Richard Crane

Nanoscale zero-valent iron: Future prospects for an emerging water treatment technology

For the past 15 years, nanoscale metallic iron (nZVI) has been investigated as a new tool for the treatment of contaminated water and soil. The technology has reached commercial status in many countries worldwide, however is yet to gain universal acceptance. This review summarises our contemporary knowledge of nZVI aqueous corrosion, manufacture and deployment, along with methods to enhance particle reactivity, stability and subsurface mobility. Reasons for a lack of universal acceptance are also explored. Key factors include: concerns over the long-term fate, transformation and ecotoxicity of nZVI in environmental systems and, a lack of comparable studies for different nZVI materials and deployment strategies. It is highlighted that few investigations to date have examined systems directly analogous to the chemistry, biology and architecture of the terrestrial environment. Such emerging studies have highlighted new concerns, including the prospect for remobilisation of heavy metals and radionuclides over extended periods. The fundamental importance of being able to accurately predict the long-term physical, chemical and biological fate of contaminated sites following nZVI treatment is emphasised and, as part of this, a universal empirical testing framework for nZVI is suggested.

Magnetite and zero-valent iron nanoparticles for the remediation of uranium contaminated environmental water

The current work presents a comparative and site specific study for the application of zero-valent iron nanoparticles (nano-Fe(0)) and magnetite nanoparticles (nano-Fe(3)O(4)) for the removal of U from carbonate-rich environmental water taken from the Lişava valley, Banat, Romania. Nanoparticles were introduced to the Lişava water under surface and deep aquifer oxygen conditions, with a U(VI)-only solution studied as a simple system comparator. Thebatch systems were analysed over an 84 day reaction period, during which the liquid and nanoparticulate solids were periodically sampled to determine chemical evolution of the solutions and particulates. Results indicated that U was removed by all nano-Fe(0) systems to <10 μg L(-1) (>98% removal) within 2 h of reaction, below EPA and WHO specified drinking water regulations. Similar U concentrations were maintained until approximately 48 h. X-ray photoelectron spectroscopy analysis of the nanoparticulate solids confirmed partial chemical reduction of U(VI) to U(IV) concurrent with Fe oxidation. In contrast, nano-Fe(3)O(4) failed to achieve >20% U removal from the Lişava water. Whilst the outer surface of both the nano-Fe(0) and nano-Fe(3)O(4) was initially near-stoichiometric magnetite, the greater performance exhibited by nano-Fe(0) is attributed to the presence of a Fe(0) core for enhanced aqueous reactivity, sufficient to achieve near-total removal of aqueous U despite any competing reactions within the carbonate-rich Lişava water. Over extended reaction periods (>1 week) the chemically simple U(VI)-only solution treated using nano-Fe(0) exhibited near-complete and maintained U removal. In contrast, appreciable U re-release was recorded for the Lişava water solutions treated using nano-Fe(0). This behaviour is attributed to the high stability of U in the presence of ligands (predominantly carbonate) within the Lişava water, inducing preferential re-release to the aqueous phase during nano-Fe(0) corrosion. The current study therefore provides clear evidence for the removal and immobilisation of U from environmental waters using Fe-based nanoparticles. As a contrast to previous experimental studies reporting impressive figures for U removal and retention from simple aqueous systems, the present work demonstrates both nanomaterials as ineffective on timescales >1 week. Consequently further research is required to develop nanomaterials that exhibit greater reactivity and extended retention of inorganic contaminants in chemically complex environmental waters.

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.

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.

The removal of uranium onto nanoscale zero-valent iron particles in anoxic batch systems

The removal of uranium (U) onto nanoscale zero-valent iron particles has been studied for uranium-bearing mine water and synthetic uranyl solutions in the presence and absence of dissolved oxygen. The work has been conducted in order to investigate the differential nanoparticle corrosion behaviour and associated mechanisms of U removal behaviour in conditions representative of near-surface and deep groundwater systems. Batch systems were analysed over a 28-day reaction period during which the liquid and nanoparticulate solids were periodically analysed to determine chemical evolution of the solutions and particulates. Analysis of aqueous samples using inductively coupled plasma mass spectrometry recorded near-total U removal after 1 hour of reaction in all systems studied. However, in the latter stages of the reaction (after 48 hours), significant rerelease of uranium was recorded for the mine water batch system with dissolved O2 present. In contrast, less than 2% uranium rerelease was recorded for the anoxic batch system. Concurrent analysis of extracted nanoparticle solids using X-ray diffraction recorded significantly slower corrosion of the nanoparticles in the anoxic batch system, with residual metallic iron maintained until after 28 days of reaction compared to only 7 days of reaction in systems with dissolved O2 present. Results provide clear evidence that the corrosion lifespan and associated U6+ removal efficacy of nanoscale zero-valent iron replace enhanced in the absence of dissolved oxygen.

