EPR characterization of the catalytic activity of clays for PCE removal by gamma-radiation induced by acid and thermal treatments

Clays from tidal flat sediments showed efficient catalytic activity in the decomposition of PCE by gamma-radiation. The highest PCE removal of 98.6% was obtained with clays heated to 700 degrees C after acid treatment. The improved catalytic activity was identified by electron paramagnetic resonance (EPR) spectroscopy. The EPR spectra of clays were significantly changed by the acid and thermal treatments. The intensity of a narrow signal at g=2 (signal III) was decreased with increasing thermal treatment temperature and this increased the PCE removal efficiency. The acid treatment completely removed a broad signal at g=2 (signal II), decreased the intensity of signal III, and improved the gamma-radiation treatment of PCE.     

Die Umsetzung des EU Weißbuches zur Chemikalienpolitik

Background

Aim and Scope. Implementation of the European Union White Paper on chemicals policy shall provide more safety and more transparency in chemicals use. In the past, when assessing existing commercial substances there was often a lack of information in the fields of application of the chemicals and the exposures arising in those contexts. The White Paper therefore calls for ‘shared responsibility’. Processors and commercial users of substances are to be involved much more closely in the risk evaluation process than has hitherto been the case. They are to provide data on substance applications and exposures, and, to some extent, they are also to carry out exposure assessments and risk assessments themselves. By analysing case studies, the paper highlights the consequences of this approach.

Results and Discussion

Fear has often been voiced that these new tasks will completely overburden small and medium-sized enterprises. It is assumed that many chemicals are no longer available for smallvolume applications, as — for cost reasons — producers do not include these applications in their registration. The wording of the White Paper is not precise enough to be able to appraise the costs that will be associated with the required intensified communication. In this situation, it is essential to analyse prototypical substances and their applications in order to gain an improved understanding of the principle of shared responsibility.

Conclusions

The concrete study of several product chains has shown that the flow of information required between producers and users is very likely feasible within the context of the REACH system. For the producers of chemicals, the intensified communication will presumably make it simpler to procure information in the fields of application and exposures. However, in order to avoid users being overburdened, it will be important that registration requirements and focuses are shaped in a manner doing justice to practical realities. Users will need to undertake community-wide efforts on an industry federation and branch level. In this context, the protection of company know-how also needs to be ensured.

Recommendation and Outlook

In practice, implementation of the principle of shared responsibility can lead to intensified communication among the producers and users of chemicals. This can greatly facilitate exposure assessments and risk assessments. There is a need to develop manageable procedures that can also be implemented by small and medium-sized enterprises. Numerous proposals have been made in this context, and extensive reference material is now available.     

Selective leaching of valuable metals from waste printed circuit boards

This study was carried out to recover valuable metals from the printed circuit boards (PCBs) of waste computers. PCB samples were crushed to smaller than 1 mm by a shredder and initially separated into 30% conducting and 70% nonconducting materials by an electrostatic separator. The conducting materials, which contained the valuable metals, were then used as the feed material for magnetic separation, where it was found that 42% of the conducting materials were magnetic and 58% were nonmagnetic. Leaching of the nonmagnetic component using 2 M H2SO4 and 0.2 M H2O2 at 85 degrees C for 12 hr resulted in greater than 95% extraction of Cu, Fe, Zn, Ni, and Al. Au and Ag were extracted at 40 degrees C with a leaching solution of 0.2 M (NH4)2S2O3, 0.02 M CuSO4, and 0.4 M NH4OH, which resulted in recovery of more than 95% of the Au within 48 hr and 100% of the Ag within 24 hr. The residues were next reacted with a 2 M NaCl solution to leach out Pb, which took place within 2 hr at room temperature.     

Chemische Reaktionen von Chlorvinylarsinverbindungen (Lewisit)

2,2′-Dichlorodivinylarsine chloride (Lewisite II) react by room temperature quickly with alcohols in an equilibrium reaction to yield 2,2′-Dichlorodivinylarsine ether. The reactions are not quantitative. The methyl-, ethyl-and propylether are not stable.     

