Physicochemical characterization of hydroxyapatite and its application towards removal of nitrate from water

A laboratory study was conducted to investigate the efficiency of hydroxyapatite (HAP) towards removal of nitrate from synthetic nitrate solution. In the present research HAP synthesized from egg-shell was characterized using SEM, XRD, FTIR and TGA–DSC. The removal of nitrate was 96% under neutral conditions, using 0.3 g of adsorbent in 100 mL of nitrate solution having an initial concentration of 100 mg/L. An adsorption kinetic study revealed that the adsorption process followed first order kinetics. Adsorption data were fitted to a linearly transformed Langmuir isotherm with correlation coefficient (R²) > 0.98. Thermodynamic parameters were also calculated to study the effect of temperature on the removal process. In order to understand the adsorption type, equilibrium data were tested with the Dubinin–Radushkevich isotherm. The process was rapid and equilibrium was established within the first 40 min.     

Treatment and toxicity evaluation of methylene blue using electrochemical oxidation,fly ash adsorption and combined electrochemical oxidation-fly ash adsorption

Treatment of a basic dye, methylene blue, by electrochemical oxidation, fly ash adsorption, and combined electrochemical oxidation-fly ash adsorption was compared. Methylene blue at 100 mg L^?1 was used in this study. The toxicity was also monitored by the Vibrio fischeri light inhibition test.When electrochemical oxidation was used, 99% color and 84% COD were removed from the methylene blue solution in 20 min at a current density of 428 A m^?2, NaCl of 1000 mg L^?1, and pH₀ of 7. However, the decolorized solution showed high toxicity (100% light inhibition).For fly ash adsorption, a high dose of fly ash (>20,000 mg L^?1) was needed to remove methylene blue, and the Freundlich isotherm described the adsorption behavior well.In the combined electrochemical oxidation-fly ash adsorption treatment, the addition of 4000 mg L^?1 fly ash effectively reduced intermediate toxicity and decreased the COD of the electrochemical oxidation-treated methylene blue solution. The results indicated that the combined process effectively removed color, COD, and intermediate toxicity of the methylene blue solution.     

Transfer characteristics of cobalt from soil to crops in the suburban areas of Fujian Province,southeast China

The bioavailability of cobalt and its transfer from soil to vegetables and rice were investigated. Among 312 soils collected from vegetable and paddy fields in the suburban areas of some major cities of Fujian Province, southeast China, total soil Co ranged from 3.5 to 21.7 mg kg^?1, indicating a slight accumulation compared with the background value of the province. DTPA extracted 0.1–8.5% of soil total Co. Total and DTPA-extractable Co correlated with soil pH, CEC, free Fe, total Mn, clay and silt content more significantly in paddy soils than in the soils from vegetable fields. The average Co concentrations in the edible parts of vegetables and rice were 15.4 μg kg^?1 and 15.5 μg kg^?1, respectively. The transfer factor (the ratio of plant Co to soil DTPA-extractable Co, TF_DTPA) ranged from 0.003 to 0.126 with a median of 0.049. The TF_DTPA decreased in the order of leafy vegetables > fruit vegetables > root vegetables > rice. The TF_DTPA of all crops decreased with increasing DTPA-extractable Co. Increase in pH, CEC, organic matter, clay, silt, free iron and total Mn limited the soil-to-plant transfer of Co to varying degrees. The transfer of Co from the soils to the edible parts of the crops was lower than that of Zn, Cu and Cd, but higher than that of Pb in the same areas. The concentrations of Co in rice and vegetables in the study areas were considered to be safe for the local residents because of the slight anthropogenic input and the low transfer potential to the edible parts of Co from the soils.     

