Mutagenicity of photochemical reaction products of polycyclic aromatic hydrocarbons with nitrite

Six kinds of polycyclic aromatic hydrocarbons (PAHs) were subjected to ultraviolet light irradiation with nitrite for 1, 4, 8 and 24 h, and the irradiated samples were tested for mutagenicity towards Salmonella typhimurium TA 98, TA 100 and TA 1538. Irradiated samples of pyrene, fluoranthene and benzo[a]pyrene showed marked mutagen responses towards TA 98 and TA 1538, especially in the absence of S9 mix. The direct-acting mutagenic activity of these samples, showing high activities at 1-8 h, decreased greatly with the development of irradiation. Further, these direct-acting mutagens were mostly present in the neutral fraction. On the other hand, the mutagenicity of the irradiated sample of 5,6-benzoquinoline was high both with and without S9 mix, and was mostly present in the basic fraction because of its authentic characteristic. There was no correlation between the yield of 1-nitropyrene and the mutagenic activity of the photochemical reaction product of pyrene with nitrite. Further studies by TLC separation suggested that a considerable number of direct-acting mutagens formed in this experiment were more polar than nitrated PAH such as 1-nitropyrene.     

A novel dry photopolymer for volume‐phase holograms

A novel photopolymer for the fabrication of high‐resolution volume‐phase holograms, which primarily are used for holographic optical elements, is reported. This photopolymer consists of a thermosetting resin as a polymeric binder, a polyfunctional monomer, a photoinitiator, and a sensitizing dye. The chemistry to form images is based on the polymerization of an acrylic monomer initiated by radical species while making the holographic exposure, and accelerated diffusion transfer of the polymerized monomer with postexposure baking, and of a bisphenol‐type epoxy resin as a binder initiated by cations with UV exposure, which are generated through photodecomposition of a diaryliodonium salt‐sensitized 3‐ketocoumarin dye. Exposure of these photopolymer films to an Ar⁺ laser beam emitting 514.5 nm light at 60–150 mJ/cm² and subsequent heat treatment resulted in a refractive index alteration according to the light intensity. With this dry process, high diffraction efficiency and heat‐stable holograms can be formed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2189–2200, 2000     

Thresholds for the effects of pesticides on invertebrate communities and leaf breakdown in stream ecosystems

We compiled data from eight field studies conducted between 1998 and 2010 in Europe, Siberia, and Australia to derive thresholds for the effects of pesticides on macroinvertebrate communities and the ecosystem function leaf breakdown. Dose-response models for the relationship of pesticide toxicity with the abundance of sensitive macroinvertebrate taxa showed significant differences to reference sites at 1/1000 to 1/10,000 of the median acute effect concentration (EC50) for Daphnia magna, depending on the model specification and whether forested upstream sections were present. Hence, the analysis revealed effects well below the threshold of 1/100 of the EC50 for D. magna incorporated in the European Union Uniform Principles (UP) for registration of single pesticides. Moreover, the abundances of sensitive macroinvertebrates in the communities were reduced by 27% to 61% at concentrations related to 1/100 of the EC50 for D. magna. The invertebrate leaf breakdown rate was positively linearly related to the abundance of pesticide-sensitive macroinvertebrate species in the communities, though only for two of the three countries examined. We argue that the low effect thresholds observed were not mainly because of an underestimation of field exposure or confounding factors. From the results gathered we derive that the UP threshold for single pesticides based on D. magna is not protective for field communities subject to multiple stressors, pesticide mixtures, and repeated exposures and that risk mitigation measures, such as forested landscape patches, can alleviate effects of pesticides.     

Weiterentwicklung einer Methode zur Bienenbruthaltung unter Laborbedingungen

In the LAVES Institute for Apiculture honey bee brood has been reared in the laboratory according to the method of Aupinel et al. (Bull Insectol 58:107?C111, 2005) for studies on the effects of plant protection products as well as for further improvement of the method since 2008. The introduced methodological changes have a positive effect on the number of larvae available for experimental purposes. Furthermore, the treatment with MBC-solution (methyl-benzethonium chloride) could be replaced by pasteurization, which is to be viewed positively from a health perspective for the personnel but also in terms of possible synergistic effects with active ingredients.     

