Liquid biofuels for aviation: valorisation of the by-product biochar

Biochar is a carbonaceous material produced through pyrolysis of biomass. One promising application of biochar is phosphorus recovery from wastewater. Phosphorus is a vital nutrient for plant growth, but its use in fertilizers often leads to runoff or leaching. Wastewater treatment plants discharge large amounts of phosphorus-rich wastewater, contributing to eutrophication and ecological harm. Biochar can sorb phosphorus, retaining it in solid form. In this thesis, two composites made of biomass and dolomite or shells exhibited superior phosphate sorption compared to biochar alone, reaching up to 100% sorption. Biochar also finds use in soil remediation, specifically in cleaning up contaminated soil. Polycyclic aromatic hydrocarbons (PAHs), which can be carcinogenic and toxic, can be present in soil. Biochar adsorb PAHs, preventing their leakage or bioaccumulation. Hetero-PAHs, a subclass of PAHs with nitrogen, sulfur, or oxygen atoms in their ring structures, are particularly challenging to degrade. Little is known about their behavior or sorption onto biochar. In this thesis, biochar and activated carbon were effective in immobilizing PAHs and hetero-PAHs in real soils, with rates of immobilization reaching 100%. Biochar performed equally or better than activated carbon, offering a cost-effective alternative due to its lower price. Biochar reduce of metal(loid)s mobility in soil. Metal(loid)s like lead, zinc, and arsenic can contaminate soil through industrial sources, agricultural runoff, and other pollution, and are toxic to plants and animals, rendering the soil unsuitable for agriculture. When biochar is added to contaminated soil, it binds to metal(loid)s, preventing leaching into the environment. A biomass-dolomite composite was compared to activated carbon for immobilizing metal(loid)s in contaminated soils. The composite generally outperformed activated carbon and exhibited the ability to immobilize arsenic. In summary, biochar shows promise for phosphorus recovery, soil remediation, and reducing the mobility of heavy metals, offering cost-effective and sustainable solutions to these environmental challenges.

Metsäteollisuuden sivutuotepolttoaineiden hyödyntäminen Etelä-Karjalassa

Tässä diplomityössä on selvitetty merkittävimpien kotimaisten polttoaineiden määrät Etelä-Karjalassa vuonna 1999. Pääpaino työssä on metsäteollisuuden sivutuotepolttoaineiden tarkastelussa. Metsähakkeelle ja kierrätyspolttoaineille on määritetty tuotantopotentiaalit. Myös turpeen tuotantomäärät on selvitetty. Lisäksi työssä on tarkasteltu alueella sijaitsevien teollisuuslaitosten ja kuntien energialaitosten polttoaineiden käyttöä. Työn tuloksia käytetään tutkimuksen seuraavassa vaiheessa, jolloin pyritään kehittämään teollisuusyritysten ja yhdyskuntien välistä energiaintegraatiota. Etelä-Karjalan kemiallisen metsäteollisuuden oman käytön ylijäävä sivutuotepolttoaineiden määrä oli vuonna 1999 yli 230 000 k-m3 (370 GWh). Mekaanisen metsäteollisuuden vastaava luku oli noin 210 000 k-m3 (330 GWh). Puunkäyttömäärien, energiankäyttötietojen ja kirjallisuudesta saatavien osuuksien perusteella mekaanisen metsäteollisuuden sivutuotepolttoaineiden oman käytön ylijäävä määrä olisi noin 350 000 k-m3 (580 GWh). Eroa selittävät lähinnä tilastolliset virheet, sivutuoteliiketoiminnan vähyys ja vaihtoehtoiset käyttökohteet. Metsähakkeen tuotantopotentiaali oli vuoden 1999 hakkuutietoihin perustuen yli 640 000 k-m3, josta tekniset, taloudelliset ja ympäristölliset seikat huomioiden noin 210 000 k-m3 (410 GWh) olisi voitu hyödyntää energiantuotannossa. Etelä-Karjalassa vuonna 1999 syntyneistä jätemääristä olisi arvioiden mukaan voitu valmistaa noin 25 000 tonnia (100 GWh) kierrätyspolttoaineita. Kierrätyspolttoaineiden valmistus alkaa Joutsenossa vuosien 2003 - 2004 välillä. Turpeen tuotantomäärä oli vuonna 1999 noin 1 200 000 tonnia (1020 GWh). Etelä-Karjalan teollisuus ja kuntien energialaitokset käyttivät vuonna 1999 yli 17400 GWh polttoaineita. Ostopolttoaineiden tarve oli noin 4700 GWh, josta lähes 85 % täytettiin maakaasulla. Alueen kunnista kaikki, joissa ei ole kemiallista metsäteollisuutta, pystyisivät teoriassa täyttämään teollisuuden ja energialaitostensa ostopolttoaineiden tarpeen oman kunnan alueelta saatavilla kotimaisilla polttoaineilla.