CO2 capture from hot stove gas in steel making process

The capture of CO₂ from a hot stove gas in steel making process containing 30 vol% CO₂ by chemical absorption in a rotating packed bed (RPB) was studied. The RPB had an inner diameter of 7.6 cm, an outer diameter of 16 cm, and a height of 2 cm. The aqueous solutions containing 30 wt% of single and mixed monoethanolamine (MEA), 2-(2-aminoethylamino)ethanol (AEEA), and piperazine (PZ) were used. The CO₂ capture efficiency was found to increase with increasing temperature in a range of 303–333 K. It was also found to be more dependent on gas and liquid flow rates but less dependent on rotating speed when the speed was higher than 700 rpm. The obtained results indicated that the mixed alkanolamine solutions containing PZ were more effective than the single alkanolamine solutions. This was attributed to the highest reaction rate of PZ with CO₂. A higher portion of PZ in the mixture was more favorable to CO₂ capture. The highest gas flow rates allowed to achieve a desired CO₂ capture efficiency and the correspondent height of transfer unit (HTU) were determined at different aqueous solution flow rates. Because all the 30 wt% single and mixed alkanolamine solutions could result in a HTU less than 5.0 cm at a liquid flow rate of 100 mL/min, chemical absorption in a RPB instead of a packed bed adsorber is therefore suggested to capture CO₂ from the flue gases in steel making processes.     

Kinetics of sulfur dioxide- and oxygen-induced degradation of aqueous monoethanolamine solution during CO2 absorption from power plant flue gas streams

Studies of the kinetics of sulfur dioxide (SO₂)- and oxygen (O₂)-induced degradation of aqueous monoethanolamine (MEA) during the absorption of carbon dioxide (CO₂) from flue gases derived from coal- or natural gas-fired power plants were conducted as a function of temperature and the liquid phase concentrations of MEA, O₂, SO₂ and CO₂. The kinetic data were based on the initial rate which shows the propensity for amine degradation and obtained under a range of conditions typical of the CO₂ absorption process (3–7 kmol/m³ MEA, 6% O₂, 0–196 ppm SO₂, 0–0.55 CO₂ loading, and 328–393 K temperature). The results showed that an increase in temperature and the concentrations of MEA, O₂ and SO₂ resulted in a higher MEA degradation rate. An increase in CO₂ concentration gave the opposite effect. A semi-empirical model based on the initial rate, ?r_MEA = {6.74 × 10⁹ e^?(29,403/RT)[MEA]^0.02([O]^2.91 + [SO₂]^3.52)}/{1 + 1.18[CO₂]^0.18} was developed to fit the experimental data. With the higher order of reaction, SO₂ has a higher propensity to cause MEA to degrade than O₂. Unlike previous models, this model shows an improvement in that any of the parameters (i.e. O₂, SO₂, and CO₂) can be removed without affecting the usability of the model.     

Kinetic studies on the adsorption of phenol, 4-chlorophenol,and 2,4-dichlorophenol from water using activated carbons

This study uses rate parameters in pseudo-first-order (PFO) and pseudo-second-order (PSO) equations (k₁ and k₂q_e, respectively) to judge the extent for approaching equilibrium in an adsorption process. Out of fifty-six systems collected from the literature, the adsorption processes with a k₂q_e value between 0.1 and 0.8 min^?1 account for as much as 70% of the total. These are classified as fast processes. This work compares the validity of PFO and PSO equations for the adsorption of phenol, 4-chlorophenol (4-CP), and 2,4-dichlorophenol (2,4-DCP) on activated carbons prepared from pistachio shells at different NaOH/char ratios. The activated carbons, recognized as microporous materials, had a surface area ranging from 939 to 1936 m²/g. Findings show that the adsorption of phenol, 4-CP, and 2,4-DCP on activated carbons had a k₂q_e value of 0.15–0.58 min^?1, reflecting the fast process. Evaluating the operating time by rate parameters revealed that k₂q_e was 1.6–1.8 times larger than k₁. These findings demonstrate the significance of using an appropriate kinetic equation for adsorption process design.     

