Sorbent characterization for circulating fluidized bed scrubbers

Harmful sulfur dioxide (SO2) emissions from power plants have increasingly been restricted since the 1970’s. Circulating fluidized bed (CFB) scrubber is a dry flue gas desulfurization method of absorbing SO2 out of the flue gas with sorbent. In current commercial plants, the used sorbent is commercial or on-site hydrated calcium hydroxide. The CFB scrubber process is characterized by a close but adequate approach to the flue gas saturation temperature that is achieved by spraying water to the absorber followed by a particulate control device. Very high SO2 removal is achieved along with a dry byproduct that is continuously recirculated back to the absorber for enhanced sorbent utilization. The aim of this work is to develop a method that would characterize the reactivity of sorbents used in CFB scrubbers and to conclude how different process parameters and sorbent properties affect the sulfur absorption. The developed characterization method is based on a fixed bed of sorbent and inert silica sand, through which an SO2 containing gas mixture is led. The reaction occurs in the bed and the SO2 concentration in the outlet as a function of time, a breakthrough curve, is obtained from the analyzer. Reactivity of the sorbents are evaluated by the absorbed sulfur amount. Results suggest that out of process parameters, lower SO2 concentration, lower temperature and higher moisture content enhance the desulfurization. Between different sorbents, specific surface area seems to be the most significant parameter. Large surface area linearly leads to more efficient desulfurization. Overall, the solid conversion levels in the tests were very low creating uncertainty to the validity of the results. New desing is being planned to overcome the problems of the device.

Development of bean plants in soil contaminated with trifloxysulfuron-sodium after Stizolobium aterrimum and Canavalia ensiformis cultivation

Phytoremediation, the use of plants to decontaminate soils and water resources from organic pollutants such as herbicides, is economically and environmentally a promising technique applied in many areas, including agriculture. The objective of this work was to evaluate the development of bean plants cultivated in the field, in soil with different levels of trifloxysulfuron-sodium contamination, following cultivation of two green manure species, as well as to evaluate the possibility of recontamination of the area by such herbicide with the straw permanence on the soil. The experiment was carried out in Coimbra, MG, Brazil, on a sandy clayey Red - Yellow Argisol from March to November 2003. Four levels of soil contamination with trifloxysulfuron-sodium (0.00; 3.75; 7.50; and 15.00 g ha-1) were used as well as the following five types of cultivation prior to bean sowing in the area after herbicide application: black velvet beans (Stizolobium aterrimum) followed by removal of straw; S. aterrimum, followed by permanence of straw; jack bean (Canavalia ensiformis), followed by removal of straw; C. ensiformis followed by permanence of straw; and without prior cultivation, weed-free (weeded control). The leguminous plants were kept in the area for 65 days, cut close to the soil, and with its aerial part left or not on the surface of the experimental plot, depending on the treatment. Fifteen days after the species were cut, bean was sown in the area. At 45 days after emergence (DAE) of the bean plants, plant height and dry mass of the aerial part were evaluated. Grain productivity was determined during harvest. Height, dry matter of the aerial part and grain productivity of the bean plants, cultivated in an area previously contaminated with trifloxysulfuron-sodium at any of the levels tested, were higher with prior cultivation of S. aterrimum or C. ensiformis. At the lowest level of herbicide contamination, prior cultivation of C. ensiformis was found to be more efficient than that of S. aterrimum in mitigating the harmful effects of trifloxysulfuron-sodium on bean grain production. The permanence of the straw of the green manure species during the bean cycle did not harm the development of the plants or caused culture productivity losses, indicating that straw permanence in the area does not promote recontamination of the area.

