The Suitability of Metallic Iron for Environmental Remediation

Chicgoua Noubactep t Go ttingen, Goldschmidtstrae 3, D-37077 Go ttingen, Germany; cnoubac@gwdg.de Angewandte Geologie, Universita (for correspondence)
Published online 19 November 2009 in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ep.10406

Aqueous contaminant removal in the presence of metallic iron is often regarded as a reductive transformation mediated by the Fe0 surface. However, successful removal of theoretically nonreducible contaminants has been largely reported. This article presents a rebuttal of the concept of contaminant reductive transformation. It is argued through a careful examination of the evolution of the volume and adsorptive properties of iron and its corrosion products that contaminants are primarily adsorbed and coprecipitated with iron corrosion products. One may wonder how the Fe0 technology will develop with the new concept.
2009 American Institute of Chemical Engineers Environ Prog, 29: 286291, 2010

Keywords: adsorption, co-precipitation, contaminant, removal, zerovalent iron

INTRODUCTION

In 1990 Canadian hydrogeologists have rediscovered iron corrosion as metallic iron (Fe0) became a remediation agent for contaminated aquifers, soils, and waters. It was fortuitously found that Fe0 eliminated trichloroethylene from aqueous solutions [13]. Since then intensive efforts have been devoted to remediation with Fe0 materials. As result Fe0 is now regarded as a very competent reactive agent for remediation of systems that are contaminated with reducible substances (including chlorinated hydrocarbons, nitrate, nitro aromatics, chromium, uranium) [48]. The rediscovery of iron corrosion was followed by a seminal work on the mechanism of aqueous contaminant removal in the presence of Fe0 (e.g. in Fe0/ H2O systems) [9]. These authors proposed three possible mechanisms for contaminant removal: (1) contaminant adsorption onto the surface of in situ formed corrosion products, (2) contaminant reduction by Fe0 (direct reduction), (3) contaminant reduction by FeII
2009 American Institute of Chemical Engineers

or H2/H (indirect reduction). The work of Matheson and Tratnyek [9] was reevaluated by Weber [10] and the results indicate that (1) direct reduction (electrons from Fe0) is the major reaction pathway, and (2) reductive transformation by Fe0 is a surface-mediated process. Accordingly, the involved contaminant must contact the Fe0 surface for electron transfer to take place. Alternatively, the oxide lm on Fe0 must be electronic conductive or the system must contain appropriate electron mediators (so-called electron shuttles). Since the work of Weber [10] the know-why of contaminant removal in Fe0/H2O systems was considered to be achieved and the iron/sand mixture lost his nickname of magic sand [2]. However, the acceptance of the concept of reductive transformation was primarily a consensus [4] as this concept failed to consistently explained many experimental facts [1114]. For example, while using differential pulse polarography to investigate the reduction of nitrobenzene in Fe0/H2O systems, Lavine et al. [11] concluded that their studies were very informative but they couldnt evidence reduction of organic compounds as mediated by the Fe0 surface. Similarly, a very recent work of Jiao et al. [14] has shown that the reduction of carbon tetrachloride in the presence of Fe0 is primarily mediated by adsorbed H from iron corrosion (indirect reduction). Moreover, the quantitative removal for nonreducible species as methylene blue [15], triazoles [16] and zinc [17] in Fe0/H2O systems has been reported. Because of the inconsistency of the consensus on the mechanism of contaminant removal in Fe0/ H2O systems, it was pertinent to reconsider the Fe0/ H2O system as a whole. For this purpose it is necessary to go back to the literature on metal corrosion.
FUNDAMENTAL ASPECTS OF AQUEOUS METAL CORROSION

Most metals (M) in their natural state are not pure metals (M0), but are in the form of metallic salts (mostly oxidesMxOy, sulphidesMxSy, and carbo-

