Special Issue "Sustainable Remediation Using Metallic Iron: Quo Vadis?"

A special issue of Water (ISSN 2073-4441). This special issue belongs to the section "Wastewater Treatment and Reuse".

Deadline for manuscript submissions: closed (10 April 2023) | Viewed by 10759

Special Issue Editors

Angewandte Geologie, Universität Göttingen, Goldschmidtstraße 3, D-37077 Göttingen, Germany
Interests: adsorption; decentralized systems; filtration; rainwater harvesting; water treatment; zerovalent iron
Special Issues, Collections and Topics in MDPI journals
Faculty of Industrial Chemistry and Environmental Engineering, Politehnica University Timisoara, Bd. V. Parvan Nr. 6, 300223 Timisoara, Romania
Interests: water treatment; adsorption processes; zerovalent iron; biosorbents; heavy metals

Special Issue Information

Dear Colleagues,

During the past three decades, groundwater remediation using permeable reactive barriers (PRBs) containing metallic iron (Fe0) has become a well-established technology. However, many uncertainties exist regarding their design, suggesting that Fe0 PRBs is still an innovative technology.

Research on Fe0 PRBs started in the early 1990s and has boomed in the past three decades. Sufficient data and observations have been accumulated to establish the science of the Fe0/H2O system. To explain the initial observation that there were losses of chlorinated organic contaminants from aqueous solutions in contact with a variety of metals (including Fe0), it was proposed that reductive dechlorination was the main cause, with electrons coming from the metal body. In the meantime, Fe0 is described in the literature as “reservoir of electrons” for contaminant transformation. However, considering Fe0 as source of electrons for dissolved species, including O2, contradicts the century-old knowledge that, under environmental conditions, the Fe0 surface is covered by a non-conductive oxide scale, hindering any electron transfer from the Fe0 body. This state of affairs implies that abiotic reductive transformations in Fe0/H2O systems are mediated by secondary reducing agents such as FeII species, FeII/FeIII species, and H2. Biotic transformations are also reported, using FeII or H2 as electron sources. In other words, the still widely accepted operating mode of Fe0/H2O systems seems not to have a scientific basis. The other evidence against this operating mode is that its establishment was not based on any holistic approach since the essence of aqueous iron corrosion is by water and is found in trace amounts (humidity). Clearly, the conversion of data and observations into knowledge constitutes a great challenge for the Fe0 research community.

This Special Issue welcomes papers highlighting: (i) established or innovative Fe0 materials for water treatment; (ii) models and research tools applied to advancing the understanding of the Fe0/H2O system; and (iii) case studies, conceptual frameworks, viewpoints, and field applications. Special attention is given (but is not limited) to the assessment of operation modes of innovative materials (e.g., composites) and their sustainability under field conditions. The objective is to give state-of-the-art knowledge of the development of Fe0 PRBs-based recent advances in understanding the operating mode of the Fe0/H2O system, and in particular, the view that Fe0 is not a stand-alone reducing agent under environmental conditions.

Dr. Chicgoua Noubactep
Dr. Marius Gheju
Guest Editors

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Keywords

  • corrosion kinetics
  • groundwater remediation
  • iron corrosion, permeable reactive barrier (PRB)
  • permeability loss, reactivity loss, scrap iron filing
  • zero-valent iron

Published Papers (9 papers)

