Cellulose-based wastes can be degraded into short-chain organic acids at the cementitious radioactive waste repository. Isosaccharinic acid (ISA), one of the main degradation products, can form the chelate complex with metals and radionuclides, and these complexes have a potential that can accelerate to move the radionuclides to far-field from the repository. This study characterized the amount of generated ISA from typical cellulosic materials in the repository. Two different degradation experiments were conducted under alkaline conditions (saturated with Ca(OH)2 at pH 12.4): i) cellulosic material mixture under an opened condition (partially aerobic), and ii) cellulosic material under an anaerobic condition in a nitrogen-purged glove box. In the first case, three different types of cellulosic materials–paper, cotton, and wood– were mixed at the same ratio, and the experiments were carried out at three different temperatures (20°C, 40°C, and 60°C). It revealed that both the cellulose degradation rate and generated ISA concentration were high at high reaction temperatures, and various soluble degradation products such as formic acid and lactic acid were generated. The cellulose degradation in this work seems to still stay at a peeling-off process. In the second study, each type of cellulosic material was applied in its own batch experiments, and the amount of generated ISA was in the order of paper > wood > cotton. The above two experiments are supposed to be a long-term study until the generated ISA reaches an equilibrium state.
A rapid chemical dewatering of the in-situ hydraulically dredged coastal sediment suspensions treated with cationic cetyl-trimethyl-ammonium-bromide (CTAB) was investigated. The dewatering process consisted of coating or adsorption of the surfactant on the surface of sediment to change its hydrophobicity and hexane spraying to enhance moisture removal from the sediment surface. The dredged wet sediment sample was wet-sieved with the #450 sieve (32 μm) and synthetic sea-water made of bay salt (3.5%). The sieved sediment was settled and then freeze-dried. Considering the field process, the freeze-dried sediment was pre-treated by adding 5 M H2O2 and 0.5% Tween 80 to remove organics in the sediment and then adding 0.5% alum and 0.001% PAC for flocculation. The mean water content of the pre-treated sediment was 55.8~59.1%. The CTAB dosage was in the range of 0.001 to 1.0 g per 10 g of the pre-treated sediment (0.01 to 0.10 (wt/wt) of CTAB/sediment ratio). After addition, the sediment and CTAB mixture was mixed thoroughly by using a vortex followed by freeze-dried. For hydrophobicity test, 0.5 g of the freeze-dried samples were taken into the two-layer solutions mixed with hexane (20 mL) and deionized water (20 mL). The higher amount of the samples were migrated into the hexane layer as the CTAB dosage increased to 0.1 g (Fig. 1), indicating that the surface charge of the sediment was neutralized by electrostatic attraction of negative charged sediment particles with cationic CTAB. The additional dosage of CTAB to 1.0 g per 10 g sediment led to transfer some of the sediment back into the water layer (Fig. 1). The optimum dosage of CTAB was 0.1 to 0.2 g per 10 g sediment. The sediments with the optimum dosage were transferred onto the filter paper and treated with spraying 0.25 to 1.0 mL of hexane per 1 g sediment, resulting in the significant decrease in the water content to 21% at 1.0 mL hexane/g sediment.
In Korea, the chemical oxygen demand(CODsed) in freshwater sediments has been measured by the potassium permanganate method used for marine sediment because of the absence of authorized analytical method. However, this method has not been fully verified for the freshwater sediment. Therefore, the use or modification of the potassium permanganate method or the development of the new CODsed analytical method may be necessary. In this study, two modified CODsed analytical methods such as the modified potassium permanganate method for CODMn and the modified closed reflux method using potassium dichromate for CODCr were compared. In the preliminary experiment to estimate the capability of the two oxidants for glucose oxidation, CODMn and CODCr were about 70% and 100% of theoretical oxygen demand(ThOD), respectively, indicating that CODCr was very close to the ThOD. The effective titration ranges in CODMn and CODCr were 3.2 to 7.5 mL and 1.0 to 5.0 mL for glucose, 4.3 to 7.5 mL and 1.4 to 4.3 mL for lake sediment, and 2.5 to 5.8 mL and 3.6 to 4.5 mL for river sediment, respectively, within 10% errors. For estimating CODsed recovery(%) in glucose-spiked sediment after aging for 1 day, the mass balances of the CODMn and CODCr among glucose, sediments and glucose-spiked sediments were compared. The recoveries of CODMn and CODCr were 78% and 78% in glucose-spiked river sediments, 91% and 86% in glucose-spiked lake sediments, 97% and 104% in glucose-spiked sand, and 134% and 107% in glucose-spiked clay, respectively. In conclusion, both methods have high confidence levels in terms of analytical methodology but show significant different CODsed concentrations due to difference in the oxidation powers of the oxidants.