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natesMx(CO3)y). When these metal ores are rened or smelted, a losing battle with thermodynamics begins with the metal tending toward formation of metallic oxides, sulphides, or carbonates depending on the working environment [1820]. The rate and the extent at which a metal dissolves in an aqueous environment (immersed metal corrosion) depends on many interdependant factors [18, 21, 22] including: (1) the chemistry of water (pH, salinity, and concentration of chelating agents), (2) the nature of the oxide layer formed by initial metal corrosion (composition, electronic conductivity, porosity, and thickness), (3) the manufacturing history of the metal (e.g. whether the metal been cast, forged, wrought, or welded), and (4) the metal thermodynamic susceptibility to oxidation (position on the reduction-potential scale). It has been established that the most important factor responsible for immersed metal corrosion under conditions pertinent to natural waters (4.5 pH 9.5) is the electronic conductivity and the porosity of the oxide layer [23]. This statement will be supported by a classical example. Aluminium (E0 5 21.71 V) is more susceptible to oxidation than iron (E0 5 20.44 V) but Al is known to be relatively inert to atmospheric and aqueous corrosion, whereas Fe is very corrosive. There are two main reasons for this. First, the oxidation of Al0 exclusively yields a nonconductive layer of Al2O3 whereas the oxidation of Fe0 may yield a conductive layer of FeII/FeIII species (e.g. Fe3O4, green rust) [24]. Accordingly an oxide lm on Fe0 may act as a semiconductor and mediate electron transfer from Fe0 [2527]. In this situation Fe0 corrosion continues despite the presence of the oxide lm. It is evident, that this behaviour can not be observed under oxic conditions where FeII is instable and (at least) the outer layer of the oxide lm will exclusively consist of nonconductive FeIII oxides (FeOOH or Fe2O3). Second, the unit-cell in Al and Al2O3 are very similar to one another; thus the aluminium oxide can adhere tightly to the metallic aluminium beneath it [23]. The oxidized surface provides a protective layer that prevents oxygen from getting to the underlying Al surface. In contrast, the packing dimensions of Fe Fe0 and Fe oxides are not particularly close; thus there is no tendency for an iron oxide layer to adhere to metallic iron. Therefore, regarding its protective properties for iron corrosion, the curse of rust [23] is not that it forms, but that it constantly akes off and exposes fresh iron surface for attack [23, 24]. This curse of rust became a blessing in using Fe0 for environmental remediation.
METALLIC IRON FOR ENVIRONMENTAL REMEDIATION

waters [310]. This consideration is not acceptable even from a pure thermodynamic perspective as the electrode potential of iron is almost the same (about 20.44 V) in low alloyed and stainless steels (Fe-based alloys). Accordingly, various Fe0 materials should have exhibited similar behaviour for the removal of the same species. This has not been the case as for example Miehr et al. [28] reported variation of rate constants for contaminant removal varying over up to four orders of magnitude due to differences in Fe0 type. Fe0 materials for environmental remediation are primarily susceptible to oxidation, complete passivation can only result from the transformation of initially nonprotective lms to impervious layers under specic environmental conditions. Therefore, a sake for an overview of factors likely to inuence lm formation and transformation (stability and breakdown) under environmental conditions should be undertaken. This could be a very difcult task because chemical breakdown occurs when the lm is dissolved (e.g. by a chelating agent) or penetrated chemically (e.g. by a contaminant or Cl ions).
FUNDAMENTAL ASPECTS OF CONTAMINANT REMOVAL IN Fe0/H2O SYSTEMS

Fe-based alloys (Fe0 materials, mostly cast iron and steel) are certainly suitable for environmental remediation because of their low tendency to passivity due to the porosity and the instability of generated oxide layers. Instead of this trivial reason, Fe0 has been considered as a strong reducing agent for the reductive transformation of several species in natural

While considering Fe0 as a reducing agent for contaminant reductive transformation it has been impossible to explain several experimental and eld observations as recalled above (also see Refs. 29 and 30). The main reason for this is that iron corrosion products (oxide lm) have been regarded as simple coatings, mediating at most electron transfer from Fe0 to the contaminant. However, the oxide lm formation and transformation (recrystallization, dissolution, and precipitation) is a dynamic process occurring in the presence of contaminants. Moreover, the oxide lm formation can be regarded as the process of iron precipitation [3133]. Here, iron precipitation occurs in the presence of small amounts of foreign species (including contaminants). These foreign species are necessarily sequestrated within the oxide lm as discussed in the next section [34]. In this manner contaminants are primarily removed from the aqueous phase by a nonspecic mechanism as they are just sequestrated in the matrix of precipitating iron oxides [33]. This process is widely used in water treatment by electrocoagulation using Fe electrodes (Fe0 EC) [35, 36] and explains why bacteria, viruses, and thermodynamically nonreducible substances (e.g. Zn) have been quantitatively removed in Fe0/H2O systems. There are two main differences between passive Fe0/H2O systems and iron electrocoagulation: (1) Fe0 oxidation is electrically accelerated in Fe0 EC as the aim is to quantitatively produce iron hydroxides for contaminant removal by occulation, and (2) while contaminants are occulated from the bulk solution in Fe0 EC, they are precipitated in the vicinity of Fe0 in passive Fe0/H2O systems. Accordingly a passive Fe0/H2O system could be regarded as a lter (working on the principle of size exclusion) in which species are additionally trapped by in situ generated iron hydroxides (and oxides).
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Table 1. Relevant reactions for the process of aqueous Fe0 dissolution, iron corrosion products formation and

