Solubilization of water-insoluble beta-glucan isolated from Ganoderma lucidum

The fungal beta-D-glucan is a biological response modifier (BRM), but a major obstacle to the clinical utilization of beta-glucan BRMs is thei relative lack of solubility in aqueous media. Water insoluble fungal glucans extracted by alkali from the mycelia of Ganoderma lucidum were sulfated to yield their corresponding water-soluble derivatives. Insoluble glucan is dissolved in methyl sulfoxide and urea, and is partially sulfated with sulfuric acid. The sulfated glucan (SGL) yield prepared from insoluble glucan (IGL) was 85%, the sulfation degree of SGL was about 14.9%, and the solubility of SGL was above 95% in water. The monosugar SGL content was 34.9% alpha-glucose and 35.9% beta-glucose. The mean molecular weight (MW) of SGL was shown as a single peak on Sepharose CL-4B column chromatography, and their MW was approximately 9.3 kDa. The 13C NMR spectrum analysis shows that SGL has a high similarity with the beta-(1-->3)-linked triple-helical control.     

The Emissions of Major Aromatic Voc as Landfill Gas from Urban Landfill Sites in Korea

In this study, concentrations of major aromatic VOCs were determined from landfill gas (LFG) at a total of five municipal landfill sites in Korea including Nan Ji (NJ), Woon Jung (WJ), Sam Poong (SP), Hoei Chun (HC), and No Hyung (NH). The concentration levels of those VOC were found to be significantly different, mainly as a function of such a parameter as landfill aging. The VOC concentrations measured from the unclosed landfill sites (e.g., WJ) were characterized by exceedingly high values above a few tens of ppm. However, the results of the abandoned site (e.g., SP) were about three orders of magnitude lower than the others so as to merely exceed the typical ambient concentration levels. It was most striking to find a systematic dominance of toluene over other aromatic VOC under most circumstances. The LFG flux values of all aromatic VOC and the four specific major ones (termed as BTEX: benzene, toluene, ethylbenzene, and xylene) were also computed for each vent pipe from all study sites using their concentrations and the concurrently determined environmental parameters. The results, if calculated in terms of the average BTEX quantity emitted per vent pipe, showed that the magnitude of their emissions can vary substantially, with the values ranging from 0.05 (SP) to 49.2 kg yr⁻¹ (WJ in wintertime). The LFG flux values of aromatic VOC, when compared to the contribution of non-methane hydrocarbons (NMHC), were able to explain a constant, but minor, proportion of the LFG carbon budget.     

Highly siliceous MCM-48 from rice husk ash for CO2 adsorption

Mesoporous MCM-48 silica was synthesized using a cationic-neutral surfactant mixture as the structure-directing template and rice husk ash (RHA) as the silica source. The MCM-48 samples were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), N₂ physisorption and SEM. X-ray diffraction pattern of the resulting MCM-48 revealed typical pattern of cubic Ia3d mesophase. BET results showed the MCM-48 to have a surface area of 1024 m²/g and FT-IR revealed a silanol functional group at about 3460 cm⁻¹. Breakthrough experiments in the presence of MCM-48 were also carried out to test the material's CO₂ adsorption capacity. The breakthrough time for CO₂ was found to decrease as the temperature increased from 298 K to 348 K. The steep slopes observed shows the CO₂ adsorption occurred very quickly, with only a minimal mass transfer effect and very fast kinetics. In addition, amine grafted MCM-48, APTS-MCM-48 (RHA), was prepared with the 3-aminopropyltriethoxysilane (APTS) to investigate the effect of amine functional group in CO₂ separation. An order of magnitude higher CO₂ adsorption capacity was obtained in the presence of APTS-MCM-48 (RHA) compared to that with MCM-48 (RHA). These results suggest that MCM-48 synthesized from rice husk ash could be usefully applied for CO₂ removal.     

