Studies were undertaken to determine the reasons why published information regarding the efficiency of metallic iron (Fe 0 ) for water treatment is conflicting and even confusing. The reactivity of eight Fe 0 materials was characterized by Fe dissolution in a dilute solution of ethylenediaminetetraacetate (Na 2 -EDTA; 2 mM). Both batch (4 days) and column (100 days) experiments were used. A total of 30 different systems were characterized for the extent of Fe release in EDTA. The effects of Fe 0 type (granular iron, iron nails and steel wool) and pretreatment procedure (socking in acetone, EDTA, H 2 O, HCl and NaCl for 17 h) were assessed. The results roughly show an increased iron dissolution with increasing reactive sites (decreasing particle size: wool > filings > nails), but there were large differences between materials from the same group. The main output of this work is that available results are hardly comparable as they were achieved under very different experimental conditions. A conceptual framework is presented for future research directed towards a more processed understanding.Sustainability 2019, 11, 671 2 of 20 organic [27,28], fluoride [29][30][31], heavy metals [32,33], nitrate [34,35], pathogens [36][37][38] and radionuclides [32,39]. The desalination of water using Fe 0 has also been reported [40][41][42][43]. The two key advantages of Fe 0 are its affordability and its universal availability (iron nails, scrap iron and steel wool) [9,10,44,45]. It is commonly reported that the major drawback of Fe 0 -based technologies for water treatment is the low intrinsic reactivity of granular materials [28,33,46]. This situation is said to be aggravated by the inherent generation of an oxide scale at the Fe 0 surface (passivation). Countermeasures to overcome Fe 0 passivation were recently reviewed by Guan et al. [28] and further discussed by Noubactep [47]. It is recalled that, considering passivation as a "curse" contradicts the evidence that Fe 0 -based subsurface permeable barriers have been successfully working for more than one decade [48][49][50]. On the other hand, increased "passivation" should have occurred in the spongy iron filters in Antwerpen as well [2,19]. Clarifying this contradiction is certainly a progress for the whole Fe 0 technology. Clearly, an understanding of the role of "passivation" in the process of decontamination using Fe 0 should be useful for enhancing the system's efficiency in practice [30,31,47].There is an agreement on the evidence that using Fe 0 for water treatment and environmental remediation is "putting corrosion to use" [51][52][53]. There is otherwise a contradiction on practically any other aspect concerning the Fe 0 /H 2 O system, including the reaction mechanisms and factors determining the long-term efficiency of such systems [9,28,47,[54][55][56][57][58]. A key reason for this is the large variability of experimental conditions used in testing Fe 0 materials [58][59][60][61][62]. The main influencing operational parameter seems to be Fe 0 itself [58,61,63,6...

There is growing interest in using pyrite minerals (FeS2) to enhance the efficiency of metallic iron (Fe0) for water treatment (Fe0/H2O systems). This approach contradicts the thermodynamic predicting suppression of FeS2 oxidation by Fe0 addition. Available results are rooted in time series correlations between aqueous and solid phases based on data collected under various operational conditions. Herein, the methylene blue method (MB method) is used to clarify the controversy. The MB method exploits the differential adsorptive affinity of MB onto sand and sand coated with iron corrosion products to assess the extent of Fe0 corrosion in Fe0/H2O systems. The effects of the addition of various amounts of FeS2 to a Fe0/sand mixture (FeS2 method) on MB discoloration were characterized in parallel quiescent batch experiments for up to 71 d (pH0 = 6.8). Pristine and aged FeS2 specimens were used. Parallel experiments with methyl orange (MO) and reactive red 120 (RR120) enabled a better discussion of the achieved results. The results clearly showed that FeS2 induces a pH shift and delays Fe precipitation and sand coating. Pristine FeS2 induced a pH shift to values lower than 4.5, but no quantitative MB discoloration occurred after 45 d. Aged FeS2 could not significantly shift the pH value (final pH ≥ 6.4) but improved the MB discoloration. The used systematic sequence of experiments demonstrated that adsorption and coprecipitation are the fundamental mechanisms of contaminant removal in Fe0/H2O systems. This research has clarified the reason why a FeS2 addition enhances the efficiency of Fe0 environmental remediation.

