Transport and retention of differently coated CeO2 nanoparticles in saturated sediment columns under laboratory and near-natural conditions.

Where surface-functionalized engineered nanoparticles (NP) occur in drinking water catchments, understanding their transport within and between environmental compartments such as surface water and groundwater is crucial for risk assessment of drinking water resources. The transport of NP is mainly controlled by (i) their surface properties, (ii) water chemistry, and (iii) surface properties of the stationary phase. Therefore, functionalization of NP surfaces by organic coatings may change their fate in the environment. In laboratory columns, we compared the mobility of CeO2 NP coated by the synthetic polymer polyacrylic acid (PAA) with CeO2 NP coated by natural organic matter (NOM) and humic acid (HA), respectively. The effect of ionic strength on transport in sand columns was investigated using deionized (DI) water and natural surface water with 2.2 mM Ca2+ (soft) and 4.5 mM Ca2+ (hard), respectively. Furthermore, the relevance of these findings was validated in a near-natural bank filtration experiment using HA-CeO2 NP. PAA-CeO2 NP were mobile under all tested water conditions, showing a breakthrough of 60% irrespective of the Ca2+ concentration. In contrast, NOM-CeO2 NP showed a lower mobility with a breakthrough of 27% in DI and < 10% in soft surface water. In hard surface water, NOM-CeO2 NP were completely retained in the first 2 cm of the column. The transport of HA-CeO2 NP in laboratory columns in soft surface water was lower compared to NOM-CeO2 NP with a strong accumulation of CeO2 NP in the first few centimeters of the column. Natural coatings were generally less stabilizing and more susceptible to increasing Ca2+ concentrations than the synthetic coating. The outdoor column experiment confirmed the low mobility of HA-CeO2 NP under more complex environmental conditions. From our experiments, we conclude that the synthetic polymer is more efficient in facilitating NP transport than natural coatings and hence, CeO2 NP mobility may vary significantly depending on the surface coating.

Colloidal stabilization of CeO2 nanomaterials with polyacrylic acid, polyvinyl alcohol or natural organic matter.

Engineered nanomaterials (ENM) such as nano-sized cerium dioxide (CeO2) are increasingly applied. Meanwhile, concerns on their environmental fate are rising. Understanding the fate of ENM within and between environmental compartments such as surface water and groundwater is crucial for the protection of drinking water resources. Therefore, the colloidal stability of CeO2 ENM (2 mg L-1) was assessed with various surface coatings featuring different physico-chemical properties such as weakly anionic polyvinyl alcohol (PVA), strongly anionic polyacrylic acid (PAA) or complex natural organic matter (NOM) at various water compositions in batch experiments (pH 2-12, ionic strength 0-5 mM KCl or CaCl2). While uncoated CeO2 ENM aggregate in the range of pH 4-8 in 1 mM KCl solution, the results show that PAA, PVA and NOM surface coatings stabilize CeO2-ENM at neutral and alkaline pH in 1 mM KCl solution. Stabilization by PAA and NOM is associated with strongly negative zeta potentials below -20 mV, suggesting electrostatic repulsion as stabilization mechanism. No aggregation was detected up to 5 mM KCl for PAA- and NOM-coated CeO2 ENM. In contrast, CaCl2 induced aggregation at >2.2 mM CaCl2 for PAA and NOM-coated CeO2 ENM respectively. PVA-coated ENM showed zeta potentials of -15 mV to -5 mV in the presence of 0-5 mM ionic strength, suggesting steric effects as stabilization mechanism. The hydrodynamic diameter of PVA-coated ENM was larger compared to PAA and NOM at low ionic strength, but the size did not increase with ionic strength of the suspensions. The effect of ionic strength and counter ion valency (pH 7) on the colloidal stability of ENM depends on the prevailing stabilization mechanism of the organic coating. NOM can be similarly effective in colloidal stabilization of CeO2-ENM as PAA. Our results suggest natural Ca-rich waters will lead to ENM agglomeration even of coated CeO2-ENM.

Physico-chemical properties of the new generation IV iron preparations ferumoxytol, iron isomaltoside 1000 and ferric carboxymaltose.

The advantage of the new generation IV iron preparations ferric carboxymaltose (FCM), ferumoxytol (FMX), and iron isomaltoside 1000 (IIM) is that they can be administered in relatively high doses in a short period of time. We investigated the physico-chemical properties of these preparations and compared them with those of the older preparations iron sucrose (IS), sodium ferric gluconate (SFG), and low molecular weight iron dextran (LMWID). Mössbauer spectroscopy, X-ray diffraction, and Fe K-edge X-ray absorption near edge structure spectroscopy indicated akaganeite structures (ß-FeOOH) for the cores of FCM, IIM and IS, and a maghemite (γ-Fe2O3) structure for that of FMX. Nuclear magnetic resonance studies confirmed the structure of the carbohydrate of FMX as a reduced, carboxymethylated, low molecular weight dextran, and that of IIM as a reduced Dextran 1000. Polarography yielded significantly different fingerprints of the investigated compounds. Reductive degradation kinetics of FMX was faster than that of FCM and IIM, which is in contrast to the high stability of FMX towards acid degradation. The labile iron content, i.e. the amount of iron that is only weakly bound in the polynuclear iron core, was assessed by a qualitative test that confirmed decreasing labile iron contents in the order SFG ≈ IS > LMWID ≥ FMX ≈ IIM ≈ FCM. The presented data are a step forward in the characterization of these non-biological complex drugs, which is a prerequisite to understand their cellular uptake mechanisms and the relationship between the structure and physiological safety as well as efficacy of these complexes.

