A pilot-scale fireside deposit study of co-firing Cynara with two coals in a fluidised bed

Costs of biofuel production from energy crops can be reduced by applying the crop residues in heat and power production. Perennial herbaceous crops like Cynara cardunculus L. are challenging fuels because they tend to have high ash and chlorine contents. Coals, however, are often rich in aluminium silicates and sulphur, and co-firing of these biofuels with coal could be expected to reduce operational problems. In addition, CO₂ emissions are lower than during coal firing alone. Blends of Cynara and two coals, South African bituminous and Spanish sub-bituminous coal, were combusted in a 20 kW bubbling bed pilot reactor to ascertain the ability of the coals to reduce operational problems by alkali capture. The Cynara fuel sample contained almost 2 wt% chlorine. The South African coal was rich in kaolinite capable of capturing alkalies from chlorides to produce alkali aluminium silicate and HCl. The Spanish coal was rich in sulphur (mostly present as FeS₂), and produced high concentrations of SO₂ that partially oxidised to SO₃. The SO₃ can capture alkalies from chlorides by sulphation. Up to 30% Cynara, on energy basis, could be co-fired with Spanish coal without operational problems, whereas the same percentage of Cynara with South African coal led to strong Cl deposition. Co-firing of Cynara with both coals resulted in high HCl emissions (up to 1500 mg/Nm³ in 6% O₂). In addition, co-firing of the Spanish coal led to very high SO₂ emissions (up to about 16,000 mg/N m³ in 6% O₂). Thus, a power plant capable of firing such blends must be equipped with flue gas cleaning equipment for effective SO₂ and HCl capture in the flue gas channel after the superheaters, or else the quality of the Cynara must be markedly improved by changing the harvesting technology and fertilisers, which could be major sources of high ash and chlorine content in the fuel.     

Dissolving grade eco-clean cellulose pulps by integrated fractionation of cardoon (Cynara cardunculus L.) stalk biomass

A biorefinery scheme with separate processing of the two main carbohydrate streams (cellulose and hemicellulose-derived) was employed to the energy crop cardoon (Cynara cardunculus L.) to fractionate the whole stalk material. A high quality xylose-enriched substrate was obtained after selective one-step dilute sulfuric acid hydrolysis of hemicelluloses, yielding 18.1 g of xylose per 100 g of dry biomass. The xylan-free solid residue was delignified by sulfur-free organosolv pulping to produce dissolving grade pulps having 93.8% of α-cellulose (33.1 g per 100 g dry initial biomass) and 79.5% degree of crystallinity. About 76% of crop lignin (13.8 g per 100 g dry initial biomass) was recovered from the spent pulping liquor as a high purity reactive precipitated organosolv lignin. Response surface methodology was used for statistical modeling and optimization of the applied separation processes. The central composite rotatable design was applied to assess the effects of the principal technological parameters on the main reaction outputs.     

Influence of outer secondary-air vane angle on combustion characteristics and NOx emissions of a down-fired pulverized-coal 300 MWe utility boiler

Industrial experiments were performed on a down-fired pulverized-coal 300 MWe utility boiler with swirl burners. Gas temperature, concentrations of gas components (O₂, CO, CO₂ and NO_x) in the burning region and carbon content in the fly ash were measured with outer secondary-air vane angles of 25°, 32.5° and 50°. Results indicate that with increasing vane angle, NO_x emission and boiler efficiency decrease. Overall evaluation boiler efficiency and NO_x emission, the vane angle of 32.5° is optimum. Using an IFA300 constant-temperature anemometer system, cold air experiments on a quarter-scaled burner model were also carried out to investigate the influence of various outer secondary-air vane angles on the flow characteristics in the burner nozzle region. No central recirculation zone appeared for vane angles of 25° and 32.5°. Most of the pulverized-coal was ignited in the external recirculation zone. For vane angles of 45° and 55°, a central recirculation zone could be observed, and air flow rigidity and axial velocities decreased rapidly.     

