Effects of common dissolved anions on the efficiency of Fe0-based remediation systems.

Quiescent batch experiments were conducted to evaluate the influences of Cl-, F-, HCO3-, HPO42-, and SO42- on the reactivity of metallic iron (Fe0) for water remediation using the methylene blue (MB) method. Strong discoloration of MB indicates high availability of solid iron corrosion products (FeCPs). Tap water was used as an operational reference. Experiments were carried out in graduated test tubes (22 mL) for up to 45 d, using 0.1 g of Fe0 and 0.5 g of sand. Operational parameters investigated were (i) equilibration time (0-45 d), (ii) 4 different types of Fe0, (iii) anion concentration (10 values), and (iv) use of MB and Orange II (O-II). The degree of dye discoloration, the pH, and the iron concentration were monitored in each system. Relative to the reference system, HCO3- enhanced the extent of MB discoloration, while Cl-, F-, HPO42-, and SO42- inhibited it. A different behavior was observed for O-II discoloration: in particular, HCO3- inhibited O-II discoloration. The increased MB discoloration in the HCO3- system was justified by considering the availability of FeCPs as contaminant scavengers, pH increase, and contact time. The addition of any other anion initially delays the availability of FeCPs. Conflicting results in the literature can be attributed to the use of inappropriate experimental conditions. The results indicate that the application of Fe0-based systems for water remediation is a highly site-specific issue which has to include the anion chemistry of the water.

Iron-fortified water: a new approach for reducing iron deficiency anemia in resource-constrained settings.

A new approach for fortification of drinking water is presented for combating iron deficiency anemia (IDA) worldwide. The idea is to leach Fe from a bed containing granular metallic iron (Fe0), primarily using ascorbic acid (AA). AA forms very stable and bioavailable complexes with ferrous iron (FeII). Calculated amounts of the FeII-AA solution can be added daily to the drinking water of households or day-care centers for children and adults (e.g. hospitals, kindergartens/schools, refugee camps) to cover the Fe needs of the populations. Granular Fe0 (e.g., sponge iron) in filters is regarded as a locally available Fe carrier in low-income settings, and, AA is also considered to be affordable in low-income countries. The primary idea of this concept is to stabilize FeII from the Fe0 filter by using an appropriate AA solution. An experiment showed that up to 12 mg Fe can be daily leached from 1.0 g of a commercial sponge iron using a 2 mM AA solution. Fe fortification of safe drinking water is a practicable, affordable and efficient method for reducing IDA in low-income communities.

The pit latrine paradox in low-income settings: A sanitation technology of choice or a pollution hotspot?

Pit latrines are widely promoted to improve sanitation in low-income settings, but their pollution and health risks receive cursory attention. The present narrative review presents the pit latrine paradox; (1) the pit latrine is considered a sanitation technology of choice to safeguard human health, and (2) conversely, pit latrines are pollution and health risk hotspots. Evidence shows that the pit latrine is a 'catch-all' receptacle for household disposal of hazardous waste, including; (1) medical wastes (COVID-19 PPE, pharmaceuticals, placenta, used condoms), (2) pesticides and pesticide containers, (3) menstrual hygiene wastes (e.g., sanitary pads), and (4) electronic wastes (batteries). Pit latrines serve as hotspot reservoirs that receive, harbour, and then transmit the following into the environment; (1) conventional contaminants (nitrates, phosphates, pesticides), (2) emerging contaminants (pharmaceuticals and personal care products, antibiotic resistance), and (3) indicator organisms, and human bacterial and viral pathogens, and disease vectors (rodents, houseflies, bats). As greenhouse gas emission hotspots, pit latrines contribute 3.3 to 9.4 Tg/year of methane, but this could be an under-estimation. Contaminants in pit latrines may migrate into surface water, and groundwater systems serving as drinking water sources and pose human health risks. In turn, this culminates into the pit latrine-groundwater-human continuum or connectivity, mediated via water and contaminant migration. Human health risks of pit latrines, a critique of current evidence, and current and emerging mitigation measures are presented, including isolation distance, hydraulic liners/ barriers, ecological sanitation, and the concept of a circular bioeconomy. Finally, future research directions on the epidemiology and fate of contaminants in pit latrines are presented. The pit latrine paradox is not meant to downplay pit latrines' role or promote open defaecation. Rather, it seeks to stimulate discussion and research to refine the technology to enhance its functionality while mitigating pollution and health risks.

