David Kistler

Dissolution of metal and metal oxide nanoparticles in aqueous media

The dissolution of Ag (citrate, gelatin, polyvinylpyrrolidone and chitosan coated), ZnO, CuO and carbon coated Cu nanoparticles (with two nominal sizes each) has been studied in artificial aqueous media, similar in chemistry to environmental waters, for up to 19 days. The dissolved fraction was determined using DGT (Diffusion Gradients in Thin films), dialysis membrane (DM) and ultrafiltration (UF). Relatively small fractions of Ag nanoparticles dissolved, whereas ZnO dissolved nearly completely within few hours. Cu and CuO dissolved as a function of pH. Using DGT, less dissolved Ag was measured compared to UF and DM, likely due to differences in diffusion of organic complexes. Similar dissolved metal concentrations of ZnO, Cu and CuO nanoparticles were determined using DGT and UF, but lower using DM. The results indicate that there is a need to apply complementary techniques to precisely determine dissolution of nanoparticles in aqueous media.

In situ trace metal speciation in a eutrophic lake using the technique of diffusion gradients in thin films (DGT)

Abstract. We evaluated the application of DGT (diffusion gradients in thin films) as a tool to determine Cu, Zn, Ni, Cd, Pb and Mn concentrations and speciation in a hardwater eutrophic lake. This technique was used in situ during six sampling periods over one year in Lake Greifen. The DGT-labile species of Cu and Ni amounted to 15–25% of the total dissolved concentrations. Speciation by ligand-exchange/DPCSV indicated that Cu and Ni were predominantly organically complexed (>99%). Thus, the DGT-labile species for Cu and Ni were much more abundant than the free ionic and inorganic species determined by ligand-exchange/DPCSV. The results can be explained by incomplete metal exchange of very strong complexes with the chelating resin in the DGT devices, metal exchange of less abundant weaker complexes, and by slow diffusion of exchangeable organic complexes. For Zn (36 to >90% DGT-labile) and Mn (50 to 100% DGT-labile), the results indicated that these metals are less strongly organically complexed. A larger fraction of Zn occurred in DGT-labile species in the hypolimnion than it did in the surface water, probably due to a larger concentration of strong ligands in the productive surface water. DGT-labile Cd- (0.01–0.02 nM) and Pb-species (0.03–0.06 nM) were detected at very low levels. The combination of measurements of dissolved and DGT-labile species showed a decrease of Cu, Zn, Cd and Mn concentration at 2.5 m from June to August, which was probably linked to intensive sedimentation of organic matter during summer stagnation. Mixing and oxygenation of the lake in winter-spring led to an increase in dissolved and DGT-labile Ni, Zn and Cd, whereas Mn decreased in the hypolimnion.

Free cupric ion concentrations and Cu complexation in selected Swiss lakes and rivers

Abstract[Cu2+] and Cu complexation parameters in some selected freshwater systems in Switzerland were determined by the technique of ligand-exchange and DPCSV. Results from the water columns of some eutrophic and oligotrophic lakes are presented and compared to small acid lakes. Cu is strongly complexed by organic ligands which with very high stability constants at low concentrations are probably biologically produced, as indicated by the seasonal variations in the eutrophic lakes and by the relationship between Cu complexation and algal activity in the eutrophic (pCu=15−16), oligotrophic (pCu=13−14) and acidic (pCu=9−10) lakes. The extent of Cu complexation in river waters was generally lower than in the eutrophic lakes, at similar DOC levels. No obvious correlation between Cu complexation and DOC was observed, indicating that Cu complexing ligands are specific organic compounds.

Size Fractionation (Dissolved, Colloidal and Particulate) of Trace Metals in the Thur River, Switzerland

The distribution of some trace metals (Cu, Zn, Ni, Co,Fe, Mn) and of DOC over a particulate (> 1 μm),a colloidal (size < 0.45 μm and molecular weight > 10 kD) and an ultrafiltered fraction (< 10 kD)was determined at several sites on the Thur River,Switzerland, at various times of the year. Thecomplexation of Cu by strong ligands in theultrafiltrate and in the conventional filtrate (<0.45 μm) was compared using a ligand-exchange/CSV method.The <0.45 μm concentrations of Cu (from anaverage of 7 nM to 24 nM), Zn (<5–23 nM), Ni (5–13 nM),Co (1.5–3 nM) and Mn (7–92 nM)increased downstream. The major part of Cu, Zn, Niand Co usually occurred in the ultrafiltratefraction at all sites, whereas Fe and Mn were mostlyin the particulate fraction, under conditions of lowsuspended matter content (< 10 mg L-1) in theriver. The percentage of metal in the colloidalfraction, with respect to the 0.45-μm filtrate,decreased in the order: Cu (median 11%) > Zn ≈Ni(median 5–6%) > Mn ≈ Co (median < 5%). DOCalso consisted mostly of molecules in the < 10 kDrange.Cu was strongly complexed by natural organic ligandsin all filtrate and ultrafiltrate samples. A largepart of the strong Cu binding ligands consisted ofcompounds in the < 10 kD range, but colloidalligands with similar properties also occurred. Cu wasdistributed among the dissolved and the colloidalligands, roughly in proportion to organic carbon.The colloidal fraction (as defined here) did notincrease in its proportional amount downstream and wasonly of limited significance in transporting traceelements in the Thur River under low discharge conditions.

