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.

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.

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 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.

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.