Effect of two types of adsorption sites of activated carbon fibers on nitrate ion adsorption.

In this study, the activation with ZnCl2 and heat treatment at 950 °C were performed to polyacrylonitrile-based carbon fiber and phenol resin to prepare two types of activated carbon fibers (ACFs) with different amounts of quaternary nitrogen (N-Q). In order to investigate the effect of chemical properties of ACFs on nitrate adsorption, various experiments and assess were conducted on these samples. The pHpzc of Py-7.0Z4-9.5HT10 and PhR-6.0Z4-9.5HT30 was about 7.1 and 7.0, respectively, and was no significant difference in the results. The C-π sites had a large effect on the amount of nitrate adsorption, and its adsorption capacity was greatest when the solution pH was about 3. However, the adsorption affinity (Ke) of C-π sites was weaker than that of N-Q, and the contribution for adsorption was small when the solution was low concentration or neutral, while the N-Q was the dominant adsorption site of ACFs. It is expected that the N-Q affected the adsorption kinetics, and the higher the amount of N-Q, the faster the adsorption rate. Py-7.0Z4-9.5HT10 had a large amount of C-π sites and N-Q. Therefore, the equilibrium adsorption amount (Qe) of Py-7.0Z4-9.5HT10 was 1.02 mmol/g at solution pH 3, and the adsorption kinetics were also fast.

Nitrate Ion Adsorption Characteristics of Activated Carbon Fibers with and without Quaternary Nitrogen Effective for Anion Adsorption.

By comparing the two types of activated carbon fibers (ACFs), characteristics of adsorption sites for nitrate ion other than quaternary nitrogen (N-Q) were investigated. Using phenol resin as precursors, activation with ZnCl2 was performed, and then heat treatment at 950 °C was carried out to prepare ACFs without N-Q, while ACFs with N-Q was prepared in the same method using polyacrylonitrile-based carbon fiber as precursors. We assessed the amount of functional groups, elemental composition, porous properties, and model of unit crystal size of graphene. For both ACFs with N-Q and without N-Q, equilibrium adsorption amount was not always simply proportional to surface area, but to the average number of benzene rings (Bz-rings) of graphene universally. PhR-5.0Z4 had only 20 benzene rings per graphene unit, but after heat treatment at 950 °C, the number drastically increased to 1088 (PhR-5.0Z4-9.5HT30). However, when the ACFs contained a large amount of oxygen, the number of Bz-rings was limited to 792 (PhR-5.0Z4-Ox-9.5HT30) even after heat treatment at 950 °C, and did not increase sufficiently. Cπ sites are more susceptible to oxygen inhibition than N-Q in adsorbing nitrate ions. For ACFs having Cπ sites as main adsorption sites, the heat treatment at 950 °C without oxidation can enhance the nitrate ion adsorption capacity.

Effects of different types of extracellular polysaccharides isolated from cyanobacterial blooms on the colony formation of unicellular Microcystis aeruginosa.

In this study, two types of extracellular polysaccharides (EPS), namely, mixed EPS (MX-EPS) and tightly bound EPS (TB-EPS), were extracted from cyanobacterial blooms using different methods. To evaluate their compositional differences, elemental composition, FTIR, and TG/DTA profile were measured for both EPS samples. Following that, unicellular Microcystis aeruginosa was cultured in a medium containing EPS, Ca2+ ion, and Mg2+ ion, and the effect of each type of EPS on the colony formation of M. aeruginosa was examined. Results showed that TB-EPS had more carboxy groups than MX-EPS, and that the TB-EPS medium contained Ca2+ and Mg2+ ions. These cations were not detected in the MX-EPS medium. During the colony formation experiment, colonies were observed when Ca2+ and Mg2+ ions were present at 250 mg/L concentration each. In addition, colony density increased when TB-EPS was added, compared to that of MX-EPS. Colonies were also observed in the medium containing only TB-EPS (100 mg/L), indicating that M. aeruginosa can form colonies using Ca2+ ion present in TB-EPS. During the MX-EPS extraction, Ca2+ ion chelated with EDTA was removed during ethanol precipitation. Therefore, the extraction protocol followed for TB-EPS was better than that of MX-EPS for maintaining Ca2+ ions, and thereby maintaining an EPS composition that enables for colony formation.

Removal and recovery of phosphate from water by calcium-silicate composites-novel adsorbents made from waste glass and shells.