contaminant (Ox) removal in Fe0/H2O system.

Process Fe0 dissolution Fe0 passivation Fe0 depassivation H2 evolution O2 reduction Fe21 oxidation Scale formation

Reaction Fe0 , Fe21 1 2e2 Fe0 1 H2O ) Fe(O)ads 1 2H1 1 2e2 Fe(O)ads 1 2H1 ) Fe21 1 H2O Fe(O)ads 1 H2O ) Fe(OH)2 Fe(O)ads 1 OH2 ) HFeO2 2 2H1 1 2e2 ) H2: O2 1 2H2O 1 4e2 ) 4OH2 Fe21 ) Fe31 1 e2 Fe21 1 2 OH2 ) Fe(OH)2 Fe31 1 3 OH2 ) Fe(OH)3 Fe(OH)2 ) FeO 1 H2O 2 Fe(OH)3 ) Fe2O3 1 3 H2O 4 Fe(OH)3 ) Fe(OH)2 1 Fe3O4 1 5 H2O 1 O2 Fe(OH)3 ) FeOOH 1 H2O Fe0 1 Ox(aq) ) Fe21 1 Red (s or aq) FeII(aq) 1 Ox(aq) ) FeIII 1 Red (s or aq) FeII(s) 1 Ox(aq or aq) ) FeIII 1 Red (s or aq) H2 1 Ox(aq or aq) ) H1 1 Red (s or aq) FeOOH 1 Ox(aq) , FeOOH2Ox x 2 y) x 2 y) , Ox[Fex(OH)(3 ]n Ox(aq) 1 n Fex(OH)(3 y y
2 y)

Eq. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 is an iron hydrox-

Ox reduction

Ox adsorption Ox coprecipitation

Red is a reduced form of Ox. FeOOH is a proxy of corrosion products and Fex(OH)y(3x ide.

It should be explicitly stated that adsorption, coprecipitation and redox transformations are not each other exclusive as adsorbed or co-precipitated contaminants may be further (1) reduced by Fe0, adsorbed or soluble FeII species or (2) oxidized by HO(/H2O2 species (Fenton-like reactions). It is however certain, that the extend of reduction is difcult to evaluate. This assertion is supported by the fact that to date, no carbon balances between reactants and supposedly reaction products have ever been successfully done for many chlorinated hydrocarbons [3]. However, one should no care about the fate of coprecipitated contaminants as they will remain sequestrated so far iron oxides are not dissolved. Alternatively and complementary, the possibility of iron oxide dissolution and its consequence for coprecipitated contaminants should be discussed at each relevant site. The next section will discuss on the suitability of the Fe0/H2O system for contaminant removal. The singularity of the Fe0/H2O system is the in situ generation of soluble FeII species and their further transformations to crystalline iron oxides and hydroxides (Fe(OH)2, Fe(OH)3, Fe3O4, Fe2O3, FeOOH, Fe5HO84H2O). The various forms of iron oxides, oxyhydroxides, and hydroxides are called iron oxides through the end of this article. Thus, in an aqueous solution, Fe0 ideally converts to crystalline iron oxides via a sequence of oxidation/hydrolysis/ precipitation/dehydration reactions (Table 1). The conversion of Fe0 to crystalline iron oxides goes
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PECULIARITY OF THE Fe0/H2O SYSTEM

