A central aspect of the contaminant removal by elemental iron materials (Fe 0 or Fe 0 materials) is that reduction reactions are mediated by the iron surface (direct reduction). This premise was introduced by the pioneers of the reactive wall technology and is widely accepted by the scientific community. In the meantime enough evidence has been provided to suggest that contaminant reduction through primary corrosion products (secondary reductants) does indeed occur (indirect reduction). It was shown for decades that iron corrosion in the pH range of natural waters (4-9) inevitably yields an obstructive oxide film of corrosion products at the metal surface (oxide film). Therefore, contaminant adsorption on to corrosion products and contaminant co-precipitation with corrosion products inevitably occurs. For adsorbed and coprecipitated contaminants to be directly reduced the oxide film should be electronic conductive. This study argues through a literature review a series of points which ultimately lead to the conclusion that, if any quantitative contaminant reduction occurs in the presence of Fe 0 materials, it takes place within the matrix of corrosion products and is not necessarily a direct reduction. It is concluded that Fe 0 materials act both as source of corrosion products for contaminant adsorption/coprecipitation and as a generator of Fe II and H 2 (H) for possible catalytic contaminant reduction.

The availability of sustainable safe drinking water is one of Millennium Development Goals (MDGs). The world is on schedule to meet the MDG to ‘halve by 2015 the proportion of people without sustainable access to safe drinking water in 2000’. However, present technologies may still leave more than 600 million people without access to safe water in 2015. The objective of the present article is to present a concept for universal water filters primarily made of metallic iron (Fe0) and sand. The concept of Fe0/sand filters is based on a combination of: (i) recent developments in slow sand filtration and (ii) recent progress in understanding the process of contaminant removal in Fe0/H2O systems. The filters should be made up of more than 60% sand and up to 40% Fe0. The actual Fe0 proportion will depend on its intrinsic reactivity. The most important question to be answered regards the selection of the material to be used. The design of the filter can be derived from existing filters. It appears that Fe0/H2O based filters could be a technology with worldwide applicability.

Over the past 30 years the literature has burgeoned with in situ approaches for groundwater remediation. Of the methods currently available, the use of metallic iron (Fe0) in permeable reactive barrier (PRB) systems is one of the most commonly applied. Despite such interest, an increasing amount of experimental and field observations have reported inconsistent Fe0 barrier operation compared to contemporary theory. In the current work, a critical review of the physical chemistry of aqueous Fe0 corrosion in porous media is presented. Subsequent implications for the design of Fe0 filtration systems are modeled. The results suggest that: (i) for the pH range of natural waters (>4.5), the high volumetric expansion of Fe0 during oxidation and precipitation dictates that Fe0 should be mixed with a non‐expansive material; (ii) naturally occurring solute precipitates have a negligible impact on permeability loss compared to Fe0 expansive corrosion; and (iii) the proliferation of H2 metabolizing bacteria may contribute to alleviate permeability loss. As a consequence, it is suggested that more emphasis must be placed on future work with regard to considering the Fe0 PRB system as a physical (size‐exclusion) water filter device.

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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 Fe 0 /H 2 O systems at near neutral pH values. A primary reason for this is that the use of elemental iron (Fe 0 ) in environmental remediation is based on the thermodynamic-founded premise that reducible contaminants are potentially reduced while Fe 0 is oxidised. However, co-precipitation portends to be of fundamental importance for the process of contaminant removal in Fe 0 /H 2 O 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. CO 2 corrosion, electrocoagulation using Fe 0 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 Fe 0 /H 2 O 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.

Abstract:The mechanism of aqueous contaminant removal by elemental iron (Fe 0 ) materials (e.g., in Fe 0 -H 2 O systems) has been largely discussed in the "iron technology" literature. Two major removal mechanisms are usually discussed: (i) contaminant adsorption onto Fe 0 oxidation products, and (ii) contaminant reduction by Fe 0 , Fe II or H/H 2 . However, a closer inspection of the chemistry of the Fe 0 -H 2 O system reveals that co-precipitation could be the primary removal mechanism. The plausibility of contaminant co-precipitation with iron corrosion products as independent contaminant removal mechanism is discussed here. It shows that the current concept does not take into account that the corrosion product generation is a dynamic process in the course of which contaminants are entrapped in the matrix of iron hydroxides. It is recalled that contaminant co-precipitation with iron hydroxides/oxides is an unspecific removal mechanism. Contaminant co-precipitation as primary removal mechanism is compatible with subsequent reduction and explains why redoxinsensitive species are quantitatively removed. Adsorption and co-precipitation precede reduction and abiotic reduction, when it takes place, occurs independently by a direct (electrons from Fe 0 ) or an indirect (electrons from Fe II /H 2 ) mechanism.

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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-fronts.