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Research

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Article
Developing the Ascorbic Acid Test: A Candidate Standard Tool for Characterizing the Intrinsic Reactivity of Metallic Iron for Water Remediation
Water 2023, 15(10), 1930; https://doi.org/10.3390/w15101930 - 19 May 2023
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Abstract
Granular metallic iron (gFe0) materials have been widely used for eliminating a wide range of pollutants from aqueous solutions over the past three decades. However, the intrinsic reactivity of gFe0 is rarely evaluated and existing methods for such evaluations have [...] Read more.
Granular metallic iron (gFe0) materials have been widely used for eliminating a wide range of pollutants from aqueous solutions over the past three decades. However, the intrinsic reactivity of gFe0 is rarely evaluated and existing methods for such evaluations have not been standardized. The aim of the present study was to develop a simple spectrophotometric method to characterize the intrinsic reactivity of gFe0 based on the extent of iron dissolution in an ascorbic acid (AA—0.002 M or 2 mM) solution. A modification of the ethylenediaminetetraacetic acid method (EDTA method) is suggested for this purpose. Being an excellent chelating agent for FeII and a reducing agent for FeIII, AA sustains the oxidative dissolution of Fe0 and the reductive dissolution of FeIII oxides from gFe0 specimens. In other words, Fe0 dissolution to FeII ions is promoted while the further oxidation to FeIII ions is blocked. Thus, unlike the EDTA method that promotes Fe0 oxidation to FeIII ions, the AA method promotes only the formation of FeII species, despite the presence of dissolved O2. The AA test is more accurate than the EDTA test and is considerably less expensive. Eight selected gFe0 specimens (ZVI1 through ZVI8) with established diversity in intrinsic reactivity were tested in parallel batch experiments (for 6 days) and three of these specimens (ZVI1, ZVI3, ZVI5) were further tested for iron leaching in column experiments (for 150 days). Results confirmed the better suitability (e.g., accuracy in assessing Fe0 dissolution) of the AA test relative to the EDTA test as a powerful screening tool to select materials for various field applications. Thus, the AA test should be routinely used to characterize and rationalize the selection of gFe0 in individual studies. Full article
(This article belongs to the Special Issue Sustainable Remediation Using Metallic Iron: Quo Vadis?)
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Article
Comparison between Different Technologies (Zerovalent Iron, Coagulation-Flocculation, Adsorption) for Arsenic Treatment at High Concentrations
Water 2023, 15(8), 1481; https://doi.org/10.3390/w15081481 - 11 Apr 2023
Cited by 2 | Viewed by 1003
Abstract
The presence of arsenic in water for human consumption is of concern, especially in developing countries, and the design of simple and economic treatments for arsenic removal is imperative. In this paper, three low-cost technologies were evaluated for As(V) or As(III) (5 mg [...] Read more.
The presence of arsenic in water for human consumption is of concern, especially in developing countries, and the design of simple and economic treatments for arsenic removal is imperative. In this paper, three low-cost technologies were evaluated for As(V) or As(III) (5 mg L−1) removal: (1) zerovalent iron (Fe(0)), as powdered (μFe(0)) and iron wool (wFe(0)); (2) coagulation-flocculation with Al2(SO4)3 or FeCl3; and (3) adsorption on a natural clay. μFe(0) was more efficient than wFe(0), requiring a minimal dose of 0.25 g L−1 to achieve [As(V)] < 0.01 mg L−1 after 288 h; the reaction time was reduced to 168 h under stirring. When starting from As(III), partial oxidation to As(V) was observed, and removal was not complete even after 648 h with 1 g L−1 μFe(0). As(V) removal using FeCl3 and Al2(SO4)3 was very fast and completed in 15 min with 0.25 g L−1 of both reagents. However, Al2(SO4)3 was not efficient to remove As(III). With the clay, doses higher than 50 g L−1 and times longer than 648 h were needed to remove both As species. Arsenic leached from μFe(0) used to treat As(III) was almost negligible. Thus, Fe(0) may be the best alternative for low-cost, small-scale applications. Full article
(This article belongs to the Special Issue Sustainable Remediation Using Metallic Iron: Quo Vadis?)
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Article
Effect of Sand Co-Presence on CrVI Removal in Fe0-H2O System
Water 2023, 15(4), 777; https://doi.org/10.3390/w15040777 - 16 Feb 2023
Cited by 3 | Viewed by 946
Abstract
The aim of the present study was to provide new knowledge regarding the effect of non-expansive inert material addition on anionic pollutant removal efficiency in Fe0-H2O system. Non-disturbed batch experiments and continuous-flow-through column tests were conducted using CrVI [...] Read more.
The aim of the present study was to provide new knowledge regarding the effect of non-expansive inert material addition on anionic pollutant removal efficiency in Fe0-H2O system. Non-disturbed batch experiments and continuous-flow-through column tests were conducted using CrVI as a redox–active contaminant in three different systems: “Fe0 + sand”, “Fe0 only” and ”sand only”. Both experimental procedures have the advantage that formation of (hydr)oxide layers on Fe0 is not altered, which makes them appropriate proxies for real Fe0-based filter technologies. Batch experiments carried out at pH 6.5 showed a slight improvement of CrVI removal in a 20% Fe0 system, compared to 50, 80 and 100% Fe0 systems. Column tests conducted at pH 6.5 supported results of batch experiments, revealing highest CrVI removal efficiencies for “Fe0 + sand” systems with lowest Fe0 ratio. However, the positive effect of sand co-presence decreases with increasing pH from 6.5 to 7.1. Scanning electron microscopy—energy dispersive angle X-ray spectrometry and X-ray diffraction spectroscopy employed for the characterization of Fe0 before and after experiments indicated that the higher the volumetric ratio of sand in “Fe0 + sand” system, the more intense the corrosion processes affecting the Fe0 grains. Results presented herein indicate the capacity of sand at sustaining the efficiency of CrVI removal in Fe0-H2O system. The outcomes of the present study suggest that a volumetric ratio Fe0:sand = 1:3 could assure not only the long-term permeability of Fe0-based filters, but also enhanced removal efficiency of CrVI from contaminated water. Full article
