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The traditionally held assumption that photo-dependent processes are the predominant source of H2O2 in natural waters has been recently questioned by an increrasing body of evidence showing the ubiquitiousness of H2O2 in dark water bodies and in groundwater. In this study, we conducted field measurement of H2O2 in an intra-meander hyporheic zone and in surface water at East River, CO. On-site detection using a sensitive chemiluminescence method suggests H2O2 concentrations in groundwater ranging from 6 nM (at the most reduced region) to ~ 80 nM (in a locally oxygen-rich area) along the intra-meander transect with a maxima of 186 nM detected in the surface water in an early afternoon, lagging the maximum solar irradiance by ∼ 1.5 h. Our results suggest that the dark profile of H2O2 in the hyporheic zone is closely correlated to local redox gradients, indicating that interactions between various redox sensitive elements could play an essential role. Due to its transient nature, the widespread presence of H2O2 in the hyporheic zone indicates the existence of a sustained balance between H2O2 production and consumption, which potentially involves a relatively rapid succession of various biogeochemically important processes (such as organic matter turnover, metal cycling and contaminant mobilization). More importantly, this study confirmed the occurrence of reactive oxygen species at a subsurface redox transition zone and further support our understanding of redox boundaries on reactive oxygen species generation and as key locations of biogeochemical activity.

The heterogeneous catalytic ozonation process is a promising treatment option for high salinity reverse osmosis concentrate (ROC) however the influence of salts on the catalyst performance is not well understood. In this work, we investigate the effect of salts on the performance of the catalytic ozonation process for treatment of synthetic ROC using a commercially available Fe-loaded Al2O3 catalyst. Our results show that the presence of salts influences the rate and extent of degradation of organic compounds present in the synthetic ROC when subjected to the heterogeneous catalytic ozonation process. Scavenging of aqueous O3 by chloride ions and/or transformation of organics (particularly humics) to more hydrophobic form as a result of charge shielding between adjacent functional groups and/or intramolecular binding by cations inhibits the bulk oxidation of organics to a measurable extent. While the scavenging of aqueous hydroxyl radicals at the salt concentrations investigated here was minimal, the accumulation of chloride ions in the electric double layer near the catalyst surface, particularly when pH< pHpzc, results in more significant scavenging of surface associated hydroxyl radicals. Overall, the presence of salts (particularly chloride ions) has a significant influence on the performance of both conventional and catalytic ozonation processes with some scope to mitigate this effect through appropriate choice of catalyst.

Digital Twins (DTs) have been developed for several pilot-scale membrane capacitive deionization (mCDI) units that are located in remote communities in China and Australia for desalination of brackish water and treated domestic wastewater. These pilot-scale mCDI units have a production capacity ranging from 5 to 50 m3/day and a water recovery rate of up to 85%. The mCDI DTs use Head-mounted Displays (HMDs) to facilitate the visualisation of transient real-time data and historical data from various sensors in the physical plants. The DTs contain device tag and sensor data display functions which greatly enhance the model functionality and user experience. By combining the DTs with Mixed Reality (MR) technology that blends elements of both Virtual Reality (VR) and Augmented Reality (AR), it was possible to use the DTs for remote control and remote operator training in an immersive environment. Our results suggest that more facile remote control and improved training outcomes could be achieved by use of DTs by the water industry compared to those achieved by conventional control and training methods.

The reactivity and early strength of cement:slag binders is usefully enhanced by the addition of sodium sulfate though the underlying mechanisms of the relationship between the enhanced hydration reactions and the structural aspects of the strength behavior remain unclear. In this study, microstructural development in the presence of Na2SO4 was investigated utilizing mercury intrusion porosimetry (MIP), NMR relaxometry, and XRD. Increased rates of early strength development and decreased rates of late strength development due to the presence of added Na2SO4 were linked to effects on capillary porosity refinement. While degree of hydration at later age was shown to have been lower in the presence of Na2SO4, and may have been responsible for the higher capillary porosity, a clear alteration in the pathway of microstructural development had occurred with inhibition to hydration of the slag component due to earlier microstructural development proposed.