Solubility of organic acids in various methanol and salt concentrations: the implication on organic acid sorption in a cosolvent system

The well-known cosolvency-induced sorption model is not applicable to predict the sorption of carboxylic acids in cosolvent system. To investigate the phenomenon, sorption and solubility of chlorinated phenols (2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP)) and carboxylic acids (benzoic acid and 2,4-dichlorophenoxyacetic acid (2,4-D)) were measured in soil-methanol mixture with various ionic strengths. The sorption (K_m) of chlorinated phenols was explained by a cosolvency-induced sorption model; the inverse log-linear relationship between the K_m and methanol volume fraction (f_c). However, the K_m of carboxylic acids increased with increasing f_c. This discrepancy was attributed to the effect of the carboxylic moiety. To explain the effect, solubility was measured for benzoic acid and 2,4,6-TCP from various liquid conditions. For both solutes, the cosolvency power (σ) increased with CaCl₂ concentrations and the salting constant (K^s) became smaller as f_c increased. However, the σ value at a given salt concentration and the K^s value at a given f_c were greater for 2,4,6-TCP than for benzoic acid, both of which were due to the greater hydrophobicity of the former. Overall, the solubility profiles of the both solutes on combination of f_c and CaCl₂ concentration evidenced no specific role of the carboxylic moiety. Therefore, it can be reasonably concluded that the positive relationship between K_m and f_c for carboxylic organic acid can be attributed to the modification of the activity coefficient occurred in the solid phase, which cannot be traceable by cosolvency-based model.     

Effect of seepage conditions on chemical attenuation of arsenic by soils across an abandoned mine site

The effect of seepage velocity on the As leaching/adsorption by soils collected from abandoned mine sites was evaluated under batch equilibrium and different seepage settings. The breakthrough curves (BTCs) of As leaching from the mine soil column initially displayed the peak export and gradually leveled off over the leaching experiment. A similar As peak was observed after a flow interruption period. Adsorption by downgradient soils was clearly nonlinear, as Freundlich N was <1. In the BTCs of the layered columns, where downgradient soils were overloaded above the mine soil, the extended lag period of As appearance and lower steady-state As concentration observed for slow seepage velocity supported the idea of kinetically limited As attenuation driven by soil adsorption. The perturbation of As concentration was insignificant when the intra-column As concentration gradient was higher. The As concentration drop and time to recovery were greater for less adsorptive soil and fast seepage velocity. Desorption of As from soils retrieved from both batch adsorption and column experiment demonstrate hysteric behavior. The results of this work demonstrated that the risk of As leaching from an abandoned mine site can be greatly attenuated by intermediate downgradient soils via chemical adsorption, which tends to be kinetically limited and energetically hysteric (i.e., non-identical energy pathway).     

Soil attenuation of As(III,V) and Se(IV,VI) seepage potential at ash disposal facilities

Leachate from ash landfills is frequently enriched with As and Se but their off-site movement is not well understood. The attenuation potential of As and Se by soils surrounding selected landfills during leachate seepage was investigated in laboratory column studies using simulated ash leachate. As(III, V) and Se(IV, VI) concentrations as well as pH, flow rate, and a tracer were monitored in influent and effluent for up to 800 pore volumes followed by sequential desorption, extraction, and digestion of column segments. Column breakthrough curves (BTCs) were compared to predictions based on previously measured sorption isotherms. Early As(V) breakthrough and retarded As(III) breakthrough relative to predicted BTCs are indicative of oxidative transformation during seepage. For Se(VI), which exhibits linear sorption and the lowest sorption propensity, measured BTCs were predicted fairly well by equilibrium sorption isotherms, except for the early arrival of Se(IV) in one site soil, which in part, may be due to higher column pH values compared to batch isotherms. Most of the As and Se retained by soils during leaching was found to be strongly sorbed (60–90%) or irreversibly bound (10–40%) with <5% readily desorbable. Redox potential favoring transformation to the more sorptive valence states of As(V) and Se(IV) will invoke additional attenuation beyond equilibrium sorption-based predictions. With the exception of Se(IV) on one site soil, results indicate that attenuation by down-gradient soils of As and Se in ash landfill seepage will often be no less than what is predicted by equilibrium sorption capacity with further attenuation expected due to favorable redox transformation processes, thus mitigating contaminant plumes and associated risks.     

Reduction of toxicity of antimicrobial compounds by degradation processes using activated sludge,gamma radiation,and UV

The occurrence and persistence of pharmacologically active compounds in the environment has been an increasingly important issue. The objectives of this study were to investigate the decomposition of aqueous antimicrobial compounds using activated sludge, γ-irradiation, and UV treatment, and to evaluate the toxicity towards green algae, Pseudokirchneriella subcapitata, before and after treatment. Tetracycline (TCN), lincomycin (LMC) and sulfamethazine (SMZ) were used as target compounds. Gamma (γ)-irradiation showed the highest removal efficiency for all target compounds, while UV and activated sludge treatment showed compound-dependent removal efficiencies. TCN and SMZ were well degraded by all three treatment methods. However, LMC showed extremely low removal efficiency for UV and activated sludge treatments. Overall, the algal toxicity after degradation processes was significantly decreased, and was closely correlated to removal efficiency. However, in the case of γ-irradiated TCN, UV and activated sludge treated LMC as well as sludge treated SMZ, the observed toxicity was higher than expected, which indicates the substantial generation of byproducts or transformed compounds of a greater toxicity in the treated sample. Consequently, γ-radiation treatment could be an effective method for removal of recalcitrant compounds such as antibiotics.     