The effect of vacuum annealing of magnetite and zero-valent iron nanoparticles on the removal of aqueous uranium

As-formed and vacuum annealed zero-valent iron nanoparticles (nano-Fe0) and magnetite nanoparticles (nano-Fe3O4) were tested for the removal of uranium from carbonate-rich mine water. Nanoparticles were introduced to batch systems containing the mine water under oxygen conditions representative of near-surface waters, with a uranyl solution studied as a simple comparator system. Despite the vacuum annealed nano-Fe0 having a 64.6% lower surface area than the standard nano-Fe0, similar U removal (>98%) was recorded during the initial stages of reaction with the mine water. In contrast, ≤15% U removal was recorded for the mine water treated with both as-formed and vacuum annealed nano-Fe3O4. Over extended reaction periods (>1 week), appreciable U rerelease was recorded for the mine water solutions treated using nano-Fe0, whilst the vacuum annealed material maintained U at <50 μg L−1 until 4 weeks reaction. XPS analysis of reacted nanoparticulate solids confirmed the partial chemical reduction of to in both nano-Fe0 water treatment systems, but with a greater amount of detected on the vacuum annealed particles. Results suggest that vacuum annealing can enhance the aqueous reactivity of nano-Fe0 and, for waters of complex chemistry, can improve the longevity of aqueous U removal.

Selective formation of copper nanoparticles from acid mine drainage using nanoscale zerovalent iron particles

Nanoscale zerovalent iron (nZVI) has been investigated for the selective formation of Cu nanoparticles from acid mine drainage (AMD) taken from a legacy mine site in the UK. Batch experiments were conducted containing unbuffered (pH 2.67 at t = 0) and pH buffered (pH < 3.1) AMD which were exposed to nZVI at 0.1-2.0 g/L. Results demonstrate that nZVI is selective for Cu, Cd and Al removal (>99.9% removal of all metals within 1 h when nZVI ≥ 1.0 g/L) from unbuffered AMD despite the coexistent of numerous other metals in the AMD, namely: Na, Ca, Mg, K, Mn and Zn. An acidic pH buffer enabled similarly high Cu removal but maximum removal of only <1.5% and <0.5% Cd and Al respectively. HRTEM-EDS confirmed the formation of discrete spherical nanoparticles comprised of up to 68% wt. Cu, with a relatively narrow size distribution (typically 20-100 nm diameter). XPS confirmed such nanoparticles as containing Cu°, with the Cu removal mechanism therefore likely via cementation with Fe°. Overall the results demonstrate nZVI as effective for the one-pot and selective formation of Cu°-bearing nanoparticles from acidic wastewater, with the technique therefore potentially highly useful for the selective upcycling of dissolved Cu in wastewater into high value nanomaterials.

The influence of syndepositional macropores on the hydraulic integrity of thick alluvial clay aquitards

Clay‐rich deposits are commonly assumed to be aquitards which act as natural hydraulic barriers due to their low hydraulic connectivity. Postdepositional weathering processes are known to increase the permeability of aquitards in the near surface but not impact on deeper parts of relatively thick formations. However, syndepositional processes affecting the hydraulic properties of aquitards have previously received little attention in the literature. Here, we analyze a 31 m deep sediment core recovered from an inland clay‐rich sedimentary sequence using a combination of techniques including particle size distribution and microscopy, centrifuge dye tracer testing and micro X‐ray CT imaging. Subaerial deposition of soils within these fine grained alluvial deposits has led to the preservation of considerable macropores (root channels or animal burrows). Connected pores and macropores thus account for vertical hydraulic conductivity (K) of urn:x-wiley:00431397:media:wrcr23221:wrcr23221-math-0001 m/s (geometric mean of 13 samples) throughout the thick aquitard, compared to a matrix K that is likely < urn:x-wiley:00431397:media:wrcr23221:wrcr23221-math-0002 m/s, the minimum K value that was measured. Our testing demonstrates that such syndepositional features may compromise the hydraulic integrity of what otherwise appears to have the characteristics of a much lower permeability aquitard. Heterogeneity within a clay‐rich matrix could also enhance vertical connectivity, as indicated by digital analysis of pore morphology in CT images. We highlight that the paleo‐environment under which the sediment was deposited must be considered when aquitards are investigated as potential natural hydraulic barriers and illustrate the value of combining multiple investigation techniques for characterizing clay‐rich deposits.