The removal and recovery of phosphate from water by calcium-silicate composite (CSC) and alkali-treated calcium-silicate composite (ASC) was investigated. ASC had a higher specific surface area and total pore volume, and exhibited better performance of phosphate adsorption than CSC. In the batch mode adsorption studies, the isotherm adsorption experiments data fitted well the Langmuir isotherm model and the maximum adsorption capacities were 120 and 73.0 mg/g for ASC and for CSC, respectively. For the kinetic study, the experimental data fitted very well the pseudo-second-order kinetic model. The uptake of phosphate could be performed well over a wide pH range, from 3.0 to 13.0 for ASC and from 4.0 to 13.0 for CSC. The adsorption of phosphate by ASC was very selective even with 10 times higher concentration of other coexistent anions. For the adsorption of low phosphate concentration (10 mg/L), ASC could efficiently remove phosphate at the dosage of 0.8 g/L, while CSC was even difficult to remove phosphate at the dosage of 4.0 g/L. Phosphate fractionation results and FTIR spectra showed that phosphate-Ca complex was formed through phosphate adsorption process. The adsorbed phosphate could be successfully desorbed by 2% citric acid solution, indicating that the adsorbent after adsorbed phosphate could be reusable as fertilizer in the agricultural field.

Adsorptive Removal of Nitrate from Aqueous Solution Using Nitrogen Doped Activated Carbon.

Activated carbon (AC) has been widely applied for adsorptive removal of organic contaminants from aqueous phase, but not for ionic pollutants. In this study, nitrogen doped AC was prepared to increase the adsorption capacity of nitrate from water. AC was oxidized with (NH4)2S2O8 solution to maximize oxygen content for the first step, and then NH3 gas treatment was carried out at 950°C to aim at forming quaternary nitrogen (N-Q) species on AC surface (Ox-9.5AG). Influence of solution pH was examined so as to elucidate the relationship between surface charge and adsorption amounts of nitrate. The results showed that Ox-9.5AG exhibited about twice higher adsorption capacity than non-treatment AC at any initial nitrate concentration and any equilibrium solution pH (pHe) investigated. The more decrease in pHe value, the more adsorption amount of negatively charged nitrate ion, because the surface charge of AC and Ox-9.5AG could become more positive in acidic solution. The oxidation and consecutive ammonia treatments lead to increase in nitrogen content from 0.35 to 6.4% and decrease in the pH of the point of zero charge (pHpzc) from 7.1 to 4.0 implying that positively charged N-Q of a Lewis acid was created on the surface of Ox-9.5AG. Based on a Langmuir data analysis, maximum adsorption capacity attained 0.5-0.6 mmol/g of nitrate and adsorption affinity was 3.5-4.0 L/mmol at pHe 2.5 for Ox-9.5AG.

Preparation of Bamboo Chars and Bamboo Activated Carbons to Remove Color and COD from Ink Wastewater.

Bamboo chars and bamboo activated carbons prepared by steam activation were applied for ink wastewater treatment. Bamboo char at 800 °C was the best for the removal of color and chemical oxygen demand (COD) from ink wastewater compared to bamboo chars at 300 to 700 °C due to higher surface area and mesopore volume. Bamboo activated carbon at 600 °C (S600) was the best compared to bamboo activated carbon at 800 °C (S800), although S800 had larger surface area (1108 m(2)/g) than S600 (734 m(2)/g). S600 had higher mesopore volume (0.20 cm(3)/g) than S800 (0.16 cm(3)/g) and therefore achieved higher color and COD removal. All bamboo activated carbons showed higher color and COD removal efficiency than commercial activated carbon. In addition, S600 had the superior adsorption capacity for methylene blue (0.89 mmol/g). Therefore, bamboo is a suitable material to prepare adsorbents for removal of organic pollutants.

Effect of Polarity of Activated Carbon Surface, Solvent and Adsorbate on Adsorption of Aromatic Compounds from Liquid Phase.

In this study, introduction of acidic functional groups onto a carbon surface and their removal were carried out through two oxidation methods and outgassing to investigate the adsorption mechanism of aromatic compounds which have different polarity (benzene and nitrobenzene). Adsorption experiments for these aromatics in aqueous solution and n-hexane solution were conducted in order to obtain the adsorption isotherms for commercial activated carbon (BAC) as a starting material, its two types of oxidized BAC samples (OXs), and their outgassed samples at 900 °C (OGs). Adsorption and desorption kinetics of nitrobenzene for the BAC, OXs and OGs in aqueous solution were also examined. The results showed that the adsorption of benzene molecules was significantly hindered by abundant acidic functional groups in aqueous solution, whereas the adsorbed amount of nitrobenzene on OXs gradually increased as the solution concentration increased, indicating that nitrobenzene can adsorb favourably on a hydrophilic surface due to its high dipole moment, in contrast to benzene. In n-hexane solution, it was difficult for benzene to adsorb on any sample owing to the high affinity between benzene and n-hexane solvent. On the other hand, adsorbed amounts of nitrobenzene on OXs were larger than those of OGs in n-hexane solution, implying that nitrobenzene can adsorb two adsorption sites, graphene layers and surface acidic functional groups. The observed adsorption and desorption rate constants of nitrobenzene on the OXs were lower than those on the BAC due to disturbance of diffusion by the acidic functional groups.

