Adele M. Jones

Superoxide-mediated formation and charging of silver nanoparticles.

Contemporary studies indicate that reactive oxygen species (ROS) such as superoxide play a key role in the toxicity and behavior of silver nanoparticles (AgNPs). While there have been suggestions that superoxide is able to reduce silver(I) ions with resultant production of AgNPs, no experimental evidence that this process actually occurs has been produced. Here we present definitive experimental evidence for the reduction of silver(I) by superoxide. A second-order rate constant of 64.5 ± 16.3 M(-1)·s(-1) is determined for this reaction in the absence of AgNPs. The overall rate constant, however, increases by at least 4 orders of magnitude in the presence of AgNPs. A model based on electron charging and discharging of AgNPs satisfactorily describes the kinetics of this process. The ability for AgNPs to undergo catalytic cycling provides a pathway for the continual generation of ROS and the regeneration of AgNPs following oxidation.

A new formula for the dynamic mobility in a concentrated colloid

Abstract The dynamic mobility μ D is the analogue of the electrophoretic mobility in an alternating electric field. It can be determined for suspensions of arbitrary concentration at MHz frequencies using electroacoustic measurements. A considerable amount of effort has been expended during the last decade in the derivation of theories for the dynamic mobility in concentrated suspensions. The objective has been to come up with a formula that can be used to calculate particle size and zeta potential from dynamic mobility measurements in concentrated suspensions. Some of these theories are based on cell models, others are based on coupled phase models and another involves the use of experimentally determined parameters. In this paper we present a new approach to this problem. We derive a formula that does not involve any ad hoc boundary conditions or adjustable parameters. The formula is compared with experimental measurements, and is used to determine size and zeta potential for a number of concentrated colloids.

The reduction of 4-chloronitrobenzene by Fe(II)-Fe(III) oxide systems - correlations with reduction potential and inhibition by silicate.

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.

Donnan membrane speciation of Al, Fe, trace metals and REEs in coastal lowland acid sulfate soil-impacted drainage waters.

Donnan dialysis has been applied to forty filtered drainage waters collected from five coastal lowland acid sulfate soil (CLASS) catchments across north-eastern NSW, Australia. Despite having average pH values<3.9, 78 and 58% of Al and total Fe, respectively, were present as neutral or negatively-charged species. Complementary isotope dilution experiments with (55)Fe and (26)Al demonstrated that only soluble (i.e. no colloidal) species were present. Trivalent rare earth elements (REEs) were also mainly present (>70%) as negatively-charged complexes. In contrast, the speciation of the divalent trace metals Co, Mn, Ni and Zn was dominated by positively-charged complexes and was strongly correlated with the alkaline earth metals Ca and Mg. Thermodynamic equilibrium speciation calculations indicated that natural organic matter (NOM) complexes dominated Fe(III) speciation in agreement with that obtained by Donnan dialysis. In the case of Fe(II), however, the free cation was predicted to dominate under thermodynamic equilibrium, whilst our results indicated that Fe(II) was mainly present as neutral or negatively-charged complexes (most likely with sulfate). For all other divalent metals thermodynamic equilibrium speciation calculations agreed well with the Donnan dialysis results. The proportion of Al and REEs predicted to be negatively-charged was also grossly underestimated, relative to the experimental results, highlighting possible inaccuracies in the stability constants developed for these trivalent Me(SO4)2(-) and/or Me-NOM complexes and difficulties in modeling complex environmental samples. These results will help improve metal mobility and toxicity models developed for CLASS-affected environments, and also demonstrate that Australian CLASS environments can discharge REEs at concentrations an order of magnitude greater than previously reported.

Mechanistic and kinetic insights into the ligand-promoted depassivation of bimetallic zero-valent iron nanoparticles

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.

The impacts of low-cost treatment options upon scale formation potential in remote communities reliant on hard groundwaters. A case study: Northern Territory, Australia.