[FeIII(OH)(tpena)]+ (tpena- = N,N,N′-tris(2-pyridylmethyl)ethylenediamine-N′-acetate) catalytically activates H2O2 with the concomitant formation of the active oxidants [FeIV(O)(tpena)]+ and HO• in aqueous solutions at pH 8. A kinetic model is used to demonstrate that the activation of [FeIII(OH)(tpena)]+ by H2O2 proceeds by the formation of [FeIII(OOH)(tpena)]+. Two previously unreported reactions of [FeIII(OOH)(tpena)]+, the first with another H2O2 molecule to afford [FeIII(OH)(tpena)]+, O2•-, and HO• and the second, and dominant, with [FeIII(OH)(tpena)]+ to yield 2 equiv of [FeIV(O)(tpena)]+ and H2O, are found to be the major pathways for the formation of HO• and [FeIV(O)(tpena)]+, respectively. The production of HO• was quantified by a chemiluminescence method showing that [FeIV(O)(tpena)]+ is produced in much larger yields than HO•. The generation of HO• compromises the stability of [FeIII(OH)(tpena)]+ unless an external substrate is present that can outcompete [FeIII(OH)(tpena)]+ for HO•. Significantly, we demonstrate that the reaction commonly assumed to occur in the decay of nonheme iron(III)hydroperoxides, homolytic O-O bond cleavage, is of minor significance for the generation of HO• and the iron(IV)oxo complex. The production of both a reactive high-valent iron-oxo species and HO• under mild, aqueous ambient conditions represents a significant contribution to the current state of the art for biomimetic nonheme chemistry in water.

The action of added sodium sulfate (Na2SO4) leading to increased reactivity and early strength in slag: cement binders remains unclear. In this study, early hydration reactions and resultant compressive strength in a 50:50 slag:cement binder in the presence of Na2SO4 were investigated. Early strength increases in the presence of Na2SO4 were shown to be due to a combination of increased alite hydration and increased slag dissolution. Increased alite hydration was due to neither reduced dissolved Al concentration nor increased alite under-saturation but related to increased ionic strength. Increased slag dissolution was associated with both increased pH and decreased Ca activity with the two being connected through the portlandite solubility limit. Na2SO4 was shown to substantially enhance slag dissolution at fixed pH 13 with this action attributed to greater under-saturation of slag as a result of ettringite formation. Na2SO4 was shown to be superior to alternate activators in a slag:cement binder.

The oxygenation of mackinawite (FeS) frequently occurs at anoxic-oxic interfaces in both natural and engineered systems such as intertidal sediment, in activated sludge in water treatment processes, and during sulfidized zero-valent iron particle corrosion. During reoxygenation events, FeS may drive a Fenton-like process leading to the production of strong oxidants though the details of this process are poorly understood. In this study, benzoic acid (BA) has been used to probe both the magnitude and identity of these strong oxidants under circumneutral pH conditions. The major product of BA oxidation during FeS oxygenation was found to be 2,5-dihydroxybenzoic acid (2,5-DHBA) rather than monohydroxybenzoic acids identified to be the major products in a range of hydroxyl radical (HO·)-dominated systems. Based upon relative reactivity with other competitive probes and nature of the hydroxybenzoate product distribution, it is hypothesized that the strong oxidant must be a surface-localized entity such as high-valent iron or surface-associated hydroxyl or sulfur-based radicals with reactivity differing from those formed in free solution. The importance of both the reactivity of the oxidant and adsorption of the substrate to the surface is demonstrated.

While flow-electrode capacitive deionization (FCDI) operated in short-circuited closed cycle (SCC) mode appears to hold promise for removal of salt from brackish source waters, there has been limited investigation on the removal of other water constituents such as nitrate, fluoride or bromide in combination with salt removal. Of particular concern is the effectiveness of FCDI when ions, such as nitrate, are recognized to non-electrostatically adsorb strongly to activated carbon particles thereby potentially rendering it difficult to regenerate these particles. In this study, SCC FCDI was used to desalt source waters containing nitrate at different concentrations. Results indicate that nitrate can be removed from source waters using FCDI to concentrations < 1 mg NO 3 -N L -1 though a lower quality target such as 10 mg L -1 would be more cost-effective, particularly where the influent nitrate concentration is high (50 mg NO 3 -N L -1 ). Although studies of the fate of nitrate in the FCDI system show that physico-chemical adsorption of nitrate to the carbon initially plays a vital role in nitrate removal, the ongoing process of nitrate removal is not significantly affected by this phenomenon with this lack of effect most likely due to the continued formation of electrical double layers enabling capacitive nitrate removal. In contrast to conventional CDI systems, constant voltage mode is shown to be more favorable in maintaining stable effluent quality in SCC FCDI because the decrease in electrical potential that occurs in constant current operation leads to a reduction in the extent of salt removal from the brackish source waters. Through periodic replacement of the electrolyte at a water recovery of 91.4%, we show that the FCDI system can achieve a continuous desalting performance with the effluent NO 3 -N concentration below 1 mg NO 3 -N L -1 at low energy consumption (~0.5 kWh m -3 ) but high productivity.