Photosynthetic activity of cassava plants under weed competition

The objective of this work was to evaluate characteristics associated with the photosynthetic activity of cassava plants under weed competition. The trial was carried out under field conditions, and experimental units consisted of 150 dm³ fiberglass boxes containing red yellow Latosol, previously corrected and fertilized. Treatments consisted in the cultivation of cassava plants which were free of weed competition and associated with three weed species: Bidens pilosa, Commelina benghalensis or Brachiaria plantaginea. After manioc sprouting started, 15 days after being planted, weeds that had been sown when manioc was planted were thinned, there were then eight plants left per experimental unit in accordance with specified treatments: cassava free of competition, cassava competing with B. pilosa, cassava competing with C. benghalensis and cassava competing with B. plantaginea. Sixty days after crop emergence leaf internal CO2 concentration (Ci), leaf temperature at the time of evaluation (Tleaf) and photosynthetic rate (A) were evaluated, also the CO2 consumption rate (ΔC) of cassava plants was calculated. A correlation matrix between variables was also obtained. All characteristics associated with photosynthesis in cassava plants were influenced by weed species. Cassava was more affected by B. pilosa and B. plantaginea in which concerns its exposition to solar radiation and water, while C. benghalensis seems to mostly affect the composition of incident light on the culture, allowing cassava to anticipate imposition when competing, even before it reaches harmful levels.

Interactions between soybean and weeds in a replacement series system, considering the effects of water stress

Due to the increase of water deficiency in many farm regions and its meaning on weed interference, competitive interactions between soybean and three weeds were evaluated under water stress (20 to 40 days after transplanting) and no stress conditions. Three independent experiments were carried out in a growth chamber, being each one composed by the weeds Alternanthera tenella, Tridax procumbens or Digitaria ciliaris, along with the crop, in which soil water condition and plant composition effects were evaluated while in competition. A replacement series system was used, including both monoculture of each species and a mixture with a ratio of 50% between weed and soybean. A completely randomized design was used in factorial arrangement, with treatments distributed in three levels for plant composition factor (soybean and weeds monocultures, in addition to the soybean + weed mixture) and two levels for the water factor (with or without stress), amounting six treatments in each experiment. Soybean dry mass was higher than weed dry mass, when growing without water stress. However, under water stress conditions, the dry mass of soy was reduced in all experiments, mainly in the D. ciliaris comparative experiment. Water restriction was also significant in the plants' photosynthesis reduction in most of the experiments, reducing leaf area duration and efficiency of water use. Analysing all variables shows greater weed tolerance than soybean when submitted to water deficit and with distinct changes of their interactions and mechanism of competition, in each experiment.

Comparison of sustainability of technologies for water desalination

The aim of this work is to perform an in-depth overview on the sustainability of several major commercialized technologies for water desalination and to identify the challenges and propose suggestions for the development of water desalination technologies. The overview of those technologies mainly focuses on the sustainability from the viewpoint of total capital investment, total product cost, energy consumption and global warming index. Additionally, a systematic sustainability assessment methodology has been introduced to validate the assessment process. Conclusions are:1) Reverse osmosis desalination (RO) plants are better than multi-stage flash distillation (MSF) desalination plants and multiple-effect distillation (MED) desalination plants from the viewpoint of energy consumption, global warming index and total production cost; 2)Though energy intensive, MSF plants and MED plants secure their advantages over RO plants by lower total capital investment, wider applicability and purer water desalted and they are still likely to flourish in energy-rich area;3) Water production stage and wastewater disposal stage are the two stages during which most pollutant gases are emitted. The water production stage alone contributes approximately 80~90% of the total pollutant gases emission during its life cycle; 4)The total capital cost per m3 desalted water decreases remarkably with the increasing of plant capacity. The differences between the capital cost per m3 desalted water of RO and other desalination plants will decrease as the capacity increases; 5) It is found that utilities costs serve as the major part of the total product cost, and they account for 91.16%, 85.55% and 71.26% of the total product cost for MSF, MED and RO plants, respectively; 6) The absolute superiority of given technology depends on the actual social-economic situation (energy prices, social policies, technology advancements).

