• Journal of Soil and Groundwater Environment
• /
• v.11 no.6
• /
• pp.35-42
• /
• 2006

Experimental study was conducted to identify the active agent for reductive dechlorination of TCE in cement/Fe(II) systems. Several potential materials-hematite (${\alpha}-Fe_2O_3$), lepidocrocite (${\gamma}$-FeOOH), akaganeite (${\beta}$-FeOOH), ettringite ($Ca_6Al_2(SO_4)_3(OH)_{12}$)-that are cement components or parts of cement hydrates were tested if they could act as reducing agents by conducting TCE degradation experiments. From the initial degradation experiments, hematite was selected as a potential active agent. The pseudo-first-order degradation rate constant ($k\;=\;0.637\;day^{-1}$) for the system containing 200 mM Fe(II), hematite and CaO was close to that ($k\;=\;0.645\;day^{-1}$) obtained from the system containing cement and 200 mM Fe(II). CaO, which was originally added to simulate pH of the cement/Fe(II) system, was found to play an important role in degradation reactions. The reactivity of the hematite/CaO/Fe(II) system initially increased with increase of CaO dosage. However, the tendency declined in the higher CaO dosage region, implying a saturation type of behavior. The SEM analysis revealed that the hexagonal plane-shaped crystals were formed during the reaction with increasing degradation efficiency, which was brought about by increasing the CaO dosage. It was suspected that the crystals could be portlandite or green rust ($SO_4$) or Friedel's salt. The XRD analysis of the same sample identified the peaks of hematite, magnetite/maghemite, green rust ($SO_4$). Either instrumental analysis predicted the presence of the green rust ($SO_4$). Therefore, the green rust ($SO_4$) would potentially be a reactive agent for reductive dechlorination in cement/Fe(II) systems.

• Membrane and Water Treatment
• /
• v.11 no.3
• /
• pp.207-215
• /
• 2020

Vivianite (Fe₃²⁺(PO₄)2·8H₂O) and green rust ([Fe₄²⁺Fe₂³⁺(OH)^-₁₂][SO₄^2-·2H₂O]^2-), ferrous containing minerals, could remove aqueous U(VI) in 5 min. and the efficiencies of green rust were roughly 2 times higher than that of vivianite. The zeta potential measurement results implies that the better performance of green rust might be attributed to the favorable surface charge toward uranyl phosphate species. The removal behaviors of the minerals were well fitted by pseudo-second order kinetic model (R² > 0.990) indicating the dominant removal process was chemical adsorption. Effects of Ca²⁺ and CO₃^2- at pH 7 were examined in terms of removal kinetic and capacity. The kinetic constants of aqueous U(VI) were 8 and 13 times lower (0.492 × 10^-3 g/(mg·min); 0.305 × 10^-3 g/(mg·min)) compared to the value in the absence of the ions. The thermodynamic equilibrium calculation showed that the stable uranyl species (uranyl tri-carbonate) were newly formed at the condition. Surface investigation on the reacted mineral with uranyl phosphates species were carried out by XPS. Ferrous iron and U(VI) on the green rust surface were completely oxidized and reduced into Fe(III) and U(IV) after 7 d. It suggests that the ferrous minerals can retard U(VI) migration in phosphate-rich groundwater through the adsorption and subsequent reduction processes.

• Korean Journal of Mineralogy and Petrology
• /
• v.35 no.2
• /
• pp.111-123
• /
• 2022