Iron (oxyhydr)oxides are widespread in natural and engineered systems, potent adsorbents of contaminants and a source of energy for iron-reducing bacteria. Microbial reduction of iron (oxyhydr)oxides results in the formation of Fe(II) which can induce the transformation of these iron minerals, typically from less crystalline to more crystalline forms, affecting the biogeochemical cycling of iron and the behavior of any species adsorbed to the iron (oxyhydr)oxides. Factors influencing the transformation rate of the poorly crystalline iron (oxyhydr)oxide, ferrihydrite, to more crystalline forms in the presence of the iron reducing bacterium Shewanella oneidensis MR-1 are investigated under controlled laboratory conditions in this work. In particular, the amount of Fe(II) produced increased the transformation rate while increasing concentrations of the electron donor, lactate, decreased the rate. Using kinetic parameters determined from abiotic controls, the results of transformation experiments in the presence of Shewanella oneidensis were modeled with this exercise revealing that less goethite and more lepidocrocite formed than expected. Conversely, studies using the Shewanella exudate only, containing biogenic Fe(II), displayed rates of transformation that were satisfactorily modeled using these abiotic control kinetic parameters. This result suggests that the physical presence of the microbes is pivotal to the reduction in ferrihydrite transformation rate observed in the biotic experiments relative to the analogous abiotic controls.

While flow-electrode capacitive deionization (FCDI) is a potential alternative to brackish and/or sea water desalination, there is limited understanding of both the fate of ions following migration across the ion exchange membranes and the mechanisms responsible for ion separation. In this study, we investigate the desalting performance of an FCDI system operated over a range of conditions. Results show that although ion transport as a result of electrodialysis is inevitable in FCDI (and is principally responsible for pH excursion in the flow electrode), the use of high carbon content ensures that a high proportion of the charge and counterions are retained in the electrical double layers of the flowing carbon particles, even at high charging voltages (e.g., 2.0 V) during the deionization process. Estimation of the portions of sodium and chloride ions adsorbed in the flow electrode after migration through the membranes suggests that the ongoing capacitive adsorption exhibits asymmetric behavior with the anodic particles demonstrating better affinity for Cl− (than the cathodic particles for Na+) during electrosorption. These findings provide an explanation for the change in electrode properties that are observed under imperfect adsorption scenarios and provide insight into aspects of the design and operation of flow electrode pairs that is critical to achieving effective desalination by FCDI.

A novel cost-effective flow-electrode capacitive deionization unit combined with a hydrophobic gas-permeable hollow fiber membrane contactor (designated "CapAmm") is described here and used for efficient recovery of ammonia from dilute synthetic wastewaters. During operation, ammonia migrates across a cation exchange membrane and selectively accumulates in the cathode chamber of a flow electrode followed by transformation to dissolved NH3 with subsequent stripping via a membrane contactor and recovery as ammonium sulfate. Our results demonstrate that the CapAmm process can achieve an ammonia removal efficiency of ∼90% and a recovery efficiency of ∼60%. At current densities of 5.8 and 11.5 A m-2 (normalized by the effective cation exchange membrane area) and a hydraulic retention time of 1.48 min, the energies required for ammonia recovery were 9.9 and 21.1 kWh (kg of N)-1, respectively, with these values being comparable with those of other similar electrochemical ammonia recovery systems. These findings suggest that the CapAmm technology described here has the potential for the dual purposes of cost-effective salt removal and the recovery of ammonia from wastewaters, with greater stability, better flexibility, and greater energy efficiency compared to those of other methods.

