No abstract

A gas chromatography/mass spectrometry method for the simultaneous quantitative determination of natural and synthetic estrogens (17beta-estradiol, estrone, 17alpha-ethinylestradiol, and mestranol), phytoestrogens (genistein and beta-sitosterol), and xenoestrogens (benzyl butyl phthalate, dibutyl phthalate, bisphenol A, 4-nonylphenol [NP], 4-nonylphenoxyacetic acid [NP1EC], 4-nonylphenol diethoxylate [NP2EO], and alpha-endosulfan) in effluents of sewage treatment plants (STPs) was developed. Identification and quantification were carried out with the standard addition method using analyte-specific and, in some cases, deuterium-labeled internal standards. The effluents of 18 STPs were investigated. Apart from alpha-endosulfan and mestranol, all selected substances were detected in the majority of samples. The median concentrations of steroidal estrogens were between 0.4 ng/L (17alpha-ethinylestradiol) and 1.6 ng/L (17beta-estradiol). The metabolites of the nonylphenol polyethoxylates, NP, NPIEC, and NP2EO were found in concentrations ranging from the upper-ng/L-range (NP) to the lower-microg/L range (NP1EC). For all substances except mestranol and alpha-endosulfan, median values were calculated and compared to the results of other investigations in Europe and the United States. Possible dependencies of measured concentrations on the geographical location, the capacity, the influent composition, and the technical fitting of the STPs are discussed.

No abstract

The proliferation test with human estrogen receptor-positive MCF-7 breast cancer cells (E-Screen assay) was applied for quantitative determination of total estrogenic activity in 24-h composite effluent samples from 16 municipal and two industrial sewage treatment plants (STPs) in the state of Baden-Württemberg, southwestern Germany. The estrogenic efficacy relative to the positive control, 17beta-estradiol, was between 26 and 74% (median, 48%) for the 16 municipal STPs. Estradiol equivalent concentrations (EEQs) were between 0.2 and 7.8 ng/L (median, 1.6 ng/L) and, thereby, were lower than those found in a pilot study, which revealed EEQs of greater than 10 ng/L in the effluents of two other STPs. The EEQs in 14 of the 16 effluent samples were very similar (0.9-3.3 ng/L), indicating a rather constant input of estrogenic substances via STPs into rivers. Additional activated charcoal filtration turned out to be very efficient in further eliminating estrogenic activity from effluents. The EEQs of the E-Screen assay and those calculated from the results of extensive chemical analysis using the estradiol equivalency factors determined for 13 natural and synthetic estrogenic substances were comparable for most of the effluent samples. 17beta-Estradiol, 17alpha-ethinylestradiol, and, to a lesser extent, estrone contributed to 90% or more of the EEQ value.

We present a first-principles density functional theory study of doped ZnO with focus on its application as a transparent conducting oxide, having both high optical transparency and high electrical conductivity. Investigated is the impact of grain boundaries on the physics of atomic defects, and especially the formation energies of oxygen vacancies, cation dopants Al and Ga, and anion dopants N and P are determined. The main goal is to obtain information about the positions of the defect levels generated by the different dopants in the electronic band gap. Because of the known deficiency of the local density approximation (LDA) to yield accurate values for band gap energies for insulators such as ZnO a self-interaction correction (SIC) to the LDA is employed. As atomistic supercell models which contain grain boundaries and dopants are quite large in size we implemented the SIC by means of SIC pseudopotentials which merely increase the computational costs, as compared to the LDA. The main result of our study is that grain boundaries do affect the formation energies for substitutional dopants significantly. Furthermore the position and shape of dopant-induced electronic energy levels at the grain boundaries are changed considerably with respect to the single crystal. This may help us to explain, for example, why N doping can lead to p conductivity at room temperature or why Al or Ga doping can increase the transparency

We present a density functional theory analysis of stoichiometric and nonstoichiometric, crystalline and amorphous In-Ga-Zn-O (c-IGZO, a-IGZO), which connects the recently experimentally discovered electronic subgap states to structural features of a-IGZO. In particular, we show that undercoordinated oxygen atoms create electronic defect levels in the lower half of the band gap up to about 1.5 eV above the valence band edge. As a second class of fundamental defects that appear in a-IGZO, we identify mainly pairs of metal atoms which are not separated by oxygen atoms in between. These defects cause electronic defect levels in the upper part of the band gap. Furthermore, we show that hydrogen doping can suppress the deep levels due to undercoordinated oxygen atoms while those of metal defects just undergo a shift within the band gap. Altogether our results provide an explanation for the experimentally observed effect that hydrogen doping increases the transparency and improves the conductivity of a-IGZO

No abstract

The use of recycled paper for the manufacture of food contact materials is widespread, but very little is known about the presence of potential contaminants in the paper. The purpose of this study was to assess the worst-case migration of estrogenic active compounds using extracts of paper for household use. Twenty different brands of kitchen rolls, nine of which were made from recycled paper and the remainder from virgin paper, were obtained from retail shops. Paper extracts were subjected to (a) determination of the total estrogenic activity by using an in vitro estrogen screen based on yeast cells stably transfected with the human estrogen receptor alpha and (b) chemical analysis and quantification by GC/MS, GC/FTIR/MS, and GC/FID for detection of a variety of estrogenic compounds. A marked estrogenic response was observed in nine of the extracts, seven of which were made from recycled paper and two from virgin paper. The chemical analysis revealed that extracts made from recycled paper contained levels of bisphenol A ranging from 0.6 to 24 mg/kg of kitchen roll, whereas extracts from virgin paper contained no bisphenol A or only negligible amounts. In contrast, 4-tert-octylphenol, 4-nonylphenols, and di-n-butyl and diisobutyl phthalate were present to a varying degree in both recycled and virgin paper with no apparent preferable distribution between the two paper types. The estrogenic response of the two extracts made from virgin paper appeared to be due partly to the presence of the preservative propyl paraben. Diisopropylnaphthalene, which turned out to be weakly estrogenic active in vitro (EC(50) = 53 microM), was detected in minor amounts in most of the extracts with the major part, ranging from 0.3 to 4.7 mg/kg of paper, found in recycled paper. Our findings that recycled kitchen rolls contain bisphenol A and other xenoestrogens may apply to other types of recycled paper used for food packaging and emphasize the importance of identifying this and other contaminants in recycled paper in general. These data indicate that bisphenol A may be useful as a purity indicator for recycled paper.