Influence of vent air valve opening on combustion characteristics of a down-fired pulverized-coal 300 MWe utility boiler

Industrial experiments have been performed on a down-fired pulverized-coal 300 MWe utility boiler with vent air valve opening of 100% and 40%. The gas temperature distribution along the primary air and coal mixture flow, gas temperature distribution in the furnace, and gas components such as O₂, CO, CO₂ and NO_x in the near-wall region were measured for the first time. The influence of vent air valve opening on coal combustion in the furnace was determined. The results indicate that ignition of the primary air and pulverized-coal mixture is delayed. The position of the gas temperature peak is above the arches. Emission of NO_x is up to 2101 mg/m³ (at 6% O₂ dry) with vent valve opening of 40%.     

Co-firing of coal and biomass in oxy-fuel fluidized bed for CO2 capture: A review of recent advances

The co-firing of coal and biomass in oxy-fuel fluidized beds is one of the most promising technologies for capturing CO₂. This technology has attracted wide attention from academia and industry in recent years as a negative emission method to capture CO₂ produced by carbon contained in biomass. In the past decades, many studies have been carried out regarding experiments and numerical simulations under oxy-fuel combustion conditions. This paper firstly briefly discusses the techno-economic viability of the biomass and coal co-firing with oxycombustion and then presents a review of recent advancements involving experimental research and computational fluid dynamics (CFD) simulations in this field. Experimental studies on mechanism research, such as thermogravimetric analysis and tube furnace experiments, and fluidized bed experiments based on oxy-fuel fluidized beds with different sizes as well as the main findings, are summarized as a part of this review. It has been recognized that CFD is a useful approach for understanding the behaviors of the co-firing of coal and biomass in oxyfuel fluidized beds. We summarize a recent survey of published CFD research on oxy-fuel fluidized bed combustion, which categorized into Eulerian and Lagrangian methods. Finally, we discuss the challenges and interests for future research.     

Numerical investigation of NOx emissions from a tangentially-fired utility boiler under conventional and overfire air operation

A CFD investigation has been carried out about the performance of a 600 MW_e tangentially coal-fired boiler, focusing on the reduction of NO_x attainable by using overfire air. To this purpose, a comprehensive combination of NO_x chemistry models has been used, coupled with the numerical simulation of fluid and particle flow, solid fuel combustion and heat and mass transfer. Predicted values of gas temperature and species concentration have been adopted to validate the model against actual measurements from the full-scale boiler, under conventional and overfire air arrangements. A reasonable agreement has been attained in most cases. Additionally, modelling sensitivity has been evaluated against variations in some fuel-dependent parameters hard to measure or estimate (devolatilisation rates, nitrogen content in volatiles and char, reburning rates). As a result, an analysis tool is available to study the response of this kind of boilers to a variety of coal feedstock and combustion conditions, in a feasible and economic manner.     

Emissions during co-firing of RDF-5 with bituminous coal, paper sludge and waste tires in a commercial circulating fluidized bed co-generation boiler

Biomass fuel is the largest renewable energy resource and the fourth largest primary energy supply in the world. Because of its complex characteristics when compared to fossil fuel, potential problems, such as combustion system stability, the corrosion of heat transfer tubes, the qualities of the ash, and the emission of pollutants, are major concerns when co-firing the biomass fuel with fossil fuel in a traditional boiler. In this study, co-firing of coal with a biomass blend, including fuel derived from densified refuse, sludge, and waste tires, were conducted in a 130 ton/h steam circulating fluidized bed co-generation boiler to investigate the feasibility of utilizing biomass as a complemental fuel in a traditional commercial coal-fired boiler. The properties of the fly ash, bottom ash, and the emission of pollutants for various fuel ratios are analyzed and discussed in this study.     

Industrial test on coal re-burning at a 600 MW utility boiler and NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> reduction

This research conducts a series of industrial tests on coal reburning of a 600 MW pulverized coal boiler firing lignite, which is one part of a coal reburning demonstration project. When running steadily under 600 MW load, the boiler has an average NO _x emission of 274 mg/m³ (O₂ content in flue gas is converted to 6%), the NO _x emission is reduced by 65.36%. In the meanwhile, loss of ignition (LOI) under coal reburning rarely increases. Three operation conditions — traditional air feeding, air staging and coal reburning — are realized, respectively, during the industrial tests, and the results indicate that coal reburning has the lowest NO _x emission, while the traditional air feeding has the highest NO _x emission. Under the test conditions, the higher the proportion of the reburning coal, the higher the NO _x control can reach. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Photo-enhancement of Cr(VI) reduction by fungal biomass of Neurospora crassa