towards several intermediate stages of amorphous and poorly crystalline precipitates, including green rust formation and transformation. Intermediate stages also include solid-state transformation of oxides (recrystallization). For example, in aqueous solution crystalline Fe(OH)2 may convert to other iron oxides via oxidation/hydrolysis/dehydration. In essence, iron oxide formation involves two basic mechanisms: (1) direct precipitation from Fe21/ Fe31-containing solutions, and (2) transformation of an Fe oxide precursor. Both mechanisms may occur in natural Fe0/H2O systems, even though direct precipitation is dominant. Due to the diversity of iron corrosion products (CP), a common problem faced by studies on Fe0/H2O systems is the proper characterization of available iron oxides [3739]. A common procedure is the use of synthetic iron oxides to simulate natural CP. However, in natural Fe0/H2O systems, CP are composed primarily of different iron oxides. Individual iron oxides possess different chemical properties such as crystal structure, morphology, and adsorptive properties (Table 2). Accordingly, no synthetic iron oxides (or oxide mixtures) can rigorously simulate natural CP with regard to transformation occurring within.
TRANSFORMATIONS WITHIN Fe0/H2O SYSTEMS

Synthetic iron oxides as simulates for natural iron oxides are prepared in the pure phase while natural oxides are precipitated and further transformed in the presence of foreign species (including contaminants). Thus a synthetic oxide can remove contaminant solely by adsorption while natural oxides incorporate

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Table 2. Some relevant characteristics of metallic iron and its main corrosion products.

Species Iron Magnetite Hematite Maghemite Goethite Akageneite Lepidocrocite Bernalite

Formula Fe Fe3O4 a-Fe2O3 g-Fe2O3 a-FeOOH b-FeOOH g-FeOOH Fe(OH)2 Fe(OH)3

Symmetry bcc Cubic Rhombohedral Cubic Orthorhombic Tetragonal Orthorhombic Trigonal Orthorhombic

Density 7.86 5.18 5.26 4.69 4.28 3.55 4.09 3.40 3.35

SSA (m2/g) <1 6.0 64 30 82 41 221 n.a. 328

Vrust/VFe 2.08 2.12 n.a. 2.91 3.48 3.03 3.75 4.20

SSA is the specic surface area. Vrust/VFe is theoretical ratio between the volume of expansive corrosion products and the volume of iron in the Fe0 material. Data from Refs. 4042. n.a. 5 not available.

contaminant in their structure while precipitating (adsorption and coprecipitation). At any moment after implementation of a Fe0 reactive wall, a natural Fe0/H2O system is made up of Fe0 and various iron oxides, possibly including transforming phases like FeO which are not stable under natural (sub)surface conditions. Given that the iron oxides are of various reactivity toward contaminant removal, the contribution of individual removal mechanisms to decontamination is difcult to access. However, it is the goal of this article to demonstrate that, beside adsorption, contaminant sequestration (coprecipitation) is the sole certain removal mechanism. The occurrence and the extent of all other processes can be discussed on a contaminant-specic basis. Therefore adsorption and co-precipitation are the fundamental mechanisms of contaminant removal in Fe0/H2O system. To illustrate the transformations yielding to contaminant sequestration, the evolution of three iron atoms from the Fe0 material will be discussed. The three atoms (3 Fe0) will be rst oxidized to 3 II Fe species and may further be oxidized (e.g. by O2) to 3 FeIII species. Then they will be transformed to colloidal species partly having specic surface areas (SSA) higher than 500 m2/g [43, 44] before they aggregate and crystallize to one Fe3O4, 1.5 Fe2O3 or 3 Fe(OH)2, Fe(OH)3 or FeOOH. The relative variation of the volume of resulted crystalline oxides is represented in Figure 1 using values from Table 2. Figure 1 clearly shows volume expansion relative to 3 Fe0 for all iron oxides except magnetite for which a volume reduction of 30% was noticed. However, it should be kept in mine that even magnetite is a nal state of a transformation going through even more voluminous colloidal, amorphous and highly adsorptive species (SSA values in Table 2). Although volume expansion is discussed here on the basis of the volume of crystallized iron oxides, this process is a rule in the process iron corrosion, irrespective from the nature and the crystallinity of the nal products. Thus iron oxidative dissolution and iron oxide precipitation should be regarded a cycle of volume expansion/ contraction in the course of which available contaminants are adsorbed and sequestrated. Sequestrated

Figure 1. Relative volumes of iron and selected crys-

talline corrosion reaction products. The values are the bar represents the expansion coefcient. The calculations were made for three iron atoms and show that a volume compression will occur upon formation of Fe3O4. Strictly any crystallization goes through dissolution, nucleation, and aggregation. Intermediate species are of high specic area and even more voluminous than crystalline Fe(OH)3.

contaminants could be further transformed (oxidized or reduced).

