931 resultados para Exchange energy functional


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Mangrove forests are ecosystems susceptible to changing water levels and temperatures due to climate change as well as perturbations resulting from tropical storms. Numerical models can be used to project mangrove forest responses to regional and global environmental changes, and the reliability of these models depends on surface energy balance closure. However, for tidal ecosystems, the surface energy balance is complex because the energy transport associated with tidal activity remains poorly understood. This study aimed to quantify impacts of tidal flows on energy dynamics within a mangrove ecosystem. To address the research objective, an intensive 10-day study was conducted in a mangrove forest located along the Shark River in the Everglades National Park, FL, USA. Forest–atmosphere turbulent exchanges of energy were quantified with an eddy covariance system installed on a 30-m-tall flux tower. Energy transport associated with tidal activity was calculated based on a coupled mass and energy balance approach. The mass balance included tidal flows and accumulation of water on the forest floor. The energy balance included temporal changes in enthalpy, resulting from tidal flows and temperature changes in the water column. By serving as a net sink or a source of available energy, flood waters reduced the impact of high radiational loads on the mangrove forest. Also, the regression slope of available energy versus sink terms increased from 0.730 to 0.754 and from 0.798 to 0.857, including total enthalpy change in the water column in the surface energy balance for 30-min periods and daily daytime sums, respectively. Results indicated that tidal inundation provides an important mechanism for heat removal and that tidal exchange should be considered in surface energy budgets of coastal ecosystems. Results also demonstrated the importance of including tidal energy advection in mangrove biophysical models that are used for predicting ecosystem response to changing climate and regional freshwater management practices.

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The electromagnetic form factors are the most fundamental observables that encode information about the internal structure of the nucleon. The electric (GE) and the magnetic ( GM) form factors contain information about the spatial distribution of the charge and magnetization inside the nucleon. A significant discrepancy exists between the Rosenbluth and the polarization transfer measurements of the electromagnetic form factors of the proton. One possible explanation for the discrepancy is the contributions of two-photon exchange (TPE) effects. Theoretical calculations estimating the magnitude of the TPE effect are highly model dependent, and limited experimental evidence for such effects exists. Experimentally, the TPE effect can be measured by comparing the ratio of positron-proton elastic scattering cross section to that of the electron-proton [R = σ(e +p)/σ(e+p)]. The ratio R was measured over a wide range of kinematics, utilizing a 5.6 GeV primary electron beam produced by the Continuous Electron Beam Accelerator Facility (CEBAF) at Jefferson Lab. This dissertation explored dependence of R on kinematic variables such as squared four-momentum transfer (Q2) and the virtual photon polarization parameter (&epsis;). A mixed electron-positron beam was produced from the primary electron beam in experimental Hall B. The mixed beam was scattered from a liquid hydrogen (LH2) target. Both the scattered lepton and the recoil proton were detected by the CEBAF Large Acceptance Spectrometer (CLAS). The elastic events were then identified by using elastic scattering kinematics. This work extracted the Q2 dependence of R at high &epsis;(&epsis; > 0.8) and the $&epsis; dependence of R at ⟨Q 2⟩ approx 0.85 GeV2. In these kinematics, our data confirm the validity of the hadronic calculations of the TPE effect by Blunden, Melnitchouk, and Tjon. This hadronic TPE effect, with additional corrections contributed by higher excitations of the intermediate state nucleon, largely reconciles the Rosenbluth and the polarization transfer measurements of the electromagnetic form factors.

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The future power grid will effectively utilize renewable energy resources and distributed generation to respond to energy demand while incorporating information technology and communication infrastructure for their optimum operation. This dissertation contributes to the development of real-time techniques, for wide-area monitoring and secure real-time control and operation of hybrid power systems. ^ To handle the increased level of real-time data exchange, this dissertation develops a supervisory control and data acquisition (SCADA) system that is equipped with a state estimation scheme from the real-time data. This system is verified on a specially developed laboratory-based test bed facility, as a hardware and software platform, to emulate the actual scenarios of a real hybrid power system with the highest level of similarities and capabilities to practical utility systems. It includes phasor measurements at hundreds of measurement points on the system. These measurements were obtained from especially developed laboratory based Phasor Measurement Unit (PMU) that is utilized in addition to existing commercially based PMU’s. The developed PMU was used in conjunction with the interconnected system along with the commercial PMU’s. The tested studies included a new technique for detecting the partially islanded micro grids in addition to several real-time techniques for synchronization and parameter identifications of hybrid systems. ^ Moreover, due to numerous integration of renewable energy resources through DC microgrids, this dissertation performs several practical cases for improvement of interoperability of such systems. Moreover, increased number of small and dispersed generating stations and their need to connect fast and properly into the AC grids, urged this work to explore the challenges that arise in synchronization of generators to the grid and through introduction of a Dynamic Brake system to improve the process of connecting distributed generators to the power grid.^ Real time operation and control requires data communication security. A research effort in this dissertation was developed based on Trusted Sensing Base (TSB) process for data communication security. The innovative TSB approach improves the security aspect of the power grid as a cyber-physical system. It is based on available GPS synchronization technology and provides protection against confidentiality attacks in critical power system infrastructures. ^