Equilibrium studies of copper ion adsorption onto palm kernel fibre

The equilibrium sorption of copper ions from aqueous solution using a new adsorbent, palm kernel fibre, has been studied. Palm kernel fibre is obtained in large amounts as a waste product of palm oil production. Batch equilibrium studies were carried out and system variables such as solution pH, sorbent dose, and sorption temperature were varied. The equilibrium sorption data was then analyzed using the Langmuir, Freundlich, Dubinin–Radushkevich (D–R) and Temkin isotherms. The fit of these isotherm models to the equilibrium sorption data was determined, using the linear coefficient of determination, r², and the non-linear Chi-square, χ² error analysis.The results revealed that sorption was pH dependent and increased with increasing solution pH above the pH_PZC of the palm kernel fibre with an optimum dose of 10 g/dm³. The equilibrium data were found to fit the Langmuir isotherm model best, with a monolayer capacity of 3.17 × 10^?4 mol/g at 339 K. The sorption equilibrium constant, K_a, increased with increasing temperature, indicating that bond strength between sorbate and sorbent increased with temperature and sorption was endothermic. This was confirmed by the increase in the values of the Temkin isotherm constant, B₁, with increasing temperature. The Dubinin–Radushkevich (D–R) isotherm parameter, free energy, E, was in the range of 15.7–16.7 kJ/mol suggesting that the sorption mechanism was ion exchange. Desorption studies showed that a high percentage of the copper was desorbed from the adsorbent using acid solutions (HCl, HNO₃ and CH₃COOH) and the desorption percentage increased with acid concentration. The thermodynamics of the copper ions/palm kernel fibre system indicate that the process is spontaneous and endothermic.     

Effect of salinity on metal-complex dye biosorption by Rhizopus arrhizus

In this study the biosorption of Yellow RL, a metal-complex anionic dye, by dried Rhizopus arrhizus, a filamentous fungus, was investigated as a function of initial solution pH, initial dye concentration and initial salt (sodium chloride) concentration. The fungus exhibited the maximal dye uptake at pH 2 in the absence and in the presence of salt. Dye uptake increased with the dye concentration up to 1000 mg l^?1 and diminished considerably in the presence of increasing concentrations of salt up to 50 g l^?1. The fungus biosorbed 85.4 mg dye g^?1of dried biomass at 100 mg l^?1 initial dye concentration in the absence of salt. When 50 g l^?1 salt was added to the biosorption medium, this value dropped to 60.8 mg g^?1 resulting in 28.8% reduction in biosorption capacity. The Redlich–Peterson and Langmuir–Freundlich were the most suitable adsorption models for describing the biosorption equilibrium data of the dye both individually and in salt containing medium. The pseudo-second-order and saturation type kinetic models depicted the biosorption kinetics accurately for all cases studied. Equilibrium and kinetic constants varied with the level of salt were expressed as a function of salt concentration.     

Airborne manganese concentrations on the Korean peninsula from 1991 to 2006

In this study, the distribution of airborne manganese (Mn) bound with particulate matters (PM) was investigated using data sets collected from 15 major cities in Korea over a 16-year time span (1991–2006). The mean Mn concentration measured from all the major cities in Korea throughout the entire study period was 71 ng m^?3, while the annual mean values of different cities ranged from 10.5 ng m^?3 in Yeosu (2003) to 615 ng m^?3 in Wonju (2006). The Mn levels were considerably larger in industrialized areas than in other land-use types. The Mn concentrations in the major industrial cities of Pohang, Incheon, and Ansan averaged 255, 98.2, and 84.6 ng m^?3, respectively; these values were far higher than those measured typically at most cities, e.g., 20–60 ng m^?3. Seasonal patterns characterized by the peak occurrence in spring and the noticeable drop in summer reflected the effects of the massive PM inflow from China (spring) and effective washout by summer monsoon in East Asia, respectively. Examination of Mn data over a long-term period indicated that the temporal trends of Mn seen in most cities were fairly constant through time since the 1990s, although some abnormalities were observed in cities of strong man-made activities (e.g., Pohang and Wonju). In light of the severity of airborne Mn pollution in many urban areas, it is desirable to establish an abatement strategy that can help effectively reduce Mn levels.     