Various organisms such as fungus are capable of reducing Cr(VI) to less toxic Cr(III). However, light-induced Cr(VI) reduction by fungus is less reported and needs to be explored since anthropogenic or natural activities may bring these two reactants into a sunlit environment. In this study, the interactions and reaction mechanisms of Cr(VI) on a model fungus, Neurospora crassa, were evaluated in the presence or absence of light. The influence of ferric ion, a widely distributed metal, on Cr(VI) reduction by the fungus was also investigated under illumination. The results show that 20–54% of added Cr(VI) (96.2 μM) was removed by 1 g of dead fungal biomass (i.e., 1–2.7 mg Cr(VI) reduction by 1 g biomass) at pH 1–3, after 6 h reaction in the dark. However, 96.2 μM Cr(VI) disappeared completely (i.e., 5 mg Cr(VI) reduction by 1 g biomass) under the same reaction time and experimental conditions when light was present. The rapid disappearance of Cr(VI) in solution was due to the reduction of Cr(VI) by the excited biomass upon light absorption, and the rates of redox reactions increased with a decrease at pH. Cr(VI) reduction could be further increased with the addition of 89.5 μM Fe(III) because the formation of Fe(II) from the photolysis of Fe–organic complexes enhanced Cr(VI) reduction. Spectroscopic studies indicated that the amide, NH, and carboxyl groups of N. c.-biomass may be responsible for initiating Cr(VI) reduction; comparatively, the cyclo-carbons of chitin, glucan, and their derivatives were more persistent to the oxidation by Cr(VI). Accordingly, fungi containing high amount of carboxyl, amide, and NH groups may be preferable as efficient reductants for scavenging Cr(VI) from environment. Upon the absorption of a renewable light source, Cr(VI) could be converted rapidly by the biomaterials to the less toxic Cr(III).     

In vitro and in vivo release of cefuroxime axetil from bioactive glass as an implantable delivery system in experimental osteomyelitis

The aim of this study was to evaluate the characterisation, in vitro and in vivo biocompatibility and antimicrobial activity of bioactive glass (BG) impregnated with an antibiotic. The BG was prepared by normal glass melting procedures as a controlled release device to treat experimental osteomyelitis. The study design was for prospective in vivo experimental study. Two sets of porous bioactive glass ceramic blocks (9 mm × 4 mm × 4 mm and 20 mm × 9 mm × 9 mm) were fabricated using bioactive glass powder and subsequently antibiotic cefuroxime axetil (CFA) (55 and 125 mg on an average) was impregnated in these two sets of blocks, respectively. Osteomyelitis was produced in the right tibia of the rabbits according to the model of Norden. After thorough in vitro characterization of the porous blocks [including X-ray diffraction (XRD), Fourier-transformed infra-red spectroscopy (FTIR), thorough chemical analysis by inductively coupled plasma-atomic emission spectra (ICP-AES) and field-emission scanning electron microscopy (FESEM)] and in vitro elution of the said drug, in vivo test was carried out with rabbit species split into two groups: (a) animals treated with CFA impregnated bioactive glass and (b) parenteral [intra muscular (IM)] administration of CFA. Histological, radiological and drug concentration in bone and serum (measured by HPLC) in both groups were carried out. HPLC technique was used for determination of concentration both in vitro and in vivo. Fabricated porous struts showed amorphous microstructure without formation of any crystallite. The elution of said drug was stopped after 6 days in vitro. Histological studies at 3 and 6 weeks revealed formation of well-developed lamellar bone and havarsian canal. Radiological evaluation pointed out disappearance of sequestrum and existence of newly formed bony specules. Concentration of cefuroxime axetil in bone and serum showed highest value on day 21 which reduced marginally by day 42 and these values were higher than minimum inhibitory concentration (MIC) against Staphylococcus aureus (known pathogen for chronic osteomyelitis). It could be concluded that the biodegradable antibiotic carrier system developed in this study proved to be an effective therapeutic approach toward an experimental model of osteomyelitis. Based particularly on the in vivo results of the study, this cefuroxime axetil incorporated bioactive glass blocks can be successfully used in clinical cases of osteomyelitis in veterinary as well as human orthopaedic surgery.     

