Carbon capture from biomass flue gases for CO2 enrichment in greenhouses.

Heating and CO2 enrichment systems can improve yields in intensive greenhouse agriculture Combining both techniques, which are currently applied commercially, can potentially enhance their effect. The CO2 must be separated from the other noxious gases present (such as CO, NOX, and SO2) to avoid them becoming part of the supply. The CO2 is then provided to the greenhouse on demand in the same way as the heating. In this work, we show that an improved food productivity of a pilot-scale greenhouse system combined with CO2 capture by adsorption using activated carbon and heating with alternative fuel. The proposed system's overall performance was evaluated and optimized. The best values were 46.7 g/kg of CO2 storage capacity on the adsorbent bed, 99.99 % removal rate harmful gases from the gas supplied to the greenhouse, CO2 levels of 1851.0 ± 262.8 mg/Nm3 of the CO2 levels in the greenhouse, and an enrichment time of 2.18 ± 0.92 h/day. The system's effective performance over extended periods (November-February) was confirmed and the productivity of a crop species (tomato) was compared to a control, showing an increment of 18 %. The results indicate that this is a valuable option for increasing the crop yield. By integrating this combined system with advanced climate control strategies, it is possible to maximize the CO2 provided per day, leading to higher yields. The system proved to be stable under real pilot-scale conditions over winter periods (four months).

Modelling of photosynthesis, respiration, and nutrient yield coefficients in Scenedemus almeriensis culture as a function of nitrogen and phosphorus.

Photo-respirometric tecniques are applied for evaluating photosynthetic activity in phototrophic organisms. These methods allow to evaluate photosynthetic response under different conditions. In this work, the influence of nutrient availability (nitrate, ammonium, and phosphate) on the photosynthesis and respiration of Scenedesmus almeriensis was studied using short photo-respirometric measurements. Both photosynthesis and respiration increasing until saturation value and consecutively diminishing, presenting inhibition by high concentrations. Regarding the influence of phosphorus concentration in microalgae cells, a similar hyperbolic trend was observed but no inhibition was observed at high concentration. Based on these experimental data, the respiration, and the photosynthesis rate of S. almeriensis were modelled using Haldane equation for nitrate and ammonium data, and Monod equation for phosphate data. In addition, experiments were performed to determine the yield coefficients for both nitrogen and phosphorus in S. almeriensis cultures. The data showed that the nitrogen and phosphorous coefficient yields are not constant, being modified as a function of nutrients concentration, presenting the luxury uptake phenomena. Finally, the proposed models were incorporated into a simulation tool to evaluate the photosynthetic activity and the nutrient yield coefficients of S. almeriensis when different culture media and wastewaters are used as a nitrogen and phosphorous source for its growth. Key points • Microalgal photosynthesis/respiration vary as a function of nutrients availability. • Photosynthesis inhibition appears at high N-NO 3 - and N-NH4+ concentrations. • Nutrient yield coefficients are influenced by luxury uptake phenomenon.

Evaluation of photosynthetic light integration by microalgae in a pilot-scale raceway reactor.

The improvement of photosynthetic efficiency in a 100 m2 raceway reactor by enhancement of light regime to which the cells are exposed is here reported. From Computational Fluid Dynamics it was calculated that the light exposure times ranged from 0.4 to 3.6 s while the exposure times to darkness were much longer, from 6 to 21 s. It was demonstrated that these times are too long for light integration, the cells fully adapting to local irradiances. This phenomenon was validated in the real outdoor raceway at different seasons. Simulations allows to confirm that if total light integration is achieved biomass productivity can increase up to 40 g/m2·day compared to 29 g/m2·day obtained considering local adaptation, which is close to the experimental value of 25 g/m2·day. This paper provides clear evidence of microalgae cell adaptation to local irradiance because of the unfavourable cell movement pattern in raceway reactors.

Utilization of centrate for the outdoor production of marine microalgae at pilot-scale in flat-panel photobioreactors.

The outdoor production of marine microalgae biomass in pilot scale flat panels photobioreactors, under not sterile conditions and using centrate as nutrients source, was studied. Experiments were performed modifying the centrate percentage, dilution rate and orientation of the photobioreactors. The strain Geitlerinema sp. was that one prevailing independently of the culture conditions. The higher productivity of 47.7 gbiomass m-2·day-1 dry weight and photosynthetic efficiency of 2.8%, was achieved when using 20% centrate and a dilution rate of 0.3 day-1, whatever the orientation of the reactor, maximal nutrient removal capacities of 82%, 85% and 100% for carbon, nitrogen and phosphorus being obtained. Under non-optimal conditions up to 80% of the nitrogen and 60% of the phosphorus were lost by stripping and precipitation, respectively. Carbohydrates was the major component of the biomass followed by proteins and lipids. These results support the possibility to produce microalgae biomass below 0.59 €/kg, useful to produce biofertilizers and animal feed.

