Biohydrogen production from microalgae—Major bottlenecks and future research perspectives

The imprudent use of fossil fuels has resulted in high greenhouse gas (GHG) emissions, leading to climate change and global warming. Reduction in GHG emissions and energy insecurity imposed by the depleting fossil fuel reserves led to the search for alternative sustainable fuels. Hydrogen is a potential alternative energy carrier and is of particular interest because hydrogen combustion releases only water. Hydrogen is also an important industrial feedstock. As an alternative energy carrier, hydrogen can be used in fuel cells for power generation. Current hydrogen production mainly relies on fossil fuels and is usually energy and CO₂-emission intensive, thus the use of fossil fuel-derived hydrogen as a carbon-free fuel source is fallacious. Biohydrogen production can be achieved via microbial methods, and the use of microalgae for hydrogen production is outstanding due to the carbon mitigating effects and the utilization of solar energy as an energy source by microalgae. This review provides comprehensive information on the mechanisms of hydrogen production by microalgae and the enzymes involved. The major challenges in the commercialization of microalgae-based photobiological hydrogen production are critically analyzed and future research perspectives are discussed. Life cycle analysis and economic assessment of hydrogen production by microalgae are also presented.     

Alkaline Fuel Cells with Novel Gortex‐Based Electrodes are Powered Remarkably Efficiently by Methane Containing 5% Hydrogen

Numerous electric and gas utilities are actively pursuing “power‐to‐gas” technology, which involves using unwanted, excess renewable energy to manufacture hydrogen gas (H₂) that is then injected into the existing natural gas pipeline network in 5–10% by volume. This work reports an alkaline fuel cell that has the potential to harness such gas mixtures for downstream generation of electric power. The fuel cell, which employs novel Gortex‐based electrodes layered with Pd/Pt catalysts, generates electricity remarkably efficiently when fuelled with methane (CH₄) containing 5% hydrogen. Methane constitutes the major component of natural gas. The fuel cell has been studied over a range of hydrogen to methane ratios using Tafel plots and electrochemical impedance spectroscopy. These show that, in terms of fundamental operation, there is, astonishingly, almost no difference between using pure hydrogen and 5% hydrogen in methane, as the fuel. The Gortex electrodes and alkaline electrolyte are clearly able to utilize the dilute hydrogen as a fuel with remarkable efficiency. The methane acts as an inert carrier gas and is not consumed.     

Life cycle assessment of natural gas power plants in Thailand

Background, aim, and scope  The main primary energy for electricity in Thailand is natural gas, accounting for 73% of the grid mix. Electricity generation from natural gas combustion is associated with substantial air emissions. The two technologies currently used in Thailand, thermal and combined cycle power plant, have been evaluated for the potential environmental impacts in a “cradle-to-grid” study according to the life cycle assessment (LCA) method. This study evaluates the environmental impacts of each process of the natural gas power production over the entire life cycle and compares two different power plant technologies currently used in Thailand, namely, combined cycle and thermal. Materials and methods  LCA is used as a tool for the assessment of resource consumption and associated impacts generated from utilization of natural gas in power production. The details follow the methodology outlined in ISO 14040. The scope of this research includes natural gas extraction, natural gas separation, natural gas transmission, and natural gas power production. Most of the inventory data have been collected from Thailand, except for the upstream of fuel oil and fuel transmission, which have been computed from Greenhouse gases, Regulated Emissions, and Energy use in Transportation version 1.7 and Global Emission Model for Integrated Systems version 4.3. The impact categories considered are global warming, acidification, photochemical ozone formation, and nutrient enrichment potential (NEP). Results  The comparison reveals that the combined cycle power plant, which has a higher efficiency, performs better than the thermal power plant for global warming potential (GWP), acidification potential (ACP), and photochemical ozone formation potential (POCP), but not for NEP where the thermal power plant is preferable. Discussion  For the thermal power plant, the most significant environmental impacts are from power production followed by upstream of fuel oil, natural gas extraction, separation, and transportation. For the combined cycle power plant, the most significant environmental impacts are from power production followed by natural gas extraction, separation, and transportation. The significant difference between the two types of power production is mainly from the combustion process and feedstock in power plant. Conclusions  The thermal power plant uses a mix of natural gas (56% by energy content) and fuel oil (44% by energy content); whereas, the combined cycle power plant operates primarily on natural gas. The largest contribution to GWP, ACP, and NEP is from power production for both thermal as well as combined cycle power plants. The POCP for the thermal power plant is also from power production; whereas, for combined cycle power plant, it is mainly from transmission of natural gas. Recommendations and perspectives  In this research, we have examined the environmental impact of electricity generation technology between thermal and combined cycle natural gas power plants. This is the overview of the whole life cycle of natural gas power plant, which will help in decision making. The results of this study will be useful for future power plants as natural gas is the major feedstock being promoted in Thailand for power production. Also, these results will be used in further research for comparison with other feedstocks and power production technologies.     