Parkinson's disease is the second most common neurodegenerative disease. While age is the most significant risk factor, the exact cause of this disease and the most effective approaches to mitigation remain unclear. It has long been proposed that dopamine may play a role in the pathology of Parkinson's disease in view of its ability to generate both protein-modifying quinones such as aminochrome and reactive oxygen species, especially in the presence of pathological iron accumulation in the primary site of neuron loss. Given the clinically measured acidosis of post-mortem Parkinson's disease brain tissue, the interaction between dopamine and iron was investigated over a pH range of 7.4 to 6.5 with emphasis on the accumulation of toxic quinones and generation of reactive oxygen species. Our results show that the presence of iron accelerates the formation of aminochrome with ferrous iron (Fe[II]) being more efficient in this regard than ferric iron (Fe[III]). Our results further suggest that a reduced aminochrome rearrangement rate coupled with an enhanced turnover rate of Fe[II] as a result of brain tissue acidosis could result in aminochrome accumulation within cells. Additionally, under these conditions, the enhanced redox cycling of iron in the presence of dopamine aggravates oxidative stress as a result of the production of damaging reactive species, including hydroxyl radicals.

Over the past decade, capacitive deionization (CDI) has realized a surge in attention in the field of water desalination and can now be considered as an important technology class, along with reverse osmosis and electrodialysis. While many of the recently developed technologies no longer use a mechanism that follows the strict definition of the term "capacitive", these methods nevertheless share many common elements that encourage treating them with similar metrics and analyses. Specifically, they all involve electrically driven removal of ions from a feed stream, storage in an electrode (i.e., ion electrosorption) and release, in charge/discharge cycles. Grouping all these methods in the technology class of CDI makes it possible to treat evolving new technologies in standardized terms and compare them to other technologies in the same class.

During the 1960s, small quantities of radioactive materials were codisposed with chemical waste at the Little Forest Legacy Site (Sydney, Australia) in 3-meter-deep, unlined trenches. Chemical and microbial analyses, including functional and taxonomic information derived from shotgun metagenomics, were collected across a 6-week period immediately after a prolonged rainfall event to assess the impact of changing water levels upon the microbial ecology and contaminant mobility. Collectively, results demonstrated that oxygen-laden rainwater rapidly altered the redox balance in the trench water, strongly impacting microbial functioning as well as the radiochemistry. Two contaminants of concern, plutonium and americium, were shown to transition from solid-iron-associated species immediately after the initial rainwater pulse to progressively more soluble moieties as reducing conditions were enhanced. Functional metagenomics revealed the potentially important role that the taxonomically diverse microbial community played in this transition. In particular, aerobes dominated in the first day, followed by an increase of facultative anaerobes/denitrifiers at day 4. Toward the mid-end of the sampling period, the functional and taxonomic profiles depicted an anaerobic community distinguished by a higher representation of dissimilatory sulfate reduction and methanogenesis pathways. Our results have important implications to similar near-surface environmental systems in which redox cycling occurs.

Removal of recalcitrant anthropogenic contaminants from water calls for the development of cost-effective treatment technologies. In this work, a novel electrochemical membrane filtration (EMF) process using a conducting microfiltration membrane as the cathode has been developed and the degradation of sulphanilic acid (SA) examined. The electrochemical degradation of SA in flow-by mode followed pseudo-first-order kinetics with the degradation rate enhanced with increase in charging voltage. Hydrogen peroxide as well as oxidants such as HO• and Fe(IV)O2+ were generated electrochemically with HO• found to be the dominant oxidant responsible for SA degradation. In addition to the anodic splitting of water, HO• was formed via a heterogeneous Fenton process with surface-bound Fe(II) resulting from aerobic corrosion of the steel mesh. In flow-through mode, the removal rate of SA was 13.0% greater than obtained in flow-by mode, presumably due to the better contact of the contaminant with the oxidants generated in the vicinity of the membrane surface. A variety of oxidized products including hydroquinone, p-benzoquinone, oxamic acid, maleic acid, fumaric acid, acetic acid, formic acid, and oxalic acid were identified and an electrochemical degradation pathway proposed. These findings highlight the potential of the cathodic EMF process as an effective technology for water purification.