Optimization of carbon dioxide supply in raceway reactors: Influence of carbon dioxide molar fraction and gas flow rate.

Influence of CO2 composition and gas flow rate to control pH in a pilot-scale raceway producing Scenedesmus sp. was studied. Light and temperature determined the biomass productivity whereas neither the CO2 molar fraction nor the gas flow rate used influenced it; because pH was always controlled and carbon limitation did not take place. The CO2 molar fraction and the gas flow rate influenced carbon loss in the system. At low CO2 molar fraction (2-6%) or gas flow rate (75-100l·min(-1)) the carbon efficiency in the sump was higher than 95%, 85% of the injected carbon being transformed into biomass. Conversely, at high CO2 molar fraction (14%) or gas flow rate (150l·min(-1)) the carbon efficiency in the sump was lower than 67%, 32% of the carbon being fixed as biomass. Analysis here reported allows the pH control to be optimized and production costs to be reduced by optimizing CO2 efficiency.

A quantitative study of eicosapentaenoic acid (EPA) production by Nannochloropsis gaditana for aquaculture as a function of dilution rate, temperature and average irradiance.

Different pilot-scale outdoor photobioreactors using medium recycling were operated in a greenhouse under different environmental conditions and the growth rates (0.1 to 0.5 day(-1)) obtained evaluated in order to compare them with traditional systems used in aquaculture. The annualized volumetric growth rate for Nannochloropsis gaditana was 0.26 g l(-1) day(-1) (peak 0.4 g l(-1) day(-1)) at 0.4 day(-1) in a 5-cm wide flat-panel bioreactor (FP-PBR). The biomass productivity achieved in this reactor was 10-fold higher than in traditional reactors, reaching values of 28 % and 45 % dry weight (d.w.) of lipids and proteins, respectively, with a 4.3 % (d.w.) content of eicosapentaenoic acid (EPA). A model for predicting EPA productivity from N. gaditana cultures that takes into account the existence of photolimitation and photoinhibition of growth under outdoor conditions is presented. The effect of temperature and average irradiance on EPA content is also studied. The maximum EPA productivity attained is 30 mg l(-1) day(-1).

Development of a process for the production of L-amino-acids concentrates from microalgae by enzymatic hydrolysis.

A process for the production of l-amino-acids concentrates from microalgae biomass by enzymatic hydrolysis has been developed. The process includes pre-treatment for cell-disruption, enzymatic hydrolysis and final separation by centrifugation. Thermal and mechanical cell-disruption methods have been tested, selecting mechanical disruption using bead milling for 30 min. The enzymatic hydrolysis was done using the commercial enzymes Alcalase and Flavourzyme. Maximum hydrolysis was obtained for biomass concentrations under 270 g/l and previous additional treatment with Viscozyme, reaching a 42% hydrolysis. Repeated reaction steps increased the hydrolysis from 42% (4h) with a single step to 59% (8h) after two successive steps. Further increase of the number of steps had a meagre impact on the global yield. The process widens the portfolio of products that can be obtained from microalgae biomass and is a new possibility to enhance the economic viability of microalgae-based biofuels production processes.

Utilization of Anabaena sp. in CO2 removal processes: modelling of biomass, exopolysaccharides productivities and CO2 fixation rate.

This paper focuses on modelling the growth rate and exopolysaccharides production of Anabaena sp. ATCC 33047, to be used in carbon dioxide removal and biofuels production. For this, the influence of dilution rate, irradiance and aeration rate on the biomass and exopolysaccharides productivity, as well as on the CO(2) fixation rate, have been studied. The productivity of the cultures was maximum at the highest irradiance and dilution rate assayed, resulting to 0.5 g(bio) l(-1) day(-1) and 0.2 g(eps) l(-1) day(-1), and the CO(2) fixation rate measured was 1.0 gCO(2) l(-1) day(-1). The results showed that although Anabaena sp. was partially photo-inhibited at irradiances higher than 1,300 µE m(-2) s(-1), its growth rate increases hyperbolically with the average irradiance inside the culture, and so does the specific exopolysaccharides production rate. The latter, on the other hand, decreases under high external irradiances, indicating that the exopolysaccharides metabolism hindered by photo-damage. Mathematical models that consider these phenomena have been proposed. Regarding aeration, the yield of the cultures decreased at rates over 0.5 v/v/min or when shear rates were higher than 60 s(-1), demonstrating the existence of thus existence of stress damage by aeration. The behaviour of the cultures has been verified outdoors in a pilot-scale airlift tubular photobioreactor. From this study it is concluded that Anabaena sp. is highly recommended to transform CO(2) into valuable products as has been proved capable of metabolizing carbon dioxide at rates of 1.2 gCO(2) l(-1) day(-1) outdoors. The adequacy of the proposed equations is demonstrated, resulting to a useful tool in the design and operation of photobioreactors using this strain.

