Structural information on nanometer-sized gold particles has been limited, due in part to the problem of preparing homogeneous material. Here we report the crystallization and x-ray structure determination of a p-mercaptobenzoic acid (p-MBA)-protected gold nanoparticle, which comprises 102 gold atoms and 44 p-MBAs. The central gold atoms are packed in a Marks decahedron, surrounded by additional layers of gold atoms in unanticipated geometries. The p-MBAs interact not only with the gold but also with one another, forming a rigid surface layer. The particles are chiral, with the two enantiomers alternating in the crystal lattice. The discrete nature of the particle may be explained by the closing of a 58-electron shell.

http://science.sciencemag.org/content/sci/318/5849/430.full.pdf

Structure of a thiol monolayer-protected gold nanoparticle at 1.1 A resolution

Interpretation of europium(III) spectra

Comparison of the Chernobyl and Fukushima nuclear accidents: a review of the environmental impacts.

Environmental risk assessments of engineered nanoparticles require thorough characterization of nanoparticles and their aggregates. Furthermore, quantitative analytical methods are required to determine environmental concentrations and enable both effect and exposure assessments. Many methods still need optimization and development, especially for new types of nanoparticles in water, but extensive experience can be gained from the fields of environmental chemistry of natural nanomaterials and from fundamental colloid chemistry. This review briefly describes most methods that are being exploited in nanoecotoxicology for analysis and characterization of nanomaterials. Methodological aspects are discussed in relation to the fields of nanometrology, particle size analysis and analytical chemistry. Differences in both the type of size measures (length, radius, aspect ratio, etc.), and the type of average or distributions afforded by the specific measures are compared. The strengths of single particle methods, such as electron microscopy and atomic force microscopy, with respect to imaging, shape determinations and application to particle process studies are discussed, together with their limitations in terms of counting statistics and sample preparation. Methods based on the measurement of particle populations are discussed in terms of their quantitative analyses, but the necessity of knowing their limitations in size range and concentration range is also considered. The advantage of combining complementary methods is highlighted.

Nanoparticle analysis and characterization methodologies in environmental risk assessment of engineered nanoparticles

. On 11 March 2011, an earthquake occurred about 130 km off the Pacific coast of Japan's main island Honshu, followed by a large tsunami. The resulting loss of electric power at the Fukushima Dai-ichi nuclear power plant developed into a disaster causing massive release of radioactivity into the atmosphere. In this study, we determine the emissions into the atmosphere of two isotopes, the noble gas xenon-133 (133Xe) and the aerosol-bound caesium-137 (137Cs), which have very different release characteristics as well as behavior in the atmosphere. To determine radionuclide emissions as a function of height and time until 20 April, we made a first guess of release rates based on fuel inventories and documented accident events at the site. This first guess was subsequently improved by inverse modeling, which combined it with the results of an atmospheric transport model, FLEXPART, and measurement data from several dozen stations in Japan, North America and other regions. We used both atmospheric activity concentration measurements as well as, for 137Cs, measurements of bulk deposition. Regarding 133Xe, we find a total release of 15.3 (uncertainty range 12.2–18.3) EBq, which is more than twice as high as the total release from Chernobyl and likely the largest radioactive noble gas release in history. The entire noble gas inventory of reactor units 1–3 was set free into the atmosphere between 11 and 15 March 2011. In fact, our release estimate is higher than the entire estimated 133Xe inventory of the Fukushima Dai-ichi nuclear power plant, which we explain with the decay of iodine-133 (half-life of 20.8 h) into 133Xe. There is strong evidence that the 133Xe release started before the first active venting was made, possibly indicating structural damage to reactor components and/or leaks due to overpressure which would have allowed early release of noble gases. For 137Cs, the inversion results give a total emission of 36.6 (20.1–53.1) PBq, or about 43% of the estimated Chernobyl emission. Our results indicate that 137Cs emissions peaked on 14–15 March but were generally high from 12 until 19 March, when they suddenly dropped by orders of magnitude at the time when spraying of water on the spent-fuel pool of unit 4 started. This indicates that emissions may not have originated only from the damaged reactor cores, but also from the spent-fuel pool of unit 4. This would also confirm that the spraying was an effective countermeasure. We explore the main dispersion and deposition patterns of the radioactive cloud, both regionally for Japan as well as for the entire Northern Hemisphere. While at first sight it seemed fortunate that westerly winds prevailed most of the time during the accident, a different picture emerges from our detailed analysis. Exactly during and following the period of the strongest 137Cs emissions on 14 and 15 March as well as after another period with strong emissions on 19 March, the radioactive plume was advected over Eastern Honshu Island, where precipitation deposited a large fraction of 137Cs on land surfaces. Radioactive clouds reached North America on 15 March and Europe on 22 March. By middle of April, 133Xe was fairly uniformly distributed in the middle latitudes of the entire Northern Hemisphere and was for the first time also measured in the Southern Hemisphere (Darwin station, Australia). In general, simulated and observed concentrations of 133Xe and 137Cs both at Japanese as well as at remote sites were in good quantitative agreement. Altogether, we estimate that 6.4 PBq of 137Cs, or 18% of the total fallout until 20 April, were deposited over Japanese land areas, while most of the rest fell over the North Pacific Ocean. Only 0.7 PBq, or 1.9% of the total fallout were deposited on land areas other than Japan.