Simultaneous allergen inactivation and detoxification of castor bean cake by treatment with calcium compounds

Ricinus communis L. is of great economic importance due to the oil extracted from its seeds. Castor oil has been used for pharmaceutical and industrial applications, as a lubricant or coating agent, as a component of plastic products, as a fungicide or in the synthesis of biodiesel fuels. After oil extraction, a castor cake with a large amount of protein is obtained. However, this by-product cannot be used as animal feed due to the presence of toxic (ricin) and allergenic (2S albumin) proteins. Here, we propose two processes for detoxification and allergen inactivation of the castor cake. In addition, we establish a biological test to detect ricin and validate these detoxification processes. In this test, Vero cells were treated with ricin, and cell death was assessed by cell counting and measurement of lactate dehydrogenase activity. The limit of detection of the Vero cell assay was 10 ng/mL using a concentration of 1.6 x 10(5) cells/well. Solid-state fermentation (SSF) and treatment with calcium compounds were used as cake detoxification processes. For SSF, Aspergillus niger was grown using a castor cake as a substrate, and this cake was analyzed after 24, 48, 72, and 96 h of SSF. Ricin was eliminated after 24 h of SSF treatment. The cake was treated with 4 or 8% Ca(OH)2 or CaO, and both the toxicity and the allergenic properties were entirely abolished. A by-product free of toxicity and allergens was obtained.

Rapid and sensitive method for the determination of acetaldehyde in fuel ethanol by high-performance liquid chromatography with UV-Vis detection

A high-performance liquid chromatography (HPLC) method for the determination of acetaldehyde in fuel ethanol was developed. Acetaldehyde was derivatized with 0.900 mL 2,4-dinitrophenylhydrazine (DNPHi) reagent and 50 mu L phosphoric acid 1 mol L-1 at a controlled room temperature of 15 degrees C for 20 min. The separation of acetaldehyde- DNPH (ADNPH) was carried out on a Shimadzu Shim-pack C-18 column, using methanol/LiCl(aq) 1.0 mM (80/20, v/v) as a mobile phase under isocratic elution and UV-Vis detection at 365 nm. The standard curve of ADNPH was linear in the range 3-300 amg L-1 per injection (20 mu L) and the limit of detection (LOD) for acetaldehyde was 2.03 mu g L-1, with a correlation coefficient greater than 0.999 and a precision (relative standard deviation, RSD) of 5.6% (n=5). Recovery studies were performed by fortifying fuel samples with acetaldehyde at various concentrations and the results were in the range 98.7-102%, with a coefficient of variation (CV) from 0.2% to 7.2%. Several fuel samples collected from various gas stations were analyzed and the method was successfully applied to the analysis of acetaldehyde in fuel ethanol samples.