Development of a process for efficient use of CO2 from flue gases in the production of photosynthetic microorganisms.

A new methodology to use efficiently flue gases as CO(2) source in the production of photosynthetic microorganisms is proposed. The CO(2) is absorbed in an aqueous phase that is then regenerated by microalgae. Carbonated solutions could absorb up to 80% of the CO(2) from diluted gas reaching total inorganic carbon (TIC) concentrations up to 2.0 g/L. The pH of the solution was maintained at 8.0-10.0 by the bicarbonate/carbonate buffer, so it is compatible with biological regeneration. The absorption process was modeled and the kinetic parameters were determined. Anabaena sp. demonstrated to tolerate pH (8.0-10.0) and TIC (up to 2.0 g/L) conditions imposed by the absorption step. Experiments of regeneration of the liquid phase demonstrated the feasibility of the overall process, converting CO(2) into organic matter. The developed process avoids heating to regenerate the liquid whereas maximizing the efficiency of CO(2) use, which is relevant to achieve the commercial production of biofuels from microalgae.

Biotechnological production of lutein and its applications.

Lutein is an antioxidant that has gathered increasing attention due to its potential role in preventing or ameliorating age-related macular degeneration. Currently, it is produced from marigold oleoresin, but continuous reports of lutein-producing microalgae pose the question if those microorganisms can become an alternative source. Several microalgae have higher lutein contents than most marigold cultivars and have been shown to yield productivities hundreds of times higher than marigold crops on a per square meter basis. Microalgae and marigold are opposite alternatives in the use of resources such as land and labor and the prevalence of one or the other could change in the future as the lutein demand rises and if labor or land becomes more restricted or expensive in the producing countries. The potential of microalgae as a lutein source is analyzed and compared to marigold. It is suggested that, in the current state of the art, microalgae could compete with marigold even without counting on any of the improvements in microalgal technology that can be expected in the near future.

Utilization of the cyanobacteria Anabaena sp. ATCC 33047 in CO2 removal processes.

In this paper the utilization of the cyanobacteria Anabaena sp. in carbon dioxide removal processes is evaluated. For this, continuous cultures of this strain were performed at different dilution rates; alternatives for the recovery of the organic matter produced being also studied. A maximum CO(2) fixation rate of 1.45 g CO(2) L(-1) day(-1) was measured experimentally, but it can be increased up to 3.0 g CO(2) L(-1) day(-1) outdoors. The CO(2) is mainly transformed into exopolysaccharides, biomass representing one third of the total organic matter produced. Organic matter can be recovered by sedimentation with efficiencies higher than 90%, the velocity of sedimentation being 2.10(-4) s(-1). The major compounds were carbohydrates and proteins with productivities of 0.70 and 0.12 g L(-1) day(-1), respectively. The behaviour of the cultures of Anabaena sp. has been modelized, also the characteristics parameters requested to design separation units being reported. Finally, to valorizate the organic matter as biofertilizers and biofuels is proposed.

Combined photo-Fenton and biological oxidation for pesticide degradation: effect of photo-treated intermediates on biodegradation kinetics.

Biodegradability of a partially photo-oxidized pesticide mixture is demonstrated and the effect of photo-Fenton treatment time on growth and substrate consumption of the bacteria Pseudomonas putida CECT 324 is shown. Four commercial pesticides, laition, metasystox, sevnol and ultracid, usually employed in citric orchards in eastern Spain, were chosen for these experiments. The active ingredients are, respectively, dimethoate, oxydemeton-methyl, carbaryl and methidathion. Judging by biomass measurements, dissolved organic carbon measurements and biodegradation efficiency, it may be concluded that 90min

Cost-effective production of 13C, 15N stable isotope-labelled biomass from phototrophic microalgae for various biotechnological applications.

