Effects of Calcium on TCE Degradation Reaction in Cement/Fe(II) and Hematite/Fe(II) Systems

doi:10.7857/JSGE.2011.16.1.082

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2011 Vol.16, Issue 1 Preview Page

Effects of Calcium on TCE Degradation Reaction in Cement/Fe(II) and Hematite/Fe(II) Systems 시멘트/Fe(II) 및 hematite/Fe(II) 시스템의 TCE 분해반응 시 Ca 성분의 영향: 김홍석;황경엽;안준영;이주영;황인성;
Kim, Hong-Seok;Hwang, Kyung-Yup;Ahn, Jun-Young;Yi, Jou-Young;Hwang, In-Seong;

28 February 2011. pp. 82 ~ 90

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Abstract

Reactive reductants of cement/Fe(II) systems in dechlorinating chlorinated hydrocarbons have not been identified. The previous studies showed that a hematite/CaO/Fe(II) system had TCE degradation characteristics similar to those of cement/Fe(II) systems with regard to degradation kinetics and that lime (CaO) plays an important role in enhancing the reactivity for TCE dechlorination. The current study shows identified the formation of gypsum ($CaSO_4$) in the hematite/CaO/$FeSO_4$ system through the XRD analysis. The amounts of the gypsum increased with increment of the initial CaO dose. However, when CaO in the hematite/CaO/$FeSO_4$ system was replaced with gypsum, TCE degradation was not observed. Ca-removed Portland cement extracts (CPCX) in combination with $FeSO_4(CPCX/FeSO_4)$ showed no TCE degradation. On the other hands, the Portland cement extracts (PCX) in the presence of $FeSO_4(PCX/FeSO_4)$ and CPCX/CaO/$FeSO_4$ systems degraded 0.2 mM TCE within 5 days, indicating that CaO also played an important role dechlorination reactions in the systems. The pseudo-first-order rate constants (k) of the CPCX/CaO/$FeSO_4$ systems were 0.20, 0.24, and 0.72 $day^{-1}$, when the CaO dosages were 25, 50 and 75 g/L, respectively. The XRD analyses showed identified the common peaks having the d-values of 3.02, 2.27, and 1.87 in the reaction systems that showed TCE degradation. However, it was not possible to clearly identify the crystalline minerals having the three peaks from the references in JCPDS cards. This study reveals that the reactive agents in the cement/Fe(II) and the hematite/Fe(II) systems are likely to be those containing CaO and Fe(II).

Keywords

Cement;Hematite;Fe(II);CaO;TCE;Reductive dechlorination;

References

김정배, 2000, 황화철을 이용한 할로겐 화합물의 탈염소화 반응에 관한 연구, J. Nakdongkang Environ. Res. Institute, 5(1), 19-31.
환경부, 2008, 2007 전국 지하수 수질측정망 운영결과.
환경부, 1998, 유해폐기물의 안정화/고형화 처리기술.
Butler, E.C. and Kim, F.H., 2001, Factors influencing rates and products in the transformation of trichloroethylene by iron sulfide and iron metal, Environ. Sci. Technol., 35, 3884-3891.10.1021/es010620f
Casanova, P.L., Cwiertny, D.M., and Scherer, M.M., 2010, Nanogoethote formation from oxidation of Fe(II) sorbed on aluminum reduction. Environ. Sci. Technol., 44, 3765-3771.10.1021/es903171y
Charlet, L., Silvester, E., and Liger, E., 1998, N-compound reduction and actinide immobilization in surficial fluid by Fe(II): the surface$\equiv$FeIIIOFeIIOH0 species, as major reductant, Chemical Geology, 151, 85-93.10.1016/S0009-2541(98)00072-2
Elsner, M., Schwarzenbach, R., and Haderlein, S., 2004, Reactivity of Fe(II)-bearing minerals toward reductive transformation of organic contaminants, Environ. Sci. Technol., 38, 799-807.10.1021/es0345569
Kim, H.S., Kang, W.H., Kim, M, Park, J.Y., and Hwang, I., 2008, Comparison of Hematite/Fe(II) Systems with Cement/Fe(II) Systems in Reductively Dechlorinating Trichloroethylene, Chemosphere, 73, 813-816.10.1016/j.chemosphere.2008.04.092
Ko, S., 2005, Identification of active agents for tetrachloroethylene degradation in Portland cement slurry containing ferrous iron, Ph.D. Dissertation, Texas A&M University.
Ko, S. and Batchelor, B., 2007, Identification of active agents for tetrachloroethylene degradation in portland cement slurry containing ferrous iron. Environ. Sci. Technol., 41, 5824-5832.10.1021/es070361f
Handler, R.M., Beard, B.L., Johnson, C.M., and Scherer, M.M., 2009, Atom exchange between aqueous Fe(II) and goethite : An Fe isotope tracer study, Environ. Sci. Technol., 43, 1102-1107.10.1021/es802402m
Hwang, I. and Batchelor, B., 2000, Reductive dechlorination of tetrachloro- ethylene by Fe(II) in cement slurries, Environ. Sci. Technol., 34, 5017-5022.10.1021/es991377b
Hwang, I. and Batchelor, B., 2001, Reductive dechlorination of tetrachloroethylene in soils by Fe(II) based degradative solidification/stabilization, Environ. Sci. Technol., 35, 3792-3797.10.1021/es010619g
Hawang, I. and Batchelor, B., 2002, Reductive dechlorination of chlorinated methanes in cement slurries containing Fe(II), Chemosphere, 48(10), 1019-1027.10.1016/S0045-6535(02)00152-2
Hwang, I., Batchelor, B., Schlautman, M.A., and Wang, R., 2002, Effects of ferrous iron and molecular oxygen on chromium(IV) redox kinetics in the presence of aquifer solids, J. Hazard. Mater., 92(2), 143-159.10.1016/S0304-3894(02)00006-7
Kang, W.H., 2006, Reductive dechlorination of chlorinated ethylenes using cement and steel slag amended with Fe(II), Ph.D. Dissertation, Hanyang University, Seoul, Korea, p. 186.
Kim, S.D., Park, K.S., and Gu., M.B., 2002, Toxicity of hexavalent chromium to daphnia magma: influence of reduction reaction by ferrous iron, J. Hazard. Mater., A93, 155-164.10.1016/S0304-3894(02)00057-2
Taylor, H.F.W., 1997, Cement chemistry 2nd ed., Thomas, London, England.

