Continuous Determination of the Oxidation State in a Soda-Lime-Silica Glassmelt During Refining

Influences on the oxidation state of glassmelts can be studied by using an electrochemical oxygen sensor which allows in-situ measurements at melting temperatures. The action of fining agents such as arsenic and sodium sulfate was investigated. The behavior of arsenic (i.e. release and uptake of oxygen) and the decomposition of sodium sulfate with and without carbon additions can be seen electrochemically.     

Synthesis of carbon nanotube films by thermal CVD in the presence of supported catalyst particles. Part I: The silicon substrate/nanotube film interface

The interface between the silicon substrate and a carbon nanotube film grown by thermal CVD with acetylene (C₂H₂) and hydrogen at 750 or 900 °C has been characterized by high resolution and analytical transmission electron microscopy, including electron spectroscopic imaging. Silicon (0 0 2) substrates coated with a thin (2.8 nm) iron film were heat treated in the CVD furnace at the deposition temperature in a mixture of flowing argon and hydrogen whereby nanosized particles of (Fe,Si)₃O₄ formed. These particles were reduced to catalytic iron silicides with the –(Fe, Si), ₂–Fe₂Si and ₁–Fe₂Si structures during CVD at 900 °C, and multi-wall carbon nanotubes grew from supported particles via a base-growth mechanism. A limited number of intermediate iron carbides, hexagonal and orthorhombic Fe₇C₃, were also present on the substrate surface after CVD at 900 °C. The reduction of the preformed (Fe, Si)₃O₄ particles during thermal CVD at 750 °C was accompanied by disintegration leading to the formation of a number of smaller (<5 and up to 10 nm) iron and silicon containing particles. It is believed that the formation of these small particles is a prerequisite for the growth of aligned multi-wall carbon nanotube films.     

Selenium biotransformations in an insect ecosystem: effects of insects on phytoremediation

Phytoremediation of selenium-contaminated soils may be influenced by higher trophic levels including insects. We examined how selenium affects the behavior, survival, and development of the wasp parasitoid Cotesia marginiventris, parasitizing its natural host, the beet armyworm Spodoptera exigua, feeding on alfalfa, Medicago sativa, irrigated with water containing selenate. X-ray absorption spectroscopy was used to quantify the selenium chemical forms in each trophic level. Alfalfa partially transformed selenate to organoselenium. S. exigua contained only organoselenium, both directly absorbed from M. sativa and transformed from selenate. C. marginiventris cocoons collected shortly after larval emergence contained only organoselenium derived from the host. The surprising finding of trimethylselenonium-like species in adult parasitoids and the cocoons from which they emerged suggests that adults and pharates can detoxify excess selenium through methylation and volatilization. Adult parasitoids do not discriminate against selenium-containing alfalfa, even though alfalfa generates selenium volatiles. Parasitoids raised on selenium-fed larvae emerged later and pupae weighed less than their selenium-free counterparts. We conclude therefore that C. marginiventris can be used to control S. exigua damage to M. sativa being used to remove selenium from soils. Moreover, the presence of such insects may improve phytoremediation by increasing biotransformation of inorganic selenium and release of volatile selenium species.     

Characterization of the binding site for inhibitors of the HPV11 E1-E2 protein interaction on the E2 transactivation domain by photoaffinity labeling and mass spectrometry

An indandione-containing class of inhibitors abrogates DNA replication of human papillomavirus (HPV) types 6 and 11 by binding reversibly to the transactivation domain (TAD) of the viral E2 protein and inhibiting its interaction with the viral E1 helicase. To locate the binding site of this class of protein-protein interaction inhibitors, a benzophenone derivative was used to generate an irreversibly labeled E2-TAD polypeptide. The single site of covalent modification of the E2-TAD was identified by proteolytic digestions using trypsin, LysC, and V8 proteases and characterization of the resulting peptides by LC-MS procedures. Through this methodology, the benzophenone attachment point was located at the terminal methyl of residue Met101. Evidence further pinpointed the site of photoaffinity attachment to the terminal carbon atom, which is significant in providing a definitive example of the ability to locate photoinduced cross-linking to a polypeptide with atomic resolution using solely mass spectrometric detection. The location of the inhibitor binding site vis-à-vis the Glu39 and Glu100 residues sensitive to mutation for HPV 11 E2-TAD is discussed in relation to the crystal structure of the E2-TAD from the related HPV type 16.     

Individual monitoring for internal exposure in Europe and the integration of dosimetric data

The European Radiation Dosimetry Group, EURADOS, established a working group consisting of experts whose aim is to assist in the process of harmonisation of individual monitoring as part of the protection of occupationally exposed workers. A catalogue of facilities and internal dosimetric techniques related to individual monitoring in Europe has been completed as a result of this EURADOS study. A questionnaire was sent in 2002 to services requesting information on various topics including type of exposures, techniques used for direct and indirect measurements including calibration and sensitivity data and the methods employed for the assessment of internal doses. Information relating to Quality Control procedures for direct and indirect measurements, Quality Assurance Programmes in the facilities and legal requirements for "approved dosimetric services" were also considered. A total of 71 completed questionnaires were returned by internal dosimetry facilities in 26 countries. This results in an overview of the actual status of the processes used in internal exposure estimation in Europe. In many ways harmonisation is a reality in internal dose assessments, especially when taking into account the measurements of the activity retained or excreted from the body. However, a future study detailing the estimation of minimum detectable activity in the laboratories is highly recommended. Points to focus on in future harmonisation activities are as follows: the process of calculation of doses from measured activity, establishment of guidelines, similar dosimetric tools and application of the same ICRP recommendations. This would lead to a better and more harmonised approach to the estimation of internal exposures in all European facilities.     

