Review: The fundamental mechanism of aqueous contaminant removal by metallic iron

Contaminant co-precipitation with continuously generated and transformed iron corrosion products has received relatively little attention in comparison to other possible removal mechanisms (adsorption, oxidation, precipitation) in Fe0/H2O systems at near neutral pH values. A primary reason for this is that the use of elemental iron (Fe0) in environmental remediation is based on the thermodynamic-founded premise that reducible contaminants are potentially reduced while Fe0 is oxidised. However, co-precipitation portends to be of fundamental importance for the process of contaminant removal in Fe0/H2O systems, as the successful removal of bacteria, viruses and non reducible organic (e.g. methylene blue, triazoles) and inorganic (e.g. Zn) compounds has been reported. This later consideration has led to a search for the reasons why the importance of co-precipitation has almost been overlooked for more than a decade. Three major reasons have been identified: the improper consideration of the huge literature of iron corrosion by pioneer works, yielding to propagation of misconceptions in the iron technology literature; the improper consideration of available results from other branches of environmental science (e.g. CO2 corrosion, electrocoagulation using Fe0 electrodes, Fe or Mn geochemistry); and the use of inappropriate experimental procedures (in particular, mixing operations). The present paper demonstrates that contaminant co-precipitation with iron corrosion products is the fundamental mechanism of contaminant removal in Fe0/H2O systems. Therefore, the ‘iron technology’ as a whole is to be revisited as the ‘know-why’ of contaminant removal is yet to be properly addressed.Keywords: adsorption, co-precipitation, iron corrosion, iron oxhydroxides, zerovalent iro

Review Aqueous contaminant removal by metallic iron: Is the paradigm shifting?

Chemical reduction has long dominated thinking about the mechanism of aqueous contaminant removal in the presence of metallic iron (e.g. Fe0/H2O systems). However, a large body of experimental evidence indicates that chemical reduction is not adequate to satisfactorily explain the efficiency of Fe0/H2O systems for several substances or classes of substances. By contrast, the alternative approach, that contaminants are fundamentally adsorbed and co-precipitated by iron corrosion products seems to provide a better explanation of observed efficiency. The new approach appears to not be fully understood. The present communication aims at clarifying this key issue. It seems that a paradigm shift is necessary for the further development of the technology using Fe0 for water treatment

Nanoscale Metallic Iron for Environmental Remediation: Prospects and Limitations

The amendment of the subsurface with nanoscale metallic iron particles (nano-Fe0) has been discussed in the literature as an efficient in situ technology for groundwater remediation. However, the introduction of this technology was controversial and its efficiency has never been univocally established. This unsatisfying situation has motivated this communication whose objective was a comprehensive discussion of the intrinsic reactivity of nano-Fe0 based on the contemporary knowledge on the mechanism of contaminant removal by Fe0 and a mathematical model. It is showed that due to limitations of the mass transfer of nano-Fe0 to contaminants, available concepts cannot explain the success of nano-Fe0 injection for in situ groundwater remediation. It is recommended to test the possibility of introducing nano-Fe0 to initiate the formation of roll-fronts which propagation would induce the reductive transformation of both dissolved and adsorbed contaminants. Within a roll-front, FeII from nano-Fe0 is the reducing agent for contaminants. FeII is recycled by biotic or abiotic FeIII reduction. While the roll-front concept could explain the success of already implemented reaction zones, more research is needed for a science-based recommendation of nano- Fe0 for subsurface treatment by roll-front

Viscoelastic gels of guar and xanthan gum mixtures provide long-term stabilization of iron micro- and nanoparticles

Iron micro- and nanoparticles used for groundwater remediation and medical applications are prone to fast aggregation and sedimentation. Diluted single biopolymer water solutions of guar gum (GG) or xanthan gum (XG) can stabilize these particles for few hours providing steric repulsion and by increasing the viscosity of the suspension. The goal of the study is to demonstrate that amending GG solutions with small amounts of XG (XG/GG weight ratio 1:19; 3 g/L of total biopolymer concentration) can significantly improve the capability of the biopolymer to stabilize highly concentrated iron micro- and nanoparticle suspensions. The synergistic effect between GG and XG generates a viscoelastic gel that can maintain 20 g/L iron particles suspended for over 24 h. This is attributed to (i) an increase in the static viscosity, (ii) a combined polymer structure the yield stress of which contrasts the downward stress exerted by the iron particles, and (iii) the adsorption of the polymers to the iron surface having an anchoring effect on the particles. The XG/GG viscoelastic gel is characterized by a marked shear thinning behavior. This property, coupled with the low biopolymer concentration, determines small viscosity values at high shear rates, facilitating the injection in porous media. Furthermore, the thermosensitivity of the soft elastic polymeric network promotes higher stability and longer storage times at low temperatures and rapid decrease of viscosity at higher temperatures. This feature can be exploited in order to improve the flowability and the delivery of the suspensions to the target as well as to effectively tune and control the release of the iron particle

Characterizing the effects of shaking intensity on the kinetics of metallic iron dissolution in EDTA.

Despite two decades of intensive laboratory investigations, several aspects of contaminant removal from aqueous solutions by elemental iron materials (e.g., in Fe(0)/H2O systems) are not really understood. One of the main reasons for this is the lack of a unified procedure for conducting batch removal experiments. This study gives a qualitative and semi-quantitative characterization of the effect of the mixing intensity on the oxidative dissolution of iron from two Fe(0)-materials (materials A and B) in a diluted aqueous ethylenediaminetetraacetic solution (2 mM EDTA). Material A (fillings) was a scrap iron and material B (spherical) a commercial material. The Fe(0)/H2O/EDTA systems were shaken on a rotational shaker at shaking intensities between 0 and 250 min(-1) and the time dependence evolution of the iron concentration was recorded. The systems were characterized by the initial iron dissolution rate (k(EDTA)). The results showed an increased rate of iron dissolution with increasing shaking intensity for both materials. The increased corrosion through shaking was also evidenced through the characterization of the effects of pre-shaking time on k(EDTA) from material A. Altogether, the results disprove the popular assumption that mixing batch experiments is a tool to limit or eliminate diffusion as dominant transport process of contaminant to the Fe(0) surface