Constructing the electricity-carbohydrate-hydrogen cycle for a sustainability revolution

In this opinion, we suggest the electricity-carbohydrate-hydrogen (ECHo) cycle which bridges primary energies and secondary energies. Carbohydrates are sources of food, feed, liquid biofuels, and renewable materials and are a high-density hydrogen carrier and electricity storage compounds (e.g. >3000 Wh/kg). One element of this ECHo cycle can be converted to another reversibly and efficiently depending on resource availability, needs and costs. This cycle not only supplements current and future primary energy utilization systems for facilitating electricity and hydrogen storage and enhancing secondary energy conversion efficiencies, but also addresses such sustainability challenges as transportation fuel production, CO(2) utilization, fresh water conservation, and maintenance of a small closed ecosystem in emergency situations.     

Development of Effective Catalysts for Hydrogen Storage Technology Using Formic Acid

Hydrogen has attracted considerable attention as an energy source, and various attempts to develop suitable methods for hydrogen generation are made at the National Institute of Advanced Industrial Science and Technology. In this paper, the authors introduce their recent strategies to store hydrogen using formic acid (FA) as a hydrogen carrier. FA, which is believed to be one of the most promising liquid organic hydrogen carriers, can provide a viable method for safe hydrogen transportation. In order to optimize the performance of hydrogen storage with FA, the authors have investigated both homogeneous and heterogeneous catalysts. For example, Ir catalysts anchoring N^N‐bidentate ligands show high catalytic activity for both the reactions of FA synthesis and hydrogen generation from FA. Ultrafine Pd‐based nanoparticles are also immobilized on various supports, which show excellent catalytic performance for FA dehydrogenation under mild conditions. The authors also develop both homogeneous and heterogeneous catalysts to generate high‐pressure gases (H₂ and CO₂) over 120 and 35 MPa, respectively, from direct FA dehydrogenation without any compressing procedures. The generated high‐pressure gases (H₂ and CO₂) can be easily and simply separated by changing the fluid phase from the supercritical to gas–liquid phase by cooling without depressurization.     

Hydrogen production by photosynthetic green algae

Oxygenic photosynthetic organisms such as cyanobacteria, green algae and diatoms are capable of absorbing light and storing up to 10-13% of its energy into the H-H bond of hydrogen gas. This process, which takes advantage of the photosynthetic apparatus of these organisms to convert sunlight into chemical energy, could conceivably be harnessed for production of significant amounts of energy from a renewable resource, water. The harnessed energy could then be coupled to a fuel cell for electricity generation and recycling of water molecules. In this review, current biochemical understanding of this reaction in green algae, and some of the major challenges facing the development of future commercial algal photobiological systems for H2 production have been discussed.     

Life Cycle Inventory Information of the United States Electricity System (11/17 pp)

Goal and Scope This study estimates the life cycle inventory (LCI) of the electricity system in the United States, including the 10 NERC (North American Electric Reliability Council) regions, Alaska, Hawaii, off-grid non-utility plants and the US average figures. The greenhouse gas emissions associated with the United States electricity system are also estimated. Methods The fuel mix of the electricity system based on year 2000 data is used. The environmental burdens associated with raw material extraction, petroleum oil production and transportation for petroleum oil and natural gas to power plants are adopted from the DEAMTM LCA database. Coal transportation from a mining site to a power plant is specified with the data from the Energy Information Administration (EIA), which includes the mode of transportation as well as the distance traveled. The gate-to-gate environmental burdens associated with generating electricity from a fossil-fired power plant are obtained from the DEAMTM LCA database and the eGRID model developed by the United States Environmental Protection Agency. For nuclear power plants and hydroelectric power plants, the data from the DEAMTM LCA database are used.Results and Discussion Selected environmental profiles of the US electricity system are presented in the paper version, while the on-line version presents the whole LCI data. The overall US electricity system in the year 2000 released about 2,654 Tg CO2 eq. of greenhouse gas emissions based on 100-year global warming potentials with 193 g CO2 eq. MJe–1 as an weighted average emission rate per one MJ electricity generated. Most greenhouse gases are released during combusting fossil fuels, accounting for 78–95% of the total. The greenhouse gas emissions released from coal-fired power plants account for 81% of the total greenhouse gas emissions associated with electricity generation, and natural gas-fired power plants contribute about 16% of the total. The most significant regions for the total greenhouse gas emissions are the SERC (Southeastern Electric Reliability Council) and ECAR (East Central Area Reliability Coordination Agreement) regions, which account for 22% and 21% of the total, respectively. A sensitivity analysis on the generation and consumption based calculations indicates that the environmental profiles of electricity based on consumption are more uncertain than those based on generation unless exchange data from the same year are available because the exchange rates (region to region import and export of electricity) vary significantly from year to year.Conclusions and Outlook Those who are interested in the LCI data of the US electricity system can refer to the on-line version. When the inventory data presented in the on-line version are used in a life cycle assessment study, the distribution and transmission losses should be taken into account, which is about 9.5% of the net generation [1]. The comprehensive technical information presented in this study can be used in estimating the environmental burdens when new information on the regional fuel mix or the upstream processes is available. The exchange rates presented in this study also offer useful information in consequential LCI studies.     