Immobilized enzyme-linked DNA-hybridization assay with electrochemical detection for Cryptosporidium parvum hsp70 mRNA

An electrochemical enzyme-linked immobilized DNA-hybridization assay for the detection of Cryptosporidium parvum in water has been developed. The target molecule was a 121-nucleotide sequence from the C. parvum heat shock protein 70 (hsp70 mRNA from U71181 gene). This analyte offers the possibility of distinguishing dead from live oocysts. The assay involves covalent attachment of a primary DNA probe via its 5'-amine-terminus to self-assembled monolayers of mercaptoundecanoic acid to a gold surface. The primary DNA probe was used to capture the target (sequence 1039-1082 of U71181 gene for the mRNA), by hybridization to a 20-base complementary sequence on the target (at sequence 1063-1082). A secondary DNA probe labeled with alkaline phosphatase (AP) was then hybridized to base sequence 1039-1062 on the target. p-Aminophenol, which is enzymatically generated by the immobilized AP from p-aminophenyl phosphate (PAPP), is detected using electrochemistry. The peak current of cyclic voltammograms from a PAPP solution, in which gold-coated silicon wafer modified with the complete assembly of the assay components was incubated, is linear with concentration of the target (5-50 microg/mL, where P1 and P2-AP concentrations are 50 microg/mL). A detection limit of 2 microg/mL (or 146 nM) of the DNA target was obtained. Cross-reactivity tests showed high selectivity for heat-shocked C. parvum. No signal was obtained for either the synthetic DNA for hsp70 of Campylobacter lari, Escherichia coli, Giardia lamblia, Salmonella typhimurium, and Listeria monocytogenes or for the products of heat-shocked whole organisms of E. coli, G. lamblia, Staphylococcus aureus, and Cryptosporidium muris.     

The Hydrogeochemistry of Arsenic in the Clara Mine,Germany

Abstract.   The oxidative dissolution of primary arsenic-bearing sulfide minerals in barite-fluorite veins is a potential source of arsenic in the Clara Mine. Geological structures, especially the mineral veins, provide potential pathways for the water. The highest arsenic concentrations are found in ground water within the eastern part of the mine. Arsenic and major ions are positively correlated and provide evidence that arsenic is likely derived locally from the water-vein/water-rock interaction. Geochemical modeling with PHREEQC shows all the arsenate mineral phases to be significantly undersaturated, although secondary arsenate minerals are common in the oxidized part of the deposit. The mine waters plot near the boundary of Fe(OH)₃ and Fe²⁺ in the pH-Eh diagram for the As-Fe-S-H₂O-system. Arsenic occurs as the 5-valent species and . Statistical analysis illustrates a strong association between As, Fe, pH, and HCO₃. Oxidation of the primary As-bearing minerals, such as pyrite and arsenopyrite, and the subsequent behavior of the oxyanion, arsenate, generally controls the distribution and speciation of arsenic. The low concentrations of dissolved As is due to co-precipitation and adsorption of arsenate by Fe, Al, and Mn (oxy)hydroxides.     

Experience from retrospective radon exposure estimations for individuals in a radon epidemiological study using solid-state nuclear track detectors

The relation between increased risk of lung cancer and exposure to indoor radon is assessed in epidemiological studies. Both the quality and reliability of smoking data and the radon exposure data are of primary importance. Contemporary measurement of radon concentration in the dwellings of individuals in a case-control study is traditionally used to assess past history of radon exposure. These assessments are somewhat unreliable since presently measured radon concentration might not be representative for a given location long ago. The measurement of long-lived decay products from 222Rn remaining indoors on hard surfaces, such as glass, makes it possible to assess the exposure to indoor radon. At the Swedish Radiation Protection Institute, a combination of two different solid-state nuclear track detectors has been developed to assess the 210Pb activity implanted in glass surfaces by measuring 210Po alpha activity. This detector (a RETRO detector) is used in the Swedish radon epidemiological case-control study of non-smokers with the aim to provide an alternative estimate of individual radon exposure and to evaluate the usefulness of RETRO measurements. A total of 576 different objects were found and 568 were measured. For 225 individuals, we measured two personal objects that had been in the same person's possession for more than 20 years. The standard deviation of the average radon concentration obtained from these two objects had a median value of 13 Bq/m3 indicating a precision of exposure of approximately 20%. The correlation between 210Po surface activity measured earlier and the mean values of radon concentrations in a number of Swedish dwellings is used to estimate the historical, average radon concentration. This average correlation factor seems also to be valid for measurements in the non-smoker epidemiological study.