Natural analogue of the rise and dissolution of liquid CO2 in the ocean

The behavior of natural carbon dioxide (CO₂) droplets (8–10 mm in diameter) were observed in a seafloor hydrothermal system at the Okinawa Trough. The natural CO₂ droplet contain 95–98% of CO₂, 2–3% of H₂S, and other gas species. The ascending CO₂ droplets were tracked by a remotely operated vehicle (ROV), and depth, temperature, salinity, pH and partial pressure of CO₂ (pCO₂) in seawater near the CO₂ droplets were measured during droplet ascent by a conductivity-temperature-depth sensor (CTD) and in situ pH/pCO₂ sensor. The visual images of the rising CO₂ droplets were recorded with a high definition television camera on the ROV. A mapping survey (400 m × 400 m; 4 horizontal layers) revealed a dominant distribution of low pH area over the natural CO₂ venting site. The size and rise rate of CO₂ droplets decreased during their ascent in the water column from depths of 1424 to 679 m (a tracking interval of 745 m). The CO₂ droplets dissolved gradually to become small flakes of CO₂ hydrate while rising, and these ascending flakes were found to disappear at 679 m depth. Although a pH as low as 5 was detected just above the liquid CO₂ venting site on the seafloor, no detectable pH depression in the water column ambient to the rising CO₂ droplets was observed. The results of the pH mapping survey showed only localized pH depression over the CO₂ venting site.     

Kinetics of CO2 absorption in aqueous ammonia solution

The kinetics of CO₂ absorption in unloaded aqueous ammonia solution were measured using a string of discs contactor with the aqueous ammonia concentrations ranging 0.9–5.4 kmol/m³ and temperatures ranging 298.3–321.9 K. The reaction rates strongly increase with the concentration and less strongly with temperature. Both the termolecular and zwitterion models were applied in this study as amine solutions. The parameters for both of the models were interpreted. The kinetic rate constants for CO₂ absorption in aqueous ammonia were compared with those for other amines and were found to be around 1/10 that for monoethanolamine. The fitting results for the termolecular mechanism seem more robust than those for the zwitterion mechanism from a statistical perspective.     

Electrocoagulation of blue reactive,red disperse and mixed dyes,and application in treating textile effluent

This study investigated the efficiency of electrocoagulation in removing color from synthetic and real textile wastewater. Two representative dye molecules were selected for the synthetic dye wastewater: a blue reactive dye (Reactive Blue 140) and a disperse dye (Disperse Red 1). The electrochemical technique showed satisfactory color removal efficiency and reliable performance in treating both individual and mixed dye types. The removal efficiency and energy consumption data showed that, for a given current density, iron was superior to aluminum in treating both the reactive dye and the disperse dye. With an initial dye concentration of 100 mg L^?1, the energy cost in achieving >95% color removal was on the order of 1 kWh m^?3 for both dyes. The effect of changing the initial pH of the samples on the removal efficiency and energy consumption was also studied. It was found that the design parameters used for the synthetic wastewater were less effective for treatment of real textile wastewater, with 1 in 5 tests on real wastewater failing.     

A preliminary investigation of the efficacy of riparian fencing schemes for reducing contributions from eroding channel banks to the siltation of salmonid spawning gravels across the south west UK

The low productivity of salmonids in many river systems across the UK is testament to their intolerance of water quality perturbations including those associated with excessive sedimentation. Catchment and fishery managers concerned with combating such issues require reliable information on the key sources of the sediment problem to target management and on the efficacy of the mitigation options being implemented. In recognition of the latter requirement, a pre- and post-remediation sediment sourcing survey was used to examine the potential for using sediment tracing to assemble preliminary information on the efficacy of riparian fencing schemes for reducing sediment contributions from eroding channel banks to salmonid spawning gravels in the Rivers Camel, Fal, Lynher, Plym, Tamar and Tavy in the south west of the UK. Respective estimates of the overall mean proportion (±95% confidence limits) of the interstitial sediment input to salmonid spawning gravels originating from eroding channel banks during the pre- (1999–2000) and post-remediation (2008–2009) study periods were computed at 97 ± 1% vs. 69 ± 1%, 94 ± 1% vs. 91 ± 1%, 12 ± 1% vs. 10 ± 1%, 92 ± 1% vs. 34 ± 1%, 31 ± 1% vs. 16 ± 1% and 90 ± 1% vs. 66 ± 1%. Whilst the study demonstrates the potential utility of the fingerprinting approach for helping to assemble important information on the efficacy of bank fencing as a sediment source control measure at catchment scale, a number of limitations of the work and some suggestions for improving experimental design are discussed. Equivalent data are urgently required for many sediment mitigation options to help inform the development of water quality policy packages designed to protect aquatic ecosystems.     