Effect of surface property of activated carbon on adsorption of nitrate ion.

In this study, the removal of acidic functional groups and introduction of basic groups/sites on activated carbons (ACs) by outgassing and ammonia gas treatment were respectively carried out to enhance the nitrate ion adsorption in aqueous solution. Then, the relationships between nitrate ion adsorption and solution pH as well as surface charge of AC were investigated to understand the basic mechanisms of nitrate ion adsorption by AC. The result showed that the nitrate ion adsorption depended on the equilibrium solution pH (pHe) and the adsorption amount was promoted with decreasing pHe. The ACs treated by outgassing and ammonia gas treatment showed larger amount of nitrate ion adsorption than that by untreated AC. These results indicated that, since basic groups/sites could adsorb protons in the solution, the AC surface would be charged positively, and that the nitrate ion would be electrically interacted with positively charged carbon surface. Accordingly, it was concluded that basic groups/sites on the surface of AC could promote nitrate ion adsorption.

Cadmium(II) adsorption using functional mesoporous silica and activated carbon.

The role of surface functionality on silica and carbonaceous materials for adsorption of cadmium(II) was examined using various mesoporous silica and activated carbon. Silica surfaces were principally functionalized by mono-amino- and mercapto-groups, while carboxylic group was introduced to the activated carbons by oxidation. Functional groups on silica surface were formed using grafting and co-condensation techniques in their preparation. Mono-amino group was found more effective than di- and tri-amino groups for cadmium(II) adsorption on the grafted silica. Mono-amino groups prepared by co-condensation adsorbed cadmium(II) as much as 0.25mmol/g compared to mercapto- and carboxyl-groups which adsorbed around 0.12mmol/g, whereas Langmuir adsorption affinities were as strong as 50-60L/mmol for all of the three functions. The working pH range was wider for mercapto- and carboxyl-functions than for amino-group. Basic site could be an adsorption center for amino-functional groups while ion exchange sites were found to work for the mercapto- and carboxyl-functions to adsorb cadmium(II) from aqueous phase. Based on the experimental results, surface functional groups rather than structure of silica and carbon seemed to play a decisive role for cadmium(II) adsorption.

Adsorption of heavy metals onto activated carbons derived from polyacrylonitrile fiber.

The aim of this research is to produce activated carbons derived from polyacrylonitrile (PAN) fiber and to examine their feasibility of removing heavy metals from aqueous solution. Thermogravimetric analysis was used to identify the suitable conditions for preparing oxidized fiber and coke as activated carbon precursors. Steam and CO(2) were used to activate the precursors. Activated carbons were characterized by their pore texture, elemental compositions and surface functionalities. Batch adsorption and desorption studies were carried out to determine the metal-binding ability of activated carbons. Two commercial activated carbon fibers (ACFs), i.e., A-20 and W10-W, were employed to compare the removal performance of PAN derived activated carbons. Influence of oxidation treatment of PAN fiber prior to steam activation was also explored and discussed. Results indicated that steam produced a higher surface area but a lower resultant yield as compared to CO(2). Also, precursors activated by steam showed a greater removal performance. For both activation methods, fiber displayed a better metal-binding ability than coke. A small nitrogen loss from PAN fiber as a result of oxidation treatment assisted a greater removal of Cu(II) and Pb(II), but the interaction to Cu(II) was found stronger. It is proposed that the formation of cyclized structure by oxidation treatment minimized the nitrogen loss during steam activation, hence increased the uptake performance.

Effect of phosphorus fluctuation caused by river water dilution in eutrophic lake on competition between blue-green alga Microcystis aeruginosa and diatom Cyclotella sp.