Numerical investigation on the flow, combustion and NOx emission characteristics in a 500 MWe tangentially fired pulverized-coal boiler

The characteristics of the flow, combustion, temperature and NO_x emissions in a 500 MW_e tangentially fired pulverized-coal boiler are numerically studied using comprehensive models, with emphasis on fuel and thermal NO_x formations. The comparison between the measured values and predicted results shows good agreement, which implies that the adopted combustion and NO_x formation models are suitable for correctly predicting characteristics of the boiler. The relations among the predicted temperature, O₂ and CO₂ mass fractions are discussed based on the calculated distributions. The predicted results clearly show that NO_x formation within the boiler highly depends on the combustion processes as well as the temperature and species concentrations. The results obtained from this study have shown that overfire air (OFA) operation is an efficient way to reduce the NO_x emissions of the pulverized-coal fired boiler. Air staging combustion technology (OFA operation) adopted in this boiler has helped reduce fuel NO_x formation as well as thermal NO_x formation under the present simulated conditions. The decrease in the formation of fuel NO_x is due to the decreased contact of the nitrogen from the fuel with the oxygen within the combustion air, while the decrease in thermal NO_x formation is caused by a decrease in temperature. The detailed results presented in this paper may enhance the understanding of complex flow patterns, combustion processes and NO_x emissions in tangentially fired pulverized-coal boilers, and may also provide a useful basis for NO_x reduction and control.     

Operando FTIR study of the photocatalytic oxidation of acetone in air over TiO2–ZrO2 thin films

Operando FTIR spectroscopy has been used to study the photocatalytic oxidation of acetone vapors over semiconductors films containing TiO₂ and ZrO₂. Preparation of these coatings was carried out by dipping a silicon wafer in stable sols containing particles of TiO₂, Ti_1−xZr_xO₂, or a mixture of ZrO₂ and TiO₂. These differences in chemical composition and phase homogeneity were selected in order to determine their effect on the photocatalytic performance. A transmission cell specifically designed for in situ studies of photocatalytic coatings was utilized for the FTIR experiments under reaction conditions. In contrast with investigations with powdered photocatalysts, the use of thin films guarantees that the whole semiconductor is irradiated, and for that reason purely photochemical reactions are monitored. Acetone adsorption takes place molecularly and is higher on the Ti_1−xZr_xO₂ coating. This fact is very likely related to the higher specific surface of the samples containing Zr. However, the maximum photocatalytic rate for acetone degradation corresponds to the films composed by a binary mixture of TiO₂ and ZrO₂. On the other hand, remarkable differences on the type and concentration of intermediates appearing as a result of the photocatalytic oxidation of acetone are found for the coatings studied. A simple kinetic model was applied to analyze the evolution of both gas phase and surface species. The parameters obtained indicate that each specific surface process is affected in a different way by the variation in the composition of the photoactive films.     

Investigation of the flow, combustion, heat-transfer and emissions from a 609 MW utility tangentially fired pulverized-coal boiler

A numerical approach is given to investigate the performance of a 609 MW tangentially fired pulverized-coal boiler, with emphasis on formation mechanism of gas flow deviation and uneven wall temperature in crossover pass and on NO_x emission. To achieve this purpose and obtain a reliable solution, some different strategies with the existing researches are used. Good agreement of simulation results with design parameters and site operation records indicates this simulation is pretty reasonable and thus the conclusions of the gas flow deviation, emissions, combustion and heat transfer are reliable. These conclusions can be used to guide the design and operation of boilers of similar types.     

Improvement of the growth of Arthrospira (Spirulina) platensis from Toliara (Madagascar): Effect of agitation, salinity and CO2 addition

Arthrospira (Spirulina) platensis Toliara isolated from alkaline and salt lakes in the south-western area of Madagascar is a potential source of proteins that could efficiently fight against food deficiency in developing countries like Madagascar. Up to now, productivity in this country has been low, so a better understanding of the growth conditions of this species is needed to improve its production. Growth experiments were undertaken in bubble columns at laboratory scale. The influence of agitation of the culture, medium salinity (ranging from 13 to 35 g L⁻¹) and CO₂ addition (ranging from 0 to 2%, v/v) on growth and protein content was examined. Because Arthrospira cells are fragile, a bubble column without additional mixing gave the best growth. Arthrospira (Spirulina) platensis showed higher specific growth rate (μ_max) and protein content for lower salinity. Addition of 1% of CO₂ improved the productivity by near 60%. The feasability of semi-continuous culture was demonstrated and optimal culture conditions led to a mean productivity of 0.22 ± 0.03 g L⁻¹ d⁻¹, a mean specific growth rate of 0.015 ± 0.002 h⁻¹ and a protein content of 53 ± 2% of total dry weight.     