Sorption of acidic organic solute onto kaolinitic soils from methanol-water mixtures

The fate of the acidic organic solute from the soil-water-solvent system is not well-understood. In this study, the effect of the acidic functional group of organic solute in the sorption from cosolvent system was evaluated. The sorption of naphthalene (NAP) and 1-naphthoic acid (1-NAPA) by three kaolinitic soils and two model sorbents (kaolinite and humic acid) were measured as functions of the methanol volume fractions (f _c ≤ 0.4) and ionic compositions (CaCl₂ and KCl). The solubility of 1-NAPA was also measured in various ionic compositions. The sorption data were interpreted using the cosolvency-induced sorption model. The K _m values (= the linear sorption coefficient) of NAP with kaolinitic soil for both ionic compositions was log linearly decreased with f _c. However, the K _m values of 1-NAPA with both ionic compositions remained relatively constant over the f _c range. For the model sorbent, the K _m values of 1-NAPA with kaolinite for the KCl system and with humic acid for both ionic compositions decreased with f _c, while the sorption of 1-NAPA with kaolinite for the CaCl₂ system was increased with f _c. From the solubility data of 1-NAPA with f _c, no significant difference was observed with the different ionic compositions, indicating an insignificant change in the aqueous activity of the liquid phase. In conclusion, the enhanced 1-NAPA sorption, greater than that predicted from the cosolvency-induced model, was due to an untraceable interaction between the carboxylate and hydrophilic soil domain in the methanol-water system. Therefore, in order to accurately predict the environmental fate of acidic pesticides and organic solutes, an effort to quantitatively incorporate the enhanced hydrophilic sorption into the current cosolvency-induced sorption model is required.     

Heavy metal immobilization in soil near abandoned mines using eggshell waste and rapeseed residue

Heavy metal contamination of agricultural soils has received great concern due to potential risk to human health. Cadmium and Pb are largely released from abandoned or closed mines in Korea, resulting in soil contamination. The objective of this study was to evaluate the effects of eggshell waste in combination with the conventional nitrogen, phosphorous, and potassium fertilizer (also known as NPK fertilizer) or the rapeseed residue on immobilization of Cd and Pb in the rice paddy soil. Cadmium and Pb extractabilities were tested using two methods of (1) the toxicity characteristics leaching procedure (TCLP) and (2) the 0.1 M HCl extraction. With 5 % eggshell addition, the values of soil pH were increased from 6.33 and 6.51 to 8.15 and 8.04 in combination with NPK fertilizer and rapeseed residue, respectively, compared to no eggshell addition. The increase in soil pH may contribute to heavy metal immobilization by altering heavy metals into more stable in soils. Concentrations of TCLP-extracted Cd and Pb were reduced by up to 67.9 and 93.2 % by addition of 5 % eggshell compared to control. For 0.1 M HCl extraction method, the concentration of 0.1 M HCl-Cd in soils treated with NPK fertilizer and rapeseed residue was significantly reduced by up to 34.01 and 46.1 %, respectively, with 5 % eggshell addition compared to control. A decrease in acid phosphatase activity and an increase in alkaline phosphatase activity at high soil pH were also observed. Combined application of eggshell waste and rapeseed residue can be cost-effective and beneficial way to remediate the soil contaminated with heavy metals.     

Analysis of Long-Term Settlement of Municipal Solid Waste Landfills as Determined by Various Settlement Estimation Methods

Abstract

In this study, several existing municipal solid waste (MSW) settlement estimation methods are reviewed and applied to analyze the settlement data of nine MSW land-fills. Because a biodegradation-related settlement contributes differently to a long-term total settlement depending on the age of landfills, the actual MSW landfill sites are classified into three groups to specifically address the validity of each method in its prediction of a long-term settlement for each age category. Results demonstrate that there are considerable decreases in predicted settlement potentials as fill age increases. Comparisons indicate that the individual estimation methods display a considerable variation in predicting settlements in the fresh MSW landfills. On the other hand, for the old refuse landfills, all of the estimation methods, except the extended soil model, predict low settlement potentials.