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The exponential growth of studies on the biological response to ocean acidification over the last few decades has generated a large amount of data. To facilitate data comparison, a data compilation hosted at the data publisher PANGAEA was initiated in 2008 and is updated on a regular basis (doi:10.1594/PANGAEA.149999). By January 2015, a total of 581 data sets (over 4 000 000 data points) from 539 papers had been archived. Here we present the developments of this data compilation five years since its first description by Nisumaa et al. (2010). Most of study sites from which data archived are still in the Northern Hemisphere and the number of archived data from studies from the Southern Hemisphere and polar oceans are still relatively low. Data from 60 studies that investigated the response of a mix of organisms or natural communities were all added after 2010, indicating a welcomed shift from the study of individual organisms to communities and ecosystems. The initial imbalance of considerably more data archived on calcification and primary production than on other processes has improved. There is also a clear tendency towards more data archived from multifactorial studies after 2010. For easier and more effective access to ocean acidification data, the ocean acidification community is strongly encouraged to contribute to the data archiving effort, and help develop standard vocabularies describing the variables and define best practices for archiving ocean acidification data.

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Dengue virus is an important patogen that causes Dengue desease in all world, and belongs to Flavivirus gender. The virus consists of enveloped RNA with a single strand positive sense, 11Kb genome. The RNA is translated into a polyprotein precursor, wich is cleaved into 3 structural proteins (C, prM e E) and 7 non-structural proteins (NS1, NS2A, NS2B, NS3, NS4A, NS4B e NS5). The NS3 is a multifunctional protein, that besides to promote the polyprotein precursor cleavage, also have NTPase, helicase and RTPase activity. The NS3 needs a hydrophilic segment of 40 residues from the transmembrane NS2B protein (who acts like cofator) to realize this functions. Actually, there's no vacines available on the market, and the treatment are just symptomatic. The tetrapeptide inhibitor Bz-Nle-Lys-Arg-Arg-H (Ki de 5,8-7,0 M) was showed as a potent inhibitor μ for NS3prot in Dengue virus. That is a inteligent alternative to treat the dengue desease. The present work aimed analyse the interactions of the ligand bounded to the activity site to provid a clear and depth vision of that interaction. For this purpouse, it was conducted an in silico study, by using quantum mechanical calculations based on Density Functional Theory (DFT), with Generalized Gradient approximation (GGA) to describe the effects of exchange and correlation. The interaction energy of each amino acid belonging to the binding site to the ligand was calculated the using the method of molecular fragmentation with conjugated caps (MFCC). Besides energy, we calculated the distances, types of molecular interactions and atomic groups involved. The theoretical models used were satisfactory and show a more accurate description when the dielectric constant = 20 ε and 80 was used. The results demonstrate that the interaction energy of the system reached convergence at 13.5 A. Within a radius of 13,5A the most important residues were identified. Met49, Met84 and Asp81 perform interactions of hydrogen with the ligant. The Asp79 and Asp75 residues present high energy of attraction. Arg54, Arg85 and Lys 131 perform hydrogen interactions with the ligand, however, appear in BIRD graph having high repulsion energy with the inhibitor. The data also emphasizes the importance of residue Tyr161 and the involvement of the catalytic triad composed by Asp75, His51 and Ser135

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While molecular and cellular processes are often modeled as stochastic processes, such as Brownian motion, chemical reaction networks and gene regulatory networks, there are few attempts to program a molecular-scale process to physically implement stochastic processes. DNA has been used as a substrate for programming molecular interactions, but its applications are restricted to deterministic functions and unfavorable properties such as slow processing, thermal annealing, aqueous solvents and difficult readout limit them to proof-of-concept purposes. To date, whether there exists a molecular process that can be programmed to implement stochastic processes for practical applications remains unknown.

