Daeseung Kyung

Effect of Organic Matters on CO2 Hydrate Formation in Ulleung Basin Sediment Suspensions

Marine sediment core samples collected from a gas hydrate deposit site (Ulleung Basin (UB), East Sea, Korea) were explored to identify the role of sediment organic matters (SOMs) on the formation of CO(2) hydrate. Two distinct CO(2) hydrate formation regimes (favorable (≤40 min) and unfavorable (>250 min)) were observed from the hydrate formation tests. CO(2) hydrate induction time in UB sediment suspensions was approximately seven times faster than that in UB sediment suspensions without SOMs (baked UB), showing a direct influence of SOMs. Spectrometric and spectroscopic analyses confirmed the existence of different types of SOMs including nonhumic and humic substances in UB sediment samples. We found SOMs with aromatic ring structures in all sediment extracts and SOMs with amine and amide groups and lignin in alkaline extracts. SOMs were extracted from UB sediment core samples (1 g each). Measured CO(2) hydrate induction times were different in baked UB sediment suspensions with different extracts of UB sediments. The experimental results demonstrated that SOMs can play a significant role to accelerate the formation of CO(2) hydrate in UB sediment suspensions, suggesting that the gas hydrate deposit site at UB may be a proper place for CO(2) sequestration as a form of CO(2) hydrate.

Effect of Organic Matter on CO2 Hydrate Phase Equilibrium in Phyllosilicate Suspensions

In this study, we examined various CO2 hydrate phase equilibria under diverse, heterogeneous conditions, to provide basic knowledge for successful ocean CO2 sequestration in offshore marine sediments. We investigated the effect of geochemical factors on CO2 hydrate phase equilibrium. The three-phase (liquid-hydrate-vapor) equilibrium of CO2 hydrate in the presence of (i) organic matter (glycine, glucose, and urea), (ii) phyllosilicates [illite, kaolinite, and Na-montmorillonite (Na-MMT)], and (iii) mixtures of them was measured in the ranges of 274.5-277.0 K and 14-22 bar. Organic matter inhibited the phase equilibrium of CO2 hydrate by association with water molecules. The inhibition effect decreased in the order: urea < glycine < glucose. Illite and kaolinite (unexpandable clays) barely affected the CO2 hydrate phase equilibrium, while Na-MMT (expandable clay) affected the phase equilibrium because of its interlayer cations. The CO2 hydrate equilibrium conditions, in the illite and kaolinite suspensions with organic matter, were very similar to those in the aqueous organic matter solutions. However, the equilibrium condition in the Na-MMT suspension with organic matter changed because of reduction of its inhibition effect by intercalated organic matter associated with cations in the Na-MMT interlayer.

Synergistic effect of nano-sized mackinawite with cyano-cobalamin in cement slurries for reductive dechlorination of tetrachloroethylene

Experiments were conducted to investigate the reductive dechlorination of tetrachloroethylene (PCE) by nano-Mackinawite (nFeS) with cyano-cobalamin (Cbl(III)) in cement slurries. Almost complete degradation of PCE by nFeS-Cbl(III) was observed in cement slurries in 5 h and its degradation kinetics (k(obs-PCE)=0.57 h(-1)) was 6-times faster than that of nFeS-Cbl(III) without the cement slurries. PCE was finally transformed to non-chlorinated organic compounds such as ethylene, acetylene, and C3-C4 hydrocarbons by nFeS-Cbl(III) in cement slurries. X-ray photoelectron spectroscopy and PCE degradation by cement components (SiO2, Al2O3, and CaO) revealed that both the reduced Co species in Cbl(III) and the presence of Ca in cement played an important role for the enhanced reductive dechlorination of PCE. The increase in the concentration of Cbl(III) (0.005-0.1 mM), cement ratio (0.05-0.2), and suspension pH (11.5-13.5) accelerated the PCE degradation kinetics by providing more favorable environments for the production of reactive Ca species and reduction of Co species. We also observed that the degradation efficiency of PCE by nFeS-Cbl(III)-cement lasted even at high concentration of PCE. The experimental results obtained from this study could provide fundamental knowledge of redox interactions among nFeS, Cbl(III), and cement, which could significantly enhance reductive dechlorination of chlorinated organics in contaminated natural and engineered environments.

Molecular identification of Cr(VI) removal mechanism on vivianite surface

Experimental and theoretical studies were conducted to identify the molecular-scale reaction mechanism for Cr(VI) removal by a ferrous phosphate mineral, vivianite. The surface-normalized rate constant for Cr(VI) removal in a vivianite suspension at pH 7 was higher than those obtained for other Fe(II)-containing minerals (i.e., magnetite and pyrite). The highest rate constant was obtained at pH 5, which was 35- and 264-times higher than those obtained at pH 7 and 9, respectively, indicating the dramatic acceleration of removal kinetics with decreasing pH of suspension. The X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) spectroscopy revealed that Cr(VI) removal involved reduction of Cr(VI) to Cr(III) coupled with oxidation of Fe(II) to Fe(III) on the vivianite surface. In addition, the density functional theory (DFT)-optimized structure of the Cr(VI)-vivianite complex was consistent with that obtained from extended X-ray absorption fine structure (EXAFS) spectroscopy and revealed the transformation of vivianite to amorphous Fe(III) phosphate. We also demonstrated that both Cr(VI) species, HCrO4̅ and CrO42-, can effectively bind to the vivianite surface, particularly on the Fe sites having 6 neighboring Fe molecules with 4 H2O and 2 PO4 moieties. Our results show that Cr(VI) is readily reduced to Cr(III) by vivianite via adsorption and inner-sphere complexation, suggesting that in anoxic iron-phosphate-enriched environments, vivianite may significantly influence the fate and transport of Cr(VI).