A critical survey of the abundant literature on environmental remediation and water treatment using metallic iron (Fe0) as reactive agent raises two major concerns: (i) the peculiar properties of the used materials are not properly considered and characterized, and, (ii) the literature review in individual publications is very selective, thereby excluding some fundamental principles. Fe0 specimens for water treatment are typically small in size. Before the advent of this technology and its application for environmental remediation, such small Fe0 particles have never been allowed to freely corrode for the long-term spanning several years. As concerning the selective literature review, the root cause is that Fe0 was considered as a (strong) reducing agent under environmental conditions. Subsequent interpretation of research results was mainly directed at supporting this mistaken view. The net result is that, within three decades, the Fe0 research community has developed itself to a sort of modern knowledge system. This communication is a further attempt to bring Fe0 research back to the highway of mainstream corrosion science, where the fundamentals of Fe0 technology are rooted. The inherent errors of selected approaches, currently considered as countermeasures to address the inherent limitations of the Fe0 technology are demonstrated. The misuse of the terms “reactivity”, and “efficiency”, and adsorption kinetics and isotherm models for Fe0 systems is also elucidated. The immense importance of Fe0/H2O systems in solving the long-lasting issue of universal safe drinking water provision and wastewater treatment calls for a science-based system design.

The general suitability of water treatment systems involving metallic iron (Fe0) is well-established. Various attempts have been made to improve the efficiency of conventional Fe0 systems. One promising approach combines granular Fe0 and an iron sulfide mineral to form Fe0/Fe-sulfide/H2O systems. An improved understanding of the fundamental principles by which such systems operate is still needed. Through a systematic analysis of possible reactions and the probability of their occurrence, this study establishes that sulfide minerals primarily sustain iron corrosion by lowering the pH of the system. Thus, chemical reduction mediated by FeII species (indirect reduction) is a plausible explanation for the documented reductive transformations. Such a mechanism is consistent with the nature and distribution of reported reaction products. While considering the mass balance of iron, it appears that lowering the pH value increases Fe0 dissolution, and thus subsequent precipitation of hydroxides. This precipitation reaction is coupled with the occlusion of contaminants (co-precipitation or irreversible adsorption). The extent to which individual sulfides impact the efficiency of the tested systems depends on their intrinsic reactivities and the operational conditions (e.g., sulfide dosage, particle size, experimental duration). Future research directions, including the extension of Fe0/Fe-sulfide/H2O systems to drinking water filters and (domestic) wastewater treatment using the multi-soil-layering method are highlighted.

There is a burgeoning interest in reliably characterizing the intrinsic reactivity of metallic iron materials (Fe0) or zero-valent iron materials (ZVI) used in the water treatment industry. The present work is a contribution to a science-based selection of Fe0 for water treatment. A total of eight (8) granular ZVI materials (ZVI1 to ZVI8) were tested. Fe0 dissolution in ethylenediaminetetraacetic acid (EDTA test) and 1,10-Phenanthroline (Phen test) is characterized in parallel experiments for up to 250 h (10 days). 50 mL of each solution and 0.1 g of each Fe0 material are equilibrated in quiescent batch experiments using 2 mM EDTA or Phen. Results indicated a far higher extent of iron dissolution in EDTA than in Phen under the experimental conditions. The tested materials could be grouped into three reactivity classes: (i) low (ZVI4, ZVI6, ZVI7, and ZVI8), (ii) moderate (ZVI1 and ZVI5) and (iii) high (ZVI2 and ZVI3). The order of reactivity was the same for both tests: ZVI2 ≅ ZVI3 > ZVI1 ≅ ZVI5 > ZVI4 ≅ ZVI6 ≅ ZVI7 ≅ ZVI8. Phen results revealed for the first time the time-dependent variation of the kinetics of iron corrosion (corrosion rate) in short-term batch experiments. Overall, the results demonstrated the superiority of the Phen test for evaluating the initial stage of Fe0 dissolution. Long-term column experiments are recommended to deepen the acquired knowledge.