While microalgae have been suggested as a promising substitute to conventional fossil fuels, their cost effective cultivation and harvesting constitutes a major challenge. In the work described here, a novel photosynthetic microbial fuel cell (PMFC) in which a stainless steel mesh with biofilm formed on it serves as both the cathode and filtration material has been developed. Results of this study reveal that, in addition to inducing oxygen reduction reactions under illumination, the biocathode is effective in preventing the washout of algae during continuous operation, resulting in retained biomass concentrations reaching 3.5–6.5 g L−1. The maximum output current density reached ∼200 mA m−2 under irradiation, which is comparable with recent PMFC studies. Microbial diversity analyses targeting 16S and 18S rRNA genes indicated that the eukaryotic species belonging to the genus Chlorella was able to sustain its community dominance (>96%) over other competing species over the course of the studies. In the absence of catalysts such as Pt, a consortium of photosynthetic organisms including plant growth-promoting bacteria such as Azospirillum and Rhizobium were overrepresented in the biofilm, with these organisms most likely contributing to cathodic electron transfer. Energy flow analysis suggested that the PMFC system held the potential to achieve theoretical energy balance in simultaneous algae production and wastewater treatment.

The Fe(II)-catalyzed transformation of the poorly crystalline Fe(III) oxyhydroxide mineral, ferrihydrite (Fh), to more crystalline Fe(III) mineral species such as magnetite, goethite, and lepidocrocite has been quantitatively evaluated under various conditions using X-ray adsorption spectroscopy (XAS) and Fourier transform infrared (FTIR) spectroscopy. Using the peak height of signature FTIR peaks of sub-micron sized lepidocrocite and goethite references minerals, the FTIR results were comparable to the XAS results within experimental error. This was independent of whether the Fe(II)-catalyzed transformation was initiated by the Fe(III)-reducing bacterium Shewanella oneidensis MR-1 or by added ferrous ammonium sulfate in the presence or absence of lactate. Whilst the use of FTIR has not been previously employed to follow this transformation process, it has advantages relative to XAS including a lower sample requirement (approximately 30-fold lower), greater accessibility and greater safety of operation. Whilst problems with quantifying magnetite in the presence of lepidocrocite were identified in this study using reference Fe(III) oxyhydroxide suspensions, large amounts of magnetite were not produced during transformation under the conditions employed in this study. Reference spectra of lath-like nano-goethite particles (with dimensions of approx. 10 × 50 nm) also resulted in higher IR absorbance and a slight red-shift in signature peak positions relative to sub-micron sized goethite particles with this shift potentially affecting the reliable quantification of samples of unknown size. Despite this, good agreement between the XAS and FTIR data for samples containing iron oxides undergoing continuous transformation was obtained suggesting that FTIR may be a convenient, inexpensive means of following such mineral transformations.

The effectiveness of using ligand-assisted strategies to improve the performance of palladium-doped nanoscale zero-valent iron particles (Pd-nZVI) towards contaminant removal has been investigated previously, however, little attention has been given to either the thermodynamics and kinetics of the Pd-nZVI depassivation process or the effect of the presence of co-existent cations. Results of laboratory investigations using EDTA as the ligand of choice indicate that the presence of Ca(ii) and Mg(ii) ions can significantly improve the ligand-promoted dechlorination efficiency of polychlorinated biphenyls (PCB) with the effect of divalent cations on PCB removal being more significant at higher concentrations of EDTA. The improvement in particle reactivity in the presence of Ca(ii) and Mg(ii) could be attributed to moderate elimination of outer Fe oxide layers induced by the relatively slow release of free EDTA from Ca and Mg-EDTA complexes. The slow release of free EDTA prevented excessive initial loss of Fe oxide surface sites required for PCB sequestration and ensured that sufficient EDTA remained available for the later-time removal of Fe oxide layers that were continuously formed as Fe0 was oxidized. A mechanistically-based kinetic model for the ligand-promoted dissolution of Pd-nZVI has been developed with this model enabling quantitative understanding of the relatively complex interplay among Ca(ii) and Mg(ii) ions, EDTA and passivating Fe oxide layers during the contaminant degradation process.

