Critical nanomaterial attributes of iron-carbohydrate nanoparticles: Leveraging orthogonal methods to resolve the 3-dimensional structure.

Intravenous iron-carbohydrate nanomedicines are widely used to treat iron deficiency and iron deficiency anemia across a wide breadth of patient populations. These colloidal solutions of nanoparticles are complex drugs which inherently makes physicochemical characterization more challenging than small molecule drugs. There have been advancements in physicochemical characterization techniques such as dynamic light scattering and zeta potential measurement, that have provided a better understanding of the physical structure of these drug products in vitro. However, establishment and validation of complementary and orthogonal approaches are necessary to better understand the 3-dimensional physical structure of the iron-carbohydrate complexes, particularly with regard to their physical state in the context of the nanoparticle interaction with biological components such as whole blood (i.e. the nano-bio interface).

Microbially influenced corrosion and rust tubercle formation on sheet piles in freshwater systems.

The extent of how complex natural microbial communities contribute to metal corrosion is still not fully resolved, especially not for freshwater environments. In order to elucidate the key processes, we investigated rust tubercles forming massively on sheet piles along the river Havel (Germany) applying a complementary set of techniques. In-situ microsensor profiling revealed steep gradients of O2 , redox potential and pH within the tubercle. Micro-computed tomography and scanning electron microscopy showed a multi-layered inner structure with chambers and channels and various organisms embedded in the mineral matrix. Using Mössbauer spectroscopy we identified typical corrosion products including electrically conductive iron (Fe) minerals. Determination of bacterial gene copy numbers and sequencing of 16S rRNA and 18S rRNA amplicons supported a densely populated tubercle matrix with a phylogenetically and metabolically diverse microbial community. Based on our results and previous models of physic(electro)chemical reactions, we propose here a comprehensive concept of tubercle formation highlighting the crucial reactions and microorganisms involved (such as phototrophs, fermenting bacteria, dissimilatory sulphate and Fe(III) reducers) in metal corrosion in freshwaters.

Nitrate leaching and its implication for Fe and As mobility in a Southeast Asian aquifer.

The drinking water quality in Southeast Asia is at risk due to arsenic (As) groundwater contamination. Intensive use of fertilizers may lead to nitrate (NO3-) leaching into aquifers, yet very little is known about its effect on iron (Fe) and As mobility in water. We ran a set of microcosm experiments using aquifer sediment from Vietnam supplemented with 15NO3- and 13CH4. To assess the effect of nitrate-dependent anaerobic methane oxidation (N-DAMO) we also inoculated the sediment with two different N-DAMO enrichment cultures. We found that native microorganisms and both N-DAMO enrichments could efficiently consume all NO3- in 5 days. However, CH4 oxidation was observed only in the inoculated microcosms, suggesting that the native microbial community did not perform N-DAMO. In uninoculated microcosms, NO3- was preferentially used over Fe(III) as an electron acceptor and consequently inhibited Fe(III) reduction and As mobilization. The addition of N-DAMO enrichment cultures led to Fe(III) reduction and stimulated As and Mn release into the water. The archaeal community in all treatments was dominated by Ca. Methanoperedens while the bacterial community consisted of various denitrifiers. Our results suggest that input of N fertilizers to the aquifer decreases As mobility and that CH4 cannot serve as an electron donor for NO3- reduction.

Role of Iron Sulfide Phases in the Stability of Noncrystalline Tetravalent Uranium in Sediments.

Uranium (U) in situ bioremediation has been investigated as a cost-effective strategy to tackle U contamination in the subsurface. While uraninite was believed to be the only product of bioreduction, numerous studies have revealed that noncrystalline U(IV) species (NCU(IV)) are dominant. This finding brings into question the effectiveness of bioremediation because NCU(IV) species are expected to be labile and susceptible to oxidation. Thus, understanding the stability of NCU(IV) in the environment is of crucial importance. Fe(II) minerals (such as FeS) are often associated with U(IV) in bioremediated or naturally reduced sediments. Their impact on the stability of NCU(IV) is not well understood. Here, we show that, at high dissolved oxygen concentrations, FeS accelerates NCU(IV) reoxidation. We hypothesize that either highly reactive ferric minerals or radical S species produced by the oxidation of FeS drive this rapid reoxidation of NCU(IV). Furthermore, we found evidence for the contribution of reactive oxygen species to NCU(IV) reoxidation. This work refines our understanding of the role of iron sulfide minerals in the stability of tetravalent uranium in the presence of oxygen in a field setting such as contaminated sites or uranium-bearing naturally reduced zones.

Effects of different forms of nitrogen fertilizers on arsenic uptake by rice plants.

A pot microcosm experiment was conducted to investigate the effect of different forms of N fertilizers on As uptake by rice. Compared to a nontreated control, addition of nitrate reduced Fe(II) concentration in soil solution, while treatment with ammonium enhanced Fe(III) reduction, probably coupled to NH(4)(+) oxidation in the nonrhizosphere. Most-probable-number (MPN) enumerations revealed high densities of nitrate-dependent Fe(II)-oxidizing microorganisms. The addition of nitrate decreased Fe plaque formation on the root surface, accompanied by much lower dissolved Fe(II) concentrations in the rhizosphere soil solution compared to the nonamended control. Nitrate addition also reduced As uptake by the rice plant. These results suggest that nitrate may inhibit Fe(III) reduction and/or stimulate nitrate-dependent Fe(II) oxidation, leading to As coprecipitation with, or adsorption to, Fe(III) minerals in the soil. Although Fe plaque formation on the root surface is reduced, nitrate-dependent stimulation of Fe(II) oxidation and/or inhibition of Fe(III) reduction in the bulk soil sequesters mobile As in the soil, resulting in reduced As uptake by rice.