In this dissertation, a fully specified Resonance Energy Transfer (RET) network between chromophores is accurately fabricated via DNA self-assembly, and the exciton dynamics in the RET network physically implement a stochastic process, specifically a continuous-time Markov chain (CTMC), which has a direct mapping to the physical geometry of the chromophore network. Excited by a light source, a RET network generates random samples in the temporal domain in the form of fluorescence photons which can be detected by a photon detector. The intrinsic sampling distribution of a RET network is derived as a phase-type distribution configured by its CTMC model. The conclusion is that the exciton dynamics in a RET network implement a general and important class of stochastic processes that can be directly and accurately programmed and used for practical applications of photonics and optoelectronics. Different approaches to using RET networks exist with vast potential applications. As an entropy source that can directly generate samples from virtually arbitrary distributions, RET networks can benefit applications that rely on generating random samples such as 1) fluorescent taggants and 2) stochastic computing.

By using RET networks between chromophores to implement fluorescent taggants with temporally coded signatures, the taggant design is not constrained by resolvable dyes and has a significantly larger coding capacity than spectrally or lifetime coded fluorescent taggants. Meanwhile, the taggant detection process becomes highly efficient, and the Maximum Likelihood Estimation (MLE) based taggant identification guarantees high accuracy even with only a few hundred detected photons.

Meanwhile, RET-based sampling units (RSU) can be constructed to accelerate probabilistic algorithms for wide applications in machine learning and data analytics. Because probabilistic algorithms often rely on iteratively sampling from parameterized distributions, they can be inefficient in practice on the deterministic hardware traditional computers use, especially for high-dimensional and complex problems. As an efficient universal sampling unit, the proposed RSU can be integrated into a processor / GPU as specialized functional units or organized as a discrete accelerator to bring substantial speedups and power savings.

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The aim of this study was to explore symptom burden and its relationship to functional performance in patients with COPD. A descriptive, cross-sectional, correlational survey design was used and a sample of 214 patients with COPD. The sample was recruited from patients attending one of the major teaching hospitals in Dublin. Symptom burden was measured using the Memorial Symptom Assessment Scale (MSAS), and the functional performance was measured using the Functional Performance Inventory-Short Form (FPISF). Findings revealed that participants experienced a median of 13 symptoms. The most burdensome symptoms were shortness of breath, lack of energy, difficulty sleeping, worrying, dry mouth, feeling nervous, feeling irritable, and feeling sad. Participants with very severe COPD had the greatest symptom burden, followed by those with severe COPD, moderate COPD, and mild COPD. Symptom burden was higher for the psychological symptoms compared to the physical symptoms. Participants with mild COPD had the highest functional performance, followed by those with moderate COPD, very severe COPD, and severe COPD. Twenty symptoms were negatively correlated with overall functional performance, indicating that high symptom burden for those symptoms was associated with low overall functional performance. Moderate, negative, statistically significant correlations were found between the total symptom burden and overall functional performance, physical symptom burden and overall functional performance and psychological symptom burden and overall functional performance. A negative linear relationship was found between total symptom burden and overall functional performance among all stages of COPD except the mild group. No relationship was found between total symptom burden and overall functional performance for the moderate group. Healthcare professionals need to broaden the clinical and research assessment of physical and psychological symptoms in COPD; alleviating the burden of these symptoms may promote improved functional performance.

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Rab GTPases are the largest family of the Ras superfamily and are key regulators of membrane trafficking within the cell. There are over 60 members of the Rab family which localise to specific membrane compartments and interact with effector proteins to regulate membrane trafficking processes, such as vesicle formation, vesicle trafficking within the cell and fusion with an acceptor compartment. Multiple effector proteins have been identified for many Rabs, some of which can interact with more than one Rab to link their function at a specific membrane location or to link them together in a Rab activation cascade. Rabin8 is one such protein which is an effector for Rab11a and a Guanine nucleotide Exchange Factor (GEF) for Rab8a. Rabin8 participates in a conserved Rab activation cascade which is critical in the formation of primary cilia. Data presented in this thesis has shown that GRAB interacts with Rab3a, Rab8a, Rab11a and Rab11b in a nucleotide dependent manner. Furthermore, the minimal interacting regionbetween these proteins has been investigated. The functional outcome of GRAB knockdown has also been examined and data in this thesis highlights the phenotypic outcome.