Uracil-DNA glycosylase–DNA substrate and product structures: Conformational strain promotes catalytic efficiency by coupled stereoelectronic effects

Enzymatic transformations of macromolecular substrates such as DNA repair enzyme/DNA transformations are commonly interpreted primarily by active-site functional-group chemistry that ignores their extensive interfaces. Yet human uracil–DNA glycosylase (UDG), an archetypical enzyme that initiates DNA base-excision repair, efficiently excises the damaged base uracil resulting from cytosine deamination even when active-site functional groups are deleted by mutagenesis. The 1.8-Å resolution substrate analogue and 2.0-Å resolution cleaved product cocrystal structures of UDG bound to double-stranded DNA suggest enzyme–DNA substrate-binding energy from the macromolecular interface is funneled into catalytic power at the active site. The architecturally stabilized closing of UDG enforces distortions of the uracil and deoxyribose in the flipped-out nucleotide substrate that are relieved by glycosylic bond cleavage in the product complex. This experimentally defined substrate stereochemistry implies the enzyme alters the orientation of three orthogonal electron orbitals to favor electron transpositions for glycosylic bond cleavage. By revealing the coupling of this anomeric effect to a delocalization of the glycosylic bond electrons into the uracil aromatic system, this structurally implicated mechanism resolves apparent paradoxes concerning the transpositions of electrons among orthogonal orbitals and the retention of catalytic efficiency despite mutational removal of active-site functional groups. These UDG/DNA structures and their implied dissociative excision chemistry suggest biology favors a chemistry for base-excision repair initiation that optimizes pathway coordination by product binding to avoid the release of cytotoxic and mutagenic intermediates. Similar excision chemistry may apply to other biological reaction pathways requiring the coordination of complex multistep chemical transformations.

A techno-economic comparison of power production by biomass fast pyrolysis with gasification and combustion

This paper presents an assessment of the technical and economic performance of thermal processes to generate electricity from a wood chip feedstock by combustion, gasification and fast pyrolysis. The scope of the work begins with the delivery of a wood chip feedstock at a conversion plant and ends with the supply of electricity to the grid, incorporating wood chip preparation, thermal conversion, and electricity generation in dual fuel diesel engines. Net generating capacities of 1–20 MWe are evaluated. The techno-economic assessment is achieved through the development of a suite of models that are combined to give cost and performance data for the integrated system. The models include feed pretreatment, combustion, atmospheric and pressure gasification, fast pyrolysis with pyrolysis liquid storage and transport (an optional step in de-coupled systems) and diesel engine or turbine power generation. The models calculate system efficiencies, capital costs and production costs. An identical methodology is applied in the development of all the models so that all of the results are directly comparable. The electricity production costs have been calculated for 10th plant systems, indicating the costs that are achievable in the medium term after the high initial costs associated with novel technologies have reduced. The costs converge at the larger scale with the mean electricity price paid in the EU by a large consumer, and there is therefore potential for fast pyrolysis and diesel engine systems to sell electricity directly to large consumers or for on-site generation. However, competition will be fierce at all capacities since electricity production costs vary only slightly between the four biomass to electricity systems that are evaluated. Systems de-coupling is one way that the fast pyrolysis and diesel engine system can distinguish itself from the other conversion technologies. Evaluations in this work show that situations requiring several remote generators are much better served by a large fast pyrolysis plant that supplies fuel to de-coupled diesel engines than by constructing an entire close-coupled system at each generating site. Another advantage of de-coupling is that the fast pyrolysis conversion step and the diesel engine generation step can operate independently, with intermediate storage of the fast pyrolysis liquid fuel, increasing overall reliability. Peak load or seasonal power requirements would also benefit from de-coupling since a small fast pyrolysis plant could operate continuously to produce fuel that is stored for use in the engine on demand. Current electricity production costs for a fast pyrolysis and diesel engine system are 0.091/kWh at 1 MWe when learning effects are included. These systems are handicapped by the typical characteristics of a novel technology: high capital cost, high labour, and low reliability. As such the more established combustion and steam cycle produces lower cost electricity under current conditions. The fast pyrolysis and diesel engine system is a low capital cost option but it also suffers from relatively low system efficiency particularly at high capacities. This low efficiency is the result of a low conversion efficiency of feed energy into the pyrolysis liquid, because of the energy in the char by-product. A sensitivity analysis has highlighted the high impact on electricity production costs of the fast pyrolysis liquids yield. The liquids yield should be set realistically during design, and it should be maintained in practice by careful attention to plant operation and feed quality. Another problem is the high power consumption during feedstock grinding. Efficiencies may be enhanced in ablative fast pyrolysis which can tolerate a chipped feedstock. This has yet to be demonstrated at commercial scale. In summary, the fast pyrolysis and diesel engine system has great potential to generate electricity at a profit in the long term, and at a lower cost than any other biomass to electricity system at small scale. This future viability can only be achieved through the construction of early plant that could, in the short term, be more expensive than the combustion alternative. Profitability in the short term can best be achieved by exploiting niches in the market place and specific features of fast pyrolysis. These include: •countries or regions with fiscal incentives for renewable energy such as premium electricity prices or capital grants; •locations with high electricity prices so that electricity can be sold direct to large consumers or generated on-site by companies who wish to reduce their consumption from the grid; •waste disposal opportunities where feedstocks can attract a gate fee rather than incur a cost; •the ability to store fast pyrolysis liquids as a buffer against shutdowns or as a fuel for peak-load generating plant; •de-coupling opportunities where a large, single pyrolysis plant supplies fuel to several small and remote generators; •small-scale combined heat and power opportunities; •sales of the excess char, although a market has yet to be established for this by-product; and •potential co-production of speciality chemicals and fuel for power generation in fast pyrolysis systems.