Metallic iron (Fe0)-based materials for aqueous phosphate removal: A critical review.

The discharge of excessive phosphate from wastewater sources into the aquatic environment has been identified as a major environmental threat responsible for eutrophication. It has become essential to develop efficient but affordable techniques to remove excess phosphate from wastewater before discharging into freshwater bodies. The use of metallic iron (Fe0) as a reactive agent for aqueous phosphate removal has received a wide attention. Fe0 in-situ generates positively charged iron corrosion products (FeCPs) at pH > 4.5, with high binding affinity for anionic phosphate. This study critically reviews the literature that focuses on the utilization of Fe0-based materials for aqueous phosphate removal. The fundamental science of aqueous iron corrosion and historical background of the application of Fe0 for phosphate removal are elucidated. The main mechanisms for phosphate removal are identified and extensively discussed based on the chemistry of the Fe0/H2O system. This critical evaluation confirms that the removal process is highly influenced by several operational factors including contact time, Fe0 type, influent geochemistry, initial phosphate concentration, mixing conditions, and pH value. The difficulty in comparing independent results owing to diverse experimental conditions is highlighted. Moreover, contemporary research in progress including Fe0/oxidant systems, nano-Fe0 application, Fe0 material selection, desorption studies, and proper design of Fe0-based systems for improved phosphate removal have been discussed. Finally, potential strategies to close the loop in Fe0-based phosphate remediation systems are discussed. This review presents a science-based guide to optimize the efficient design of Fe0-based systems for phosphate removal.

Should the term 'metallic iron' appear in the title of a research paper?

Over the past three decades, groundwater remediation using permeable reactive barriers (PRBs) has proven to be effective. The majority of installed PRBs uses metallic iron (Fe(0)) as a reactive material. However, the success of implemented Fe(0) PRBs is yet to be rationalized as Fe(0) is a generator of iron oxides (contaminant scavengers) and secondary reducing agents (e.g. Fe(II), Fe3O4, H2, green rust), This communication demonstrates that Fe(0) is not an environmental reducing agent. Therefore, more science-based investigations are needed to optimize the operation of Fe(0) PRBs. In particular, Fe(0) PRBs and Fe(0)-based water filters should be regarded as particular cases of "metal corrosion in porous media". A key feature of such systems is that the extent of Fe0 corrosion temporally depends on the residual porosity (capillarity). Thus, the functionality of any Fe0 PRB should be monitored in a way that the time-dependent variation of the kinetic of iron corrosion is discussed.

Investigating the Fe0/H2O systems using the methylene blue method: Validity, applications, and future directions.

An innovative approach to characterize the reactivity of metallic iron (Fe0) for aqueous contaminant removal has been in use for a decade: The methylene blue method (MB method). The approach considers the differential adsorptive affinity of methylene blue (MB) for sand and iron oxides. The MB method characterizes MB discoloration by sand as it is progressively coated by in-situ generated iron corrosion products (FeCPs) to deduce the extent of iron corrosion. The MB method is a semi-quantitative tool that has successfully clarified some contradicting reports on the Fe0/H2O system. Moreover, it has the potential to serve as a powerful tool for routine tests in the Fe0 remediation industry, including quality assurance and quality control (QA/QC). However, MB is widely used as a 'molecular probe' to characterize the Fe0/H2O system, for instance for wastewater treatment. Thus, there is scope to avoid confusion created by the multiple uses of MB in Fe0/H2O systems. The present communication aims at filling this gap by presenting the science of the MB method, and its application and limitations. It is concluded that the MB method is very suitable for Fe0 material screening and optimization of operational designs. However, the MB method only provides semi-quantitative information, but gives no data on the solid-phase characterization of solid Fe0 and its reaction products. In other words, further comprehensive investigations with microscopic and spectroscopic surface and solid-state analyses are needed to complement results from the MB method.