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The prospective impact of nanomaterials in science and technology has followed an increasing trend due to their unique chemical and physical properties compared to bulk. Significant advances in current technologies in areas such as clean energy production, electronics, medicine, and environment have fuelled major research and development efforts in nanotechnology around the world. This leads to the opportunity to use such nanostructured materials in novel applications and devices. Ceria, zirconia, alumina and titania are some of the major oxides which find vast applications as a nanomaterial on a wider side.

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This project supported the planning and conduct of a two-day Iowa Department of Transportation–hosted peer exchange for state agencies that have implemented some or all of the suggested strategies outlined in the Second Strategic Highway Research Program–sponsored project R10, Project Management Strategies for Complex Projects. Presentations were made by participating states, and several opportunities were provided for directed discussion. General themes emerging from the presentations and discussions were identified as follows: To implement improvements in project management processes, agency leadership needs to decide that a new approach to project management is worth pursuing and then dedicate resources to developing a project management plan. The change to formalized project management and five-dimensional project management (5DPM) requires a culture shift in agencies from segmented “silo” processes to collaborative, cooperative processes that make communication and collaboration high priorities. Agencies need trained project managers who are empowered to execute the project management plan, as well as properly trained functional staff. Project management can be centralized or decentralized with equal effect. After an agency’s project management plan and structure are developed, software tools and other resources should be implemented to support the plan and structure. All projects will benefit from enhanced project management, but the project management plan should specify appropriate approaches for several project levels as defined by factors in addition to dollar value. Project management should be included in an agency’s project development manual.

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The aim of this work was to study the convective drying of anchovy (Engraulis anchoita) fillets and to evaluate the final product characteristics through its biochemical and functional properties. The drying temperatures were of 50, 60 and 70°C, and the fillet samples were dried with the skins down (with air flow one or the two sides) and skins up (with air flow one side). The drying experimental data were analyzed by Henderson–Pabis model, which showed a good fit (R2 > 0.99 and REQM < 0.05). The moisture effective diffusivity values ranged from 4.1 10–10 to 8.6 10–10 m2 s−1 with the skin down and 2.2 10–10 to 5.5 10–10 m2 s−1 with the skin up, and the activation energy values were 32.2 and 38.4 kJ mol−1, respectively. The product characteristics were significantly affected (p < 0.05) by drying operation conditions. The lower change was in drying at 60°C with air flow for two sides of the samples and skin up. In this condition, the product showed solubility 22.3%; in vitro digestibility 87.4%; contents of available lysine and methionine 7.21 and 2.64 g 100 g−1, respectively; TBA value 1.16 mgMDA kg−1; specific antioxidant activity was 1.91 mMDPPH g−1 min−1, and variation total color was 10.72.

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Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.

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The current energy market requires urgent revision for the introduction of renewable, less-polluting and inexpensive energy sources. Biohydrogen (bioH2) is considered to be one of the most appropriate options for this model shift, being easily produced through the anaerobic fermentation of carbohydrate-containing biomass. Ideally, the feedstock should be low-cost, widely available and convertible into a product of interest. Microalgae are considered to possess the referred properties, being also highly valued for their capability to assimilate CO2 [1]. The microalga Spirogyra sp. is able to accumulate high concentrations of intracellular starch, a preferential carbon source for some bioH2 producing bacteria such as Clostridium butyricum [2]. In the present work, Spirogyra biomass was submitted to acid hydrolysis to degrade polymeric components and increase the biomass fermentability. Initial tests of bioH2 production in 120 mL reactors with C. butyricum yielded a maximum volumetric productivity of 141 mL H2/L.h and a H2 production yield of 3.78 mol H2/mol consumed sugars. Subsequently, a sequential batch reactor (SBR) was used for the continuous H2 production from Spirogyra hydrolysate. After 3 consecutive batches, the fermentation achieved a maximum volumetric productivity of 324 mL H2/L.h, higher than most results obtained in similar production systems [3] and a potential H2 production yield of 10.4 L H2/L hydrolysate per day. The H2 yield achieved in the SBR was 2.59 mol H2/mol, a value that is comparable to those attained with several thermophilic microorganisms [3], [4]. In the present work, a detailed energy consumption of the microalgae value-chain is presented and compared with previous results from the literature. The specific energy requirements were determined and the functional unit considered was gH2 and MJH2. It was possible to identify the process stages responsible for the highest energy consumption during bioH2 production from Spirogyra biomass for further optimisation.