Extraction and Simultaneous Determination of Glyphosate, AMPA and Compounds of the Shikimic Acid Pathway in Plants

This study has aimed to develop a method for simultaneous extraction and determination by liquid chromatography and mass spectrometry (LC-MS/MS) of glyphosate, aminomethylphosphonic acid (AMPA), shikimic acid, quinic acid, phenylalanine, tyrosine and tryptophan. For the joint analysis of these compounds the best conditions of ionization in mass spectrometry and for chromatographic separation of the compounds were selected. Calibration curves and linearity ranges were also determined for each compound. Different extraction systems of the compounds were tested from plant tissues collected from sugarcane (Saccharum officinarum) and eucalyptus (Eucalyptus urophylla platiphylla) plants two days after the glyphosate application at the dose of 720 g a.e. ha-1. The plant material was dried in a forced air circulation drying oven and in a lyophilizer, and subsequently the extractions with acidified water (pH 2.5), acetonitrile-water (50:50) [v/v] and methanol-water (50:50) [v/v] were tested. To verify the recovery of the compounds in the plant matrix with acidified water as an extracting solution, the samples were fortified with a solution containing the mixture of the different analytical standards present so that this one presented the same levels of 50 and 100 μg L-1 of each compound. All experiments were conducted with three replicates. The analytical method developed was efficient for compounds quantifications. The extraction from the samples dried in an oven and using acidified water allowed better extraction levels for all compounds. The recovery levels of the compounds in the fortified samples with known amounts of each compound for both plants samples were rather satisfactory.

The effect of water stress on seed germination of three terrestrial bromeliads from restinga

Bromeliad seedlings are rarely found on sandy coastal plains (restinga), limited, probably, by stressful conditions and/or specific abiotic requirements for germination. The effect of water stress on rate, time, synchronicity and spreading of germination was evaluated here for three terrestrial bromeliads from the restinga of Maricá using osmotic solutions of polyethyleneglicol 6000 (PEG 6000), from 0.0 to -0.26 MPa for 30 days. Water stress induced by PEG lowered rate and increased time and synchronicity values, besides the number of daily events of bromeliad seed germination, under water potentials between 0.00 to -0.14 MPa. No seeds germinated under water potentials lower than -0.14 MPa. These results reinforce a constant and/or high moisture requirement for bromeliad seeds to germinate. We conclude that bromeliads are not able to act as pioneer plants through germination outside the vegetation islands of the restinga of Maricá, due to the inability of seeds to germinate under lower water potential.

Modified nano- and microcellulose based adsorption materials in water treatment

In recent decades, industrial activity growth and increasing water usage worldwide have led to the release of various pollutants, such as toxic heavy metals and nutrients, into the aquatic environment. Modified nanocellulose and microcellulose-based adsorption materials have the potential to remove these contaminants from aqueous solutions. The present research consisted of the preparation of five different nano/microcellulose-based adsorbents, their characterization, the study of adsorption kinetics and isotherms, the determination of adsorption mechanisms, and an evaluation of adsorbents’ regeneration properties. The same well known reactions and modification methods that were used for modifying conventional cellulose also worked for microfibrillated cellulose (MFC). The use of succinic anhydride modified mercerized nanocellulose, and aminosilane and hydroxyapatite modified nanostructured MFC for the removal of heavy metals from aqueous solutions exhibited promising results. Aminosilane, epoxy and hydroxyapatite modified MFC could be used as a promising alternative for H2S removal from aqueous solutions. In addition, new knowledge about the adsorption properties of carbonated hydroxyapatite modified MFC as multifunctional adsorbent for the removal of both cations and anions ions from water was obtained. The maghemite nanoparticles (Fe3O4) modified MFC was found to be a highly promising adsorbent for the removal of As(V) from aqueous solutions due to its magnetic properties, high surface area, and high adsorption capacity . The maximum removal efficiencies of each adsorbent were studied in batch mode. The results of adsorption kinetics indicated very fast removal rates for all the studied pollutants. Modeling of adsorption isotherms and adsorption kinetics using various theoretical models provided information about the adsorbent’s surface properties and the adsorption mechanisms. This knowledge is important for instance, in designing water treatment units/plants. Furthermore, the correspondence between the theory behind the model and properties of the adsorbent as well as adsorption mechanisms were also discussed. On the whole, both the experimental results and theoretical considerations supported the potential applicability of the studied nano/microcellulose-based adsorbents in water treatment applications.