Information

Publisher :The Korean Society of Soil and Groundwater Environment
Publisher(Ko) :한국지하수토양환경학회
Journal Title :Journal of Soil and Groundwater Environment
Journal Title(Ko) :지하수토양환경
Volume : 16
No :1
Pages :82 ~ 90
DOI :https://doi.org/10.7857/JSGE.2011.16.1.082

[1] 김정배, 2000, 황화철을 이용한 할로겐 화합물의 탈염소화 반응에 관한 연구, J. Nakdongkang Environ. Res. Institute, 5(1), 19-31.

[2] 환경부, 2008, 2007 전국 지하수 수질측정망 운영결과.

[3] 환경부, 1998, 유해폐기물의 안정화/고형화 처리기술.

[4] Butler, E.C. and Kim, F.H., 2001, Factors influencing rates and products in the transformation of trichloroethylene by iron sulfide and iron metal, Environ. Sci. Technol., 35, 3884-3891.10.1021/es010620f

[5] Casanova, P.L., Cwiertny, D.M., and Scherer, M.M., 2010, Nanogoethote formation from oxidation of Fe(II) sorbed on aluminum reduction. Environ. Sci. Technol., 44, 3765-3771.10.1021/es903171y

[6] Charlet, L., Silvester, E., and Liger, E., 1998, N-compound reduction and actinide immobilization in surficial fluid by Fe(II): the surface$\equiv$FeIIIOFeIIOH0 species, as major reductant, Chemical Geology, 151, 85-93.10.1016/S0009-2541(98)00072-2

[7] Elsner, M., Schwarzenbach, R., and Haderlein, S., 2004, Reactivity of Fe(II)-bearing minerals toward reductive transformation of organic contaminants, Environ. Sci. Technol., 38, 799-807.10.1021/es0345569

[8] Kim, H.S., Kang, W.H., Kim, M, Park, J.Y., and Hwang, I., 2008, Comparison of Hematite/Fe(II) Systems with Cement/Fe(II) Systems in Reductively Dechlorinating Trichloroethylene, Chemosphere, 73, 813-816.10.1016/j.chemosphere.2008.04.092

[9] Ko, S., 2005, Identification of active agents for tetrachloroethylene degradation in Portland cement slurry containing ferrous iron, Ph.D. Dissertation, Texas A&M University.

[10] Ko, S. and Batchelor, B., 2007, Identification of active agents for tetrachloroethylene degradation in portland cement slurry containing ferrous iron. Environ. Sci. Technol., 41, 5824-5832.10.1021/es070361f

[11] Handler, R.M., Beard, B.L., Johnson, C.M., and Scherer, M.M., 2009, Atom exchange between aqueous Fe(II) and goethite : An Fe isotope tracer study, Environ. Sci. Technol., 43, 1102-1107.10.1021/es802402m

[12] Hwang, I. and Batchelor, B., 2000, Reductive dechlorination of tetrachloro- ethylene by Fe(II) in cement slurries, Environ. Sci. Technol., 34, 5017-5022.10.1021/es991377b

[13] Hwang, I. and Batchelor, B., 2001, Reductive dechlorination of tetrachloroethylene in soils by Fe(II) based degradative solidification/stabilization, Environ. Sci. Technol., 35, 3792-3797.10.1021/es010619g

[14] Hawang, I. and Batchelor, B., 2002, Reductive dechlorination of chlorinated methanes in cement slurries containing Fe(II), Chemosphere, 48(10), 1019-1027.10.1016/S0045-6535(02)00152-2

[15] Hwang, I., Batchelor, B., Schlautman, M.A., and Wang, R., 2002, Effects of ferrous iron and molecular oxygen on chromium(IV) redox kinetics in the presence of aquifer solids, J. Hazard. Mater., 92(2), 143-159.10.1016/S0304-3894(02)00006-7

[16] Kang, W.H., 2006, Reductive dechlorination of chlorinated ethylenes using cement and steel slag amended with Fe(II), Ph.D. Dissertation, Hanyang University, Seoul, Korea, p. 186.

[17] Kim, S.D., Park, K.S., and Gu., M.B., 2002, Toxicity of hexavalent chromium to daphnia magma: influence of reduction reaction by ferrous iron, J. Hazard. Mater., A93, 155-164.10.1016/S0304-3894(02)00057-2

[18] Taylor, H.F.W., 1997, Cement chemistry 2nd ed., Thomas, London, England.

Journal of Soil and Groundwater Environment ISSN:1598-6438(Print) 2287-8831(Online) 지하수토양환경

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