Storage and characterization of cotton gin waste for ethanol production

In 2002, about 17.1 million bales of cotton were ginned in the United States and the estimated cotton gin waste was 2.25 × 10⁹ kg. The disposal of cotton gin waste (CGW) is a significant problem in the cotton ginning industry, but CGW could be potentially used as feedstock for bioethanol. Freshly discharged CGW and stored CGW were characterized for storage stability and potential for ethanol production by determining their summative compositions. The bulk densities of the fresh wet and dry CGW were 210.2 ± 59.9 kg m⁻³ and 183.3 ± 52.2 kg m⁻³, respectively. After six months of storage the volume of piles A, B, and C decreased by 38.7%, 41.5%, and 33.3%, respectively, relative to the volume of the pile at the start of the storage. The ash content of the CGW was very high ranging from 10% to 21% and the acid-insoluble fraction was high (21–24%). The total carbohydrate content was very low and ranged from 34% to 49%. After three months storage, chemical compositional analysis showed the loss of total carbohydrates was minimal but after six months, the losses were as high as 25%. This loss of carbohydrates suggests that under open storage conditions, the feedstock must be processed within three months to reduce ethanol yield losses.     

Energy balances,greenhouse gas emissions and economics of biochar production from palm oil empty fruit bunches

This paper presents results from a gate-to-gate analysis of the energy balance, greenhouse gas (GHG) emissions and economic efficiency of biochar production from palm oil empty fruit bunches (EFB). The analysis is based on data obtained from EFB combustion in a slow pyrolysis plant in Selangor, Malaysia. The outputs of the slow pyrolysis plant are biochar, syngas, bio-oil and water vapor. The net energy yield of the biochar produced in the Selangor plant is 11.47 MJ kg⁻¹ EFB. The energy content of the biochar produced is higher than the energy required for producing the biochar, i.e. the energy balance of biochar production is positive. The combustion of EFB using diesel fuel has the largest energy demand of 2.31 MJ kg⁻¹ EFB in the pyrolysis process. Comparatively smaller amounts of energy are required as electricity (0.39 MJ kg⁻¹ EFB) and for transportation of biochar to the warehouse and the field (0.13 MJ kg⁻¹ EFB). The net greenhouse gas emissions of the studied biochar production account for 0.046 kg CO₂-equiv. kg⁻¹ EFB yr⁻¹ without considering fertilizer substitution effects and carbon accumulation from biochar in the soil. The studied biochar production is profitable where biochar can be sold for at least 533 US-$ t⁻¹. Potential measures for improvement are discussed, including higher productivity of biochar production, reduced energy consumption and efficient use of the byproducts from the slow pyrolysis.     

Rate modeling of CO2 stripping from potassium carbonate promoted by piperazine

This work presents results from a rate-based model of strippers at normal pressure (160 kPa) and vacuum (30 kPa) in Aspen Custom Modeler^® (ACM) for the desorption of CO₂ from 5 m K⁺/2.5 m piperazine (PZ). The model solves the material, equilibrium, summation and enthalpy (MESH) equations, the heat and mass transfer rate equations, and computes the reboiler duty and equivalent work for the stripping process. Simulations were performed with IMTP #40 random packing and a temperature approach on the hot side of the cross-exchanger of 5 °C and 10 °C. A “short and fat” stripper requires 7–15% less total equivalent work than a “tall and skinny” one because of the reduced pressure drop. The vacuum and normal pressure strippers require 230 s and 115 s of liquid retention time to get an equivalent work 4% greater than the minimum work. Stripping at 30 kPa was controlled by mass transfer with reaction in the boundary layer and diffusion of reactants and products (88% resistance at the rich end and 71% resistance at the lean end). Stripping at 160 kPa was controlled by mass transfer with equilibrium reactions (84% resistance at the rich end and 74% resistance at the lean end) at 80% flood. The typical predicted energy requirement for stripping and compression to 10 MPa to achieve 90% CO₂ removal was 37 kJ/gmol CO₂. This is about 25% of the net output of a 500 MW power plant with 90% CO₂ removal.     

