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Frontiers of Environmental Science & Engineering

Front. Environ. Sci. Eng.    2015, Vol. 9 Issue (5) : 939-947     https://doi.org/10.1007/s11783-015-0807-9
RESEARCH ARTICLE
Iron-carbon composite microspheres prepared through a facile aerosol-based process for the simultaneous adsorption and reduction of chlorinated hydrocarbons
Bhanukiran SUNKARA1,Yang SU1,Jingjing ZHAN1,Jibao HE3,Gary L. MCPHERSON3,Vijay T. JOHN1,*()
1. Department of Chemical and Biomolecular Engineering, Tulane University, New Orleans, LA 70118, USA
2. Coordinated Instrumentation Facility, Tulane University, New Orleans, LA 70118, USA
3. Department of Chemistry, Tulane University, New Orleans, LA 70118, USA
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Abstract

Iron-carbon (Fe-C) composite microspheres prepared through a facile aerosol-based process are effective remediation agents for the simultaneous adsorption and reduction of chlorinated hydrocarbons. Complete dechlorination was achieved for the class of chlorinated ethenes that include tetrachloroethylene (PCE), trichloroethylene (TCE), cis- and trans-1,2-dicloroethylene (c-DCE, t-DCE), 1,1-dichloroethylene (1,1-DCE) and, vinyl chloride (VC). The Fe-C particles potentially provides multi-functionality with requisite characteristics of adsorption, reaction, and transport for the effective in situ remediation of chlorinated hydrocarbons. The carbon support immobilizes the ferromagnetic iron nanoparticles onto its surface, thereby inhibiting aggregation. The adsorptive nature of the carbon support prevents the release of toxic intermediates such as the dichloroethylenes and vinyl chloride. The adsorption of chlorinated ethenes on the Fe-C composites is higher (>80%) than that of humic acid (<35%) and comparable to adsorption on commercial activated carbons (>90%). The aerosol-based process is an efficient method to prepare adsorptive-reactive composite particles in the optimal size range for transport through the porous media and as effective targeted delivery agents for the in situ remediation of soil and groundwater contaminants.

Keywords chlorinated ethene      iron-carbon      aerosol      adsorption      reductive dechlorination     
Corresponding Author(s): Vijay T. JOHN   
Online First Date: 20 July 2015    Issue Date: 12 October 2015
 Cite this article:   
Yang SU,Jingjing ZHAN,Jibao HE, et al. Iron-carbon composite microspheres prepared through a facile aerosol-based process for the simultaneous adsorption and reduction of chlorinated hydrocarbons[J]. Front. Environ. Sci. Eng., 2015, 9(5): 939-947.
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http://journal.hep.com.cn/fese/EN/10.1007/s11783-015-0807-9
http://journal.hep.com.cn/fese/EN/Y2015/V9/I5/939
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Yang SU
Jingjing ZHAN
Jibao HE
Gary L. MCPHERSON
Bhanukiran SUNKARA
Vijay T. JOHN
Fig.1  (a) Schematic showing the aerosol process for composite particles synthesis and (b) schematic of reaction in an aerosol droplet
Fig.2  (a) SEM (b) TEM and (c) High resolution TEM of Fe-C composite particles prepared by the aerosol-based process. The inset in Fig. 2(a) is the single particle SEM of the Fe-C composite
chlorinated ethylene abbreviation, formula kobs (apparent reaction rate constant) /h−1 km,obs (mass-normalized reaction rate constant) /(L·h−1·g−1)
tetrachloroethene PCE, C2Cl4 0.895 0.358
trichloroethene TCE, C2HCl3 1.101 0.441
1,2-dichloroethene (mixture of cis- and trans-) 1,2-DCE, C2H2Cl2 1.145 0.458
1,1-dichloroethene 1,1-DCE, C2H2Cl2 1.328 0.531
vinyl chloride VC, C2H3Cl 2.4709 0.988
Tab.1  Observed overall reaction rate constants for reduction of the various chlorinated ethenes using the aerosol-based Fe-C composite particles
Fig.3  Representative headspace analyses using gas chromatography showing (a) PCE and (b) TCE degradation and reaction product evolution at various reaction times
Fig.4  (a) PCE and (b) TCE removal from solution and gas product evolution rates for Fe-C composites. M/M0 is the fraction of the original chlorinated ethylene remaining and P/Pf is the ratio of the gas product peak to the gas product peak at the end of reaction. The initial sharp decrease of the chlorinated ethylene (PCE, TCE) peak is due to the strong adsorption of carbon in the Fe-C composite. The subsequent slow evolution of gas phase dechlorination products indicates that the dechlorination of the chlorinated ethene is responsible for the second, slower step in the coupled adsorption and reaction sequence. km,obs is the mass normalized rate constant based on the mass of zerovalent iron
Fig.5  Reaction kinetics of the intermediate chlorinated ethenes (a) 1,2-DCE, (b) 1,1-DCE, and (c) VC. M/M0 is the fraction of the original chlorinated ethene remaining and P/Pf is the ratio of the gas product peak to the gas product peak at the end of reaction. The initial sharp decrease of the chlorinated ethene (1,2-DCE, 1,1-DCE and VC) peak is due to the strong adsorption of carbon in the Fe-C composite. The subsequent slow evolution of gas phase dechlorination products indicates that the dechlorination of the chlorinated ethene is responsible for the second, slower step in the coupled adsorption and reaction sequence. km,obs is the mass normalized rate constant based on the mass of zerovalent iron
Fig.6  Comparison of adsorption capacities of humic acid, Fe salt-C from the aerosol-based process and commercial activated carbon. In all experiments, 20 mL of a 20 ppm chlorinated ethylene ((a) PCE, (b) TCE, (c) 1,2-DCE, (d) 1,1-DCE, and (e) VC) solution and 0.2g of particles were used. The adsorption capacity was measured 5 min after the addition of particles to the chlorinated ethene solution. The results show that the adsorption of chlorinated ethenes on aerosol based iron-carbon composites is higher than that of humic acid and is comparable to the adsorption on commercially available granular and irregularly defined activated carbons
chlorinated ethene partition coefficient (Kp) aerosol Fe salt-C
tetrachloroethylene 898
trichloroethylene 1897
cis- 1,2-dichloroethylene 5927
trans- 1,2-dichloroethylene 3057
1, 1-dichloroethylene 4536
vinyl chloride 145
Tab.2  Calculated partition coefficient of chlorinated hydrocarbons adsorption on aerosol-based Fe salt-C composites
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