The present study outlines a process for the cost-effective production of 13C/15N-labelled biomass of microalgae on a commercial scale. The core of the process is a bubble column photobioreactor with exhaust gas recirculation by means of a low-pressure compressor. To avoid accumulation of dissolved oxygen in the culture, the exhaust gas is bubbled through a sodium sulphite solution prior to its return to the reactor. The engineered system can be used for the production of 13C, 15N, and 13C-15N stable isotope-labelled biomass as required. To produce 13C-labelled biomass, 13CO2 is injected on demand for pH control and carbon supply, whereas for 15N-labelled biomass Na15NO3 is supplied as nitrogen source at the stochiometric concentration. The reactor is operated in semicontinuous mode at different biomass concentrations, yielding a maximum mean biomass productivity of 0.3 gL(-1) day(-1). In order to maximize the uptake efficiency of the labelled substrates, the inorganic carbon is recovered from the supernatant by acidification/desorption processes, while the nitrate is delivered at stochiometric concentration and the harvesting of biomass is performed when the 15NO3- is depleted. In these conditions, elemental analysis of both biomass and supernatant shows that 89.2% of the injected carbon is assimilated into the biomass and 6.9% remains in the supernatant. Based on elemental analysis, 97.8% of the supplied nitrogen is assimilated into the biomass and 1.3% remains in the supernatant. Stable isotope-labelling enrichment has been analysed by GC-MS results showing that the biomass is highly labelled. All the fatty acids are labelled; more than 96% of the carbon present in these fatty acids is 13C. The engineered system was stably operated for 3 months, producing over 160 g of 13C and/or 15N-labelled biomass. The engineered bioreactor can be applied for the labelling of various microalgae.

Influence of power supply in the feasibility of Phaeodactylum tricornutum cultures.

The influence of fluid-dynamic conditions on the yield of Phaeodactylum tricornutum microalgal cultures was analyzed in two stages: first, the influence of air flow rate; second, the influence of using fluid-moving pumps for recirculating the culture. With respect to the air flow rate, the yield of the cultures increased with the aeration rate up to values of 2.0 v/v/min, then stress was observed and the yield of the cultures decreased. With respect to the influence of mechanical power supply for liquid impulsion, three different types of pumps--centrifugal, pulse, and peristaltic--were essayed at different power supplies. The cultures were stressed for the three types of pumps essayed. For each pump, the higher the power supply the lower was the Fv/Fm value and the higher was the stress at which cells were exposed. The highest measured stress was when the culture was moved with the centrifugal pump. Despite measured stress, for all the experiments stable steady states were reached, thus indicating that cells reduced their yield but did not die, as was verified by cell viability measurements. It was observed that the increase of the power supply improved the frequency of light exposition thus enhancing the yield of the cultures. However, the higher the power supply, the lower the microeddy length scale; therefore, stress could appear. Data demonstrated that the microeddy length scale was always much higher than cell size and therefore the turbulence was not responsible for stress. Also, the mass transfer was discarded as responsible for yield reduction. It was concluded that the shear rate was the factor determining the existence of stress phenomena. The evaluation of these shear rates demonstrated that values above 30-80 s(-1) damaged the cells strongly. These data were verified in an outdoor pilot-scale tubular photobioreactor that was implemented with the same type of pumps, thus demonstrating the necessity to take into account this factor in the design and scale-up of microalgal photobioreactors.

Recovery of microalgal biomass and metabolites: process options and economics.

Commercial production of intracellular microalgal metabolites requires the following: (1) large-scale monoseptic production of the appropriate microalgal biomass; (2) recovery of the biomass from a relatively dilute broth; (3) extraction of the metabolite from the biomass; and (4) purification of the crude extract. This review examines the options available for recovery of the biomass and the intracellular metabolites from the biomass. Economics of monoseptic production of microalgae in photobioreactors and the downstream recovery of metabolites are discussed using eicosapentaenoic acid (EPA) recovery as a representative case study.

Minimization of carbon losses in pilot-scale outdoor photobioreactors by model-based predictive control.

The optimization of carbon use in pilot-scale outdoor tubular photobioreactors is investigated in this study. The behavior of a 0.20-m(3) tubular photobioreactor was studied, with and without algae, by steady-state and pulse dynamic-response analysis experiments. A model of the system was obtained and implemented in a programmable control unit and was used to control the reactor under normal production conditions. Results showed that, using and on-off control, the mean daily CO(2) flow in the reactor was 0.86 g min(-1), 19.7% of this being lost. By using a predictive control algorithm the mean daily CO(2) flow was reduced to 0.74 g min(-1), with losses being reduced to 15.6%. In this case, pH tracking was not adequate, especially at the beginning and end of the daylight period, because the variation in solar irradiance was not considered. Taking solar irradiance into account resulted in better performance, with mean daily CO(2) flow reduced to 0.70 g min(-1), and carbon losses reduced to 5.5%. pH tracking was improved and valve actuation was reduced. Improvement of pH control reduced pH gradients in the culture, which increased the photosynthesis rate and biomass productivity of the system. Biomass productivity increased from 1.28 to 1.48 g L(-1) day-(1) when on-off control was replaced by model-based predictive control plus solar irradiance effect mode. Implementation of this methodology in outdoor photobioreactors can increase productivity by 15% and reduce the cost of producing biomass by >6%. Clearly, application of effective control techniques, such as model-based predictive control (MPC), must be considered when developing these processes.