The majority of small, remote communities within the Northern Territory (NT) in Central Australia are reliant on groundwater as their primary supply of domestic, potable water. Saturation indices for a variety of relevant minerals were calculated using available thermodynamic speciation codes on collected groundwater data across the NT. These saturation indices were used to assess the theoretical formation of problematic mineral-scale, which manifests itself by forming stubborn coatings on domestic appliances and fixtures. The results of this research show that 63% of the measured sites within the NT have the potential to form calcium carbonate (CaCO(3)) scale, increasing to 91% in arid, central regions. The data also suggests that all groundwaters are over-saturated with respect to amorphous calcium-bridged ferric-silica polymers, based on the crystalline mineral index (Ca(3)Fe(2)Si(3)O(12)), although the quantitative impact of this scale is limited by low iron concentrations. An assessment of possible low-cost/low-technology management options was made, including; lowering the temperature of hot-water systems, diluting groundwater with rainwater and modifying the pH of the source water. Source water pH modification (generally a reduction to pH 7.0) was shown to clearly alleviate potential carbonate-based scale formation, over and above the other two options, albeit at a greater technical and capital expense. Although low-cost/low-technology treatment options are unlikely to remove severe scale-related issues, their place in small, remote communities with minor scale problems should be investigated further, owing to the social, technical and capital barriers involved with installing advanced treatment plants (e.g. reverse osmosis) in such locations.

Reductive reactivity of borohydride- and dithionite-synthesized iron-based nanoparticles: A comparative study.

In this study sodium dithionite (NaS2O4) and sodium borohydride (NaBH4) were employed as reducing agents for the synthesis of nanosized iron-based particles. The particles formed using NaBH4 (denoted nFe(BH4)) principally contained (as expected) Fe(0) according to XAS and XRD analyses while the particles synthesized using NaS2O4, (denoted nFe(S2O4)) were dominated by the mixed Fe(II)/Fe(III) mineral magnetite (Fe3O4) though with possible presence of Fe(0). The ability of both particles to reduce trichloroethylene (TCE) under analogous conditions demonstrated remarkable differences with nFe(BH4) resulting in complete reduction of 1.5mM of TCE in 2h while nFe(S2O4) were unable to effect complete reduction of TCE in 120 h. Moreover, acetylene was the major reaction product formed in the presence of nFe(S2O4) while the major reaction product formed following reaction with nFe(BH4) was ethylene, which was further reduced to ethane as the reaction proceeded. Considering that effective Pd reduction to Pd(0) requires the presence of Fe(0), this is consistent with our finding that Fe(0) is not the dominant phase formed when employing dithionite as a reducing agent under the conditions employed in this study.

Effect of Shewanella oneidensis on the Kinetics of Fe(II)-Catalyzed Transformation of Ferrihydrite to Crystalline Iron Oxides

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.

Use of fourier transform infrared spectroscopy to examine the Fe(II)-Catalyzed transformation of ferrihydrite

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 × 50nm) 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.

Fe(II) Interactions with Smectites: Temporal Changes in Redox Reactivity and the Formation of Green Rust

In this study, temporal changes in the redox properties of three 0.5 g/L smectite suspensions were investigated-a montmorillonite (MAu-1) and two nontronites (NAu-1 and NAu-2) in the presence of 1 mM aqueous Fe(II) at pH 7.8. X-ray absorption spectroscopy revealed that the amount of Fe(II) added quantitatively transformed into chloride-green rust (Cl-GR) within 5 min and persisted over 18 days. Over the same time, the reduction potential of all three suspensions increased by 50 to 150 mV to equilibrate at approximately -100 mV vs SHE. The reduction of a model organic contaminant, 4-chloronitrobenzene (4-CINB), also became increasingly slower over time with virtually no 4-CINB reduction being observed after 18 days. There was a strong correlation between reduction potential and the quantity of 4-ClNB reduced by MAu-1, although other factors were likely involved in the decreased redox reactivity observed in the nontronites. It is hypothesized that the temporal increase in reduction potential results from clay mineral dissolution resulting in increased Fe(III) contents in the Cl-GR. These results demonstrate that long-term studies are recommended to accurately predict contaminant management strategies.