A new risk assessment approach for the prioritization of 500 classical and emerging organic microcontaminants as potential river basin specific pollutants under the European Water Framework Directive

Given the huge number of chemicals released into the environment and existing time and budget constraints, there is a need to prioritize chemicals for risk assessment and monitoring in the context of the European Union Water Framework Directive (EU WFD). This study is the first to assess the risk of 500 organic substances based on observations in the four European river basins of the Elbe, Scheldt, Danube and Llobregat. A decision tree is introduced that first classifies chemicals into six categories depending on the information available, which allows water managers to focus on the next steps (e.g. derivation of Environmental Quality Standards (EQS), improvement of analytical methods, etc.). The priority within each category is then evaluated based on two indicators, the Frequency of Exceedance and the Extent of Exceedance of Predicted No-Effect Concentrations (PNECs). These two indictors are based on maximum environmental concentrations (MEC), rather than the commonly used statistically based averages (Predicted Effect Concentration, PEC), and compared to the lowest acute-based (PNEC_acute) or chronic-based thresholds (PNEC_chronic). For 56% of the compounds, PNECs were available from existing risk assessments, and the majority of these PNECs were derived from chronic toxicity data or simulated ecosystem studies (mesocosm) with rather low assessment factors. The limitations of this concept for risk assessment purposes are discussed. For the remainder, provisional PNECs (P-PNECs) were established from read-across models for acute toxicity to the standard test organisms Daphnia magna, Pimephales promelas and Selenastrum capricornutum. On the one hand, the prioritization revealed that about three-quarter of the 44 substances with MEC/PNEC ratios above ten were pesticides. On the other hand, based on the monitoring data used in this study, no risk with regard to the water phase could be found for eight of the 41 priority substances, indicating a first success of the implementation of the WFD in the investigated river basins.     

Occurrence and toxicity of 331 organic pollutants in large rivers of north Germany over a decade (1994 to 2004)

We analyzed the detection frequencies and concentrations for 331 organic compounds measured between 1994 and 2004 in the four largest rivers of north Germany, the Elbe, Weser, Aller, and Ems Rivers, and we assessed the potential risk for aquatic fauna using experimental and predicted acute toxicity data for the green alga Pseudokirchneriella subcapitata, the crustacean Daphnia magna, and the fish Pimephales promelas. The detection frequency for most compounds decreased significantly from 1994 to 2004. Polycyclic aromatic hydrocarbons (PAHs) were most frequently detected, while pesticides were the most important chemical group concerning toxicity for the standard test organisms. The predicted toxicity for D. magna was significantly higher than for the other organisms and reached levels envisaging acute toxic effects on the invertebrate fauna, still in 2004. Most of the compounds responsible for potential acute effects on aquatic organisms are currently not considered as priority substances in the European Union, while only 2 of 25 priority substances that have been measured occurred at levels that may be relevant in terms of toxicity for the selected test organisms. We conclude that attenuation of pesticides and other organic toxicants should play an increased role in river basin management.     