CONCLUSIONS

This article has contributed to open a new avenue for the scientic understanding of processes of contaminant removal in Fe0/H2O systems. Researchers and practitioners have long recognized the limits of the reductive transformation concept [1114]. However, the view that contaminants are primarily adsorbed and coprecipitated with iron corrosion products [29, 30, 33] has partly faced with very sceptic views [45, 46] or is just degraded to an alternative hypothesis to be considered [47]. Fortunately, sceptic views are based on the large acceptability of the concept of reductive transformation which was a consenOctober 2010 289

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sus [4] and not the results of hard experimental facts. While former attempts to disprove the reductive transformation concept were based on extensive literature review [29, 30] and a munitions examination of the abundance of reactive species in Fe0/H2O systems [33], the present study is based on a simple analysis of processes occurring in a Fe0/H2O system. The major output is that Fe0 oxidative dissolution and iron oxide precipitation should by regarded as a cycle of volume expansion/contraction in the course of which chemical contaminants and pathogens are adsorbed and sequestrated. Because this argument does not care about the nature of a contaminant, it should be denitively clear that specic interactions are an exception and not the rule in a Fe0/H2O system (statement 1). Statement 1 is the cornerstone on which comprehensive knowledge on the behavior of Fe0/H2O systems under natural conditions should be acquired. In this effort, it is almost impossible to transfer good results from the open aqueous iron corrosion. For example, corrosion inhibition of mild steel by methylene blue (MB) has been reported [48]. However, corrosion inhibition is effective with 5.0 mM (1595 mg/L) MB in HCl at temperatures varying from 30 to 608C. The used temperatures are not relevant for groundwater remediation and the needed concentration (1595 mg/L) is even non relevant for wastewater situations. Additionally the reaction took place in a strong acidic solution (2 M HCl).
ACKNOWLEDGMENTS

The work was supported by the Deutsche Forschungsgemeinschaft (DFG-No. 626/2-2).

LITERATURE CITED

1. Reynolds, G.W., Hoff, J.T., & Gillham, R.W. (1990). Sampling bias caused by materials used to monitor halocarbons in groundwater, Environmental and Science Technology, 24, 135142. 2. Tratnyek, P.G. (1996). Putting corrosion to use: Remediating contaminated groundwater with zero-valent metals, Chemistry and Industry, 13, 499503. 3. Lee, G., Rho, S., & Jahng, D. (2004). Design considerations for groundwater remediation using reduced metals, Korean Journal of Chemical Engineering, 21, 621628. 4. OHannesin, S.F., & Gillham, R.W. (1998). Longterm performance of an in situ iron wall for remediation of VOCs, Ground Water, 36, 164 170. 5. Jambor, J.L., Raudsepp, M., & Mountjoy, K. (2005). Mineralogy of permeable reactive barriers for the attenuation of subsurface contaminants, The Canadian Mineralogist, 43, 21172140. 6. Henderson, A.D., & Demond, A.H. (2007). Longterm performance of zero-valent iron permeable reactive barriers: A critical review, Environmental Engineering Science, 24, 401423. 7. Cundy, A.B., Hopkinson, L., & Whitby, R.L.D. (2008). Use of iron-based technologies in contaminated land and groundwater remediation: A review, Science of Total Environment, 400, 4251.
290 October 2010