Tega-numa (Lake Tega) is one of the eutrophic lakes in Japan. For the improvement of water quality in Lake Tega, the North-chiba Water Conveyance Channel was constructed in 2000, which transfer water from Tone River into the lake. After 2000, the dominant species of diatoms, mainly Cyclotella sp., have been replacing blue-green algae, mainly Microcystis aeruginosa in Lake Tega. This transition of dominant species would be due to the dilution, but the detail mechanism has not been understood yet. This study examined the relationship between phosphorus fluctuation caused by river water dilution to Lake Tega and dominance of algal species, M. aeruginosa or Cyclotella sp. based on the single-species and the mixed-species culture experiments. The single-species culture experiment showed that the half-saturation constant and uptake rate of phosphorus were one order lower and seven times higher for M. aeruginosa than those for Cyclotella sp. These findings implied that M. aeruginosa would possess a potential for the growth and survival over Cyclotella sp. in the phosphorus limited condition. The superiority of M. aeruginosa was reflected in the outcome of the mixed-species culture experiment, i.e., dominance of M. aeruginosa, even phosphorus concentration was lowered to 0.01 mg-P/L. Therefore, it could be concluded that the decrease in phosphorus concentration due to the river water dilution to Lake Tega would be interpreted as a minor factor for the transition of dominant species from M. aeruginosa to Cyclotella sp.

Adsorption of aqueous metal ions on cattle-manure-compost based activated carbons.

The objective of this study is to examine the suitability and performance of cattle-manure-compost (CMC) based activated carbons in removing heavy metal ions from aqueous solution. The influence of ZnCl(2) activation ratios and solution pH on the removal of Cu(II) and Pb(II) were studied. Pore texture, available surface functional groups, pH of point zero charge (pH(PZC)), thermogravimetric analysis and elemental compositions were obtained to characterize the activated carbons. Batch adsorption technique was used to determine the metal-binding ability of activated carbons. The equilibrium data were characterized using Langmuir, Freundlich and Redlich-Peterson models. It was found that the uptake of aqueous metal ions by activated carbons could be well described by Langmuir equation. It is suggested that the increase of surface area and mesopore ratio as a result of increasing activation ratios favored the removal of Cu(II), while activated carbon rich in acidic groups showed selective adsorption towards Pb(II). The preferable removal of Cu(II) over Pb(II) could be due to the rich nitrogen content as well as the higher mesoporous surface area in the CMC activated carbons. The impregnated CMC activated carbons also showed a better performance for Cu(II) removal at varying solution pH than Filtrasorb 400 (F400), while a similar performance was observed for Pb(II) removal.

Prediction of microcystis blooms based on TN:TP ratio and lake origin.

We evaluated the relationship between TN:TP ratio and Microcystis growth via a database that includes worldwide lakes based on four types of lake origin (dammed, tectonic, coastal, and volcanic lakes). We used microcosm and mesocosm for the nutrient elution tests with lake water and four kinds of sediment (nontreated, MgO sprinkling treated, dissolved air flotation [DAF] treated, and combined treated sediment) in order to control TN:TP ratio and to suppress Microcystis growth. Microcystis growth was related to TN:TP ratio, with the maximum value at an optimum TN:TP ratio and the minimum values when the TN:TP ratios reached to 0 or "V. The kurtosis of the distribution curve varied with the type of lake origin; the lowest kurtosis was found in dammed lakes, while the highest was found in volcanic lakes. The lake trophic state could affect the change in the kurtosis, providing much lower kurtosis at eutrophic lakes (dammed lakes) than that at oligotrophic lakes (volcanic lakes). The relationship between TN:TP ratio and Microcystis growth could be explained by the nutrient elution tests under controlled TN:TP ratios through the various sediment treatments. A significant suppression of Microcystis growth of 70% could be achieved when the TN:TP ratios exceeded 21. Lake origin could be regarded as an index including morphological and geographical factors, and controlling the trophic state in lakes. The origin rather than trophic state for lakes could be considered as an important factor of TN:TP influences on Microcystis growth.

Inhibition of nitrobenzene adsorption by water cluster formation at acidic oxygen functional groups on activated carbon.

The inhibition effect of nitrobenzene adsorption by water clusters formed at the acidic groups on activated carbon was examined in aqueous and n-hexane solution. The activated carbon was oxidized with nitric acid to introduce CO complexes and then outgassed in helium flow at 1273 K to remove them completely without changing the structural properties of the carbon as a reference adsorbent. The amounts of acidic functional groups were determined by applying Boehm titration. A relative humidity of 95% was used to adsorb water onto the carbon surface. Strong adsorption of water onto the oxidized carbon can be observed by thermogravimetric analysis. The adsorption kinetic rate was estimated to be controlled by diffusion from the kinetic analysis. Significant decline in both capacity and kinetic rate for nitrobenzene adsorption onto the oxidized carbon was also observed in n-hexane solution by preadsorption of water to the carbon surface, whereas it was not detected for the outgassed carbons. These results might reveal that water molecules forming clusters at the CO complexes inhibited the entrance of nitrobenzene into the interparticles of the carbon.

