Kerstin Leopold

Methods for the determination and speciation of mercury in natural waters—A review

This review summarises current knowledge on Hg species and their distribution in the hydrosphere and gives typical concentration ranges in open ocean, coastal and estuarine waters, as well as in rivers, lakes, rain and ground waters. The importance of reliable methods for the determination of Hg species in natural waters and the analytical challenges associated with them are discussed. Approaches for sample collection and storage, pre-concentration, separation, and detection are critically compared. The review covers well established methods for total mercury determination and identifies new approaches that offer advantages such as ease of use and reduced risk of contamination. Pre-concentration and separation techniques for Hg speciation are divided into chromatographic and non-chromatographic methods. Derivatisation methods and the coupling of pre-concentration and/or separation methods to suitable detection techniques are also discussed. Techniques for sample pre-treatment, pre-concentration, separation, and quantification of Hg species, together with examples of total Hg determination and Hg speciation analysis in different natural (non-spiked) waters are summarised in tables, with a focus on applications from the last decade.

Palladium nanoparticles induce disturbances in cell cycle entry and progression of peripheral blood mononuclear cells: paramount role of ions.

There is concern about the possible toxicity of palladium nanoparticles (Pd-NP), as they are released in the environment through many applications. We previously studied the toxicity of Pd-NP at high concentrations; here we address the possible toxicity of Pd-NP at low, subtoxic doses. In particular, we have exposed normal human PBMC entering into the first in vitro mitotic division to Pd-NP and to Pd(IV) ions to evaluate ROS generation and cell cycle progression. We have measured a statistically significant increase of intracellular ROS in Pd(IV) exposed cells, but not in Pd-NP exposed cells. TEM revealed accumulation of lipid droplets and autophagic and mitophagic vacuoles, which appeared more conspicuous in cells exposed to Pd(IV) ions than to Pd-NP. Pd-NP were visible in the cytoplasm of Pd-NP exposed cells. Pd-NP addition was associated with a significant increase of cells within the G0/G1-phase and a significant reduction in GS- and G2/M-phases. Cells exposed to Pd(IV) ions showed a significant amplification of these cell cycle alterations. These results suggest that ions, per se or released by NPs, are the true inducers of Pd toxicity. It will be essential to verify whether the observed disturbance represents a temporary response or might result in permanent alterations.

Gold-Coated Silica as a Preconcentration Phase for the Determination of Total Dissolved Mercury in Natural Waters Using Atomic Fluorescence Spectrometry

A novel solid-phase preconcentration method is reported, using in-house gold-coated silica adsorbent packed in a microcolumn, for the determination of dissolved mercury in natural waters by atomic fluorescence spectrometry (AFS). The adsorbent was prepared by chemical reduction of a Au(III) solution with hydroxylamine in the presence of suspended silica particles. The resulting Au nanoparticles on the silica surface were highly efficient for adsorbing different mercury species from acidified waters without additional reagents. The acidified aqueous samples were passed over the microcolumn, either incorporated in a fully automated flow injection (FI) system directly coupled to the AFS or as part of a portable FI system for in situ preconcentration. After rinsing and drying of the column, Hg(0) was released by heating and directed to the AFS cell for quantification. The method offers significant advantages because no reagents are needed for species conversion, preconcentration, sample storage, or desorption and therefore the risk of contamination is minimized and blank values are lowered. This results in a low detection limit of 180 pg L(-1) using a sample volume of only 7 mL and good reproducibility, with relative standard deviations <3.2% (n = 10, [Hg] = 5 ng L(-1)). Recoveries were all >90% in spiked river waters (spiked [Hg] = 0, 1, 5, 10 ng L(-1)), and the experimental value for the certified reference material ORMS-4 (elevated mercury in river water) was 22.3 +/- 2.6 ng Hg L(-1) which was in good agreement with the certified value of 22.0 +/- 1.6 ng Hg L(-1) (recovery = 101%). The method was successfully applied to seven different natural waters and wastewaters ([Hg] 0.5-4.6 ng L(-1)) from south west England.

Palladium exposure of barley: uptake and effects.

Motor vehicles are now equipped with exhaust gas catalytic converters containing rare metals, such as palladium (Pd), platinum and rhodium, as catalytic active materials, leading to significantly increased emission of these metals. Compared with platinum and rhodium, low concentrations of Pd have been shown to have more serious effects on cells and organisms. In the present study, uptake of Pd by barley and behaviour of Pd nanoparticles in nutrient solutions used to grow plants were observed in order to develop a model of Pd exposure of plant systems. Pd determination was performed using a selective separation and pre-concentration procedure, which was further developed for this study, and coupled to graphite furnace atomic absorption spectrometry. The results show that uptake of Pd depends on Pd particle diameter. Compared to other toxic metals, like mercury, Pd causes stress effects in leaves at lower concentrations in nutrient solutions. Furthermore, Pd particles are dissolved at different rates, depending on size, in the nutrient solution during plant growth.

Pd-nanoparticles cause increased toxicity to kiwifruit pollen compared to soluble Pd(II).

In the present study, endpoints including in vitro pollen performance (i.e., germination and tube growth) and lethality were used as assessments of nanotoxicity. Pollen was treated with 5-10 nm-sized Pd particles, similar to those released into the environment by catalytic car exhaust converters. Results showed Pd-nanoparticles altered kiwifruit pollen morphology and entered the grains more rapidly and to a greater extent than soluble Pd(II). At particulate Pd concentrations well below those of soluble Pd(II), pollen grains experienced rapid losses in endogenous calcium and pollen plasma membrane damage was induced. This resulted in severe inhibition and subsequent cessation of pollen tube emergence and elongation at particulate Pd concentrations as low as 0.4 mg L(-1). Particulate Pd emissions related to automobile traffic have been increasing and are accumulating in the environment. This could seriously jeopardize in vivo pollen function, with impacts at an ecosystem level.