Potential function of added minerals as nucleation sites and effect of humic substances on mineral formation by the nitrate-reducing Fe(II)-oxidizer Acidovorax sp. BoFeN1.

The mobility of toxic metals and the transformation of organic pollutants in the environment are influenced and in many cases even controlled by iron minerals. Therefore knowing the factors influencing iron mineral formation and transformation by Fe(II)-oxidizing and Fe(III)-reducing bacteria is crucial for understanding the fate of contaminants and for the development of remediation technologies. In this study we followed mineral formation by the nitrate-reducing Fe(II)-oxidizing strain Acidovorax sp. BoFeN1 in the presence of the crystalline Fe(III) (oxyhydr)oxides goethite, magnetite and hematite added as potential nucleation sites. Mössbauer spectroscopy analysis of minerals precipitated by BoFeN1 in (57)Fe(II)-spiked microbial growth medium showed that goethite was formed in the absence of mineral additions as well as in the presence of goethite or hematite. The presence of magnetite minerals during Fe(II) oxidation induced the formation of magnetite in addition to goethite, while the addition of humic substances along with magnetite also led to goethite but no magnetite. This study showed that mineral formation not only depends on the aqueous geochemical conditions but can also be affected by the presence of mineral nucleation sites that initiate precipitation of the same underlying mineral phases.

Green rust formation during Fe(II) oxidation by the nitrate-reducing Acidovorax sp. strain BoFeN1.

Green rust (GR) as highly reactive iron mineral potentially plays a key role for the fate of (in)organic contaminants, such as chromium or arsenic, and nitroaromatic compounds functioning both as sorbent and reductant. GR forms as corrosion product of steel but is also naturally present in hydromorphic soils and sediments forming as metastable intermediate during microbial Fe(III) reduction. Although already suggested to form during microbial Fe(II) oxidation, clear evidence for GR formation during microbial Fe(II) oxidation was lacking. In the present study, powder XRD, synchrotron-based XAS, Mössbauer spectroscopy, and TEM demonstrated unambiguously the formation of GR as an intermediate product during Fe(II) oxidation by the nitrate-reducing Fe(II)-oxidizer Acidovorax sp. strain BoFeN1. The spatial distribution and Fe redox-state of the precipitates associated with the cells were visualized by STXM. It showed the presence of extracellular Fe(III), which can be explained by Fe(III) export from the cells or extracellular Fe(II) oxidation by an oxidant diffusing from the cells. Moreover, GR can be oxidized by nitrate/nitrite and is known as a catalyst for oxidation of dissolved Fe(II) by nitrite/nitrate and may thus contribute to the production of extracellular Fe(III). As a result, strain BoFeN1 may contribute to Fe(II) oxidation and nitrate reduction both by an direct enzymatic pathway and an indirect GR-mediated process.

Biogenic Fe(III) minerals lower the efficiency of iron-mineral-based commercial filter systems for arsenic removal.

Millions of people worldwide are affected by As (arsenic) contaminated groundwater. Fe(III) (oxy)hydroxides sorb As efficiently and are therefore used in water purification filters. Commercial filters containing abiogenic Fe(III) (oxy)hydroxides (GEH) showed varying As removal, and it was unclear whether Fe(II)-oxidizing bacteria influenced filter efficiency. We found up to 10(7) Fe(II)-oxidizing bacteria/g dry-weight in GEH-filters and determined the performance of filter material in the presence and absence of Fe(II)-oxidizing bacteria. GEH-material sorbed 1.7 mmol As(V)/g Fe and was ~8 times more efficient than biogenic Fe(III) minerals that sorbed only 208.3 µmol As(V)/g Fe. This was also ~5 times more efficient than a 10:1-mixture of GEH-material and biogenic Fe(III) minerals that bound 322.6 µmol As(V)/g Fe. Coprecipitation of As(V) with biogenic Fe(III) minerals removed 343.0 µmol As(V)/g Fe, while As removal by coprecipitation with biogenic minerals in the presence of GEH-material was slightly less efficient as GEH-material only and yielded 1.5 mmol As(V)/g Fe. The present study thus suggests that the formation of biogenic Fe(III) minerals lowers rather than increases As removal efficiency of the filters probably due to the repulsion of the negatively charged arsenate by the negatively charged biogenic minerals. For this reason we recommend excluding microorganisms from filters (e.g., by activated carbon filters) to maintain their high As removal capacity.

In-situ magnetic susceptibility measurements as a tool to follow geomicrobiological transformation of Fe minerals.

Fe minerals sorb nutrients and pollutants and participate in microbial and abiotic redox reactions. Formation and transformation of Fe minerals is typically followed by mineral analysis at different time points. However, in lab studies the available sample amount is often limited and sampling may even influence the experimental conditions. We therefore evaluated the suitability of in situ magnetic susceptibility (MS) measurements, which do not require sampling, as an alternative tool to follow ferro(i)magnetic mineral (trans-)formation during ferrihydrite reduction by Shewanella oneidensis MR-1, and in soil microcosms. In our experiments with MR-1, a large initial increase in volume specific MS (kappa) followed by a slight decrease correlated well with the initial formation of magnetite and further reduction of magnetite to siderite as also identified by micro-XRD. The presence of humic acids retarded magnetite formation, and even inhibited magnetite formation completely, depending on their concentration. In soil microcosms, an increase in kappa accompanied by increasing concentrations of HCl-extractable Fe occurred only in microbially active set-ups, indicating a microbially induced change in soil Fe mineralogy. Based on our results, we conclude that MS measurements are suitable to follow microbial Fe mineral transformation in pure cultures as well as in complex soil samples.