The environmental behaviors of polycyclic aromatic hydrocarbons (PAHs) are mainly governed by their solubility and partitioning properties on soil media in a subsurface system. In surfactant-enhanced remediation (SER) systems, surfactant plays a critical role in remediation. In this study, sorptive behaviors and partitioning of naphthalene in soils in the presence of surfactants were investigated. Silica and kaolin with low organic carbon contents and a natural soil with relatively higher organic carbon content were used as model sorbents. A nonionic surfactant, Triton X-100, was used to enhance dissolution of naphthalene. Sorption kinetics of naphthalene onto silica, kaolin and natural soil were investigated and analyzed using several kinetic models. The two compartment first-order kinetic model (TCFOKM) was fitted better than the other models. From the results of TCFOKM, the fast sorption coefficient of naphthalene (k1) was in the order of silica > kaolin > natural soil, whereas the slow sorbing fraction (k2) was in the reverse order. Sorption isotherms of naphthalene were linear with organic carbon content (foc) in soils, while those of Triton X-100 were nonlinear and correlated with CEC and BET surface area. Sorption of Triton X-100 was higher than that of naphthalene in all soils. The effectiveness of a SER system depends on the distribution coefficient (KD) of naphthalene between mobile and immobile phases. In surfactant-sorbed soils, naphthalene was adsorbed onto the soil surface and also partitioned onto the sorbed surfactant. The partition coefficient (KD) of naphthalene increased with surfactant concentration. However, the KD decreased as the surfactant concentration increased above CMC in all soils. This indicates that naphthalene was partitioned competitively onto both sorbed surfactants (immobile phase) and micelles (mobile phase). For the mineral soils such as silica and kaolin, naphthalene removal by mobile phase would be better than that by immobile phase because the distribution of naphthalene onto the micelles (Kmic) increased with the nonionic surfactant concentration (Triton X-100). For the natural soil with relatively higher organic carbon content, however, the naphthalene removal by immobile phase would be better than that by mobile phase, because a high amount of Triton X-100 could be sorbed onto the natural soil and the sorbed surfactant also could sorb the relatively higher amount of naphthalene.
Lab-scale Electrodialysis(ED) system with different membranes combined with before or after pyroma process were carried out to remove nitrate from two pickling acid wastewater containing high concentrations of NO3-(≈150,000 mg/L) and F-(≈160,000 mg/L) and some heavy metals(Fe, Ti, and Cr). The ED system before Pyroma process(Sample A) was not successful in NO3- removal due to cation membrane fouling by the heavy metals, whereas, in the ED system after Pyroma process(Sample B), about 98% of nitrate was removed because of relatively low NO3- concentration (about 30,000 mg/L) and no heavy metals. Mono-selective membranes(CIMS/ACS) in ED system have no selectivity for nitrate compared to divalent-selective membranes(CMX/AMX). The operation time for nitrate removal time decreased with increasing the applied voltage from 10V to 15V with no difference in the nitrate removal rate between both voltages. Nitrate adsorption of a strong-base anion exchange resin of Cl- type was also conducted. The Freundlich model(R2 > 0.996) was fitted better than Langmuir model(R2 > 0.984) to the adsorption data. The maximum adsorption capacity (Q0) was 492 mg/g for Sample A and 111 mg/g for Sample B due to the difference in initial nitrate concentrations between the two wastewater samples. In the regeneration of ion exchange resins, the nitrate removal rate in the pickling acid wastewater decreased as the adsorption step was repeated because certain amount of adsorbed NO3- remained in the resins in spite of several desorption steps for regeneration. In conclusion, the optimum system configuration to treat pickling acid wastewater from stainless-steel industry is the multi-processes of the Pyroma-Electrodialysis-Ion exchange.