Pyrrolizidine alkaloids in honey: comparison of analytical methods

Pyrrolizidine alkaloids (PAs) are a structurally diverse group of toxicologically relevant secondary plant metabolites. Currently, two analytical methods are used to determine PA content in honey. To achieve reasonably high sensitivity and selectivity, mass spectrometry detection is demanded. One method is an HPLC-ESI-MS-MS approach, the other a sum parameter method utilising HRGC-EI-MS operated in the selected ion monitoring mode (SIM). To date, no fully validated or standardised method exists to measure the PA content in honey. To establish an LC-MS method, several hundred standard pollen analysis results of raw honey were analysed. Possible PA plants were identified and typical commercially available marker PA-N-oxides (PANOs). Three distinct honey sets were analysed with both methods. Set A consisted of pure Echium honey (61-80% Echium pollen). Echium is an attractive bee plant. It is quite common in all temperate zones worldwide and is one of the major reasons for PA contamination in honey. Although only echimidine/echimidine-N-oxide were available as reference for the LC-MS target approach, the results for both analytical techniques matched very well (n = 8; PA content ranging from 311 to 520 μg kg(-1)). The second batch (B) consisted of a set of randomly picked raw honeys, mostly originating from Eupatorium spp. (0-15%), another common PA plant, usually characterised by the occurrence of lycopsamine-type PA. Again, the results showed good consistency in terms of PA-positive samples and quantification results (n = 8; ranging from 0 to 625 μg kg(-1) retronecine equivalents). The last set (C) was obtained by consciously placing beehives in areas with a high abundance of Jacobaea vulgaris (ragwort) from the Veluwe region (the Netherlands). J. vulgaris increasingly invades countrysides in Central Europe, especially areas with reduced farming or sites with natural restorations. Honey from two seasons (2007 and 2008) was sampled. While only trace amounts of ragwort pollen were detected (0-6.3%), in some cases extremely high PA values were detected (n = 31; ranging from 0 to 13019 μg kg(-1), average = 1261 or 76 μg kg(-1) for GC-MS and LC-MS, respectively). Here the results showed significantly different quantification results. The GC-MS sum parameter showed in average higher values (on average differing by a factor 17). The main reason for the discrepancy is most likely the incomplete coverage of the J. vulgaris PA pattern. Major J. vulgaris PAs like jacobine-type PAs or erucifoline/acetylerucifoline were not available as reference compounds for the LC-MS target approach. Based on the direct comparison, both methods are considered from various perspectives and the respective individual strengths and weaknesses for each method are presented in detail.     

Feeding Deterrence and Detrimental Effects of Pyrrolizidine Alkaloids Fed to Honey Bees (<Emphasis Type="Italic">Apis mellifera</Emphasis>)

Recent studies have shown the occurrence of plant derived pyrrolizidine alkaloids (PAs) in retail honeys and pollen loads, but little is known about how these compounds influence the fitness of foraging honey bees. In feeding experiments, we tested a mix of tertiary PAs and the corresponding N-oxides from Senecio vernalis, pure monocrotaline, and 1,2-dihydromonocrotaline in 50% (w/w) sucrose solutions. The bees were analyzed chemically to correlate the observed effects to the ingested amount of PAs. PA-N-oxides were deterrent at concentrations >0.2%. 1,2-Unsaturated tertiary PAs were toxic at high concentrations. The observed PAs mortality could be linked directly to the presence of the 1,2-double bond, a well established essential feature of PA cytotoxicity. In contrast, feeding experiments with 1,2-dihydromonocrotaline revealed no toxic effects. Levels of less than 50 μg 1,2-unsaturated tertiary PAs per individual adult bee were tolerated without negative effects. PA-N-oxides fed to bees were reduced partially to the corresponding tertiary PAs. Unlike some specialized insects, bees are not able to actively detoxify PAs through N-oxidation. To gain insight into how PAs are transmitted among bees, we tested for horizontal PA transfer (trophallaxis). Under laboratory conditions, up to 15% of an ingested PA diet was exchanged from bee to bee, disclosing a possible route for incorporation into the honey comb. In the absence of alternative nectar and pollen sources, PA-containing plants might exhibit a threat to vulnerable bee larvae, and this might affect the overall colony fitness.     

A case of primary endobronchial mucosa-associated lymphoid tissue lymphoma with middle lobe atelectasis

A 60-year-old woman was admitted for evaluation of an abnormal shadow in her chest X-ray. A chest roentgenogram revealed middle lobe atelectasis and a tomogram showed masses mainly in the right intermediate bronchus. In bronchoscopy, the bronchus was severely narrowed by irregularly surfaced masses. Microscopic examinations of transbronchial biopsy specimen showed the mucosal and submucosal tissue diffusedly infiltrated mainly by lymphocytes composed of small lymphocytes, centrocyte-like cells and monocytoid cells. The B-cell origin was suggested by a positive L-26 stain. Monoclonality of lymphocytes was proven by Southern blot analysis and in situ hybridization. The diagnosis was primary endobronchial lymphoma of mucosa-associated lymphoid tissue. The case was treated with chemotherapy protocol (CAMBO-VIP) and has been in complete remission for 20 months.