Influence of humic substances on sorption and methylation processes of inorganic- and organo-tin species

The influence of humic substances on sorption and methylation processes for inorganic- and organotin species is presented. Four sediment samples from different locations of the Rivers Elbe, Mulde and Spittelwasser, Germany, with different organotin and humic contents were selected to extract the humic and fulvic acids. The various fractions—the original sediment, the humic acid, the fulvic acid and the residual sediment—were analysed for their organotin content. The individual buyltin species show quite different distribution patterns. Monobutyltin is found mostly associated with humic acids. Dibutyltin shows a nonunique behaviour. At low total organotin content, dibutyltin is found bonded to humic and fulvic acids, whereas at high organotin content dibutyltin is distributed more with the residual sediment. Most of the tributyltin remains in the sediment unextracted; only small quantities of it are in the fulvic acid fraction. Tetrabutyltin is only in the humic acid fraction when it binds to humic matter; it mostly remains in the sediment. General observations indicate that ionic butyltin species bind to fulvic acids whereas the non-polar tetrabutyltin is not found in the fulvic acid fractions in any of the samples. The appearance of monomethyl- and dimethyl-tin species in the humic and fulvic acid fractions after the alkaline extraction was surprising. There is a correlation between the humic content of the sample and the formation of methyltin species. Evidence is provided by experiments that humic substances act as methylation agents.     

Quantitative Comparison Between Vacuum-Ultraviolet Irradiation and Remote Hydrogen Plasma Treatment of Hydrocarbon Polymers

The photon flux of vacuum ultraviolet (VUV) and ultraviolet (UV) radiation of a hydrogen plasma with and without a MgF₂window was recorded by fluorescence measurements of sodium salicylate layers. After the compensation of the MgF₂absorption by increasing the input power into the plasma source, a comparison between afterglow hydrogen plasma and VUV treatments was made. Polyethylene (PE), polypropylene (PP), and polystyrene (PS) were treated either with VUV radiation or with remote hydrogen plasma and mass loss and CH absorption loss were measured by a quartz crystal microbalance and by infrared reflection absorption spectroscopy, respectively. In the case of PE the effects of both treatments were found to be very similar white for PP slight differences were observed. For the actual set of experimental conditions, the radiation component is largely responsible for the efficiency of the plasma treatment. VUV and remote hydrogen plasma treatments of PS showed only a negligible loss of mass and CH absorption.     

Chemical synthesis of lymphotactin: a glycosylated chemokine with a C-terminal mucin-like domain

The synthesis of a 93-residue chemokine, lymphotactin, containing eight sites of O-linked glycosylation, was achieved using the technique of native chemical ligation. A single GalNAc residue was incorporated at each glycosylation site using standard Fmoc-chemistry to achieve the first total synthesis of a mucin-type glycoprotein. Using this approach quantities of homogeneous material were obtained for structural and functional analysis.     

Vacuum Ultraviolet Photolysis of Polyethylene,Polypropylene, and Polystyrene

Using infrared reflection absorption spectroscopy (IRRAS), quartz crystal microbalance (QMB) measurements, and X-ray photoelectron spectroscopy (XPS) in combination with chemical derivatization techniques the VUV photolysis of polyethylene (PE), polypropylene (PP), and polystyrene (PS) was investigated. A mass balance obtained from the quantification of the data was used to suggest reaction path ways. Although PE and PP behave similar, the mass loss is about 8 times higher in the case of PP. These differences originate from the higher disproportionation to recombination ratio for the branched polymer. Both polymers form double bonds and at extended treatment times they tend to crosslink. PS is rather stable due to the possibility of the energy dissipation by fluorescence.     

Mercury-cycling in surface waters and in the atmosphere — Species analysis for the investigation of transformation and transport properties of mercury

The river Elbe has been one of the most contaminated rivers with regard to mercury for many years. In 1991 a length-profile has been measured for mercury and methylmercury (CH₃Hg⁺) from Obristvi, Czech Republic, to the German bight. Total mercury has been measured by cold vapor atomic absorption spectrometry (CVAAS). The organo mercury compounds have been separated by high performance liquid chromatography (HPLC) connected on-line to an atomic fluorescence spectrometer (AFS) by a continuous flow-system. Total mercury up to 120 mg Hg⁺/kg and CH₃Hg⁺ concentrations up to 130 μg CH₃ Hg⁺/kg could be detected in special sites. The formation of CH₃Hg⁺ in sediments can be caused besides the methylation of mercury, by sulphate reducing or methanogenic bacteria and transmethylation reactions with organometals. Atmospheric mercury concentrations have been measured at three different European sites. Samples have been collected on goldcoated glass balls or on quartz wool, respectively. After thermal desorption mercury has been determined using the two step amalgamation technique with AFS detection. Compared to natural background concentrations of total gaseous mercury (TGM), slightly increased levels could be detected at a rural site in Germany. This increase can probably be explained by long-range transport processes. Within the vicinity of a inactivated mercury production plant high concentrations of up to 13.5 ng/m³ particle associated mercury (Hg_part) have been detected. Consequently, dry deposition of mercury in the particulate form can intensify the total deposition flux close to Hg-emitting sources.     

Nonsequential double recombination in intense laser fields

A second plateau in the harmonic spectra of laser-driven two-electron atoms is observed both in the numerical solution of a low-dimensional model helium atom and using an extended strong field approximation. It is shown that the harmonics well beyond the usual cutoff are due to the simultaneous recombination of the two electrons, which were emitted during different, previous half-cycles. The new cutoff is explained in terms of classical trajectories. Classical predictions and the time-frequency analysis of the ab initio quantum results are in excellent agreement. The mechanism corresponds to the inverse single photon double ionization process in the presence of a (low frequency) laser field.     

Improved measurement of the hydrogen 1S-2S transition frequency

We have measured the 1S-2S transition frequency in atomic hydrogen via two-photon spectroscopy on a 5.8 K atomic beam. We obtain f(1S-2S) = 2,466,061,413,187,035 (10) Hz for the hyperfine centroid, in agreement with, but 3.3 times better than the previous result [M. Fischer et al., Phys. Rev. Lett. 92, 230802 (2004)]. The improvement to a fractional frequency uncertainty of 4.2 × 10(-15) arises mainly from an improved stability of the spectroscopy laser, and a better determination of the main systematic uncertainties, namely, the second order Doppler and ac and dc Stark shifts. The probe laser frequency was phase coherently linked to the mobile cesium fountain clock FOM via a frequency comb.