Carbonate green rust (CGR) and sulfate green rust (SGR) commonly occur in nature. In this study, CGR and SGR were synthesized through co-precipitation, and their formation mechanisms and physicochemical properties were investigated. X-ray diffraction (XRD) and Rietveld refinement showed both CGR and SGR with layered double hydroxide structure were successfully synthesized without any secondary phases under each synthetic condition. Refined structural parameters (unit cell) for two green rusts were a (=b) = 3.17 Å and c = 22.52 Å for CGR and a (=b) = 5.50 Å and c = 10.97 Å for SGR with the crystallite size 57.8 nm in diameter from (003) reflection and 40.1 nm from (001) reflections, respectively. Scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) results showed that both CGR and SGR had typical hexagonal plate-like crystal morphologies but their chemical composition is different in the content of C and S. In addition, Fourier transform infrared (FT-IR) spectroscopy analysis revealed that carbonate (CO₃^2-) and sulfate (SO₄^2-) molecules were occupied as interlayer anions of CGR and SGR, respectively. These SEM/EDS and FT-IR results were in good agreement with XRD results. Changes in the solution chemistry (i.e., pH, Eh and residual iron concentrations (Fe(II):Fe(III)) of the mixed solution) were observed as a function of the injection time of hydroxyl ion (OH^-) into the iron solution. Three different stages were observed in the formation of both CGR and SGR; precursor, intermediator, and green rust in the formation of both CGR and SGR. This study provides co-precipitation methods for CGR and SGR in a way of the stable synthesis. In addition, our findings for the formation mechanisms of the two green rusts and their physicochemical properties will provide crucial information with researches and industrials in utilizing green rust.

• Korean Journal of Metals and Materials
• /
• v.47 no.9
• /
• pp.558-566
• /
• 2009

The alloying effect of a small amount of nickel on low alloy steel for application to flue gas desulfurization(FGD) systems was studied. The structural characteristics of the rust layer were investigated by scanning electron microscopy(SEM). The electrochemical properties were examined by means of potentiostatic polarization test, potentiodynamic polarization test, and electrochemical impedance spectroscopy(EIS) in a modified green death solution of 16.9 vol.% $H_2SO_4$+0.35 vol.% HCl at $60^{\circ}C$ and an acid rain solution of $6.25{\times}10^{-5}M\;H_2SO_4+5.5{\times}10^{-3}M\;NaCl$ at room temperature. It was found that as the amount of nickel increased, the corrosion rate increased in the modified green death solution, which seemed to result from micro-galvanic corrosion between NiS and alloy matrix. In acid rain solution, the corrosion rate decreased as the amount of nickel increased due to the repulsive force of $NiFe_2O_4$ rust against $Cl^-$ ions by electronegativity.

• Journal of Korean Society of Environmental Engineers
• /
• v.29 no.7
• /
• pp.778-782
• /
• 2007

This study investigated the dechlorination mechanisms of TCE by Fe(II) associated with cement. Batch slurry experiments were peformed to investigate the behaviors of selected ions; Fe(II), Fe(III), $Ca^{2+}$, $SO_4^{2-}$ in cement/Fe(II) system. The kinetic experiments of TCE in cement/Fe(II) systems showed that injected Fe(II) was mostly sorbed on cement within 0.5 day and 90% of injected 200 mM sulfate was sorbed on cement within 0.5 day when $[TCE]_0$ = 0.25 mM and $[Fe(II)]_0$ = 200 mM. The kinetic experiments of TCE in hematite/CaO/Fe((II) systems were conducted for simulation of cement/Fe(II) system. Calcium oxide that is one of the major components in cement hydration reactions or has a reactivity in limited conditions. Hematite assumed the ferric iron oxide component of cement. The reactivities observed in hematite/CaO/Fe(II) system were comparable to those reported for cement/Fe(II) systems containing similar molar amounts of Fe(II). The behavior of Fe(II) and $SO_4^{2-}$ sorbed on solid phase at an early stage of reaction in hematite/CaO/Fe(II) system was similar to that of cement/Fe(II) system. Ferric ion was released from hematite at an early period of reaction at low pH. The experimental evidence of kinetic test using hematite/CaO/Fe(II) system implies that the reactive reductant is a mixed-valent Fe(II)-Fe(III) mineral, which may be similar to green rust. Fe(II) sorbed on cement can be converted to new mineral phase having a reactivity such as Fe(II)-Fe(III) (hydr)oxides in cement/Fe(II) systems.