8. Thiruvenkatachari, R., Vigneswaran, S., & Naidu, R. (2008). Permeable reactive barrier for groundwater remediation, Journal of Industrial and Engineering Chemistry, 14, 145156. 9. Matheson, L.J., & Tratnyek, P.G. (1994). Reductive dehalogenation of chlorinated methanes by iron metal, Environmental and Science Technology, 28, 20452053. 10. Weber, E.J. (1996). Iron-mediated reductive transformations: Investigation of reaction mechanism, Environmental and Science Technology, 30, 716 719. 11. Lavine, B.K., Auslander, G., & Ritter, J. (2001). Polarographic studies of zero valent iron as a reductant for remediation of nitroaromatics in the environment, Microchemical Journal, 70, 6983. 12. Mantha, R., Taylor, K.E., Biswas, N., & Bewtra, J.K. (2001). A continuous system for Fe0 reduction of nitrobenzene in synthetic wastewater, Environmental and Science Technology, 35, 32313236. 13. Mielczarski, J.A., Atenas, G.M., & Mielczarski, E. (2005). Role of iron surface oxidation layers in decomposition of azo-dye water pollutants in weak acidic solutions, Applied Catalysis B Environmental 56, 289303. 14. Jiao, Y., Qiu, C., Huang, L., Wu, K., Ma, H., Chen, S., Ma, L., & Wu, L. (2009). Reductive dechlorination of carbon tetrachloride by zero-valent iron and related iron corrosion, Applied Catalysis B Environmental, 91, 434440. 15. Noubactep, C. (2009). Characterizing the discoloration of methylene blue in Fe0/H2O systems, Journal of Hazardous Matererials, 166, 7987. 16. Jia, Y., Aagaard, P., & Breedveld, G.D. (2007). Sorption of triazoles to soil and iron minerals, Chemosphere, 67, 250258. 17. Morrison, S.J., Metzler, D.R., & Dwyer, B.P. (2002). Removal of As, Mn, Mo, Se, U, V and Zn from groundwater by zero-valent iron in a passive treatment cell: Reaction progress modeling, Journal of Contaminant Hydrology, 56, 99116. 18. Van Orden, A.C. (1989). Corrosion mechanisms relevant to high-level waste repositories, Engineering Geology, 26, 331349. 19. Brondel, D., Edwards, R., Hayman, A., Hill, D., Mehta, S., & Semerad, T. (1994). Corrosion in the oil industry, Oileld Review, 6, 418. 20. Schmuki, P. (2002). From Bacon to barriers: A review on the passivity of metals and alloys, Journal of Solid State Electrochemistry, 6, 145164. 21. Wilson, E.R. (1923). The mechanism of the corrosion of iron and steel in natural waters and the calculation of specic rates of corrosion, Journal of Industrial and Engineering Chemistry, 15, 127 133. 22. Whitman, G.W., Russel, R.P., & Altieri, V.J. (1924). Effect of hydrogen-ion concentration on the submerged corrosion of steel, Journal of Industrial and Engineering Chemistry, 16, 665670. 23. Dickerson, R.E., Gray, H.B., & Haight, Jr., G.P. (1979). Chemical principles (3rd Edition), London, Amsterdam: Benjamin/Cummings Inc.

Environmental Progress & Sustainable Energy (Vol.29, No.3) DOI 10.1002/ep

24. Mu ller, W.J. (1939). Passivity and corrosion of metals (in German), Colloid and Polymer Science, 86, 150166. 25. Bonin, P.M.L., Odziemkowski, M.S., & Gillham, R.W. (1998). Inuence of chlorinated solvents on polarization and corrosion behaviour of iron in borate buffer, Corrosion Science, 40, 13911409. 26. Odziemkowski, M.S., Gui, L., Gillham, R.W., & Irish, D.E. (2000). The role of oxide lms in the reduction of N-nitreosodimethylamine with reference to the iron groundwater remediation technology. In K.R. Hebert, R.S. Lillard, & B.R. MacDougall (Eds.), Oxide Films, Proceedings of the International Symposium (Volume 2000-4, pp 357368), Pennington, NJ: The Electrochemical Society, Inc. 27. Scherer, M.M., Richter, S., Valentine, R.L., & Alvarez, P.J.J. (2000). Chemistry and microbiology of permeable reactive barriers for in situ groundwater clean up, Critical Reviews of Environmental Science and Technology, 30, 363411. 28. Miehr, R., Tratnyek, G.P., Bandstra, Z.J., Scherer, M.M., Alowitz, J.M., & Bylaska, J.E. (2004). Diversity of contaminant reduction reactions by zerovalent iron: Role of the reductate, Environmental Science and Technology, 38, 139147. 29. Noubactep, C. (2007). Processes of contaminant removal in Fe0-H2O systems revisited: The importance of co-precipitation, Open Environmental Journal, 1, 913. 30. Noubactep, C. (2008). A critical review on the mechanism of contaminant removal in Fe0-H2O systems, Environmental Technology, 29, 909920. 31. Sikora, E., & Macdonald, D.D. (2000). The passivity of iron in the presence of ethylenediaminetetraacetic acid. I. General electrochemical behavior, Journal of The Electrochemical Society, 147, 40874092. 32. Nesic, S. (2007). Key issues related to modelling of internal corrosion of oil and gas pipelinesA review, Corrosion Science, 49, 43084338. 33. Noubactep, C. (2009). An analysis of the evolution of reactive species in Fe0/H2O systems, Journal of Hazardous Materials, 168, 16261631. 34. Crawford, R.J., Harding, I.H., & Mainwaring, D.E. (1993). Adsorption and coprecipitation of single heavy metal ions onto the hydrated oxides of iron and chromium, Langmuir, 9, 30503056. 35. Mollah, M.Y.A., Schennach, R., Parga, J.R., & Cocke, D.L. (2001). Electrocoagulation (EC)Science and applications, Journal of Hazardous Matererials, 84, 2941. 36. Moreno, C.H.A., Cocke, D.L., Gomes, J.A.G., Morkovsky, P., Parga, J.R., Peterson, E., & Garcia, C. (2009). Electrochemical reactions for electrocoa-

