Sondra Klitzke

The fate of silver nanoparticles in soil solution--Sorption of solutes and aggregation.

Nanoparticles enter soils through various pathways. In the soil, they undergo various interactions with the solution and the solid phase. We tested the following hypotheses using batch experiments: i) the colloidal stability of Ag NP increases through sorption of soil-borne dissolved organic matter (DOM) and thus inhibits aggregation; ii) the presence of DOM suppresses Ag oxidation; iii) the surface charge of Ag NP governs sorption onto soil particles. Citrate-stabilized and bare Ag NPs were equilibrated with (colloid-free) soil solution extracted from a floodplain soil for 24h. Nanoparticles were removed through centrifugation. Concentrations of free Ag ions and DOC, the specific UV absorbance at a wavelength of 254 nm, and the absorption ratio α254/α410 were determined in the supernatant. Nanoparticle aggregation was studied using time-resolved dynamic light scattering (DLS) measurement following the addition of soil solution and 1.5mM Ca(2+) solution. To study the effect of surface charge on the adsorption of Ag NP onto soil particles, bare and citrate-stabilized Ag NP, differing in the zeta potential, were equilibrated with silt at a solid-to-solution ratio of 1:10 and an initial Ag concentration range of 30 to 320 μg/L. Results showed that bare Ag NPs sorb organic matter, with short-chained organic matter being preferentially adsorbed over long-chained, aromatic organic matter. Stabilizing effects of organic matter only come into play at higher Ag NP concentrations. Soil solution inhibits the release of Ag(+) ions, presumably due to organic matter coatings. Sorption to silt particles was very similar for the two particle types, suggesting that the surface charge does not control Ag NP sorption. Besides, sorption was much lower than in comparable studies with sand and glass surfaces.

Mobilization of soluble and dispersible lead, arsenic, and antimony in a polluted, organic-rich soil - effects of pH increase and counterion valency.

Liming is a common technique suggested for the stabilization of shooting range sites. We investigated the effect of an increase in pH on the mobilization of soluble and dispersible (colloidal) Pb, As, and Sb. Our hypothesis was that the addition of divalent cations counteracts the pH-induced mobilization of soluble and colloidal metal(loid)s. We determined soluble (operationally defined as the fraction < 10 nm obtained after centrifugation) and dispersible (filter cut-off 1200 nm) As, Pb, Sb, Fe, and C(org) concentrations in the filtered suspensions of batch extracts of topsoil samples (C(org): 8%) from a former shooting range site following a pH increase to values between 3.5 and 7 by adding a monovalent (KOH) or a divalent (Ca(OH)(2)) base. In the Ca(OH)(2)-treated samples, dissolved metal(loid) concentrations were 62 to 98% lower than those titrated with KOH to similar pH. Similarly, Ca reduced the concentration of dispersible Pb by 95%, but had little or no impact on dispersible As and Sb. We conclude that the counterion valency controls the mobility of metal(loid)s by affecting the mobility and sorption capacity of the sorbents (e.g., colloids, organic matter).

Investigation of coatings of natural organic matter on silver nanoparticles under environmentally relevant conditions by surface-enhanced Raman scattering

The widespread use of engineered inorganic nanoparticles (EINP) leads to a growing risk for an unintended release into the environment. Despite the good characterization of EINP in regard to their function scale and the application areas, there is still a gap of knowledge concerning their behaviour in the different environmental compartments. Due to their high surface to volume ratio, surface properties and existence or development of a coating are of high importance for their stability and transport behaviour. However, analytical methods to investigate organic coatings on nanoparticles in aqueous media are scarce. We used Raman microspectroscopy in combination with surface-enhanced Raman scattering (SERS) to investigate humic acid coatings on silver nanoparticles under environmentally relevant conditions and in real world samples. This setup is more challenging than previous mechanistic studies using SERS to characterize the humic acids in tailored settings where only one type of organic matter is present and the concentrations of the nanoparticles can be easily adjusted to the experimental needs. SERS offers the unique opportunity to work with little sample preparation directly with liquid samples, thus significantly reducing artefacts. SERS spectra of different natural organic matter brought into contact with silver nanoparticles indicate humic acid in close proximity to the nanoparticles. This coating was also present after several washing steps by centrifugation and resuspension in deionized water and after an increase in ionic strength.

