicellulose and cellulose fractions of the energy crop Arundo donax L. (giant reed), to give xylose and levulinic acid, respectively. In order to improve the sustainability of this process, a microwave-assisted hydrolysis in the presence of FeCl3 was implemented using as substrate the raw biomass without any pretreatment process. The effects of the hydrolysis reaction conditions, such as temperature, reaction time, salt amount and biomass loading, on giant reed exploitation were investigated. In the first step, under the optimized conditions (150 °C, 2.5 min and 1.6 wt% FeCl3), the xylose yield reached 98.2 mol%. In the second step, under the best conditions (190 °C, 30 min and 2.4 wt% FeCl3), the levulinic acid yield was 57.6 mol%. This novel cascade approach ensured an extensive exploitation of giant reed polysaccharides working in the respect of Green Chemistry principles.

A novel approach to biphasic strategy for intensification of the hydrothermal process to give levulinic acid: Use of an organic non-solvent.

Levulinic acid is a platform chemical obtained from acid-catalyzed hydrothermal conversion of cellulose-rich biomass. The low amounts of solid biomass which can be handled in the reactor limit the levulinic acid concentration in the aqueous stream, making the economic viability of the aqueous phase process unsuitable for large scale applications. Now a novel approach to biphasic process has been proposed, where a mineral oil has been used as non-solvent for levulinic acid, thus concentrating it in the water phase, reducing the water volume to be processed downstream but at the same time maintaining enough liquid phase to sustain the slurry processability. The work has studied: i) the optimization of the biphasic hydrolysis of corn grain to levulinic acid; ii) the characterization of the recovered oil; iii) the evaluation of the energetic properties of the recovered hydrochar for its exploitation, thus smartly closing the biorefinery cycle.

In-depth characterization of valuable char obtained from hydrothermal conversion of hazelnut shells to levulinic acid.

For the first time, the exploitation of hazelnut shells for the combined production of levulinic acid (LA) and hydrochar was investigated. The optimization of the catalytic hydrothermal treatment was performed both in autoclave and microwave reactor, approaching a maximum LA yield of ∼9-12wt%. Hydrochars recovered with high yield (∼43-47wt%) were characterized by different techniques, including elemental and proximate analysis, heating value, FT-IR, XPS, XRD, SEM-EDX, and SAA. Their "lignite-like" energetic properties make them suitable for the energy recovery within the same biorefinery plant for LA production, thus partially offsetting the cost of the entire process. Alternatively, since the synthesized hydrochars maintain high levels of oxygenated groups, they could be smartly exploited as natural sorbents for environmental applications. The proposed integrated approach makes possible to fully exploit this waste, smartly closing its biorefinery cycle in a sustainable development perspective.

Application of microwave irradiation for the removal of polychlorinated biphenyls from siloxane transformer and hydrocarbon engine oils.

The removal of polychlorinated biphenyls (PCBs) both from siloxane transformer oil and hydrocarbon engine oil was investigated through the application of microwave (MW) irradiation and a reaction system based on polyethyleneglycol (PEG) and potassium hydroxide. The influence of the main reaction parameters (MW irradiation time, molecular weight of PEG, amount of added reactants and temperature) on the dechlorination behavior was studied. Promising performances were reached, allowing about 50% of dechlorination under the best experimental conditions, together time and energy saving compared to conventional heating systems. Moreover, an interesting dechlorination degree (up to 32%) was achieved for siloxane transformer oil when MW irradiation was employed as the unique driving force. To the best of our knowledge, this is the first time in which MW irradiation is tested as the single driving force for the dechlorination of these two types of PCB-contaminated oils.

Monitoring/characterization of stickies contaminants coming from a papermaking plant--Toward an innovative exploitation of the screen rejects to levulinic acid.

Recycled paper needs a lot of mechanical/chemical treatments for its re-use in the papermaking process. Some of these ones produce considerable rejected waste fractions, such as "screen rejects", which include both cellulose fibers and non-fibrous organic contaminants, or "stickies", these last representing a shortcoming both for the papermaking process and for the quality of the final product. Instead, the accepted fractions coming from these unit operations become progressively poorer in contaminants and richer in cellulose. Here, input and output streams coming from mechanical screening systems of a papermaking plant using recycled paper for cardboard production were sampled and analyzed directly and after solvent extraction, thus confirming the abundant presence of styrene-butadiene rubber (SBR) and ethylene vinyl acetate (EVA) copolymers in the output rejected stream and cellulose in the output accepted one. Despite some significant drawbacks, the "screen reject" fraction could be traditionally used as fuel for energy recovery within the paper mill, in agreement with the integrated recycled paper mill approach. The waste, which still contains a cellulose fraction, can be also exploited by means of the hydrothermal route to give levulinic acid, a platform chemical of very high value added.

Hydrothermal Conversion of Giant Reed to Furfural and Levulinic Acid: Optimization of the Process under Microwave Irradiation and Investigation of Distinctive Agronomic Parameters.

The hydrothermal conversion of giant reed (Arundo donax L.) to furfural (FA) and levulinic acid (LA) was investigated in the presence of dilute hydrochloric acid. FA and LA yields were improved by univariate optimization of the main reaction parameters: concentration of the acid catalyst, solid/liquid ratio of the reaction mixture, hydrolysis temperature, and reaction time. The catalytic performances were investigated adopting the efficient microwave (MW) irradiation, allowing significant energy and time savings. The best FA and LA yields were further confirmed using a traditionally heated autoclave reactor, giving very high results, when compared with the literature. Hydrolysis temperature and time were the main reaction variables to be carefully optimized: FA formation needed milder reaction conditions, while LA more severe ones. The effect of the crop management (e.g., harvest time) on FA/LA production was discussed, revealing that harvest time was not a discriminating parameter for the further optimization of both FA and LA production, due to the very high productivity of the giant reed throughout the year. The promising results demonstrate that giant reed represents a very interesting candidate for a very high contemporary production of FA and LA of up to about 70% and 90% of the theoretical yields, respectively.

Novel highly active niobium catalysts for ring opening metathesis polymerization of norbornene.

Ring-opening metathesis polymerization (ROMP) of norbornene catalyzed by niobium(V) N,N-dialkylcarbamates Nb(O(2) CNR(2) )(5) , R = Et (1), Me (2) was studied in the presence of methylaluminoxane (MAO) as a cocatalyst. These novel catalytic systems resulted very active in chlorobenzene: 1 in the presence of methylaluminoxane catalyzes the ROMP of norbornene with the highest activity (29 000 kg of polymer/mol of catalyst × hour) never reported up to now for niobium catalysts. The high productivity appears particularly attractive considering that these precursors are rather cheap and easy to synthesize and to handle. Polynorbornenes were characterized by FT-IR and NMR spectroscopies and by DSC calorimetry. A new FT-IR method for the swift determination of the cis/trans content of the polymer is presented.