Hydrogenase genetics

The decreasing availability of energy resources has brought about a renewed interest in the enzyme hydrogenase. Hydrogen gas can be produced by organisms and represents a potential renewable energy source, or it can be utilized by certain organisms as a sole energy source during processes that result in the net fixation of carbon, a biosynthetic capability that might be exploited for the production of specific compounds. Both the production and utilization of hydrogen in biological systems are dependent on hydrogenase. The manipulation of the expression of hydrogenase in attempts to optimize hydrogen production or utilization will to a certain extent be dependent on existing knowledge concerning the regulation of hydrogenase and its interactions with other aspects of cellular metabolism. Information pertaining to the genetics of hydrogenases should play an important role in the construction of organisms affected in their hydrogen metabolism. The genetics of hydrogenase in enteric bacteria, in hydrogen bacteria, and in root nodule bacteria are reviewed, and the implications concerning the manipulation of hydrogenase genes are discussed.     

The spatial distribution of cereal bioenergy potential in China

Biomass energy that exists in crop residues can be used for electricity generation and fuel production. However, its spatial distribution has formed a bottleneck in its utilization. This study introduces a data fusion method that uses the Net Primary Productivity (NPP) product of the Moderate‐resolution Imaging Spectroradiometer (MODIS) data as a weighting factor to downscale crop statistics from a county scale to a 1 km² spatial resolution using GIS to accurately map the spatial distribution of cereal bioenergy potential in China. The study demonstrates that the combination of remote sensing and statistical methods improves both spatial resolution and accuracy of the results, and resolves errors and uncertainties stemming from remote sensing processes. The results of the study will allow better decision making for siting biomass power plants, which will in turn reduce the cost of transportation of materials and increase the use of bioenergy.     

Integration in a depot‐based decentralized biorefinery system: Corn stover‐based cellulosic biofuel

The current or “conventional” paradigm for producing process energy in a biorefinery processing cellulosic biomass is on‐site energy recovery through combustion of residual solids and biogas generated by the process. Excess electricity is then exported, resulting in large greenhouse gas (GHG) credits. However, this approach will cause lifecycle GHG emissions of biofuels to increase as more renewable energy sources (wind, solar, etc.) participate in grid‐electricity generation, and the GHG credits from displacing fossil fuel decrease. To overcome this drawback, a decentralized (depot‐based) biorefinery can be integrated with a coal‐fired power plant near a large urban area. In an integrated, decentralized, depot‐based biorefinery (IDB), the residual solids are co‐fired with coal either in the adjacent power plant or in coal‐fired boilers elsewhere to displace coal. An IDB system does not rely on indirect GHG credits through grid‐electricity displacement. In an IDB system, biogas from the wastewater treatment facility is also upgraded to biomethane and used as a transportation biofuel. The GHG savings per unit of cropland in the IDB systems (2.7–2.9 MgCO₂/ha) are 1.5–1.6 fold greater than those in a conventional centralized system (1.7–1.8 MgCO₂/ha). Importantly, the biofuel selling price in the IDBs is lower by 28–30 cents per gasoline‐equivalent liter than in the conventional centralized system. Furthermore, the total capital investment per annual biofuel volume in the IDB is much lower (by ~80%) than that in the conventional centralized system. Therefore, utilization of biomethane and residual solids in the IDB systems leads to much lower biofuel selling prices and significantly greater GHG savings per unit of cropland participating in the biorefinery system compared to the conventional centralized biorefineries.     

