Characterization of the Lithium/Solid Electrolyte Interface in the Presence of Nanometer-thin TiOx Layers for All-Solid-State Batteries.

It is unclear, which role space charge layers (SCLs) play within an all-solid-state battery during operation with high current densities, and to which extent they form. Herein, we use a solid electrolyte with a known SCL formation and investigate it in a symmetric cell under non-blocking conditions with Li metal electrodes. Since the used LICGC™ electrolyte is known for its instability against lithium, it is protected from rapid degradation by nanometer-thin layers of TiOx deployed by atomic layer deposition. Close attention is given to the interfacial properties, as now additional Li+ can traverse through the interface depending on the applied bias potential. The interlayer's impedance response shows efficient lithium-ion conduction for low bias potentials and a diffusion-limiting effect towards high positive and negative potentials. SCLs grow up to a thickness of 5.1 µm. Additionally, estimating the apparent rate constant of the charge transfer across the interface indicates that the potentials where kinetics are hindered coincide with the widest SCLs. In conclusion, the investigation under higher steady-state currents was only possible because of the improved stability due to the interlayer. No chemo-physical failure could be observed after 800+ hours of cycling. However, SEM study shows a new phase at the interface.

Dioxin in the river Elbe.

This paper provides a macro-analysis of the dioxin contamination in the river Elbe from the 1940s to the present. Based on different data sets, the historic dioxin concentration in the Elbe has been reconstructed. For the section between the tributary Mulde and Hamburg, during the 1940s, we find a concentration of about 1500 pg WHO-TEQ g-1. We argue that this dioxin contamination was caused mainly by emissions from a magnesium plant in Bitterfeld-Wolfen, whose effluents were discharged into a tributary of the river Mulde which flows into the Elbe. Dioxin pattern recognition with neural networks (Kohonen) confirms this. A model simulation shows that a hypothetical dioxin concentration of 10,000 pg WHO-TEQ g-1 in the tributary Mulde could have caused the reconstructed dioxin concentration of 1500 pg WHO-TEQ g-1 in the Elbe. The recent dioxin concentration (about 25-100 pg WHO-TEQ g-1) in the river Elbe, downstream the tributary Mulde, originates, according to our hypothesis, from emissions of the banks and the highly contaminated flood plains (transport of the particle bound dioxin). As other possible dioxin sources, the following could be excluded: the dioxin concentration in the Mulde, groynes, small ports, sport boat harbours, and extreme floods. Our hypothesis is supported by the results of pattern recognition techniques and a model simulation. According to these findings, we argue that remediation efforts to reduce the dioxin concentration in the river Elbe are unlikely to be successful.

The dioxin/POPs legacy of pesticide production in Hamburg: part 2--waste deposits and remediation of Georgswerder landfill.

α-HCH, ß-HCH, and γ-HCH (lindane) were listed as persistent organic pollutants in the Stockholm Convention. Therefore, they need to be globally addressed including the wastes remaining from historic use and production. While at most lindane production sites the unintentionally produced 85% HCH waste isomers have been deposited, at a former pesticide factory in Hamburg-Moorfleet HCH waste isomers have been recycled from 1953 to 1984 by thermal decomposition to chlorobenzenes and resulted in high polychlorinated dibenzo-p-dioxin/polychlorinated dibenzofuran (PCDD/PCDF)-contaminated residues. The management of the PCDD/PCDF-contaminated waste from the former pesticide factory in Hamburg has been assessed and quantified. Based on past accredited PCDD/PCDF measurements, the registered 3,700 tonnes of disposed thermal HCH decomposition residue contained 333 to 854 kg of PCDD/PCDF toxicity equivalent (I-TEQ) in 53-102 tonnes total sum of PCDD/PCDF. The wastes have been deposited together with other wastes in landfills in Hamburg and other parts of Germany. For the Georgswerder landfill (Hamburg), where approximately 50% of the PCDD/PCDF is disposed, current and previous situation and remediation activities are described. While PCDD/PCDF leaching from the landfill is controlled and incinerated, more water soluble organochlorines (vinyl chloride, cis-1,2-dichlorethene, chlorobenzenes) and benzene remain as a challenge for groundwater management. A comprehensive aftercare program has been established and will need to be operated by future generations including renewal of containment systems. Former lindane/HCH productions need-in addition to HCH deposits-to be assessed for possible recycling practice of HCH and related PCDD/PCDF-containing deposits. This could systematically be addressed within the Stockholm Convention implementation.

Vertical profile of PCDD/Fs, dioxin-like PCBs, other PCBs, PAHs, chlorobenzenes, DDX, HCHs, organotin compounds and chlorinated ethers in dated sediment/soil cores from flood-plains of the river Elbe, Germany.

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other organic micropollutants were determined in dated sediment/soil cores collected from the flood-plain of the river Elbe near Pevestorf (PT), approximately 125 km upstream of Hamburg, and Heuckenlock (HL) in southeast of Hamburg. Concentrations of PCDD/Fs peaked sharply at PT in the 1950s and at HL at the end of the 1940s. Cluster analyses provide evidence that the region of Bitterfeld-Wolfen (about 350-400 km upstream of Hamburg) could be the source of the PCDD/F contamination existing in the cores PT and HL since the 1940s. Obviously it is caused by sediments of the river Elbe of a similar composition. Whereas the PCDD/Fs, HCHs (hexacyclohexane isomers), DDX (DDT, DDD, DDE), and tetrachlorinated ethers in PT and HL presumably originated predominantly from the Bitterfeld-Wolfen region, organotin compounds in HL and dichlorinated haloethers in HL during the 1940s and 1950s can probably largely be attributed to emissions from the Hamburg region. Although they are separated by a large distance, in both sediment cores PT and HL concentrations and composition patterns of most organic micropollutants analyzed widely match. Inductively it can be concluded that similar contaminations will be found in many of the river bank soils between the Bitterfeld-Wolfen region and Hamburg. Excavation of top soils may uncover highly contaminated materials. Since the dated sediment cores show the variation in contaminants in the Elbe sediments over a defined time period, it is possible to make an approximate assessment of the actual degree of contamination to be expected in areas where in previous decades contaminated dredged sediments from the Elbe and from the Port of Hamburg have been deposited on land and used for building plots or for agricultural purposes.

Analysis of sources of dioxin contamination in sediments and soils using multivariate statistical methods and neural networks.

Multivariate statistical methods and neuronal networks were used to evaluate the concentration dioxin patterns of a large data set (407 samples) in order to identify the dioxin sources of contaminated waters (sediment and suspended particulate matter samples). The evaluations indicated that a considerable proportion of the dioxin contamination of the river Elbe in the section between the Mulde tributary and the North Sea and their flood plains (soil samples) and the Port of Hamburg was caused by pollution originating from the Bitterfeld region, an industrial area of the former German Democratic Republic. The dioxin patterns of sediment samples from tributaries of the river Elbe in the Bitterfeld area itself are similar to dioxin patterns that can be attributed to metalworking processes. The dioxin patterns of the Hamburg inner city waters could be attributed to "incineration" dioxin sources, for example waste incineration plants. The results of cluster analysis applying different modes of distance measure and linkage compared well with neuronal networks. The number of clusters was determined based on the stability of the results of different cluster analyses and background information.