37.

38. 39.

40.

41. 42.

43. 44.

45.

46.

47.

48.

gulation using iron electrodes, Industrial and Engineering Chemical Research, 48, 22752282. Mackenzie, P.D., Horney, D.P., & Sivavec, T.M. (1999). Mineral precipitation and porosity losses in granular iron columns, Journal of Hazardous Matererials, 68, 117. Roh, Y., Lee, S.Y., & Elless, M.P. (2000). Characterization of corrosion products in the permeable reactive barriers, Environmental Geology, 40, 184194. Borch, T., Camper, A.K., Biederman, J.A., Buttereld, P.W., Gerlach, R., & Amonette, J.E. (2008). Evaluation of characterization techniques for iron pipe corrosion products and iron oxide thin lms, Journal of Environmental Engineering, 134, 835844. Borggaard, O.K. (1991). Effects of phosphate on iron oxide dissolution in ethylenediamine-N,N, N0 ,N0 -tetraacetic acid and oxalate, Clays and Clay Minerals, 39, 324328. Balasubramaniam, R., Ramesh, K.A.V., & Dillmann, P. (2003). Characterization of rust on ancient Indian iron, Current Science, 85, 15461555. , S., Nguyen, Q.T., LHostis, V., & Berthaud, Care Y. (2008). Mechanical properties of the rust layer induced by impressed current method in reinforced mortar, Cement and Concrete Research, 38, 10791091. Cornell R.M., & Schwertmann U. (1996). The iron oxides, VCH: Wiley, 573 pp. Subrt, J., Bohacek, J., Stengl, V., Grygar, T., & Bezdicka, P. (1999). Uniform particles with a large surface area formed by hydrolysis of Fe2(SO4)3 with urea, Materials Research Bulletin, 34, 905914. Elsner, M., Cwiertny, D.M., Roberts, A.L., & Lollar, B.S. (2007). Response to comment on 1,1,2,2-tetrachloroethane reactions with OH-, Cr(II), granular iron, and a copper-iron bimetal: Insights from product formation and associated carbon isotope fractionation, Environmental Science and Technology 41, 79497950. Kang, S.-H., & Choi, W. (2009). Response to comment on oxidative degradation of organic compounds using zero-valent iron in the presence of natural organic matter serving as an electron shuttle, Environmental Science and Technology, 43, 39663967. Gui, L., Jeen, S.-W., Blowes, D.W., Gillham, R.W., & Yang, Y. Reply to the comment on Reduction of chromate by granular iron in the presence of dissolved CaCO3 by C. Noubactep, Applied Geochemistry (DOI: 10.1016/j.apgeochem.2009.08.006). Oguzie, E.E. (2005). Corrosion inhibition of mild steel in hydrochloric acid solution by methylene blue dye, Materials Letters, 59, 10761079.

Environmental Progress & Sustainable Energy (Vol.29, No.3) DOI 10.1002/ep

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