Modeling porosity loss in Fe0-based permeable reactive barriers with Faraday's law.

Solid iron corrosion products (FeCPs), continuously generated from iron corrosion in Fe0-based permeable reactive barriers (PRB) at pH > 4.5, can lead to significant porosity loss and possibility of system's failure. To avoid such failure and to estimate the long-term performance of PRBs, reliable models are required. In this study, a mathematical model is presented to describe the porosity change of a hypothetical Fe0-based PRB through-flowed by deionized water. The porosity loss is solely caused by iron corrosion process. The new model is based on Faraday's Law and considers the iron surface passivation. Experimental results from literature were used to calibrate the parameters of the model. The derived iron corrosion rates (2.60 mmol/(kg day), 2.07 mmol/(kg day) and 1.77 mmol/(kg day)) are significantly larger than the corrosion rate used in previous modeling studies (0.4 mmol/(kg day)). This suggests that the previous models have underestimated the impact of in-situ generated FeCPs on the porosity loss. The model results show that the assumptions for the iron corrosion rates on basis of a first-order dependency on iron surface area are only valid when no iron surface passivation is considered. The simulations demonstrate that volume-expansion by Fe0 corrosion products alone can cause a great extent of porosity loss and suggests careful evaluation of the iron corrosion process in individual Fe0-based PRB.

The key role of contact time in elucidating the mechanisms of enhanced decontamination by Fe0/MnO2/sand systems.

Metallic iron (Fe0) has shown outstanding performances for water decontamination and its efficiency has been improved by the presence of sand (Fe0/sand) and manganese oxide (Fe0/MnOx). In this study, a ternary Fe0/MnOx/sand system is characterized for its discoloration efficiency of methylene blue (MB) in quiescent batch studies for 7, 18, 25 and 47 days. The objective was to understand the fundamental mechanisms of water treatment in Fe0/H2O systems using MB as an operational tracer of reactivity. The premise was that, in the short term, both MnO2 and sand delay MB discoloration by avoiding the availability of free iron corrosion products (FeCPs). Results clearly demonstrate no monotonous increase in MB discoloration with increasing contact time. As a rule, the extent of MB discoloration is influenced by the diffusive transport of MB from the solution to the aggregates at the bottom of the vessels (test-tubes). The presence of MnOx and sand enabled the long-term generation of iron hydroxides for MB discoloration by adsorption and co-precipitation. Results clearly reveal the complexity of the Fe0/MnOx/sand system, while establishing that both MnOx and sand improve the efficiency of Fe0/H2O systems in the long-term. This study establishes the mechanisms of the promotion of water decontamination by amending Fe0-based systems with reactive MnOx.

Characterizing the impact of MnO2 addition on the efficiency of Fe0/H2O systems.

The role of manganese dioxide (MnO2) in the process of water treatment using metallic iron (Fe0/H2O) was investigated in quiescent batch experiments for t ≤ 60 d. MnO2 was used as an agent to control the availability of solid iron corrosion products (FeCPs) while methylene blue (MB) was an indicator of reactivity. The investigated systems were: (1) Fe0, (2) MnO2, (3) sand, (4) Fe0/sand, (5) Fe0/MnO2, and (6) Fe0/sand/MnO2. The experiments were performed in test tubes each containing 22.0 mL of MB (10 mg L-1) and the solid aggregates. The initial pH value was 8.2. Each system was characterized for the final concentration of H+, Fe, and MB. Results show no detectable level of dissolved iron after 47 days. Final pH values varied from 7.4 to 9.8. The MB discoloration efficiency varies from 40 to 80% as the MnO2 loading increases from 2.3 to 45 g L-1. MB discoloration is only quantitative when the operational fixation capacity of MnO2 for Fe2+ was exhausted. This corresponds to the event where adsorption and co-precipitation with FeCPs is intensive. Adsorption and co-precipitation are thus the fundamental mechanisms of decontamination in Fe0/H2O systems. Hybrid Fe0/MnO2 systems are potential candidates for the design of more sustainable Fe0 filters.