Digestibility of plant protein-based diets by largemouth bass Micropterus salmoides

Commercial farming of carnivorous fish demands the reduction of environmental impact of feeds; that requires minimal use of dietary animal protein. This study investigated the digestibility of diets formulated exclusively out of plant protein, added feed attractants, by the carnivore largemouth bass, Micropterus salmoides. Juvenile largemouth bass (14.0 +/- 1.0 cm) conditioned to accept artificial, dry feed were confined in polypropylene cages and fed ad libitum in three daily meals, seven experimental diets containing varying levels of vegetable and animal protein sources, added of different feed stimulants. After last daily meal, cages were transferred to cylindrical-conical-bottomed, 200-L aquaria, where faeces were collected by sedimentation into refrigerated containers, preserved and later analysed for chemical composition. Soybean meal can be used as partial substitute of animal protein in diets for largemouth bass; the poultry by-product meal shows as a good option as animal protein source in these rations. Control treatment - 50PP : 50AP - yielded best performances; the need for the use of fish meal in the formulation for carnivorous diets is, at least, questionable. Results of the digestibility trials demonstrated the importance of determining the diet digestibility, if precision in the formulation of least-cost feeds for carnivorous fish is the ultimate goal.

Skin-friction measurements in a supersonic combustor with crossflow fuel injection

Shock-tunnel experiments have been performed to measure the effect on skin-friction drag in a supersonic combustor of flow disturbances induced by hydrogen fuel injection transverse to the airstream. Constant-area, circular cross section combustors of lengths varying up to 0.52 m were employed. The experiments were done at a stagnation enthalpy of 7.2 MJ . kg(-1) and a Mach number of 4.3, with a boundary layer that was turbulent downstream of the 0.14-m station in the combustors. Combustor skin-friction drag was measured by a method based on the stress wave force balance, the method being validated by agreement between fuel-off skin-friction drag measurements and predictions using existing skin-friction theories. When fuel was injected, it was found that the drag remained at fuel-off values. Thus, the streamwise vortices and other flow disturbances induced by the fuel injection, mixing, and combustion, which are expected to be present in a scramjet combustor, did not influence the skin-friction drag of the combustors.

Cleanup of industrial effluents containing heavy metals: a new opportunity of valorising the biomass produced by brewing industry

Heavy metal pollution is a matter of concern in industrialised countries. Contrary to organic pollutants, heavy metals are not metabolically degraded. This fact has two main consequences: its bioremediation requires another strategy and heavy metals can be indefinitely recycled. Yeast cells of Saccharomyces cerevisiae are produced at high amounts as a by-product of brewing industry constituting a cheap raw material. In the present work, the possibility of valorising this type of biomass in the bioremediation of real industrial effluents containing heavy metals is reviewed. Given the autoaggregation capacity (flocculation) of brewing yeast cells, a fast and off-cost yeast separation is achieved after the treatment of metal-laden effluent, which reduces the costs associated with the process. This is a critical issue when we are looking for an effective, eco-friendly, and low-cost technology. The possibility of the bioremediation of industrial effluents linked with the selective recovery of metals, in a strategy of simultaneous minimisation of environmental hazard of industrial wastes with financial benefits from reselling or recycling the metals, is discussed.