Gastric emptying of liquids in rats dehydrated by water deprivation

The gastric emptying of liquids was investigated in male Wistar rats (8 to 10 weeks old, 210-300 g) dehydrated by water deprivation. In this model of dehydration, weight loss, hematocrit and plasma density were significantly higher in the dehydrated animals than in the control groups after 48 and 72 h of water deprivation (P<0.05). Three test meals (saline (N = 10), water (N = 10) and a WHO rehydrating solution containing in one liter 90 mEq sodium, 20 mEq potassium, 80 mEq chloride and 30 mEq citrate (N = 10)) were used to study gastric emptying following water deprivation for 24, 48 and 72 h. After 72 h, gastric emptying of the water (39.4% retention) and rehydrating solution (49.2% retention) test meals was significantly retarded compared to the corresponding control groups (P<0.05, Mann-Whitney test). The 72-h period of deprivation was used to study the recovery from dehydration, and water was supplied for 60 or 120 min after 67 h of deprivation. Body weight loss, hematocrit and plasma density tended to return to normal when water was offered for 120 min. In the animals supplied with water for 60 min, there was a recovery in the gastric emptying of water while the gastric emptying of the rehydrating solution was still retarded (53.1% retention; P<0.02, Kruskal-Wallis test). In the group supplied with water for 120 min, the gastric emptying of the rehydrating (51.7% retention) and gluco-saline (46.0% retention) solutions tended to be retarded (P = 0.04, Kruskal-Wallis test). In this model of dehydration caused by water deprivation, with little alteration in the body electrolyte content, gastric emptying of the rehydrating solution was retarded after rehydration with water. We conclude that the mechanisms whereby receptors in the duodenal mucosa can modify gastric motility are altered during dehydration caused by water deprivation

Zinc and water intake in rats: investigation of adrenergic and opiatergic central mechanisms

We have demonstrated that central administration of zinc in minute amounts induces a significant antidipsogenic action in dehydrated rats as well as in rats under central cholinergic and angiotensinergic stimulation. Here we show that acute third ventricle injections of zinc also block water intake induced by central ß-adrenergic stimulation in Wistar rats (190-250 g). Central inhibition of opioid pathways by naloxone reverses the zinc-induced antidipsogenic effect in dehydrated rats. After 120 min, rats receiving third ventricle injections of isoproterenol (160 nmol/rat) exhibited a significant increase in water intake (5.78 ± 0.54 ml/100 g body weight) compared to saline-treated controls (0.15 ± 0.07 ml/100 g body weight). Pretreatment with zinc (3.0, 30.0 and 300.0 pmol/rat, 45 min before isoproterenol injection) blocked water intake in a dose-dependent way. At the highest dose employed a complete blockade was demonstrable (0.54 ± 0.2 ml/100 g body weight). After 120 min, control (NaAc-treated) dehydrated rats, as expected, exhibited a high water intake (7.36 ± 0.39 ml/100 g body weight). Central administration of zinc blocked this response (2.5 ± 0.77 ml/100 g body weight). Naloxone pretreatment (82.5 nmol/rat, 30 min before zinc administration) reverted the water intake to the high levels observed in zinc-free dehydrated animals (7.04 ± 0.56 ml/100 g body weight). These data indicate that zinc is able to block water intake induced by central ß-adrenergic stimulation and that zinc-induced blockade of water intake in dehydrated rats may be, at least in part, due to stimulation of central opioid peptides.

