Prediction of Cd toxicity to Daphnia magna in the mixture of multi-walled carbon nanotubes and kaolinite

In this study, we investigated cadmium toxicity created by adsorption kinetics in several mixtures containing two types of multi-walled carbon nanotubes (COOH-MWCNT and NH₂-MWCNT) and natural kaolinite. Characteristics of two types of MWCNTs were measured by zeta potential and ATR FT-IR graphs and TEM images. The solution of CNTs and kaolinite was tested to study Cd adsorption kinetics and mechanisms of differentiation-associated toxicity using Daphnia magna in a binary system (Cd–MWCNTs and Cd–kaolinite) and a ternary system (Cd–MWCNTs–kaolinite). In the binary system, Cd removal efficiency was nearly 100% and 40% for MWCNTs and kaolinite because of surface charge, respectively, with increasing sorbent concentration. In the ternary system, the trend of adsorption rate was similar to that of binary system. In comparison with percent mortality in the binary system, the solution in the ternary system showed higher toxicity due to the interaction of MWCNTs–kaolinite coagulated particles, thereby decreasing Cd adsorption onto CNTs and kaolinites. Overall, kaolinite can affect the adsorption process of Cd on MWCNTs in negative ways, depending on adsorption state. In conclusion, our studies suggest that kaolinite differs with adsorption ability of Cd by MWCNTs, and toxicity is likely to be produced by multivariable regression in the adsorption state.

     

Simulating the Sorptive Removal of Dissolved Copper by Biocarrier Beads

Biocarrier beads containing the dead biomass of Bacillus drentensis immobilized in polymer polysulfone were synthesized in order to remove heavy metals from wastewater. A series of batch experiments were carried out to identify the sorption mechanisms and the theoretical nature of the underlying processes. A mathematical model was developed to simulate the fate and transport of copper ions in a saturated fixed bed packed with biocarrier beads. Mass balance equations were established to represent the migration and distribution of metal ions in the biocarrier beads and the surrounding bulk liquid. Numerical experiments were performed using the proposed model for quantitative analysis of the temporal changes in the distribution of copper ions in and around the biocarrier beads in a fixed bed. The simulation results show that the biosorption of heavy metals by the biocarrier beads depends largely on surface adsorption. A sensitivity analysis was carried out on the major design parameters in a fixed bed. The effects of bed height, flow velocity, and influent concentration were examined by assessing a simulated breakthrough curve. The breakthrough time occurs earlier for a decreasing bed height and increasing flow velocity and influent Cu(II) concentration, whereas the slope at 50 % breakthrough becomes steeper as the flow velocity increases and the influent concentration decreases. The simulation results show that the proposed mathematical model can provide a quantitative analysis of the distribution of metal adsorbate in and around porous particulate adsorbents in a fixed bed and that it can be used as an effective predictive tool.     

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.     

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.     

Soil washing of As-contaminated stream sediments in the vicinity of an abandoned mine in Korea

A soil washing process was applied to remediate arsenic (As)-contaminated stream sediments around an abandoned mine in Goro, Korea. Laboratory scale soil washing experiments for As-contaminated stream sediments were performed under various washing conditions in order to maximize As removal efficiency. Stream sediments were taken from two sites (S1 and S5) along the main stream connected to an abandoned mine. Stream sediments at the two sites were divided into two groups (≥0.35 and <0.35 mm in diameter), giving four types of sediments, which were thereupon used for soil washing experiments. The results of soil washing experiments involving various pH conditions suggested that As removal efficiency is very high in both strongly acidic and basic solutions (pH 1 and 13), regardless of sediment type. Removal efficiencies for fine sediments from S1 and S5 were >95% after 1 h of washing with 0.2 M citric acid (C₆H₈O₇). When using 0.2 M citric acid mixed with 0.1 M potassium phosphate (KH₂PO₄), the As removal efficiency increased to 100%. When recycled washing solution was applied, As removal efficiency was maintained at a level greater than 70%, even after eight recycling events. This suggests that the recycling of washing solution could be successfully applied as a means of decreasing the cost of the washing process. Results from the experiments suggest that soil washing is a potentially useful process for the remediation of As-contaminated stream sediments around abandoned mines.     

Implication of hydraulic properties of bioremediated diesel-contaminated soil

The hydraulic properties, such as hydraulic conductivity and water retention, of aged diesel-contaminated and bioremediated soils were examined and implications of the hydraulic properties for assessing bioremediation performance of soils were proposed. Bioremediation of diesel-contaminated soil was performed over 80 d using three treatments; (I) no nutrient added, column-packed soil, (II) nutrient added, column-packed soil, and (III) nutrient added, loosen soil. Diesel reduction in treatment I soil (control soil) was negligible while treatment III showed the greatest extent of diesel biodegradation. All treatments showed greatest rates of diesel biodegradation during the first 20 d, followed by a much retarded biodegradation rate in the remaining incubation period. Reduction of the degradation rate due to entrained diesel within inaccessible soil pores was hypothesized and tested by measuring the hydraulic properties of two column-packed soils (treatments I and II). The hydraulic conductivity of treatment II soil (nutrient added) was consistently above that of treatment I soil (no nutrient added) at pressure heads between 0 and 15 cm. In addition, the water retention of treatment II soil was greater at pressure heads <100 cm (equivalent to pore size of >30 microm), suggesting that biodegradative removal of hydrocarbons results in enhanced wettability of larger soil pores. However, water retention was not significantly different for control and biodegraded soils at pressure heads >100 cm, where smaller size soil pores were responsible for the water retention, indicating that diesel remained in smaller soil pores (e.g., <30 microm). Both incubation kinetics and hydraulic measurements suggest that hydrocarbons located in small pores with limited microbe accessibility may be recalcitrant to bioremediation.     

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 (CaCl(2) 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 CaCl(2) 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.