Prospects for cost-effective post-combustion CO2 capture from industrial CHPs

Industrial Combined Heat and Power plants (CHPs) are often operated at partial load conditions. If CO₂ is captured from a CHP, additional energy requirements can be fully or partly met by increasing the load. Load increase improves plant efficiency and, consequently, part of the additional energy consumption would be offset. If this advantage is large enough, industrial CHPs may become an attractive option for CO₂ capture and storage CCS. We therefore investigated the techno-economic performance of post-combustion CO₂ capture from small-to-medium-scale (50–200 MWe maximum electrical capacity) industrial Natural Gas Combined Cycle- (NGCC-) CHPs in comparison with large-scale (400 MWe) NGCCs in the short term (2010) and the mid-term future (2020–2025). The analyzed system encompasses NGCC, CO₂ capture, compression, and branch CO₂ pipeline.The technical results showed that CO₂ capture energy requirement for industrial NGCC-CHPs is significantly lower than that for 400 MWe NGCCs: up to 16% in the short term and up to 12% in the mid-term future. The economic results showed that at low heat-to-power ratio operations, CO₂ capture from industrial NGCC-CHPs at 100 MWe in the short term (41–44 €/tCO₂ avoided) and 200 MWe in the mid-term future (33–36 €/tCO₂ avoided) may compete with 400 MWe NGCCs (46–50 €/tCO₂ avoided short term, 30–35 €/tCO₂ avoided mid-term).     

Impacts of urban forests on offsetting carbon emissions from industrial energy use in Hangzhou,China

This study quantified carbon storage and sequestration by urban forests and carbon emissions from energy consumption by several industrial sources in Hangzhou, China. Carbon (C) storage and sequestration were quantified using urban forest inventory data and by applying volume-derived biomass equations and other models relating net primary productivity (NPP) and mean annual biomass increments. Industrial energy use C emissions were estimated by accounting for fossil fuel use and assigning C emission factors. Total C storage by Hangzhou's urban forests was estimated at 11.74 Tg C, and C storage per hectare was 30.25 t C. Carbon sequestration by urban forests was 1,328, 166.55 t C/year, and C sequestration per ha was 1.66 t C/ha/year. Carbon emissions from industrial energy use in Hangzhou were 7 Tg C/year. Urban forests, through sequestration, annually offset 18.57% of the amount of carbon emitted by industrial enterprises, and store an amount of C equivalent to 1.75 times the amount of annual C emitted by industrial energy uses within the city. Management practices for improving Hangzhou's urban forests function of offsetting C emissions from energy consumption are explored. These results can be used to evaluate the urban forests' role in reducing atmospheric carbon dioxide.     

Treatment of municipal wastewater using a contact oxidation filtration separation integrated bioreactor

A new contact oxidation filtration separation integrated bioreactor (CFBR) was used to treat municipal wastewater. The CFBR was made up of a biofilm reactor (the upper part of the CFBR) and a gravitational filtration bed (the lower part of the CFBR). Polyacrylonitrile balls (50 mm diameter, 237 m²/m³ specific surface, 90% porosity, and 50.2% packing rate) were filled into the biofilm reactor as biofilm attaching materials and anthracite coal (particle size 1–2 mm, packing density 0.947 g/cm³, non-uniform coefficient (K₈₀ = d₈₀/d₁₀) < 2.0) was placed into the gravitational filtration bed as filter media. At an organic volumetric loading rate of 2.4 kg COD/(m³ d) and an initial filtration velocity of 5 m/h in the CFBR, the average removal efficiencies of COD, ammonia nitrogen, total nitrogen and turbidity were 90.6%, 81.4%, 64.6% and 96.7% respectively, but the treatment process seemed not to be effective in phosphorus removal. The average removal efficiency of total phosphorus was 60.1%. Additionally, the power consumption of the CFBR was less than 0.15 kWh/m³ of wastewater treated, and less than 1.5 kWh/kg BOD₅ removal.