Andreas Fritzsche

Arsenic strongly associates with ferrihydrite colloids formed in a soil effluent

Arsenic mobility may increase in liquid phase due to association with colloidal Fe oxides. We studied the association of As with Fe oxide colloids in the effluent from water-saturated soil columns run under anoxic conditions. Upon exfiltration, the solutions, which contained Fe2+, were re-aerated and ferrihydrite colloids precipitated. The entire amount of effluent As was associated with the ferrihydrite colloids, although PO4(3-), SiO4(4-), CO3(2-) and dissolved organic matter were present in the effluent during ferrihydrite colloid formation. Furthermore, no subsequent release of As from the ferrihydrite colloids was observed despite the presence of these (in)organic species known to compete with As for adsorption on Fe oxides. Arsenic was bound via inner-sphere complexation on the ferrihydrite surface. FTIR spectroscopy also revealed adsorption of PO4(3-) and polymerized silica. However, these species could not impede the quantitative association of As with colloidal ferrihydrite in the soil effluents.

Size- and composition-dependent toxicity of synthetic and soil-derived Fe oxide colloids for the nematode Caenorhabditis elegans.

Colloidal iron oxides (FeOx) are increasingly released to the environment due to their use in environmental remediation and biomedical applications, potentially harming living organisms. Size and composition could affect the bioavailability and toxicity of such colloids. Therefore, we investigated the toxicity of selected FeOx with variable aggregate size and variably composed FeOx-associated organic matter (OM) toward the nematode Caenorhabditis elegans. Ferrihydrite colloids containing citrate were taken up by C. elegans with the food and accumulated inside their body. The toxicity of ferrihydrite, goethite, and akaganeite was dependent on aggregate size and specific surface area, with EC50 values for reproduction ranging from 4 to 29 mg Fe L(-1). Experiments with mutant strains lacking mitochondrial superoxide dismutase (sod-2) showed oxidative stress for two FeOx and Fe(3+)-ions, however, revealed that it was not the predominant mechanism of toxicity. The OM composition determined the toxicity of mixed OM-FeOx phases on C. elegans. FeOx associated with humic acids or citrate were less toxic than OM-free FeOx. In contrast, soil-derived ferrihydrite, containing proteins and polysaccharides from mobile OM, was even more toxic than OM-free Fh of similar aggregate size. Consequently, the careful choice of the type of FeOx and the type of associated OM may help in reducing the ecological risks if actively applied to the subsurface.

Nanosized ferrihydrite colloids facilitate microbial iron reduction under flow conditions

Recent studies indicated that nanoparticulate minerals in the environment exhibit a higher reactivity than their respective bulk materials. Lately, this has also been reported for microbial iron reduction using nanosized iron oxides as electron acceptors. However, these results have been obtained under small-scale, static batch conditions. The study presented here implies a flow regime within porous medium under low salt conditions providing information on the retention of nanosized iron oxide and the long-term sustainability of their reduction. Goethite, present as coating on quartz sand as a default electron acceptor, was reduced by Geobacter sulfurreducens and discharged as Fe 2 + up to a maximum concentration of 0.6 mM in the column effluent, finally representing 10% of the supplied ferric iron in total. Adding ferrihydrite colloids via the influent to goethite-coated quartz sand led to partial adsorption of the colloids, but also to a high reactivity with a maximum Fe 2 + discharge of 1.2 mM. In total, 1.4 mmol out of 2.6 mmol ferrihydrite colloids were reduced. Upon addition of ferrihydrite colloids to the influent of a parallel column containing quartz sand without goethite coatings, the maximum concentration of discharged Fe 2 + accounted also for 1.2 mM, and 0.4 mmol out of 0.6 mmol ferrihydrite colloids were reduced in total. The column experiments demonstrated that ferrihydrite colloids are highly reactive and bioavailable for microbial reduction under approximated in situ conditions.

Acute ecotoxicity of coated colloidal goethite nanoparticles on Daphnia magna: Evaluating the influence of exposure approaches

Synthesized iron oxide nanoparticles have been proposed as an alternative to non-dispersed iron oxides for in situ environmental remediation. Their colloidal properties enable their injection into porous media, i.e. soils and aquifers, and offer a higher efficiency in removing contaminants. However, this dispersed state is also the cause of concerns over their environmental fate and toxicity, e.g., by increasing the exposure time to aquatic organisms in groundwater remediation activities. Therefore, the objective of in situ groundwater remediation is to establish local reactive barriers in the subsurface by injection by means of reactive colloids with a controllable mobility under in situ conditions and present as colloids as shortly as possible. In this work, we examined the toxicity of humic acid-coated colloidal goethite nanoparticles in Daphnia magna. The adaptation of the ecotoxicological standard tests for nanomaterials is intensely discussed to increase comparability and reliability of results. In the present study, the effect of different exposure conditions on goethite nanoparticles colloidal behaviour and acute Daphnia immobilization effects was investigated. For this purpose, iron concentration in the water column, aggregation state and acute effects were studied in: i) a standard test, ii) test design with exposure dispersions incubated for a week and iii) water accommodated fraction. Despite the different aggregation and settling of the particles found between the approaches tested, no differences in toxicity were observed. Coated nanoparticles were found clogging up the filtering apparatus, and/or adhered to the exoskeleton, hindering the swimming and molting, and causing the immobilization and death of the organisms at doses of ≥943mg/L (EC50). The data suggests that the toxic potential of these nanoparticles is mainly related to the physical interaction with the daphnids.

Colloidal-Bound Polyphosphates and Organic Phosphates Are Bioavailable: A Nutrient Solution Study

Colloidal forms of Fe(III) minerals can be stabilized in solution by coatings of organic or poly-phosphate (P), which reduce the zeta-potential. This opens up a route toward the development of nanoforms of P fertilizers. However, it is unclear if such P forms are bioavailable. To address this question, spinach (Spinacia oleracea) was grown in nutrient solutions, at equal total P, using three different forms of P (orthophosphate = Pi; hexametaphosphate = HMP; myo-inositol hexaphosphate = IHP), free or bound to goethite/ferrihydrite colloids. After 10 days, P uptake was determined with a dose-response curve using colloid-free Pi as a reference treatment. The Pi concentration generating equal P uptake as in colloidal P treatments was used to calculate the relative bioavailability of colloidal P (RBAcolloid). The RBAcolloid was about 60% for Pi-loaded goethite, stabilized with natural organic matter. For HMP/IHP-Pi-loaded colloids, RBAcolloid ranged between 10 and 50%, in line with their higher sorption strength. In conclusion, colloidal organic P or poly-P can stabilize Fe(III) colloids in solution and can contribute to plant-available P. Soil experiments are required to assess their potential as nanofertilizers.