Xenon-133 and caesium-137 releases into the atmosphere from the Fukushima Dai-ichi nuclear power plant: determination of the source term, atmospheric dispersion, and deposition

Role of phosphate fertilizers in heavy metal uptake and detoxification of toxic metals.

Actinide colloids and particles of environmental concern

Since its inauguration in 2005, the INE-Beamline for actinide research at the synchrotron source ANKA (KIT North Campus) provides dedicated instrumentation for x-ray spectroscopic characterization of actinide samples and other radioactive materials. R&D work at the beamline focuses on various aspects of nuclear waste disposal within INE's mission to provide the scientific basis for assessing long-term safety of a final nuclear waste repository. The INE-Beamline is accessible for the actinide and radiochemistry community through the ANKA proposal system and the European Union Integrated Infrastructure Initiative ACTINET-I3. Experiments with activities up to 1 x 10(+6) times the European exemption limit are feasible within a safe but flexible containment concept. Measurements with monochromatic radiation are performed at photon energies varying between similar to 2.1 keV (P K-edge) and similar to 25 keV (Pd K-edge), including the lanthanide L-edges and the actinide M-and L3-edges up to Cf. The close proximity of the INE-Beamline to INE controlled area labs offers infrastructure unique in Europe for the spectroscopic and microscopic characterization of actinide samples. The modular beamline design enables sufficient flexibility to adapt sample environments and detection systems to many scientific questions. The well-established bulk techniques x-ray absorption fine structure (XAFS) spectroscopy in transmission and fluorescence mode have been augmented by advanced methods using a microfocused beam, including (confocal) XAFS/x-ray fluorescence detection and a combination of (micro-)XAFS and (micro-)x-ray diffraction. Additional instrumentation for high energy-resolution x-ray emission spectroscopy has been successfully developed and tested.

The INE-Beamline for actinide science at ANKA

Common explosives (TNT, RDX, HMX) and their fate in the environment: Emphasizing bioremediation

Pu(IV) oxyhydroxide colloid growth is investigated with XAFS and LIBD. From combined results a model of colloid formation is proposed, which leads to a face-centered cubic Pu sublattice having cation defects, as observed with EXAFS, and a linear dependency of log [Pu(IV)] on −log [H+] with slope −2, in accord with LIBD. The solubility for Pu(IV) measured with LIBD is close to the lower limit of the solubility curve from previously reported data.

Clemens Walther

Papers

Role of phosphate fertilizers in heavy metal uptake and detoxification of toxic metals.

Actinide colloids and particles of environmental concern

The INE-Beamline for actinide science at ANKA

Common explosives (TNT, RDX, HMX) and their fate in the environment: Emphasizing bioremediation

XAFS and LIBD Investigation of the Formation and Structure of Colloidal Pu(IV) Hydrolysis Products