Bimodal effect of exogenous hydrogen peroxide on human neutrophils: cytotoxic effect and modulation of respiratory burst in response to an agonist]

It has been found that high concentrations of exogenous hydrogen peroxide kill human neutrophils, the range of toxic concentrations being 100 times as high as that for human endothelial cells. Whereas the H2O2 doses of 30-100 mM induce a fast massive death of neutrophils, 10 mM hydrogen peroxide induces appreciable death only within several hours after treatment. H2O2 used at 30 mM decreases superoxide anion generation by neutrophils stimulated with PMA or FMLP. This decrease is commensurate in value with cell death, thus indicating a high functional resistance of survived cells. In the dose of 10 mM hydrogen peroxide potentiates FMLP (but not PMA-)-induced generation of superoxide anions. Augmentation of superoxide anion generation by H2O2-primed neutrophils in response to FMLP amounts to 200% of the control value. Hydrogen peroxide alone is incapable of inducing superoxide anion generation. It is concluded that exogenous oxidants can alter the functional activity of leukocytes freshly recruited in inflammatory and ischemic tissues.     

The Relationship between Methane Production and Concentrations of Hydrogen in the Aqueous and Gaseous Phases during Rumen Fermentation in vitro

S ummary : When rumen micro-organisms were incubated in vitro with a wide range of concentrations of hydrogen (H) in the gas phase, the amount of methane produced was linearly related to the amount of H taken up. The rate of utilization of dissolved H for methane synthesis was close to the rate of entry of H into solution from the gas phase. Hydrogen produced from formate accumulated in the aqueous phase, but methane production was not related to its concentration.     

Microbial CO conversions with applications in synthesis gas purification and bio-desulfurization

Recent advances in the field of microbial physiology demonstrate that carbon monoxide is a readily used substrate by a wide variety of anaerobic micro-organisms, and may be employed in novel biotechnological processes for production of bulk and fine chemicals or in biological treatment of waste streams. Synthesis gas produced from fossil fuels or biomass is rich in hydrogen and carbon monoxide. Conversion of carbon monoxide to hydrogen allows use of synthesis gas in existing hydrogen utilizing processes and is interesting in view of a transition from hydrogen production from fossil fuels to sustainable (CO2-neutral) biomass. The conversion of CO with H2O to CO2 and H2 is catalyzed by a rapidly increasing group of micro-organisms. Hydrogen is a preferred electron donor in biotechnological desulfurization ofwastewaters and flue gases. Additionally, CO is a good alternative electron donor considering the recent isolation of a CO oxidizing, sulfate reducing bacterium. Here we review CO utilization by various anaerobic micro-organisms and their possible role in biotechnological processes, with a focus on hydrogen production and bio-desulfurization.     

China's bioenergy potential

Despite great enthusiasm about developing renewable energy in China, the country's bioenergy potential remains unclear. Traditional utilization of bioenergy through primarily household combustion of crop residue and fuelwood is still a predominant energy source for rural China. More efficient utilization of ～300 million tons of crop residues for bioelectricity generation could add a couple of percent of renewable energy to China's total energy production. With <9% of the world's arable land supporting ～20% of the world's population, China is already a net grain importer and has little extra farmland for producing a significantly additional amount of biofuels from first‐generation energy crops, such as maize, sugarcane, and soybean. Second‐generation energy crops hold the greatest potential for bioenergy development worldwide. Miscanthus, a native perennial C4 grass that produces high biomass across almost the entire climatic zone of China, is the most promising second‐generation energy crop to domesticate and cultivate. A reasonable near‐term goal is to produce 1 billion tons of Miscanthus biomass annually from ～100 million hectares of marginal and degraded land concentrated in northern and northwestern China. This can generate ～1458 TW h electricity and mitigate ～1.7 billion tons of CO₂ emission from power coal, which account for ～45% of China's electricity output and ～28% of CO₂ emission in 2007. Furthermore, growing perennial grasses on marginal and degraded land will contribute to the ongoing efforts in China to restore vast areas of land under serious threat of desertification. With this potential taken into account, bioenergy can play a major role in meeting China's rapidly growing energy demand while substantially reducing greenhouse gas emission.     

Hydrogen production profiles using furans in microbial electrolysis cells

Microbial electrochemical cells including microbial fuel cells (MFCs) and microbial electrolysis cells (MECs) are novel biotechnological tools that can convert organic substances in wastewater or biomass into electricity or hydrogen. Electroactive microbial biofilms used in this technology have ability to transfer electrons from organic compounds to anodes. Evaluation of biofilm formation on anode is crucial for enhancing our understanding of hydrogen generation in terms of substrate utilization by microorganisms. In this study, furfural and hydroxymethylfurfural (HMF) were analyzed for hydrogen generation using single chamber membrane-free MECs (17 mL), and anode biofilms were also examined. MECs were inoculated with mixed bacterial culture enriched using chloroethane sulphonate. Hydrogen was succesfully produced in the presence of HMF, but not furfural. MECs generated similar current densities (5.9 and 6 mA/cm² furfural and HMF, respectively). Biofilm samples obtained on the 24th and 40th day of cultivation using aromatic compounds were evaluated by using epi-fluorescent microscope. Our results show a correlation between biofilm density and hydrogen generation in single chamber MECs.     

