Chicgoua Noubactep

Nanoscale Metallic Iron for Environmental Remediation: Prospects and Limitations

The amendment of the subsurface with nanoscale metallic iron particles (nano-Fe0) has been discussed in the literature as an efficient in situ technology for groundwater remediation. However, the introduction of this technology was controversial and its efficiency has never been univocally established. This unsatisfying situation has motivated this communication whose objective was a comprehensive discussion of the intrinsic reactivity of nano-Fe0 based on the contemporary knowledge on the mechanism of contaminant removal by Fe0 and a mathematical model. It is showed that due to limitations of the mass transfer of nano-Fe0 to contaminants, available concepts cannot explain the success of nano-Fe0 injection for in situ groundwater remediation. It is recommended to test the possibility of introducing nano-Fe0 to initiate the formation of roll-fronts which propagation would induce the reductive transformation of both dissolved and adsorbed contaminants. Within a roll-front, FeII from nano-Fe0 is the reducing agent for contaminants. FeII is recycled by biotic or abiotic FeIII reduction. While the roll-front concept could explain the success of already implemented reaction zones, more research is needed for a science-based recommendation of nano-Fe0 for subsurface treatment by roll-fronts.

An analysis of the evolution of reactive species in Fe0/H2O systems

Aqueous contaminant removal in the presence of metallic iron (e.g. in Fe(0)/H(2)O systems) is characterized by the large diversity of removing agents. This paper analyses the synergistic effect of adsorption, co-precipitation and reduction on the process contaminant removal in Fe(0)/H(2)O systems on the basis of simple theoretical calculations. The system evolution is characterized by the percent Fe(0) consumption. The results showed that contaminant reduction by Fe(0) is likely to significantly contribute to the removal process only in the earliest stage of Fe(0) immersion. With increasing reaction time, contaminant removal is a complex interplay of adsorption onto iron corrosion products, co-precipitation or sequestration in the matrix of iron corrosion products and reduction by Fe(0), Fe(II) or H(2)/H. The results also suggested that in real world Fe(0)/H(2)O systems, any inflowing contaminant can be regarded as foreign species in a domain of precipitating iron hydroxides. Therefore, current experimental protocols with high contaminant to Fe(0) ratios should be revisited. Possible optimising of experimental conditions is suggested.

Nano-scale metallic iron for the treatment of solutions containing multiple inorganic contaminants.

Although contaminant removal from water using zero-valent iron nanoparticles (INP) has been investigated for a wide array of chemical pollutants, the majority of studies to date have only examined the reaction of INP in simple single-contaminant systems. Such systems fail to reproduce the complexity of environmental waters and consequently fail as environmental analogues due to numerous competitive reactions not being considered. Consequently there is a high demand for multi-elemental and site-specific studies to advance the design of INP treatment infrastructure. Here INP are investigated using batch reactor systems over a range of pH for the treatment of water containing multi-element contaminants specifically U, Cu, Cr and Mo, selected to provide site-specific analogues for leachants collected from the Lişava mine, near Oraviţa in South West Romania. Concurrently, a U-only solution was also analysed as a single-system for comparison. Results confirmed the suitability of nano-Fe(0) as a highly efficient reactive material for the aqueous removal of Cr(IV), Cu(II) and U(VI) over a range of pH applicable to environmental waters. Insufficient Mo(VI) removal was observed at pH >5.7, suggesting that further studies were necessary to successfully deploy INP for the treatment of geochemically complex mine water effluents. Results also indicated that uranium removal in the multi-element system was less than for the comparator containing only uranium.

Characterizing the discoloration of methylene blue in Fe0/H2O systems

Methylene blue (MB) was used as a model molecule to characterize the aqueous reactivity of metallic iron in Fe(0)/H(2)O systems. Likely discoloration mechanisms under used experimental conditions are: (i) adsorption onto Fe(0) and Fe(0) corrosion products (CP), (ii) co-precipitation with in situ generated iron CP, (iii) reduction to colorless leukomethylene blue (LMB). MB mineralization (oxidation to CO(2)) is not expected. The kinetics of MB discoloration by Fe(0), Fe(2)O(3), Fe(3)O(4), MnO(2), and granular activated carbon were investigated in assay tubes under mechanically non-disturbed conditions. The evolution of MB discoloration was monitored spectrophotometrically. The effect of availability of CP, Fe(0) source, shaking rate, initial pH value, and chemical properties of the solution were studied. The results present evidence supporting co-precipitation of MB with in situ generated iron CP as main discoloration mechanism. Under high shaking intensities (>150 min(-1)), increased CP generation yields a brownish solution which disturbed MB determination, showing that a too high shear stress induced the suspension of in situ generated corrosion products. The present study clearly demonstrates that comparing results from various sources is difficult even when the results are achieved under seemingly similar conditions. The appeal for an unified experimental procedure for the investigation of processes in Fe(0)/H(2)O systems is reiterated.

Metallic iron for environmental remediation: learning from electrocoagulation.

The interpretation of processes yielding aqueous contaminant removal in the presence of elemental iron (e.g. in Fe(0)/H(2)O systems) is subject to numerous complications. Reductive transformations by Fe(0) and its primary corrosion products (Fe(II) and H/H(2)) as well as adsorption onto and co-precipitation with secondary and tertiary iron corrosion products (iron hydroxides, oxyhydroxides, and mixed valence Fe(II)/Fe(III) green rusts) are considered the main removal mechanisms on a case-to-case basis. Recent progress involving adsorption and co-precipitation as fundamental contaminant removal mechanisms have faced a certain scepticism. This work shows that results from electrocoagulation (EC), using iron as sacrificial electrode, support the adsorption/co-precipitation concept. It is reiterated that despite a century of commercial use of EC, the scientific understanding of the complex chemical and physical processes involved is still incomplete.