Lead, antimony and arsenic in dissolved and colloidal fractions from an amended shooting-range soil as characterised by multi-stage tangential ultrafiltration and centrifugation

Environmental context The size of soil colloids is – among other characteristics – crucial for the mobility of associated contaminants. We analysed the effect of liming on the size of colloids mobilised from strongly contaminated shooting-range soils using multi-stage tangential ultrafiltration (MTUF) for the size fractionation of dispersed soil colloids. Our results indicate the high analytical potential of MTUF and show that liming induces the aggregation of colloids, thereby decreasing the mobilisation of colloid-bound Sb and As, but increasing colloidal Pb. Abstract The size and composition of colloids are important factors controlling their relevance as carriers of metal(loid)s in soils. Liming, which is often used to reduce the effect of heavy metal contamination in soil, can alter concentrations and characteristics of colloids in soil suspension. In batch studies, we compared the influence of changing pH and cation valency on the size distribution and composition of dispersed colloids and on the concentrations of Pb, As and Sb associated with colloids and in solution following the addition of Ca(OH)2 and KOH to soil samples from a contaminated-shooting range site. Multi-stage tangential ultrafiltration (MTUF) and centrifugation were used for the size fractionation of colloids in aqueous suspension. An increase in soil pH resulted in an increase in colloid-associated Pb, with much higher concentrations in the KOH than in the Ca(OH)2 treated samples. In contrast colloid-associated Sb and As increased only in the KOH treated samples. Addition of the monovalent K-ion induced the dispersion of small (~9–220 nm) organo(-mineral) colloids, whereas the divalent Ca-ion suppressed their dispersion and led to the formation of larger colloids (220–1200 nm). Whereas centrifugation underestimated contaminants (i.e. Pb) associated with organic colloids (density <2.6 g cm–3) MTUF gave a distorted distribution of inorganic colloids (i.e. needle-shaped sesquioxides).

Retention and remobilization mechanisms of environmentally aged silver nanoparticles in an artificial riverbank filtration system

Riverbank filtration systems are important structures that ensure the cleaning of infiltrating surface water for drinking water production. In our study, we investigated the potential risk for a breakthrough of environmentally aged silver nanoparticles (Ag NP) through these systems. Additionally, we identified factors leading to the remobilization of Ag NP accumulated in surficial sediment layers in order to gain insights into remobilization mechanisms. We conducted column experiments with Ag NP in an outdoor pilot plant consisting of water-saturated sediment columns mimicking a riverbank filtration system. The NP had previously been aged in river water, soil extract, and ultrapure water, respectively. We investigated the depth-dependent breakthrough and retention of NP. In subsequent batch experiments, we studied the processes responsible for a remobilization of Ag NP retained in the upper 10 cm of the sediments, induced by ionic strength reduction, natural organic matter (NOM), and mechanical forces. We determined the amount of remobilized Ag by ICP-MS and differentiated between particulate and ionic Ag after remobilization using GFAAS. The presence of Ag-containing heteroaggregates was investigated by combining filtration with single-particle ICP-MS. Single and erratic Ag breakthrough events were mainly found in 30 cm depth and Ag NP were accumulated in the upper 20 cm of the columns. Soil-aged Ag NP showed the lowest retention of only 54%. Remobilization was induced by the reduction of ionic strength and the presence of NOM in combination with mechanical forces. The presence of calcium in the aging- as well as the remobilizing media reduced the remobilization potential. Silver NP were mainly remobilized as heteroaggregates with natural colloids, while dissolution played a minor role. Our study indicates that the breakthrough potential of Ag NP in riverbank filtration systems is generally low, but the aging in soil increases their mobility. Remobilization processes are associated to co-mobilization with natural colloids.