A Fluid Structural Interaction (FSI) approach was used to simulate fluid flow, surface shear and filtration flux as a function of aeration induced lateral fibre movement in a submerged membrane system. The two-way FSI approach integrated Computational Fluid Dynamics (CFD), to model the three-dimensional pressure/loads of the air-liquid two-phase flow, and Transient Structural Analysis, to calculate pressure induced displacement of fibres with different material, diameter and looseness. These novel, a priori simulations provide insights into the effects of both membrane intrinsic properties, fibre packing density, and two-phase flow on the critical factors for fouling control. Fibre displacement and membrane surface shear profiles on a 300mm long fibre were spatially and temporarily variable, with irregular periodical patterns established approximately 10s after initiation of aeration at 4.7Nm3/h. Average surface shear was 67% higher for 1.3mm diameter fibres compared to a 1.0mm fibre of identical Young's modulus and looseness. Increasing the fibre looseness from 0.5% to 1% increased the average surface shear by 50.4% (0.56-1.13Pa) for fibres of identical diameter and Young's modulus, whereas reducing the Young's modulus from 76 to 20MPa for fibres with identical diameter and looseness only increased average surface shear by 9.7%. The FSI modelled fibre displacement showed good agreement with experimentally measured fibre displacement data, with 8.3% difference in amplitude and 9.1% in period. The impact of fibre movement on pure water flux was assessed by quantifying the reduction in shell side pressure due to changes in flow of the surrounding liquid. This reduction in shell side pressure, together with the increase of the pressure drop in the lumen side caused by the distortion of fibre geometry, resulted in a decrease in transmembrane pressure and filtration flux for the moving fibre compared to a fixed fibre. FSI simulations of the behaviour of an idealised mult

Recent studies have demonstrated that the rate at which Fe(II)-Fe(III) oxyhydroxide systems catalyze the reduction of reducible contaminants, such as 4-chloronitrobenzene, is well correlated to their thermodynamic reduction potential. Here we confirm this effect in the presence of Fe(III) oxyhydroxide phases not previously assessed, namely ferrihydrite and nano-goethite, as well as Fe(III) oxyhydroxide phases previously examined. In addition, silicate is found to decrease the extent of Fe(II) sorption to the Fe(III) oxyhydroxide surface, increasing the reduction potential of the Fe(II)-Fe(III) oxyhydroxide suspension and, accordingly, decreasing the rate of 4-chloronitrobenzene reduction. A linear relationship between the reduction potential of the Fe(II)-Fe(III) oxyhydroxide suspensions and the reduction rate of 4-chloronitrobenzene (normalized to surface area and concentration of sorbed Fe(II)) was obtained in the presence and absence of silicate. However, when ferrihydrite was doped with Si (through co-precipitation) the reduction of 4-chloronitrobenzene was much slower than predicted from its reduction potential. The results obtained have significant implications to the likely effectiveness of naturally occurring contaminant degradation processes involving Fe(II) and Fe(III) oxyhydroxides in groundwater environments containing high concentrations of silicate, or other species which compete with Fe(II) for sorption sites.

An innovative flow electrode comprising redox-active quinones to enhance the effectiveness of water desalination using flow-electrode capacitive deionization (FCDI) is described in this study. The results show that, in addition to carbon particle contact, the presence of the aqueous hydroquinone (H2Q)/benzoquinone (Q) couple in a flowing suspension of carbon particles enhances charge transfer significantly as a result of reversible redox reactions of H2Q/Q. Ion migration through the micropores of the flow electrodes was facilitated in particular with the desalination rate significantly enhanced. The cycling behavior of the quinoid mediators in the anode flow electrode demonstrated a relatively high stability at the low pH induced, suggesting that the mediator would be suitable for long-term operation. (Chemical Equation Presented).