Electricity generation from carbon monoxide and syngas in a microbial fuel cell

Electricity generation in microbial fuel cells (MFCs) has been a subject of significant research efforts. MFCs employ the ability of electricigenic bacteria to oxidize organic substrates using an electrode as an electron acceptor. While MFC application for electricity production from a variety of organic sources has been demonstrated, very little research on electricity production from carbon monoxide and synthesis gas (syngas) in an MFC has been reported. Although most of the syngas today is produced from non-renewable sources, syngas production from renewable biomass or poorly degradable organic matter makes energy generation from syngas a sustainable process, which combines energy production with the reprocessing of solid wastes. An MFC-based process of syngas conversion to electricity might offer a number of advantages such as high Coulombic efficiency and biocatalytic activity in the presence of carbon monoxide and sulfur components. This paper presents a discussion on microorganisms and reactor designs that can be used for operating an MFC on syngas.     

Origin of hydrogen in methane produced by Methanobacterium thermoautotrophicum.

The production of deuterated methane by Methanobacterium thermoautotrophicum in H2O-D2O mixtures was examined by high-resolution mass spectrometry. The hydrogen in the methane arose solely from water and not from hydrogen gas. Hydrogen gas served only as an electron source in methanogenesis. A whole-cell product isotope discrimination of 1.5 favoring hydrogen over deuterium was observed in methane production in 81 atom% deuterated water. The distribution of deuterated methane species is described by a simple model of the overall reaction.     

Electricity generation from mixed volatile fatty acids using microbial fuel cells

Fermentative hydrogen production, as a process for clean energy recovery from organic wastewater, is limited by its low hydrogen yield due to incomplete conversion of substrates, with most of the fermentation products being volatile fatty acids (VFAs). Thus, further recovery of the energy from VFAs is expected. In this work, microbial fuel cell (MFC) was applied to recover energy in the form of electricity from mixed VFAs of acetate, propionate, and butyrate. Response surface methodology was adopted to investigate the relative contribution and possible interactions of the three components of VFAs. A stable electricity generation was demonstrated in MFCs after the enrichment of electrochemically active bacteria. Analysis showed that power density was more sensitive to the composition of mixed VFAs than coulombic efficiency. The electricity generation could mainly be attributed to the portion of acetate and propionate. However, the two components showed an antagonistic effect when propionate exceeded 19%, causing a decrease in coulombic efficiency. Butyrate was found to exert a negative impact on both power density and coulombic efficiency. Denaturing gradient gel electrophoresis profiles revealed the enrichment of electrochemically active bacteria from the inoculum sludge. Proteobacteria (Beta-, Delta-) and Bacteroidetes were predominant in all VFA-fed MFCs. Shifts in bacterial community structures were observed when different compositions of VFA mixtures were used as the electron donor. The overall electron recovery efficiency may be increased from 15.7% to 27.4% if fermentative hydrogen production and MFC processes are integrated.     

Gaining electricity from in situ oxidation of hydrogen produced by fermentative cellulose degradation

AIM: To exploit the fermentative hydrogen generation and direct hydrogen oxidation for the generation of electric current from the degradation of cellulose. METHODS AND RESULTS: Utilizing the metabolic activity of the mesophilic anaerobe Clostridium cellulolyticum and the thermophilic Clostridium thermocellum we show that electricity generation is possible from cellulose fermentation. The current generation is based on an in situ oxidation of microbially synthesized hydrogen at platinum-poly(tetrafluoroaniline) (Pt-PTFA) composite electrodes. Current densities of 130 mA l(-1) (with 3 g cellulose per litre medium) were achieved in poised potential experiments under batch and semi-batch conditions. Conclusions: The presented results show that electricity generation is possible by the in situ oxidation of hydrogen, product of the anaerobic degradation of cellulose by cellulolytic bacteria. SIGNIFICANCE AND IMPACT OF THE STUDY: For the first time, it is shown that an insoluble complex carbohydrate like cellulose can be used for electricity generation in a microbial fuel cell. The concept represents a first step to the utilization of macromolecular biomass components for microbial electricity generation.