Phase equilibria and glass formation studies in the (1 − x)TeO2-xCdO (0.05 ≤ x ≤ 0.33 mol) system

Phase equilibria and glass formation studies of the (1 − x)TeO₂-xCdO system (0.05 ≤ x ≤ 0.33 mol) were realized by using differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The samples were prepared by applying a conventional melt-quenching technique at 800 °C. The glass formation range of the system was determined as 0.05 ≤ x < 0.15 and the sample containing 10 mol% CdO showed the highest glass stability. Crystallization behavior of the TeO₂-CdO glasses was investigated and formation and/or transformation of different phases were detected for each crystallization reaction. In order to obtain thermal stability of the system, as-cast samples were heat-treated above all crystallization reaction temperatures at 550 °C for 24 h. A binary eutectic: liquid → TeO₂ + CdTe₂O₅ was detected at 638 ± 4 °C. Crystallization behavior of the TeO₂-CdO glasses and microstructural characterization of the TeO₂-CdTe₂O₅ system was realized.     

Effects of elevated CO<Subscript>2</Subscript> on foliar quality and herbivore damage in a scrub oak ecosystem

Atmospheric CO₂ concentrations have increased exponentially over the last century and continuing increases are expected to have significant effects on ecosystems. We investigated the interactions among atmospheric CO₂, foliar quality, and herbivory within a scrub oak community at the Kennedy Space Center, Florida. Sixteen plots of open-top chambers were followed; eight of which were exposed to ambient levels of CO₂ (350 ppm), and eight of which were exposed to elevated levels of CO₂ (700 ppm). We focused on three oak species, Quercus geminata, Quercus myrtifolia, Quercus chapmanii, and one nitrogen fixing legume, Galactia elliottii. There were declines in overall nitrogen and increases in C:N ratios under elevated CO₂. Total carbon, phenolics (condensed tannins, hydrolyzable tannins, total phenolics) and fiber (cellulose, hemicellulose, lignin) did not change under elevated CO₂ across plant species. Plant species differed in their relative foliar chemistries over time, however, the only consistent differences were higher nitrogen concentrations and lower C:N ratios in the nitrogen fixer when compared to the oak species. Under elevated CO₂, damage by herbivores decreased for four of the six insect groups investigated. The overall declines in both foliar quality and herbivory under elevated CO₂ treatments suggest that damage to plants may decline as atmospheric CO₂ levels continue to rise.     

CFD simulation and experimental validation of co-combustion of chicken litter and MBM with pulverized coal in a flow reactor

The influence of co-combustion of solid biomass fuels with pulverized coal on burnout and CO emissions was studied using a flow reactor. The thermal input on a fuel feeding basis of the test rig was approximately 7 kW. Accompanied with the measurements, a reactor model using the CFD code AIOLOS was set up and first applied for two pure coal flames (with and without air staging). Reasonable agreement between measurements and simulations was found. An exception was the prediction of the CO concentration under sub-stoichiometric conditions (primary zone). As model input for the volatile matter release, the HTVM (high temperature volatile matter as defined by IFRF [IFRF, www.handbook.ifrf.net/handbook/glossary.html. [1]]) was used. Furthermore, a relatively slow CO oxidation rate obtained from the literature and the ERE (Extended Resistance Equation) model for char combustion were selected. Furthermore, the model was used for simulating co-firing of coal with chicken litter (CL) and meat and bone meal (MBM). The conditions applied are relevant for future co-firing practice with high thermal shares of secondary fuels (larger than 20%). The major flue gas concentrations were quite well described, however, CO emission predictions were only qualitatively following the measured trends when O₂ is available and severely under-predicted under substoichiometric conditions. However, on an engineering level of accuracy, and concerning burnout, this work shows that co-combustion of the fuels can reasonably well be described with coal combustion sub-models.     