In this study, the rates of Fe(II) oxidation by molecular oxygen in the presence of citrate, ethylenediaminetetraacetic acid (EDTA) and Suwannee River fulvic acid (SRFA) were determined over the pH range 4.0-5.5 and, for all of the ligands investigated, found to be substantially faster than oxidation rates in the absence of any ligand. EDTA was found to be particularly effective in enhancing the rate of Fe(II) oxidation when sufficient EDTA was available to complex all Fe(II) present in solution, with a kinetic model of the process found to adequately describe all results obtained. When Fe(II) was only partially complexed by EDTA, reactions with reactive oxygen species (ROS) and heterogeneous Fe(II) oxidation were found to contribute significantly to the removal rate of iron from solution at different stages of oxidation. This was possible due to the rapid rate at which EDTA enhanced Fe(II) oxidation and formed ROS and Fe(III). The rapid rate of Fe(III) generation facilitated the formation of free ferric ion activities in excess of those required for ferric oxyhydroxide precipitation following Fe(III)-EDTA dissociation. In comparison, the rate of Fe(II) oxidation was slower in the presence of citrate, and therefore the concentrations of free Fe(III) able to form in the initial stages of Fe(II) oxidation were much lower than those formed in the presence of EDTA, despite the resultant Fe(III)-citrate complex being less stable than that of Fe(III)-EDTA. The slower rate of citrate enhanced oxidation also resulted in slower rates of ROS generation, and, as such, oxidation of the remaining inorganic Fe(II) species by ROS was negligible. Overall, this study demonstrates that organic ligands may substantially enhance the rate of Fe(II) oxidation. Even under circumstances where the ligand is not present at sufficient concentrations to complex all of the Fe(II) in solution, ensuing oxidative processes may sustain an enhanced rate of Fe(II) oxidation relative to that of aqueou

There is increasing interest in extracellular electron transfer (EET) from organisms to receptors, particularly in anaerobic biofilms at mineral surfaces. Less attention has been given to EET by planktonic organisms in oxic environments where extracellular electron generation and transport might be expected to be of limited consequence. In this study, the EET activity of the photosynthetic marine raphidophyte, Chattonella marina, was examined using a mediatorless photosynthetic microbial fuel cell with results showing positive light response. Electron output by organisms present in cell suspension was substantially higher than those present in biofilms at the electrode surface. Indeed, current generation under light illumination of the C. marina suspension continued even when contact between the organisms and the electrodes was prevented by dialysis membrane, suggesting that soluble electron carriers secreted by C. marina were facilitating the EET process. Cyclic voltammetry measurements of the cell-free exudate showed redox peaks in the range of 0.1-0.5 V (vs Ag/AgCl), confirming that redox active species were present in the cell suspension. Facilitation of electron transfer from the planktonic organism to the anode by endogenous redox-active exudates appears to be critical to current generation. The ability of these exudates to remain in their reduced state in the presence of oxygen is possibly a function of the spin-restricted nature of oxygen-mediated exudate oxidation. Quantification of the EET processes operating in this planktonic system assists in understanding the means and extent to which C. marina induces redox transformations in the external medium with these transformations presumably of benefit to the survival of this organism, potentially including facilitation of iron uptake and induction of toxicity to other organisms.

© 2014 American Chemical Society. The dechlorination of trichloroethylene (TCE) by aged Fe0 in the presence of a series of divalent cations was investigated with the result that while no significant degradation of TCE was observed in Milli-Q water or in solutions of Ba2+, Sr2+, or Ca2+, very effective TCE removal was observed in solutions containing Mg2+, Mn2+, Co2+, Fe2+, Ni2+, Zn2+, Cu2+, or Pb2+. The rate constants of TCE removal in the presence of particular cations were positively correlated to the log K representing the affinity of the cations for hydrous ferric oxide (HFO) surface sites though the treatments with Co2+ and Ni2+ were found to provide particularly strong enhancement in TCE degradation rate. The extent of Fe(II) release to solution also increased with increase in log K, while the solution pH from both experimental measurement and thermodynamic calculation decreased with increasing log K. While the peak areas of Fe and O XPS spectra of the passivated ZVI in the presence of Ba2+, Sr2+, and Ca2+ were very close to those in Milli-Q water, very significant increases in surface Fe and O (and OH) were observed in solutions of Mg2+, Mn2+, Co2+, Fe2+, Ni2+, Zn2+, Cu2+ and Pb2+, revealing that the surface oxide layer dissolution is consistent with the recovery of aged Fe0 with respect to TCE degradation. The depassivation process is proposed to involve (i) surface complexation of cations on surface coatings of aged Fe0, (ii) dissolution of the hydrated surface as a consequence of magnetite exposure, and (iii) transport of electrons from underlying Fe0 via magnetite to TCE, resulting in TCE dechlorination and, for some cations (Co2+, Ni2+, Cu2+, and Pb2+), reduction to their zero or +1 valence state (with potential for these reduced metals to enhance TCE degradation).