(This article belongs to the Special Issue Sustainable Remediation Using Metallic Iron: Quo Vadis?)
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Article
Hydrodynamic Decontamination of Groundwater and Soils Using ZVI
Water 2023, 15(3), 540; https://doi.org/10.3390/w15030540 - 29 Jan 2023
Cited by 1 | Viewed by 1906
Abstract
Polluted aquifers can be decontaminated using either ZVI (zero valent iron) permeable reactive barriers (PRB) or injected ZVI. The placement of ZVI within the aquifer may take several decades to remediate the contaminant plume. Remediation is further complicated by ZVI acting as an [...] Read more.
Polluted aquifers can be decontaminated using either ZVI (zero valent iron) permeable reactive barriers (PRB) or injected ZVI. The placement of ZVI within the aquifer may take several decades to remediate the contaminant plume. Remediation is further complicated by ZVI acting as an adsorbent to remove some pollutants, while for other pollutants, it acts as a remediation catalyst. This study investigates an alternative aquifer decontamination approach to PRB construction or n-Fe0 injection. The alternative approach reconstructs the potentiometric surface of the aquifer containing the contaminant. This reconstruction confines the contaminant plume to a stationary, doughnut shaped hydrodynamic mound. Contaminated water from the mound is abstracted, decontaminated, and then reinjected, until all the water confined within the mound is decontaminated. At this point, the decontaminated mound is allowed to dissipate into the surrounding aquifer. This approach is evaluated for potential use in treating the following: (i) immiscible liquid plumes; (ii) miscible contaminant and ionic solute plumes; (iii) naturally contaminated aquifers and soils; and (iv) contaminated or salinized soils. The results indicate that this approach, when compared with the PRB or injection approach, may accelerate the decontamination, while reducing the overall amount of ZVI required. Full article
(This article belongs to the Special Issue Sustainable Remediation Using Metallic Iron: Quo Vadis?)
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Article
Remediation of Saline Wastewater Producing a Fuel Gas Containing Alkanes and Hydrogen Using Zero Valent Iron (Fe0)
Water 2022, 14(12), 1926; https://doi.org/10.3390/w14121926 - 15 Jun 2022
Cited by 9 | Viewed by 1469
Abstract
Zero valent iron (Fe0) water remediation studies, over the last 40 years, have periodically reported the discovery of CnH2n+2 in the product water or product gas, where n = 1 to 20. Various theories have been proposed for [...] Read more.
Zero valent iron (Fe0) water remediation studies, over the last 40 years, have periodically reported the discovery of CnH2n+2 in the product water or product gas, where n = 1 to 20. Various theories have been proposed for the presence of these hydrocarbons. These include: (i) reductive transformation of a more complex organic chemical; (ii) hydrogenation of an organic chemical, as part of a degradation process; (iii) catalytic hydrogenation and polymerisation of carbonic acid; and (iv) redox transformation. This study uses wastewater (pyroligneous acid, (pH = 0.5 to 4.5)) from a carbonization reactor processing municipal waste to define the controls for the formation of CnH2n+2 (where n = 3 to 9), C3H4, and C3H6. A sealed, static diffusion, batch flow reactor, containing zero-valent metals [181 g m-Fe0 + 29 g m-Al0 + 27 g m-Cu0 + 40 g NaCl] L−1, was operated at two temperatures, 273–298 K and 348 K, respectively. The reactions, reactant quotients, and rate constants for the catalytic formation of H2(g), CO2(g), C3H4(g), C3H6(g), C3H8(g), C4H10(g), C5H12(g), C6H14(g,l), and C7H16(g,l), are defined as function of zero valent metal concentration (g L−1), reactor pressure (MPa), and reactor temperature (K). The produced fuel gas (422–1050 kJ mole−1) contained hydrogen + CnHy(gas), where n = 3 to 7. The gas production rate was: [1058 moles CnHy + 132 moles H2] m−3 liquid d−1 (operating pressure = 0.1 MPa; temperature = 348 K). Increasing the operating pressure to 1 MPa increased the fuel gas production rate to [2208 moles CnHy + 1071 moles H2] m−3 liquid d−1. In order to achieve these results, the Fe0, operated as a “Smart Material”, simultaneously multi-tasking to create self-assembly, auto-activated catalysts for hydrogen production, hydrocarbon formation, and organic chemical degradation (degrading carboxylic acids and phenolic species to CO2 and CO). Full article
(This article belongs to the Special Issue Sustainable Remediation Using Metallic Iron: Quo Vadis?)
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Article
Fe0-Supported Anaerobic Digestion for Organics and Nutrients Removal from Domestic Sewage
Water 2022, 14(10), 1623; https://doi.org/10.3390/w14101623 - 18 May 2022
Cited by 5 | Viewed by 1071 | Correction
Abstract
Results from different research suggest that metallic iron (Fe0) materials enhance anaerobic digestion (AD) systems to remove organics (chemical oxygen demand (COD)), phosphorus and nitrogen from polluted water. However, the available results are difficult to compare because they are derived from [...] Read more.
Results from different research suggest that metallic iron (Fe0) materials enhance anaerobic digestion (AD) systems to remove organics (chemical oxygen demand (COD)), phosphorus and nitrogen from polluted water. However, the available results are difficult to compare because they are derived from different experimental conditions. This research characterises the effects of Fe0 type and dosage in AD systems to simultaneously remove COD and nutrients (orthophosphate (PO43−), ammonium (NH4+), and nitrate (NO3)) Lab-scale reactors containing domestic sewage (DS) were fed with various Fe0 dosages (0 to 30 g/L). Batch AD experiments were operated at 37 ± 0.5 °C for 76 days; the initial pH value was 7.5. Scrap iron (SI) and steel wool (SW) were used as Fe0 sources. Results show that: (i) SW performed better than SI on COD and PO43 removal (ii) optimum dosage for the organics and nutrients removal was 10 g/L SI (iii) (NO3 + NH4+) was the least removed pollutant (iv) maximum observed COD, PO43− and NO3 + NH4+ removal efficiencies were 88.0%, 98.0% and 40.0% for 10 g/L SI, 88.2%, 99.9%, 25.1% for 10 g/L SW, and 68.9%, 7.3% and 0.7% for the reference system. Fe0-supported AD significantly removed the organics and nutrients from DS. Full article
(This article belongs to the Special Issue Sustainable Remediation Using Metallic Iron: Quo Vadis?)
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Review