Cadmium speciation and accumulation in periphyton in a small stream with dynamic concentration variations

Accumulation of cadmium in periphyton was investigated under field conditions while Cd concentration and speciation were dynamically varying in a small stream during rain events. Speciation in water was determined in situ by diffusion gradient in thin-films (DGT) and by modeling of complexation with fulvic acids. During the rain events, dissolved Cd concentrations increased from 0.17 nM to 0.27-0.36 nM, and 70-97% were DGT-labile. Cd content in periphyton closely followed Cd concentrations in water, despite higher concentrations of Zn and Mn, and may be controlled by either free or DGT-labile Cd concentrations. Decrease of Cd content in periphyton after the rain events was slower than the decrease of Cd concentration in water. Concentrations of Zn, Mn, Cu, Pb and Fe in periphyton also followed the dynamic variations of metal concentrations in water. Repeated exposure of periphyton to elevated dissolved Cd may lead to Cd accumulation.

Uptake of Cd(II) and Pb(II) by microalgae in presence of colloidal organic matter from wastewater treatment plant effluents

The present study addresses the key issue of linking the chemical speciation to the uptake of priority pollutants Cd(II) and Pb(II) in the wastewater treatment plant effluents, with emphasis on the role of the colloidal organic matter (EfOM). Binding of Cd(II) and Pb(II) by EfOM was examined by an ion exchange technique and flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry in parallel to bioassays with green microalga Chlorella kesslerii in ultrafiltrate (<1 kDa) and colloidal isolates (1 kDa to 0.45 mum). The uptake of Cd by C. kesslerii was consistent with the speciation analysis and measured free metal ion concentrations, while Pb uptake was much greater than that expected from the speciation measurement. Better understanding of the differences in the effects of the EfOM on Cd(II) and Pb(II) uptake required to take into account the size dependence of metal binding by EfOM.

Dissolution of metal and metal oxide nanoparticles under natural freshwater conditions

Environmental context Engineered nanomaterials (e.g. silver, zinc oxide and copper oxide) are being widely used in many consumer products such as cosmetics, food packaging and textiles. During their usage and treatment, they will be released to natural waters and partly dissolve, depending on the water type and nanomaterial characteristics. These nanomaterials may thus have some toxic effects to aquatic organisms and indirectly to humans because of higher concentrations of dissolved silver, zinc and copper in natural waters. Abstract The dissolution of some widely used nanoparticles (NPs), Ag (citrate coated), ZnO, CuO and Cu-carbon coated (Cu/C), has been studied over a period of 9 days in five different natural waters: wastewater treatment plant effluent (WWTP Dubendorf) and lakes Greifen, Lucerne, Gruere and Cristallina. These waters differ in ionic strength, pH and dissolved organic carbon (DOC). The dissolved fraction of metals from NPs was determined using DGT (diffusion gradients in thin films) and ultrafiltration (UF). ZnO-NPs and CuO-NPs dissolved to a large extent in all waters, whereas the dissolved fraction was much smaller in the case of Cu/C and Ag-NPs. All NPs dissolved to a larger extent in water from Lake Cristallina with low pH, low ionic strength and low DOC. Ag-NP dissolution was favoured at low ionic strength and low pH, whereas dissolution of CuO-NPs was mostly dependent on pH. Cu/C-NPs strongly agglomerated and sedimented and yielded low dissolved Cu concentrations. DGT and UF produced similar results, although these two methods differ in the measurement time scale. The results of this study indicate that dissolution is an important process for these NPs under conditions of natural waters or wastewaters.

Colloidal Stability and Toxicity of Gold Nanoparticles and Gold Chloride on Chlamydomonas reinhardtii

Abstract Here we have examined interactions of gold nanoparticles differing in primary particle size and coating with the green algae Chlamydomonas reinhardtii as function of the colloidal stability of the particles in the experimental media used for toxicity studies. Interactions of dissolved Au3+ ions with algae were also examined. Included endpoints were photosynthetic yield and algal growth. Morphological and structural effects were examined microscopically and by flow cytometry. The results indicate no significant toxicity of gold nanoparticles to C. reinhardtii. Analysis of published data suggests toxicity of gold nanoparticles on algal growth to relate rather to particular coatings than to the gold core.

Seasonal variations of zinc in a eutrophic lake

Depth profiles of dissolved zinc were measured monthly over one year in Lake Greifen, a eutrophic lake. The concentrations are in the range 10–40 nM and show systematic variations over time and depth. Due to the increased binding to particles and subsequent settling, concentrations of zinc in the epilimnion decrease during summer stagnation. Clear correlations between Zn and major nutrients (P, Si) are, however, not observed in the water column. No accumulation of Zn occurs in the anoxic hypolimnion. The Zn sedimentation is related to the sedimentation of algae and of manganese oxide. A mass-balance calculation shows that 87% of the Zn input is retained in the sediments of Lake Greifen.