Evolution of the local structure and electrochemical properties of spinel LiNixMn2−xO4 (0 ≤ x ≤ 0.5)

A series of Ni substituted spinel LiNi_xMn_2−xO₄ (0 ≤ x ≤ 0.5) have been synthesized to study the evolution of the local structure and their electrochemical properties. X-ray diffraction showed a few Ni cations moved to the 8a sites in heavily substituted LiNi_xMn_2−xO₄ (x ≥ 0.3). X-ray photoelectron spectroscopy confirmed Ni²⁺ cations were partially oxidized to Ni³⁺. The local structures of LiNi_xMn_2−xO₄ were studied by analyzing the and A_1g Raman bands. The most compact [Mn(Ni)O₆] octahedron with the highest bond energy of Mn(Ni)O was found for LiNi_0.2Mn_1.8O₄, which showed a Mn(Ni)O average bond length of 1.790 Å, and a force constant of 2.966 N cm⁻¹. Electrolyte decomposition during the electrochemical charging processes increased with Ni substitution. The discharge capacities at the 4.1 and 4.7 V plateaus obeyed the linear relationships with respect to the Ni substitution with the slopes of −1.9 and +1.9, which were smaller than the theoretical values of −2 and +2, respectively. The smaller slopes could be attributed to the electrochemical hysteresis and the presence of Ni³⁺ in the materials.     

Effects of Elevated CO<Subscript>2</Subscript> and Herbivore Damage on Litter Quality in a Scrub Oak Ecosystem

Atmospheric CO₂ concentrations have increased dramatically over the last century and continuing increases are expected to have significant, though currently unpredictable, effects on ecosystems. One important process that may be affected by elevated CO₂ is leaf litter decomposition. We investigated the interactions among atmospheric CO₂, herbivory, and litter quality within a scrub oak community at the Kennedy Space Center, Florida. Leaf litter chemistry in 16 plots of open-top chambers was followed for 3 years; eight were exposed to ambient levels of CO₂, and eight were exposed to elevated levels of CO₂ (ambient + 350 ppmV). We focused on three dominant oak species, Quercus geminata, Quercus myrtifolia, and Quercus chapmanii. Condensed tannin concentrations in oak leaf litter were higher under elevated CO₂. Litter chemistry differed among all plant species except for condensed tannins. Phenolic concentrations were lower, whereas lignin concentrations and lignin/nitrogen ratios were higher in herbivore-damaged litter independent of CO₂ concentration. However, changes in litter chemistry from year to year were far larger than effects of CO₂ or insect damage, suggesting that these may have only minor effects on litter decomposition.     

Preparation, characterization and electrical conductivity studies of NdYb1−xGdxZr2O7 (0 ≤ x ≤ 1.0) ceramics

Several compositions of NdYb_1−xGd_xZr₂O₇ (0 ≤ x ≤ 1.0) ceramics were prepared by pressureless-sintering method at 1973 K for 10 h in air. The relative density, microstructure and electrical conductivity of NdYb_1−xGd_xZr₂O₇ ceramics were analyzed by the Archimedes method, X-ray diffraction, scanning electron microscopy and impedance plots measurements. NdYb_1−xGd_xZr₂O₇ (0 ≤ x ≤ 0.3) ceramics have a single phase of defect fluorite-type structure, and NdYb_1−xGd_xZr₂O₇ (0.7 ≤ x ≤ 1.0) ceramics exhibit a single phase of pyrochlore-type structure; however, the NdYb_0.5Gd_0.5Zr₂O₇ composition shows mixed phases of both defect fluorite-type and pyrochlore-type structures. The measured values of the grain conductivity obey the Arrhenius relation. The grain conductivity of each composition in NdYb_1−xGd_xZr₂O₇ ceramics gradually increases with increasing temperature from 673 to 1173 K. NdYb_1−xGd_xZr₂O₇ ceramics are oxide-ion conductor in the oxygen partial pressure range of 1.0 × 10⁻⁴ to 1.0 atm at all test temperature levels. The highest grain conductivity value obtained in this work is 1.79 × 10⁻² S cm⁻¹ at 1173 K for NdYb_0.3Gd_0.7Zr₂O₇ composition.