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Review
Kanchan Arsenic Filters for Household Water Treatment: Unsuitable or Unsustainable?
Water 2022, 14(15), 2318; https://doi.org/10.3390/w14152318 - 26 Jul 2022
Cited by 1 | Viewed by 1055
Abstract
This article critically evaluates the conventional Kanchan Arsenic Filter (KAF) in order to determine the main reasons for its reported poor performance. The KAF was introduced in 2004 in Nepal and makes use of non-galvanized nails as a Fe0 source for As [...] Read more.
This article critically evaluates the conventional Kanchan Arsenic Filter (KAF) in order to determine the main reasons for its reported poor performance. The KAF was introduced in 2004 in Nepal and makes use of non-galvanized nails as a Fe0 source for As removal. As early as 2009, the KAF was demonstrated to be ineffective for As removal in many cases. This was unambiguously attributed to the Fe0 layer which is placed on top of a sand filter instead of being incorporated into a sand matrix. Despite this conceptual mistake, the conventional KAF has been largely distributed in Asia, and recent articles have assessed its sustainability. This study reiterates that the suitability of the technology, rather than its sustainability, should be addressed. Evidence shows that the KAF has the following design limitations: (i) uses iron nails of unknown reactivity, and (ii) operates on the principle of a wet/dry cycle. The latter causes a decrease in the corrosion rate of the used nails, thereby limiting the availability of the iron corrosion products which act as contaminant scavengers. Taken together, these results confirm the unsuitability of the conventional KAF. Besides correcting the design mistakes, more attention should be paid to the intrinsic reactivity of the used iron nails, including using alternative Fe0 materials (e.g., iron filings, steel wool) for filters lasting for just 6 or 18 months. Specific design considerations to be addressed in the future are highlighted. Full article
(This article belongs to the Special Issue Sustainable Remediation Using Metallic Iron: Quo Vadis?)
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Other