Long-term study of palladium in road tunnel dust and sewage sludge ash

The present work summarizes data about palladium contents of road tunnel dust from 1994 to 2007 and sewage sludge ash from 1972 to 2006. Since palladium is emitted from automotive catalytic converters as elemental particles, road dust is quiet useful to study traffic-related Pd emissions. Very high Pd values of up to 516 microg Pd kg(-1) were found in the road dust samples collected in 2007. Heavy metals of all urban emissions, also dental practice effluent, are enriched in sewage sludge ash and thus this matrix is useful for the documentation of palladium emission caused by the use of Pd alloys in dental medicine. In sewage sludge ash highest Pd contents of maximum 460 microg Pd kg(-1) were found in the years 1986-1997. In both matrices correlations of Pd content to Pd demand of industry are discussed.

Ligand-Assisted Extraction for Separation and Preconcentration of Gold Nanoparticles from Waters

A new two-step extraction procedure is proposed for separation and preconcentration of gold nanoparticles (Au-NPs) from aqueous samples. First, Au-NPs are loaded onto a reversed phase C-18 (RP-C18) column, and then ligand-assisted extraction into chloroform is performed. 1-Dodecanethiol (1-DDT, 5 mM) was used as selective ligand for quantitative extraction under ultrasonic condition. Parameters of the extraction procedure, such as sample volume, organic solvent, concentration and nature of the ligand, ultrasonication time, pH of the sample, and different coating as well as sizes of Au-NPs were investigated in regard to the extraction efficiency of Au-NPs. The optimized procedure allows separation and preconcentration of the Au-NPs with an enrichment factor of up to 250 assuring no changes in size and/or shape of the NPs. This was proved by investigation of the particles by UV-vis spectrometry and transmission electron microscopy (TEM). Furthermore, the presence of potentially interfering other metal nanoparticles (M-NPs) and dissolved organic matter (DOM) was studied. Observed minor recoveries of Au-NPs in DOM model solutions were overcome by hydrogen peroxide pretreatment up to a DOM concentration of about 4 mg/L. Feasibility of the proposed method was proved by application of the optimized procedure to 5 real water samples. Recoveries of Au-NPs in the real waters spiked in a concentration range from 0.15 to 5100 μg/L obtained by this method varied from 68.4% to 99.4%. Consequently, the proposed approach has great potential for the analysis of M-NPs in environmental waters.

Effective and selective extraction of noble metal nanoparticles from environmental water through a noncovalent reversible reaction on an ionic exchange resin

Capable of preserving the size and shape of nanoparticles, a novel method to effectively and selectively extract noble metal nanoparticles even at the 80 ng L(-1) level from real environmental water was designed and performed using a noncovalent reversible adsorption onto an ionic exchange resin.

A new fully automated on-line digestion system for ultra trace analysis of mercury in natural waters by means of FI-CV-AFS.

A fully automated flow injection (FI) system utilizing the extraordinary oxidation power of bromine monochloride (BrCl) for the transformation of dissolved mercury species to Hg(2+) and oxidation of dissolved organic carbon (DOC) has been developed and coupled to cold vapor (CV) atomic fluorescence spectrometry (AFS) for highly sensitive mercury detection. The system can be applied to natural waters, sea water as well as freshwater and provides a detection limit as low as 16 pg Hg l(-1) from a sample volume of 7 ml. The relative standard deviation is about 4-10%. A 3-fold measurement of one sample is completely processed within 15 min. Dissolved organic carbon, chloride and iodide ions are tolerated in concentrations of 15 mg DOC l(-1), >21 g Cl(-)l(-1), and 10 mg I(-)l(-1). Validation of the proposed method yielded a good recovery of total mercury in a moorland water sample and in the certified reference material ORMS-3, river water. Investigation of eight real water samples with mercury concentrations in the range of 0.3-1.4 ng l(-1) also confirmed the suitability of the proposed method.

Activated gold surfaces for the direct preconcentration of mercury species from natural waters

This paper describes for the first time the mechanism of adsorption of different dissolved mercury species onto gold surfaces directly from aqueous solutions. The surface morphology of the gold collector is critical for the adsorption behaviour of the different mercury species. Smooth gold surfaces selectively trap elemental mercury (Hg0), whereas nano-structured gold surfaces quantitatively retain all dissolved mercury species (Hg0, Hg2+, and MeHg+) from aqueous solutions. The mechanism of Hg2+ and MeHg+ adsorption can be explained by the catalytic activity of the nano-structured gold surface, whereas Hg0 adsorption is an amalgamation process. Nano-structured gold surfaces can easily be generated from gold collectors with smooth surfaces by adsorbing and thermally desorbing Hg0. Both types of gold collectors, selective collectors (smooth surface) for species specific trapping of Hg0 and active collectors (nano-structured) for the preconcentration of all Hg species can be used for quantitative analysis with recoveries of 97.0 ± 6.8% in ocean water after thermal desorption at 700 °C and atomic fluorescence spectrometric detection. This preconcentration method for the determination of total dissolved mercury in natural waters offers significant advantages over existing methods because no reagents are needed for sample pre-treatment, preconcentration or desorption and therefore the risk of contamination is minimized and blank values are lowered. This results in low detection limits for Hg2+ and MeHg+ of 101 pg L−1 and 144 pg L−1, respectively, using a sample volume of only 7 mL, and good reproducibility, with uncertainties less than 3.7% (n = 5). In addition the preparation of the active phases is very straightforward.