Central lead administration inhibits water intake and sodium appetite in rats

We have demonstrated that acute third ventricle injections of lead acetate (PbAc) exert a powerful antidipsogenic effect and induce a significant increase in renal sodium excretion. In the present study we confirm the antidipsogenic effect of lead and demonstrate that central administration of this metal, in minute amounts, significantly reduces salt intake both during dehydration and after central angiotensinergic stimulation. Adult male Wistar rats had the third ventricle cannulated seven days before the experiments. During this period they had free access to distilled water and hypertonic saline solution (1.5%). After a 24-h period of fluid deprivation, experimental animals received third ventricle injections of PbAc (0.3, N = 8 and 3.0 nmol/rat, N = 14) while controls received sodium acetate (NaAc; 3.0 nmol/rat, N = 10). Rats treated with PbAc at the highest dose showed a significant reduction (P<0.05) both in water and hypertonic saline intake when compared to controls. When the effect of lead administration on angiotensin II-induced water and salt intake was studied, normohydrated animals received third ventricle injections of angiotensin II (9.6 nmol/rat) after pretreatment with 3.0 nmol/rat of PbAc (experimental group, N = 10) or NaAc (controls, N = 8). The group pretreated with PbAc presented a significant reduction (P<0.05) in both water and salt intake compared to controls. Thus, this study confirms the antidipsogenic effect of central lead injections and demonstrates that the presence of lead in the brain exerts a significant inhibition of sodium appetite.

NIR-Vis Up-Conversion Luminescence in the Yb3+,Er3+ Doped Y2O2S, ZrO2, and NaYF4 Nanomaterials

Since the discovery of the up-conversion phenomenon, there has been an ever increasing interest in up-converting phosphors in which the absorption of two or more low energy photons is followed by emission of a higher energy photon. Most up-conversion luminescence materials operate by using a combination of a trivalent rare earth (lanthanide) sensitizer (e.g. Yb or Er) and an activator (e.g. Er, Ho, Tm or Pr) ion in a crystal lattice. Up-converting phosphors have a variety of potential applications as lasers and displays as well as inks for security printing (e.g. bank notes and bonds). One of the most sophisticated applications of lanthanide up-conversion luminescence is probably in medical diagnostics. However, there are some major problems in the use of photoluminescence based on the direct UV excitation in immunoassays. Human blood absorbs strongly UV radiation as well as the emission of the phosphor in the visible. A promising way to overcome the problems arising from the blood absorption is to use a long wavelength excitation and benefit from the up-conversion luminescence. Since there is practically no absorption by the whole-blood in the near IR region, it has no capability for up-conversion in the excitation wavelength region of the conventional up-converting phosphor based on the Yb3+ (sensitizer) and Er3+ (activator) combination. The aim of this work was to prepare nanocrystalline materials with high red (and green) up-conversion luminescence efficiency for use in quantitative whole-blood immunoassays. For coupling to biological compounds, nanometer-sized (crystallite size below 50 nm) up-converting phosphor particles are required. The nanocrystalline ZrO2:Yb3+,Er3+, Y2O2S:Yb3+,Er3+, NaYF4:Yb3+,Er3+ and NaRF4-NaR’F4 (R: Y, Yb, Er) materials, prepared with the combustion, sol-gel, flux, co-precipitation and solvothermal synthesis, were studied using the thermal analysis, FT-IR spectroscopy, transmission electron microscopy, EDX spectroscopy, XANES/EXAFS measurements, absorption spectroscopy, X-ray powder diffraction, as well as up-conversion and thermoluminescence spectroscopies. The effect of the impurities of the phosphors, crystallite size, as well as the crystal structure on the up-conversion luminescence intensity was analyzed. Finally, a new phenomenon, persistent up-conversion luminescence was introduced and discussed. For efficient use in bioassays, more work is needed to yield nanomaterials with smaller and more uniform crystallite sizes. Surface modifications need to be studied to improve the dispersion in water. On the other hand, further work must be carried out to optimize the persistent up-conversion luminescence of the nanomaterials to allow for their use as efficient immunoassay nanomaterials combining the advantages of both up-conversion and persistent luminescence.