The mechanism of contaminant removal in Fe(0)/H2O systems: The burden of a poor literature review.

The global effort to mitigate the impact of environmental pollution has led to the use of various types of metallic iron (Fe(0)) in the remediation of soil and groundwater as well as in the treatment of industrial and municipal effluents. During the past three decades, hundreds of scientific publications have controversially discussed the mechanism of contaminant removal in Fe(0)/H2O systems, with the large majority considering Fe(0) to be oxidized by contaminants of concern. This view assumes that contaminant reduction is the cathodic reaction occurring simultaneously with Fe0 oxidative dissolution (anodic reaction). This view contradicts the century-old theory of the electrochemical nature of aqueous iron corrosion and hinders progress in designing efficient and sustainable remediation Fe(0)/H2O systems. The aim of the present communication is to demonstrate the fallacy of the current prevailing view based on articles published before 1910. It is shown that properly reviewing the literature would have avoided the mistake. Going back to the roots is recommended as the way forward and should be considered first while designing laboratory experiments.

Characterizing the impact of pyrite addition on the efficiency of Fe0/H2O systems.

The role of pyrite (FeS2) in the process of water treatment using metallic iron (Fe0) was investigated. FeS2 was used as a pH-shifting agent while methylene blue (MB) and methyl orange (MO) were used as an indicator of reactivity and model contaminant, respectively. The effect of the final pH value on the extent of MB discoloration was characterized using 5 g L-1 of a Fe0 specimen. pH variation was achieved by adding 0 to 30 g L-1 of FeS2. Quiescent batch experiments with Fe0/FeS2/sand systems (sand loading: 25 g L-1) and 20 mL of MB were performed for 41 days. Final pH values varied from 3.3 to 7.0. Results demonstrated that MB discoloration is only quantitative when the final pH value was larger than 4.5 and that adsorption and co-precipitation are the fundamental mechanisms of decontamination in Fe0/H2O systems. Such mechanisms are consistent with the effects of the pH value on the decontamination process.

Redirecting Research on Fe0 for Environmental Remediation: The Search for Synergy.

A survey of the literature on using metallic iron (Fe0) for environmental remediation suggests that the time is ripe to center research on the basic relationship between iron corrosion and contaminant removal. This communication identifies the main problem, which is based on the consideration that contaminant reductive transformation is the cathodic reaction of iron oxidative dissolution. Properly considering the inherent complexities of the Fe0/H2O system will favor an appropriate research design that will enable more efficient and sustainable remediation systems. Successful applications of Fe0/H2O systems require the collective consideration of progress achieved in understanding these systems. More efforts should be made to decipher the long-term kinetics of iron corrosion, so as to provide better approaches to accurately predict the performance of the next generation Fe0-based water treatment systems.

Characterizing the reactivity of metallic iron for water defluoridation in batch studies.

The suitability of metallic iron (Fe(0)) for water defluoridation is yet to be understood. Fluoride removal ([F-]0 = 20.0 mg L-1) and Orange II discoloration ([Orange II]0 = 10.0 mg L-1) by Fe(0)/H2O batch systems are compared herein. A steel wool (SW) and a granular iron (GI) are used as Fe(0) specimens. Each essay tube contains 0.5 g sand and 0.1 g of the used Fe(0). Investigated systems were: (i) SW/sand at pH 5.0, (ii) GI/sand at pH 5.0 and (iii) SW/sand at pH 8.0. Prior to contaminant addition, Fe(0) was allowed to pre-corrode within the systems for up to 46 days. The systems were then equilibrated for 30 days with a mixture of the two model contaminants. Result confirmed (i) the higher efficiency of SW over GI in removing both contaminants, (ii) the higher efficiency of Fe(0) for Orange II discoloration and (iii) the positive impact of initial low pH values on the efficiency of Fe(0)/H2O systems. The major output of this research is that conventional Fe(0)/H2O systems are not suitable for quantitative water defluoridation. It is suggested that ways to avoid defluoridation using Fe0 must be explored. One affordable opportunity is blending fluoride-polluted water with carefully harvested rainwater.