Textural and surface chemical characteristics of activated carbons prepared from cattle manure compost.

Two activated carbons (ACs) prepared from cattle manure compost (CMC) by ZnCl(2) activation were selected and out-gassed in a helium flow at various temperatures for 2h. The pore structure and surface chemical properties of the two selected ACs and their out-gassing treated ACs were characterized using N(2) adsorption-desorption, elements analysis, SEM and Boehm titration. A basic dye, methylene blue (MB), was chosen as an adsorbate to investigate the adsorption capacity for organic contaminant onto the activated carbons. It was found that the out-gassing treatment at 400 degrees C had little effect on the textural characteristics of the carbons but significantly changed the surface chemical properties such as surface functional groups concentration, pH and pH(PZC). The CMC-based activated carbons exhibited excellent performance for MB adsorption due to their high surface area, large mesopore volume and high nitrogen content. The kinetics of MB adsorption onto the activated carbons followed a pseudo-second-order equation, and the equilibrium data agreed well with the Langmuir model under the experimental conditions. The highest adsorption rate constant of k(ad) and the largest adsorption capacity of q(m) were found be 1.44x10(-4)g/mgmin and 519mg/g, respectively. The results suggested that the CMC-based activated carbons were effective adsorbents for the removal of methylene blue from aqueous solution.

Preparation of activated carbons from cattle-manure compost by zinc chloride activation.

Dried cattle-manure compost was pyrolyzed by a one-step process to obtain activated carbon using chemical activation by zinc chloride. The influence of activation parameters such as ZnCl(2) to cattle-manure compost (ZnCl(2)/CMC) ratio, activation temperature and retention time on the final products was investigated. The resultant activated carbons were characterized by nitrogen adsorption-desorption isotherms at 77 K. The results showed that the surface area and pore volume of activated carbons, which were estimated by BET and t-plot methods, were achieved as high as 2170 m(2)/g and 1.70 cm(3)/g in their highest value, respectively. Thermogravimetric analysis (TGA) was carried out to monitor the pyrolysis process of cattle-manure compost (CMC) and ZnCl(2) impregnated one (ZnCl(2)/CMC). The capabilities of phenol adsorption were also examined for the CMC carbons prepared with various treatments.

Prediction of simultaneous adsorption of Cu(II) and Pb(II) onto activated carbon by conventional Langmuir type equations.

Removal of Cu(II) and Pb(II) by adsorption onto activated carbon was examined in single- and binary-component aqueous solutions representative of contaminated solutions containing heavy metals. Reversibility of adsorption of the heavy metals on the activated carbon was evaluated by desorption experiments. The number of the maximum adsorption sites and adsorption equilibrium constants of Cu(II) and Pb(II) were estimated by the results of single-component systems assuming the Langmuir adsorption model. The adsorption sites per gram of activated carbon resulted in similar values for Cu(II) and Pb(II) from the isotherms. The adsorption constant for Pb(II) was nearly 1.8 times greater than that of Cu(II). Rate constants of adsorption and desorption were also estimated from the kinetic analysis. Using the single set of common parameters obtained from the single-component systems, the experimental results for a binary-component system were quantitatively predicted. Competitive adsorption of Cu(II) and Pb(II) on the same adsorption sites was confirmed by both experimental and predicted results of adsorption in the binary mixture.

Historical transition of eco-structure in a tidal flat caused by expansion of sewerage treatment area.

An artificial tidal flat was prepared for the mitigation tool on coastal environment. However, it is considered that most of the flat was not restored to the sufficient amenities for aquatic living things, migratory birds, etc. because none of the ecological mechanisms were understood or planned for. It is therefore investigated in this paper that historical transition factors in ecosystem structure are selected and traced with the diffusion of a public sewerage system, and with environmental factors such as water quality, sediment condition, and aquatic producers in the Yatsu Tidal Flat. As a result, it can be defined that the tidal flat, just like a lagoon, was formed artificially with reclamation and development of its circumference at the first step of transition; the water quality and sediment condition gradually became brackish water and muddy sediment conditions, interactively. The ecosystem pyramid forming orderly layers according to trophic level appeared as a high-bio-production potential in its tidal flat. In the second step, i.e., in recent years, the characteristics of water quality and sediment conditions evolved into a foreshore tidal flat, namely, conditions in the flat observed were that the progression of water included a high concentration of chloride ion as seawater and sediment conditions became sandy. Because of that, the inflowing fresh water and organic mater from the land area decreased with the improvement of the public sewerage system. The ecosystem pyramid was distorted into a chaos pyramid, with inversion of Ulva spp.