ALBERT

Description: Metallic iron (Fe0) has been demonstrated as an excellent material for decentralized safe drinking water provision, wastewater treatment and environmental remediation. An open issue for all these applications is the rational material selection or quality assurance. Several methods for assessing Fe0 quality have been presented, but all of them are limited to characterizing its initial reactivity. The present study investigates H2 evolution in an acidic solution (pH 2.0) as an alternative method, while comparing achieved results to those of uranium removal in quiescent batch experiments at neutral pH values. The unique feature of the H2 evolution experiment is that quantitative H2 production ceased when the pH reached a value of 3.1. A total of twelve Fe0 specimens were tested. The volume of molecular H2 produced by 2.0 g of each Fe0 specimen in 560 mL H2SO4 (0.01 M) was monitored for 24 h. Additionally, the extent of U(VI) (0.084 mM) removal from an aqueous solution (20.0 mL) by 0.1 g of Fe0 was characterized. All U removal experiments were performed at room temperature (22 ± 2 °C) for 14 days. Results demonstrated the difficulty of comparing Fe0 specimens from different sources and confirmed that the elemental composition of Fe0 is not a stand-alone determining factor for reactivity. The time-dependent changes of H2 evolution in H2SO4 confirmed that tests in the neutral pH range just address the initial reactivity of Fe0 materials. In particular, materials initially reacting very fast would experience a decrease in reactivity in the long-term, and this aspect must be incorporated in designing novel materials and sustainable remediation systems. An idea is proposed that could enable the manufacturing of intrinsically long-term efficient Fe0 materials for targeted operations as a function of the geochemistry.

Description: 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.

Description: Studies were undertaken to characterize the intrinsic reactivity of Fe0-bearing steel wool (Fe0 SW) materials using the ethylenediaminetetraacetate method (EDTA test). A 2 mM Na2-EDTA solution was used in batch and column leaching experiments. A total of 15 Fe0 SW specimens and one granular iron (GI) were tested in batch experiments. Column experiments were performed with four Fe0 SW of the same grade but from various suppliers and the GI. The conventional EDTA test (0.100 g Fe0, 50 mL EDTA, 96 h) protocol was modified in two manners: (i) Decreasing the experimental duration (down to 24 h) and (ii) decreasing the Fe0 mass (down to 0.01 g). Column leaching studies involved glass columns filled to 1/4 with sand, on top of which 0.50 g of Fe0 was placed. Columns were daily gravity fed with EDTA and effluent analyzed for Fe concentration. Selected reactive Fe0 SW specimens were additionally investigated for discoloration efficiency of methylene blue (MB) in shaken batch experiments (75 rpm) for two and eight weeks. The last series of experiments tested six selected Fe0 SW for water defluoridation in Fe0/sand columns. Results showed that (i) the modifications of the conventional EDTA test enabled a better characterization of Fe0 SW; (ii) after 53 leaching events the Fe0 SW showing the best kEDTA value released the lowest amount of iron; (iii) all Fe0 specimens were efficient at discoloring cationic MB after eight weeks; (iv) limited water defluoridation by all six Fe0 SW was documented. Fluoride removal in the column systems appears to be a viable tool to characterize the Fe0 long-term corrosion kinetics. Further research should include correlation of the intrinsic reactivity of SW specimens with their efficiency at removing different contaminants in water.

Description: 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.

Description: 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.

Description: The technology of using metallic iron (Fe0) for in situ generation of iron oxides for water treatment is a very old one. The Fe0 remediation technology has been re-discovered in the framework of groundwater remediation using permeable reactive barriers (PRBs). Despite its simplicity, the improvement of Fe0 PRBs is fraught with difficulties regarding their operating modes. The literature dealing with Fe0 remediation contains ambiguities regarding its invention and its development. The present paper examines the sequence of contributions prior to the advent of Fe0 PRBs in order to clarify the seemingly complex picture. To achieve this, the current paper addresses the following questions: (i) What were the motivations of various authors in developing their respective innovations over the years?, (ii) what are the ancient achievements which can accelerate progress in knowledge for the development of Fe0 PRBs?, and (iii) was Fe0 really used for the removal of organic species for the first time in the 1970s? A careful examination of ancient works reveals that: (i) The wrong questions were asked during the past three decades, as Fe0 was premised as a reducing agent, (ii) credit for using Fe0 for water treatment belongs to no individual scientist, and (iii) credit for the use of Fe0 in filtration systems for safe drinking water provision belongs to scientists from the 1850s, while credit for the use of Fe0 for the removal of aqueous organic species does not belong to the pioneers of the Fe0 PRB technology. However, it was these pioneers who exploited Fe0 for groundwater remediation, thereby extending its potential. Complementing recent achievements with the chemistry of the Fe0/H2O system would facilitate the design of more sustainable Fe0-remediation systems.

Description: The ambitious United Nations Sustainable Development Goal for 2030 to “leave no one behind” concerning safe drinking water calls for the development of universally applicable and affordable decentralized treatment systems to provide safe drinking water. Published results suggest that well-designed biological sand filters (BSFs) amended with metallic iron (Fe0-BSFs) have the potential to achieve this goal. Fe0-BSFs quantitatively remove pathogens and a myriad of chemical pollutants. The available data were achieved under various operating conditions. A comparison of independent research results is almost impossible, especially because the used Fe0 materials are not characterized for their intrinsic reactivity. This communication summarizes the state-of-the-art knowledge on designing Fe0-BSFs for households and small communities. The results show that significant research progress has been made on Fe0-BSFs. However, well-designed laboratory and field experiments are required to improve the available knowledge in order to develop the next generation of adaptable and scalable designs of Fe0-BSFs in only two years. Tools to alleviate the permeability loss, the preferential flow, and the use of exhausted filters are presented.

Description: This study characterizes the decrease of the hydraulic conductivity (permeability loss) of a metallic iron-based household water filter (Fe0 filter) for a duration of 12 months. A commercial steel wool (SW) is used as Fe0 source. The Fe0 unit containing 300 g of SW was sandwiched between two conventional biological sand filters (BSFs). The working solution was slightly turbid natural well water polluted with pathogens (total coliform = 1950 UFC mL−1) and contaminated with nitrate ([NO3−] = 24.0 mg L−1). The system was monitored twice per month for pH value, removal of nitrate, coliforms, and turbidity, the iron concentration, as well as the permeability loss. Results revealed a quantitative removal of coliform (〉99%), nitrate (〉99%) and turbidity (〉96%). The whole column effluent depicted drinking water quality. The permeability loss after one year of operation was about 40%, and the filter was still producing 200 L of drinking water per day at a flow velocity of 12.5 L h−1. A progressive increase of the effluent pH value was also recorded from about 5.0 (influent) to 8.4 at the end of the experiment. The effluent iron concentration was constantly lower than 0.2 mg L−1, which is within the drinking-water quality standards. This study presents an affordable design that can be one-to-one translated into the real world to accelerate the achievement of the UN Sustainable Development Goals for safe drinking water.