Effect of the intracerebroventricular administration of GR 113808, a selective 5-HT4 antagonist, on water intake during hyperosmolarity and hypovolemia

We demonstrate here that acute third ventricle injections of GR 113808, a highly selective 5-HT4 antagonist, decrease water intake induced by a previous salt load while potentiating drinking elicited by hypovolemia induced by previous subcutaneous administration of polyethylene glycol in male Wistar rats (200 ± 20 g). At the dose of 160 nmol/rat, third ventricle injections of GR 113808 induced a significant reduction of water intake in salt-loaded animals after 120 min as compared to salt-loaded animals receiving third ventricle injections of saline (salt load + GR = 3.44 ± 0.41 ml, N = 12; salt load + saline = 5.74 ± 0.40 ml, N = 9). At the dose of 80 nmol/rat, GR 113808 significantly enhanced water intake in hypovolemic animals after 120 min as compared to hypovolemic animals receiving third ventricle injections of saline (hypovol + GR = 4.01 ± 0.27 ml, N = 8; hypovol + saline = 2.41 ± 0.23 ml, N = 12). We suggest that central 5-HT4 receptors may exert a positive drive on water intake due to hyperosmolarity and a negative input on drinking provoked by hypovolemia.

Review of water electrolysis technologies and design of renewable hydrogen production systems

An electric system based on renewable energy faces challenges concerning the storage and utilization of energy due to the intermittent and seasonal nature of renewable energy sources. Wind and solar photovoltaic power productions are variable and difficult to predict, and thus electricity storage will be needed in the case of basic power production. Hydrogen’s energetic potential lies in its ability and versatility to store chemical energy, to serve as an energy carrier and as feedstock for various industries. Hydrogen is also used e.g. in the production of biofuels. The amount of energy produced during hydrogen combustion is higher than any other fuel’s on a mass basis with a higher-heating-value of 39.4 kWh/kg. However, even though hydrogen is the most abundant element in the universe, on Earth most hydrogen exists in molecular forms such as water. Therefore, hydrogen must be produced and there are various methods to do so. Today, the majority hydrogen comes from fossil fuels, mainly from steam methane reforming, and only about 4 % of global hydrogen comes from water electrolysis. Combination of electrolytic production of hydrogen from water and supply of renewable energy is attracting more interest due to the sustainability and the increased flexibility of the resulting energy system. The preferred option for intermittent hydrogen storage is pressurization in tanks since at ambient conditions the volumetric energy density of hydrogen is low, and pressurized tanks are efficient and affordable when the cycling rate is high. Pressurized hydrogen enables energy storage in larger capacities compared to battery technologies and additionally the energy can be stored for longer periods of time, on a time scale of months. In this thesis, the thermodynamics and electrochemistry associated with water electrolysis are described. The main water electrolysis technologies are presented with state-of-the-art specifications. Finally, a Power-to-Hydrogen infrastructure design for Lappeenranta University of Technology is presented. Laboratory setup for water electrolysis is specified and factors affecting its commissioning in Finland are presented.

Promoting Growth in the Use of Bioenergy in Europe by Converting Existing Coal-Fired Power Plants to Biomass

Repowering existing power plants by replacing coal with biomass might offer an interesting option to ease the transition from fossil fuels to renewable energy sources and promote a fur-ther expansion of bioenergy in Europe, on account of the potential to decrease greenhouse gas emissions, as well as other pollutants (SOx, NOx, etcetera). In addition, a great part of the appeal of repowering projects comes from the opportunity to reuse the vast existing invest-ment and infrastructure associated with coal-based power generation. Even so, only a limited number of experiences with repowering are found. Therefore, efforts are required to produce technical and scientific evidence to determine whether said technology might be considered feasible for its adoption within European conditions. A detailed evaluation of the technical and economic aspects of this technology constitutes a powerful tool for decision makers to define the energy future for Europe. To better illustrate this concept, a case study is analyzed. A Slovakian pulverized coal plant was used as the basis for determining the effects on perfor-mance, operation, maintenance and cost when fuel is shifted to biomass. It was found that biomass fuel properties play a crucial role in plant repowering. Furthermore, results demon-strate that this technology offers renewable energy with low pollutant emissions at the cost of reduced capacity, relatively high levelized cost of electricity and sometimes, a maintenance-intensive operation. Lastly, regardless of the fact that existing equipment can be reutilized for the most part, extensive additions/modifications may be required to ensure a safe operation and an acceptable performance.