Investigating the suitability of Fe0 packed-beds for water defluoridation.

A commercial granular metallic iron (Fe0) specimen was used to evaluate the suitability of Fe0 materials for removing aqueous fluoride (F-) (water defluoridation). Experiments were performed to characterize the defluoridation potential of the tested Fe0 as influenced by the presence of chloride (Cl-) and bicarbonate (HCO3-) ions using tap water (H2O) as operational reference system. Duplicate column studies were conducted for 120 days (4 months) using an initial F- concentration of 22.5 mg L-1, columns flow rates were about 17 mL h-1. Each column contained a reactive layer (11 cm) made up of 100 g of Fe0 in a 1:1 volumetric Fe0:sand mixture. The reactive layer was sandwiched between two layers of the same sand. A pure sand column was used as control system. After the F- removal experiments, the columns were flushed by methylene blue (MB) and Orange II for 21 days. Removal studies revealed (i) no F- removal in the control system, (ii) no F- significant removal on the Cl- system, (iii) limited F- removal in the HCO3- system, and (iv) the best F- removal efficiency in tap water (H2O). Dye flushing studies confirmed the ion-selective nature of the Fe0/H2O system and demonstrated the relatively low efficiency of the same for F- removal. The overall results challenge the prevailing perception that water defluoridation using granular Fe0 is not possible and suggest that effective water defluoridation in Fe0 packed-beds is pure a site-specific design issue.

Role of pre-corrosion of Fe0 on its efficiency in remediation systems: An electrochemical study.

The duration of in-situ generation of iron corrosion products (FeCPs) prior the remediation process (so called "aging" of metallic iron (Fe0)), was found as the key parameter affecting the efficiency of Fe0 for water remediation. Batch experiments were performed in buffered solutions (pH 4.0, 4.7 and 5.5) and under oxic conditions (presence of dissolved oxygen) using Zn2+ as probe contaminant. The time-dependent (0-16 d) concentration changes of aqueous Fe2+ and Zn2+ were monitored using differential pulse polarography (DPP). During the time of pre-corrosion varying from 0 to 6 d, an "induction period" of the corrosion occurs in the first one - 2 h when no Fe2+ ion is released in the solution. After this period, Fe2+ was identified in solution and its concentration progressively increases up to 6 h, then starts to decrease and after 6 d nearly disappears. Experiments with Zn2+ reveal that the most efficient Fe0 remediation occurs after 6 h of pre-corrosion. This coherence thus proves that the presence, the amount and the age of FeCPs ("degree" of corrosion) significantly impact the removal efficiency of Zn2+ in Fe0/H2O systems. The present study severely refute the wording 'reactivity loss' and states that progress in designing sustainable Fe0/H2O systems will not be achieved before the role of "active" FeCPs is clarified.

Metallic iron for safe drinking water provision: Considering a lost knowledge.

Around year 1890, the technology of using metallic iron (Fe0) for safe drinking water provision was already established in Europe. The science and technology to manufacture suitable Fe0 materials were known and further developed in this period. Scientists had then developed skills to (i) explore the suitability of individual Fe0 materials (e.g. iron filling, sponge iron) for selected applications, and (ii) establish treatment processes for households and water treatment plants. The recent (1990) discovery of Fe0 as reactive agent for environmental remediation and water treatment has not yet considered this ancient knowledge. In the present work, some key aspects of the ancient knowledge are presented together with some contemporised interpretations, in an attempt to demonstrate the scientific truth contained therein. It appears that the ancient knowledge is an independent validation of the scientific concept that in water treatment (Fe0/H2O system) Fe0 materials are generators of contaminant collectors.