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Opinion
Conceptualizing the Fe0/H2O System: A Call for Collaboration to Mark the 30th Anniversary of the Fe0-Based Permeable Reactive Barrier Technology
Water 2022, 14(19), 3120; https://doi.org/10.3390/w14193120 - 03 Oct 2022
Cited by 3 | Viewed by 1031
Abstract
Science denial relates to rejecting well-established views that are no longer questioned by scientists within a given community. This expression is frequently connected with climate change and evolution. In such cases, prevailing views are built on historical facts and consensus. For water remediation [...] Read more.
Science denial relates to rejecting well-established views that are no longer questioned by scientists within a given community. This expression is frequently connected with climate change and evolution. In such cases, prevailing views are built on historical facts and consensus. For water remediation using metallic iron (Fe0), also known as the remediation Fe0/H2O system, a consensus on electro-chemical contaminant reduction was established during the 1990s and still prevails. Arguments against the reductive transformation concept have been regarded for more than a decade as ‘science denial’. However, is it the prevailing concept that denies the science of aqueous iron corrosion? This article retraces the path taken by our research group to question the reductive transformation concept. It is shown that the validity of the following has been questioned: (i) analytical applications of the arsenazo III method for the determination of uranium, (ii) molecular diffusion as sole relevant mass-transport process in the vicinity of the Fe0 surface in filtration systems, and (iii) the volumetric expansive nature of iron corrosion at pH > 4.5. Item (i) questions the capability of Fe0 to serve as an electron donor for UVI reduction under environmental conditions. Items (ii) and (iii) are inter-related, as the Fe0 surface is permanently shielded by a non-conductive oxide scale acting as a diffusion barrier to dissolved species and a barrier to electrons from Fe0. The net result is that no electron transfer from Fe0 to contaminants is possible under environmental conditions. This conclusion refutes the validity of the reductive transformation concept and calls for alternative theories. Full article
(This article belongs to the Special Issue Sustainable Remediation Using Metallic Iron: Quo Vadis?)
Correction
Correction: Bakari et al. Fe0-Supported Anaerobic Digestion for Organics and Nutrients Removal from Domestic Sewage. Water 2022, 14, 1623
Water 2022, 14(13), 2075; https://doi.org/10.3390/w14132075 - 29 Jun 2022
Viewed by 689
Abstract
There were some errors in the original publication [...] Full article
(This article belongs to the Special Issue Sustainable Remediation Using Metallic Iron: Quo Vadis?)
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