Outdoor production of Phaeodactylum tricornutum biomass in a helical reactor.

The production of microalga Phaeodactylum tricornutum in an outdoor helical reactor was analysed. The influence of temperature, solar irradiance and air flow rate on the yield of the culture was evaluated. Biomass productivities up to 1.5 g l(-1) per day and photosynthetic efficiency up to 14% were obtained by maintaining the cultures below 30 degrees C, dissolved oxygen levels less than 400% Sat. (with respect to air saturated culture) and controlling the cell density in order to achieve an average irradiance within the culture below 250 microE m(-2) s(-1). Under these conditions, the fluorescence parameter, Fv/Fm, which reflects the maximal efficiency of PSII photochemistry, remained roughly 0.6-0.7 and growth rates up to 0.050 h(-1) were achieved. The average irradiance and the light/dark cycle frequency, were the variables determining the behaviour of the cultures. A hyperbolic relationship between growth rate and biomass productivity with the average irradiance was observed, whereas both biomass productivity and photosynthetic efficiency linearly increased with the light/dark cycle frequencies. Optimum design and operational conditions which maximise the production of P. tricornutum biomass in outdoor helical reactors were determined.

Recovery of pure B-phycoerythrin from the microalga Porphyridium cruentum.

Phycoerythrin is a major light-harvesting pigment of red algae and cyanobacteria that is widely used as a fluorescent probe and analytical reagent. In this paper, B-phycoerythrin and R-phycocyanin in native state, from the red alga Porphyridium cruentum were obtained by an inexpensive and simple process. The best results of this purification procedure were scaled up by a factor of 13 to a large preparative level using an anionic chromatographic column of DEAE cellulose. Gradient elution with acetic acid-sodium acetate buffer (pH 5.5) was used. In these conditions both 32% of B-phycoerythrin and 12% of R-phycocyanin contained in the biomass of the microalgae was recovered. B-phycoerythrin was homogeneous as determined by sodium dodecyl sulfate-poly-acrylamide gel electrophoresis (SDS-PAGE), yielding three migrating bands corresponding to its three subunits, consistent with the (alpha beta)(6)gamma subunit composition characteristic of this biliprotein and the spectroscopic characterization of B-PE (UV-visible absorption and emission spectroscopy; steady-state and polarization fluorescence), is accompanied. Finally, a preliminary cost analysis of the recovery process is presented.

Carbon dioxide uptake efficiency by outdoor microalgal cultures in tubular airlift photobioreactors.

The influence of solar irradiance and carbon dioxide molar fraction of injected CO(2)-air mixtures on the behavior of outdoor continuous cultures of the microalga Phaeodactylum tricornutum in tubular airlift photobioreactors was analyzed. Instantaneous solar irradiance, pH, dissolved oxygen, temperature, biomass concentration, and the mass flow rates of both the inlet and outlet oxygen and carbon with both the liquid and gas phases were measured. In addition, elemental analysis of the biomass and the cell-free culture medium was performed. The oxygen production rate and carbon dioxide consumption rate increased hyperbolically with the incident solar irradiance on the reactor surface. Carbon losses showed a negative correlation with the daily variation of the carbon dioxide consumption rate. The maximum CO(2) uptake efficiency was 63% of the CO(2) supplied when the CO(2) concentration in the gas supplied was 60% v/v. Carbon losses were >100% during the night, due to CO(2) production by respiration, and hyperbolically decreased to values of 10% to 20% in the midday hours. An increase in the carbon fixed in the biomass with the solar cycle was observed. A slight daily decrease of carbon content of the cell-free culture medium indicated the existence of carbon accumulation in the culture. A decrease in CO(2) molar fraction in the injected gas had a double benefit: first, the biomass productivity of the system was enhanced from 2.05 to 2.47 g L(-1) day(-1) by reduction of CO(2) inhibition and/or pH gradients; and second, the carbon losses during the daylight period were reduced by 60%. The fluid dynamics in the reactor also influenced the carbon losses: the higher the liquid flow rate the higher the carbon losses. By using a previous mass transfer model the experimental results were simulated and the usefulness of this method in the evaluation and scale-up of tubular photobioreactors was established.