Human risk assessment of benzene after a gasoline station fuel leak

OBJECTIVE: To assess the health risk of exposure to benzene for a community affected by a fuel leak. METHODS: Data regarding the fuel leak accident with, which occurred in the Brasilia, Federal District, were obtained from the Fuel Distributor reports provided to the environmental authority. Information about the affected population (22 individuals) was obtained from focal groups of eight individuals. Length of exposure and water benzene concentration were estimated through a groundwater flow model associated with a benzene propagation model. The risk assessment was conducted according to the Agency for Toxic Substances and Disease Registry methodology. RESULTS: A high risk perception related to the health consequences of the accident was evident in the affected community (22 individuals), probably due to the lack of assistance and a poor risk communication from government authorities and the polluting agent. The community had been exposed to unsafe levels of benzene (> 5 µg/L) since December 2001, five months before they reported the leak. The mean benzene level in drinking water (72.2 µg/L) was higher than that obtained by the Fuel Distributer using the Risk Based Corrective Action methodology (17.2 µg/L).The estimated benzene intake from the consumption of water and food reached a maximum of 0.0091 µg/kg bw/day (5 x 10-7 cancer risk per 106 individuals). The level of benzene in water vapor while showering reached 7.5 µg/m3 for children (1 per 104 cancer risk). Total cancer risk ranged from 110 to 200 per 106 individuals. CONCLUSIONS: The population affected by the fuel leak was exposed to benzene levels that might have represented a health risk. Local government authorities need to develop better strategies to respond rapidly to these types of accidents to protect the health of the affected population and the environment.

Improvement of vegetables elemental quality by espresso coffee residues

Spent coffee grounds (SCG) are usually disposed as common garbage, without specific reuse strategies implemented so far. Due to its recognised richness in bioactive compounds, the effect of SCG on lettuce’s macro- and micro-elements was assessed to define its effectiveness for agro industrial reuse. A greenhouse pot experiment was conducted with different amounts of fresh and composted spent coffee, and potassium, magnesium, phosphorous, calcium, sodium, iron, manganese, zinc and copper were analysed. A progressive decrease on all lettuce mineral elements was verified with the increase of fresh spent coffee, except for potassium. In opposition, an increment of lettuce’s essential macro-elements was verified when low amounts of composted spent coffee were applied (5%, v/v), increasing potassium content by 40%, manganese by 30%, magnesium by 20%, and sodium by 10%, of nutritional relevance This practical approach offers an alternative reuse for this by-product, extendable to other crops, providing value-added vegetable products.

Bioproduction of succinic acid from renewable feedstocks by Actinobacillus succinogenes 130Z