Paternal investment in Poecilimon veluchianus bushcrickets: beneficial effects of nuptial feeding on offspring viability

In most bushcrickets, males transfer a large spermatophore during copulation that is afterwards consumed by the female. In some species this nuptial gift enhances offspring fitness and is therefore believed to function as paternal investment. To determine whether this is the case, I examined whether a male's own offspring benefit from spermatophore consumption in the bushcricket Poecilimon veluchianus. Females that consumed a spermatophore produced offspring with increased residuals of dry weight compared to females that were prevented from feeding on the spermatophore. This beneficial effect of spermatophore consumption occurred within the first 4 days after copulation. An increased dry weight indicates higher energy reserves because offspring dry weight correlates significantly with the lifespan of starved larvae and because spermatophore consumption increased the lifespan of starved offspring. During egg-laying, females apply a liquid substance to the soil that hardens and probably serves as protection for the egg clutch. The amount of this substance correlated with the number of eggs laid but did not differ between spermatophore treatments. In P. veluchianus, females mate frequently and there is last-male sperm precedence. The spermatophore thus only constitutes paternal investment when offspring produced before female remating benefit from spermatophore consumption. The dry weight of offspring increased during the first 4 days after spermatophore consumption and thus within the natural remating interval. This shows that the spermatophore has a paternal investment function in addition to its already known sperm protection function. Received: 15 May 1998 / Accepted after revision: 11 October 1998     

Comparison of tarsal and cuticular chemistry in the leaf beetle Gastrophysa viridula (Coleoptera: Chrysomelidae) and an evaluation of solid-phase microextraction and solvent extraction techniques

Tarsal substrate adhesion in insects is based on the effect of a thin film of liquid in the contact zone, which is deposited as droplets on the surface an insect has walked on, but as yet, little is known about the chemical composition of the liquid. In the present study, interference reflection microscopical images of the tarsal contact and footprints of Gastrophysa viridula (Coleoptera: Chrysomelidae) are depicted and the chemical composition of tarsal liquids and cuticular components are investigated by means of solid-phase microextraction and solvent extraction of whole beetles and footprints. Based on this comparative methodical approach, we are first to provide evidence from direct sampling for the chemical congruence of cuticular lipids and tarsal liquid in beetles. Furthermore, differences resulting from the applied sampling techniques are assessed and advantages of the respective methods are discussed.     

Toxikologische Bewertung von Rüstungsaltlasten

A method was developed for the risk assessment of a military waste site. The method consists of two steps: 1. evaluation of the exposure through different pathways and 2. derivation of substance-specific tolerable intake levels. In this first part of the paper the quantitative exposure analysis will be discussed. Exposure depends on the conditions at the contaminated site (e.g. soil characteristics), the type of utilisation (residential area, industrial area etc.) and the substance properties. In a specific utilisation scenario, e.g. as residential area, different exposure pathways are contributing to the total contaminant uptake. Because of the properties of nitroaromatic compounds like 2,4,6-trinitrotoluene (good resorption through skin and accumulation in plants) exposure via dermal soil contact and via consumption of plants gains special importance. With these two exposure pathways as examples we explain the quantification of the exposure through different pathways by so-called exposure factors. By comparing the total exposure with tolerable intake levels for the compounds, waste site specific soil pollutant levels can be established (see second part of the paper in UWSF 6/94).     

Freisetzung von Schwermetallen aus dem bodenbildenden Tonmineral Illit durch Aminosäuren

Kaolin W from Lohrheim (51% Illite, 31% Kaolinite, 18% Quarz, no Carbon) was loaded with various amounts of heavy metal ions (0.11–6.0 mmol/100g Cu, Ni, Cd) from their nitrate solutions. In the next step the release of the bound metals was tested with or without aminoacids (penicillamine and histidine) in solutions of weak acidity or alkalinity. It was found an evident influence of the aminoacids to the metal release in dependence of metalcoating, metal-aminoacid-ratio and experimental pH. Especially in alkali environment a multiplication of the copper release (to a factor of 39 (pen) or 27 (his)) was observed. An increased nickel (factor 53) and cadmium release (factor 4.5) was found with histidine. In this cases 80 to 100% of the heavy metals were removed from the clay-mineral-surface.     

Lipopeptide als natürliche Adjuvantien für Impfstoffe aus Gram-negativen Bakterien

Bacterial cell wall components such as lipopolysaccharide, a variety of membrane proteins, murein, and lipoprotein can act as immunoadjuvants for bacterial vaccines, thus enhancing protection from bacterial infections. Synthetically prepared N-terminal parts of the lipoprotein from Enterobacteria carrying three fatty acid residues or lipopeptide analogs containing one to four aminoacids bound to S-glycerylcysteine act as potent immunoadjuvants in vivo in combination with or covalently linked to antiges. Here we demonstrate that the supplementation ofSalmonella vaccines with these synthetic lipopeptides significantly enhances their vaccine efficiency in mice. Variations in the native lipopeptide structure regarding chain length and amino acid sequence of the peptide moiety, as well as modifications of the lipoamino acid, lead to reduction or even complete loss of the adjuvant activity. The immunoadjuvant properties of the lipopeptides as described here are mediated by an enhancement of the humoral immune response.