Biochar-based water treatment systems as a potential low-cost and sustainable technology for clean water provision.

Approximately 600 million people lack access to safe drinking water, hence achieving Sustainable Development Goal 6 (Ensure availability and sustainable management of water and sanitation for all by 2030) calls for rapid translation of recent research into practical and frugal solutions within the remaining 13 years. Biochars, with excellent capacity to remove several contaminants from aqueous solutions, constitute an untapped technology for drinking water treatment. Biochar water treatment has several potential merits compared to existing low-cost methods (i.e., sand filtration, boiling, solar disinfection, chlorination): (1) biochar is a low-cost and renewable adsorbent made using readily available biomaterials and skills, making it appropriate for low-income communities; (2) existing methods predominantly remove pathogens, but biochars remove chemical, biological and physical contaminants; (3) biochars maintain organoleptic properties of water, while existing methods generate carcinogenic by-products (e.g., chlorination) and/or increase concentrations of chemical contaminants (e.g., boiling). Biochars have co-benefits including provision of clean energy for household heating and cooking, and soil application of spent biochar improves soil quality and crop yields. Integrating biochar into the water and sanitation system transforms linear material flows into looped material cycles, consistent with terra preta sanitation. Lack of design information on biochar water treatment, and environmental and public health risks constrain the biochar technology. Seven hypotheses for future research are highlighted under three themes: (1) design and optimization of biochar water treatment; (2) ecotoxicology and human health risks associated with contaminant transfer along the biochar-soil-food-human pathway, and (3) life cycle analyses of carbon and energy footprints of biochar water treatment systems.

Research on metallic iron for environmental remediation: Stopping growing sloppy science.

Research on using metallic iron (Fe(0)) for environmental remediation has boomed during the passed two decades. Achieved results have established filtration on Fe(0) packed beds as an efficient technology for water treatment at several scales. However, the further development of Fe(0)-based filtration systems is impaired by useless discussion on the mechanism of contaminant removal. However, the whole discussion becomes superfleous while properly considering the difference between a chemical and an electrochemical reaction. This note ends the discussion and suggests practical ways to avoid the further propagation of the mistake.

Metallic iron for environmental remediation: A review of reviews.

This article critically evaluates recent review articles on using metallic iron (Fe(0)) for environmental remediation in order to provide insight for more efficient Fe(0)-based systems. The presentation is limited to peer-reviewed articles published during 2014 and 2015, excluding own contributions, dealing mostly with granular Fe(0). A literature search was conducted up to June 15th 2015 using Science Direct, SCOPUS, Springer and Web of Science databases. The search yielded eight articles that met the final inclusion criteria. The evaluation clearly shows that seven articles provide a narrative description of processes occurring in the Fe(0)/H20 system according to the concept that Fe(0) is a reducing agent. Only one article clearly follows a different path, presenting Fe(0) as a generator of adsorbing (hydroxides, oxides) and reducing (Fe(II), H/H2) agents. The apparent discrepancies between the two schools are identified and extensively discussed based on the chemistry of the Fe(0)/H20 system. The results of this evaluation indicate clearly that research on 'Fe(0) for environmental remediation' is in its infancy. Despite the current paucity of reliable data for the design of efficient Fe(0)-based systems, this review demonstrates that sensible progress could be achieved within a short period of time, specific recommendations to help guide future research are suggested.

Flaws in the design of Fe(0)-based filtration systems?

Use of metallic iron (Fe(0)) for water treatment has attracted much attention over the passed two decades. Achieved results have recalled that the formation of voluminous, low-soluble iron oxides and hydroxides within the system is ubiquitous at pH>4.0. These properties imply that efficiency and porosity of Fe(0)-based filtration systems will decrease in the long-term. Some methods have been suggested to solve the identified problems. However, they could be collectively regarded as weak because they are based on a false description of the system. This note reveals two major inherent flaws in the design of Fe(0)-based filters and shows ways to fix them.