Succinic acid (SA) is a highly versatile building block that is used in a wide range of industrial applications. The biological production of succinic acid has emerged in the last years as an efficient alternative to the chemical production based on fossil fuels. However, in order to fully replace the competing petro-based chemical process from which it has been produced so far, some challenges remain to be surpassed. In particular, one main obstacle would be to reduce its production costs, mostly associated to the use of refined sugars. The present work is focused on the development of a sustainable and cost-e↵ective microbial production process based on cheap and renewable resources, such as agroindustrial wastes. Hence, glycerol and carob pods were identified as promising feedstocks and used as inexpensive carbon sources for the bioproduction of succinic acid by Actinobacillus succinogenes 130Z, one of the best naturally producing strains. Even though glycerol is a highly available carbon source, as by-product of biodiesel production, its consumption by A. succinogenes is impaired due to a redox imbalance during cell growth. However, the use of an external electron acceptor such as dimethylsulfoxide (DMSO) may improve glycerol metabolism and succinic acid production by this strain. As such, DMSO was tested as a co-substrate for glycerol consumption and concentrations of DMSO between 1 and 4% (v/v) greatly promoted glycerol consumption and SA production by this biocatalyst. Aiming at obtaining higher succinic acid yield and production rate, batch and fed-batch experiments were performed under controlled cultivation conditions. Batch experiments resulted in a succinic acid yield on glycerol of 0.95 g SA/g GLY and a production rate of 2.13 g/L.h, with residual production of acetic and formic acids. In fed-batch experiment, the SA production rate reached 2.31 g/L.h, the highest value reported in the literature for A. succinogenes using glycerol as carbon source. DMSO dramatically improved the conversion of glycerol by A. succinogenes and may be used as a co-substrate, opening new perspectives for the use of glycerol by this biocatalyst. Carob pods, highly available in Portugal as a residue from the locust bean gum industry, contain a significant amount of fermentable sugars such as sucrose, glucose and fructose and were also used as substrate for succinic acid production. Sugar extraction from raw and roasted carobs was optimized varying solid/water ratio and extraction time, maximizing sugar recovery while minimizing the extraction of polyphenols. Kinetic studies of glucose, fructose and sucrose consumption by A. succinogenes as individual carbon sources till 30 g/L were first determined to assess possible metabolic diferences. Results showed no significant diferences related to sugar consumption and SA production between the diferent sugars. Carob pods water extracts were then used as carbon source during controlled batch cultivations. (...)

Engineering of fatty acid production and secretion in Saccharomyces cerevisiae

Tese de Doutoramento em Ciências - Especialidade em Biologia

Network revenue management with product-specific no-shows

Revenue management practices often include overbooking capacity to account for customerswho make reservations but do not show up. In this paper, we consider the network revenuemanagement problem with no-shows and overbooking, where the show-up probabilities are specificto each product. No-show rates differ significantly by product (for instance, each itinerary andfare combination for an airline) as sale restrictions and the demand characteristics vary byproduct. However, models that consider no-show rates by each individual product are difficultto handle as the state-space in dynamic programming formulations (or the variable space inapproximations) increases significantly. In this paper, we propose a randomized linear program tojointly make the capacity control and overbooking decisions with product-specific no-shows. Weestablish that our formulation gives an upper bound on the optimal expected total profit andour upper bound is tighter than a deterministic linear programming upper bound that appearsin the existing literature. Furthermore, we show that our upper bound is asymptotically tightin a regime where the leg capacities and the expected demand is scaled linearly with the samerate. We also describe how the randomized linear program can be used to obtain a bid price controlpolicy. Computational experiments indicate that our approach is quite fast, able to scale to industrialproblems and can provide significant improvements over standard benchmarks.

Use of palm-oil by-products in chicken and rabbit feeds: effect on the fatty acid and tocol composition of meat, liver and plasma

This study was undertaken in the framework of a larger European project dealing with the characterization of fat co- and by-products from the food chain, available for feed uses. In this study, we compare the effects, on the fatty acid (FA) and tocol composition of chicken and rabbit tissues, of the addition to feeds of a palm fatty acid distillate, very low in trans fatty acids (TFA), and two levels of the corresponding hydrogenated by-product, containing intermediate and high levels of TFA. Thus, the experimental design included three treatments, formulated for each species, containing the three levels of TFA defined above. Obviously, due to the use of hydrogenated fats, the levels of saturated fatty acids (SFA) show clear differences between the three dietary treatments. The results show that diets high in TFA (76 g/kg fat) compared with those low in TFA (4.4 g/kg fat) led to a lower content of tocopherols and tocotrienols in tissues, although these differences were not always statistically significant, and show a different pattern for rabbit and chicken. The TFA content in meat, liver and plasma increased from low-to-high TFA feeds in both chicken and rabbit. However, the transfer ratios from feed were not proportional to the TFA levels in feeds, reflecting certain differences according to the animal species. Moreover, feeds containing fats higher in TFA induced significant changes in tissue SFA, monounsaturated fatty acids and polyunsaturated fatty acids composition, but different patterns can be described for chicken and rabbit and for each type of tissue.