Testing the Suitability of Zerovalent Iron Materials for Reactive Walls

Environmental Context. Groundwater remediation is generally a costly, long-term process. In situ remediation using permeable reactive barriers, through which the groundwaters pass, is a potential solution. For redox-sensitive contaminants in groundwater, a metallic iron barrier (zerovalent iron, ZVI) can immobilize or degrade these dissolved pollutants. Scrap iron materials are a low-cost ZVI material but, because of the wide variation of scrap metal compositions, testing methods for characterizing the corrosion behaviour need to be developed. Abstract. Zerovalent iron (ZVI) has been proposed as reactive material in permeable in situ walls for contaminated groundwater. An economically feasible ZVI-based reactive wall requires cheap but efficient iron materials. From an uranium treatability study and results of iron dissolution in 0.002 M EDTA by five selected ZVI materials, it is shown that current research and field implementation is not based on a rational selection of application-specific iron metal sources. An experimental procedure is proposed which could enable a better material characterization. This procedure consists of mixing ZVI materials and reactive additives, including contaminant releasing materials (CRMs), in long-term batch experiments and characterizing the contaminant concentration over the time.

Exploring the influence of operational parameters on the reactivity of elemental iron materials

In an attempt to characterize material intrinsic reactivity, iron dissolution from elemental iron materials (Fe(0)) was investigated under various experimental conditions in batch tests. Dissolution experiments were performed in a dilute solution of ethylenediaminetetraacetate (Na(2)-EDTA - 2mM). The dissolution kinetics of 18 Fe(0) materials were investigated. The effects of individual operational parameters were assessed using selected materials. The effects of available reactive sites [Fe(0) particle size (<or=2.0mm) and metal loading (2-64 g L(-1))], mixing type (air bubbling, shaking), shaking intensity (0-250 min(-1)), and Fe(0) pre-treatment (ascorbate, HCl and EDTA washing) were investigated. The data were analysed using the initial dissolution rate (k(EDTA)). The results show increased iron dissolution with increasing reactive sites (decreasing particle size or increasing metal loading), and increasing mixing speed. Air bubbling and material pre-treatment also lead to increased iron dissolution. The main output of this work is that available results are hardly comparable as they were achieved under very different experimental conditions. A unified experimental procedure for the investigation of processes in Fe(0)/H(2)O systems is suitable. Alternatively, a parameter (tau(EDTA)) is introduced which could routinely used to characterize Fe(0) reactivity under given experimental conditions.

On nanoscale metallic iron for groundwater remediation.

This communication challenges the concept that nanoscale metallic iron (nano-Fe(0)) is a strong reducing agents for contaminant reductive transformation. It is shown that the inherent relationship between contaminant removal and Fe(0) oxidative dissolution which is conventionally attributed to contaminant reduction by nano-Fe(0) (direct reduction) could equally be attributed to contaminant removal by adsorption and co-precipitation. For reducible contaminants, indirect reduction by adsorbed Fe(II) or adsorbed H produced by corroding iron (indirect reduction) is even a more probable reaction path. As a result, the contaminant removal efficiency is strongly dependent on the extent of iron corrosion which is larger for nano-Fe(0) than for micro-Fe(0) in the short term. However, because of the increased reactivity, nano-Fe(0) will deplete in the short term. No more source of reducing agents (Fe(II), H and H(2)) will be available in the system. Therefore, the efficiency of nano-Fe(0) as a reducing agent for environmental remediation is yet to be demonstrated.

Elemental metals for environmental remediation: Learning from cementation process

The further development of Fe(0)-based remediation technology depends on the profound understanding of the mechanisms involved in the process of aqueous contaminant removal. The view that adsorption and co-precipitation are the fundamental contaminant removal mechanisms is currently facing a harsh scepticism. Results from electrochemical cementation are used to bring new insights in the process of contaminant removal in Fe(0)/H(2)O systems. The common feature of hydrometallurgical cementation and metal-based remediation is the heterogeneous nature of the processes which inevitably occurs in the presence of a surface scale. The major difference between both processes is that the surface of remediation metals is covered by layers of own oxide(s) while the surface of the reducing metal in covered by porous layers of the cemented metal. The porous cemented metal is necessarily electronic conductive and favours further dissolution of the reducing metal. For the remediation metal, neither a porous layer nor a conductive layer could be warrant. Therefore, the continuation of the remediation process depends on the long-term porosity of oxide scales on the metal surfaces. These considerations rationalized the superiority of Fe(0) as remediation agent compared to thermodynamically more favourable Al(0) and Zn(0). The validity of the adsorption/co-precipitation concept is corroborated.

Designing laboratory metallic iron columns for better result comparability.

Despite the amount of data available on investigating the process of aqueous contaminant removal by metallic iron (Fe(0)), there is still a significant amount of uncertainty surrounding the design of Fe(0) beds for laboratory testing to determine the suitability of Fe(0) materials for field applications. Available data were obtained under various operating conditions (e.g., column characteristics, Fe(0) characteristics, contaminant characteristics, oxygen availability, solution pH) and are hardly comparable to each other. The volumetric expansive nature of iron corrosion has been univocally reported as major drawback for Fe(0) beds. Mixing Fe(0) with inert materials has been discussed as an efficient tool to improve sustainability of Fe(0) beds. This paper discusses some problems associated with the design of Fe(0) beds and proposes a general approach for the characterization of Fe(0) beds. Each Fe(0) column should be characterized by its initial porosity, the composition of the steady phase and the volumetric proportion of individual materials. Used materials should be characterized by their density, porosity, and particle size. This work has introduced simple and reliable mathematical equations for column design, which include the normalisation of raw experimental data prior to any data treatment.