Algal wastewater treatment and biomass producing potential: nutrient removal efficiency and cell physiological responses

Microalgae are sun - light cell factories that convert carbon dioxide to biofuels, foods, feeds, and other bioproducts. The concept of microalgae cultivation as an integrated system in wastewater treatment has optimized the potential of the microalgae - based biofuel production. These microorganisms contains lipids, polysaccharides, proteins, pigments and other cell compounds, and their biomass can provide different kinds of biofuels such as biodiesel, biomethane and ethanol. The algal biomass application strongly depends on the cell composition and the production of biofuels appears to be economically convenient only in conjunction with wastewater treatment. The aim of this research thesis was to investigate a biological wastewater system on a laboratory scale growing a newly isolated freshwater microalgae, Desmodesmus communis, in effluents generated by a local wastewater reclamation facility in Cesena (Emilia Romagna, Italy) in batch and semi - continuous cultures. This work showed the potential utilization of this microorganism in an algae - based wastewater treatment; Desmodesmus communis had a great capacity to grow in the wastewater, competing with other microorganisms naturally present and adapting to various environmental conditions such as different irradiance levels and nutrient concentrations. The nutrient removal efficiency was characterized at different hydraulic retention times as well as the algal growth rate and biomass composition in terms of proteins, polysaccharides, total lipids and total fatty acids (TFAs) which are considered the substrate for biodiesel production. The biochemical analyses were coupled with the biomass elemental analysis which specified the amount of carbon and nitrogen in the algal biomass. Furthermore photosynthetic investigations were carried out to better correlate the environmental conditions with the physiology responses of the cells and consequently get more information to optimize the growth rate and the increase of TFAs and C/N ratio, cellular compounds and biomass parameter which are fundamental in the biomass energy recovery.

Biofuels Sustainability Certification Schemes: Challenges, Feasibility and Possible Approaches

The focus of this research is to develop and apply an analytical framework for evaluating the effectiveness and practicability of sustainability certification schemes for biofuels, especially in a developing country’s perspective. The main question that drives the research analysis is “Which are the main elements of and how to develop sustainability certification schemes that would be effective and practicable in certifying the contribution of biofuels in meeting the goals Governments and other stakeholders have set up?”. Biofuels have been identified as a promising tool to reach a variety of goals: climate change protection, energy security, agriculture development, and, especially in developing countries, economic development. Once the goals have been identified, and ambitious mandatory targets for biofuels use agreed at national level, concerns have been raised by the scientific community on the negative externalities that biofuels production and use can have at environment, social and economic level. Therefore certification schemes have been recognized as necessary processes to measure these externalities, and examples of such schemes are in effect, or are in a negotiating phase, both at mandatory and voluntary levels. The research focus has emerged by the concern that the ongoing examples are very demanding in terms of compliance, both for those that are subject to certification and those that have to certify, on the quantity and quality of information to be reported. A certification system, for reasons linked to costs, lack of expertise, inadequate infrastructure, absence of an administrative and legislative support, can represent an intensive burden and can act as a serious impediment for the industrial and agriculture development of developing countries, going against the principle of equity and level playing field. While this research recognizes the importance of comprehensiveness and ambition in designing an important tool for the measurement of sustainability effects of biofuels production and use, it stresses the need to focus on the effectiveness and practicability of this tool in measuring the compliance with the goal. This research that falls under the rationale of the Sustainability Science Program housed at Harvard Kennedy School, has as main objective to close the gap between the research and policy makers worlds in the field of sustainability certification schemes for biofuels.

Chemical analysis and reactivity of biomass pyrolysis products. Application to the development of carbon-neutral biofuels and chemicals

In this dissertation the pyrolytic conversion of biomass into chemicals and fuels was investigated from the analytical point of view. The study was focused on the liquid (bio-oil) and solid (char) fractions obtainable from biomass pyrolysis. The drawbacks of Py-GC-MS described so far were partially solved by coupling different analytical configurations (Py-GC-MS, Py-GC-MIP-AED and off-line Py-SPE and Py-SPME-GC-MS with derivatization procedures). The application of different techniques allowed a satisfactory comparative analysis of pyrolysis products of different biomass and a high throughput screening on effect of 33 catalysts on biomass pyrolysis. As the results of the screening showed, the most interesting catalysts were those containing copper (able to reduce the high molecular weight fraction of bio-oil without large yield decrease) and H-ZSM-5 (able to entirely convert the bio-oil into “gasoline like” aromatic products). In order to establish the noxious compounds content of the liquid product, a clean-up step was included in the Py-SPE procedure. This allowed to investigate pollutants (PAHs) generation from pyrolysis and catalytic pyrolysis of biomass. In fact, bio-oil from non-catalytic pyrolysis of biomass showed a moderate PAHs content, while the use of H-ZSM-5 catalyst for bio-oil up-grading determined an astonishing high production of PAHs (if compared to what observed in alkanes cracking), indicating an important concern in the substitution fossil fuel with bio-oil derived from biomass. Moreover, the analytical procedures developed in this thesis were directly applied for the detailed study of the most useful process scheme and up-grading route to chemical intermediates (anhydrosugars), transportation fuels or commodity chemicals (aromatic hydrocarbons). In the applied study, poplar and microalgae biomass were investigated and overall GHGs balance of pyrolysis of agricultural residues in Ravenna province was performed. A special attention was put on the comparison of the effect of bio-char different use (fuel or as soil conditioner) on the soil health and GHGs emissions.

Physiological studies to optimize algal biomass production in phytoremediation processes

Nowadays microalgae are studied, and a number of species already mass-cultivated, for their application in many fields: food and feed, chemicals, pharmaceutical, phytoremediation and renewable energy. Phytoremediation, in particular, can become a valid integrated process in many algae biomass production systems. This thesis is focused on the physiological and biochemical effects of different environmental factors, mainly macronutrients, lights and temperature on microalgae. Microalgal species have been selected on the basis of their potential in biotechnologies, and nitrogen occurs in all chapters due to its importance in physiological and applicative fields. There are 5 chapters, ready or in preparation to be submitted, with different specific matters: (i) to measure the kinetic parameters and the nutrient removal efficiencies for a selected and local strain of microalgae; (ii) to study the biochemical pathways of the microalga D. communis in presence of nitrate and ammonium; (iii) to improve the growth and the removal efficiency of a specific green microalga in mixotrophic conditions; (iv) to optimize the productivity of some microalgae with low growth-rate conditions through phytohormones and other biostimulants; and (v) to apply the phyto-removal of ammonium in an effluent from anaerobic digestion. From the results it is possible to understand how a physiological point of view is necessary to provide and optimize already existing biotechnologies and applications with microalgae.