The gas phase addition of NOx to olefins

The addition of N₂O₅ to 1-hexene in synthetic air results in 1,2-hexanedioldinitrate and 2-hexanon-1-ol-nitrate as the main products and some -hydroxy-1-ol-nitrate. In the reaction with cyclohexene, cis/trans-1,2-cyclohexanediol-dinitrate and cyclohexene-1-on-2-ol-nitrate have been detected. The addition of NO₃ to isoprene produces 4-nitrato-3-methylbutenal-2. The reaction of NO₃ with methylenecyclohexane and sabinene in air results in 1-(methylnitrate) cyclohexane-1-ol and both epimers of 1-(methylnitrate)-4-(isopropyl) cyclo-hexene-4-ol, respectively. The main products of the addition of NO₃ to - and β-pinene were probably rearranged compounds of the limonene type: -pinene produces 1-(methyl)-2-(nitrato)-4-(2-propane-2-ol)-cyclohex-1-ene and β-pinene produces 1-(methylnitrate)-4-(2-propane-2-ol)cyclohex-1-ene. Other rearrangements give rise to a variety of nitrates and ketonitrates of structures as yet unknown in the - and β-pinene systems.

The probably particle-borne addition of NO₂ to -pinene, β-pinene and camphene in air produces 2-nitrolimonene, 7-nitrolimonene and nitrocamphene as the main reaction products.     

BAT and BEP as instruments for reducing emissions of unintentionally produced POPs and development of guidelines under the stockholm convention

The 6th Intergovernmental Negotiating Committee (INC 6), under the Stockholm Convention on POPs, gave an expert group the mandate to develop guidelines for the application and implementation of best available techniques (BAT) and best environmental practices (BEP) for the prevention and reduction of unintentionally produced and emitted POPs, including polychlorinated dibenzodioxins/-furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB). Measures to reduce or eliminate the release of these POPs to the environment can be found in Article 5 of the Convention. BAT and BEP are already being applied as emission reduction instruments in a number of industrialised countries and are elements of other major international treaties, e.g. the UN ECE Protocol on POPs and the Marine Convention's OSPAR and HELCOM, and of the EU Directive for Integrated Pollution Prevention and Control (IPPC Directive). Existing concepts are presented and compared with the requirements of the Stockholm Convention. Consequences, perspectives and questions for the future intersessional work of the above-mentioned Expert Group are discussed.     

Inspection of non-CO2 greenhouse gases from emission sources and in ambient air by Fourier-transform-infrared-spectrometry: Measurements with FTIS-MAPS

Infrared spectrometry is a versatile basis to analyse greenhouse gases in the atmosphere. A multicomponent air pollution software (MAPS) was developed for retrieval of gas concentrations from radiation emission as well as absorption measurements. Concentrations of CO, CH₄, N₂O, and H₂O as well as CO₂, NO, NO₂, NH₃, SO₂, HCl, HCHO, and the temperature of warm gases are determined on-line. The analyses of greenhouse gases in gaseous emission sources and in ambient air are performed by a mobile remote sensing system using the double-pendulum interferometer K300 of the Munich company Kayser-Threde. Passive radiation measurements are performed to retrieve CO, N₂O, and H₂O as well as CO₂, NO, SO₂, and HCl concentrations in smoke stack effluents of thermal power plants and municipal incinerators and CO and H₂O as well as CO₂ and NO in exhausts of aircraft engines. Open-path radiation measurements are used to determine greenhouse gas concentrations at different ambient air conditions and greenhouse gas emission rates of diffusive sources as garbage deposits, open coal mining, stock farming together with additional compounds (e.g. NH₃), and from road traffic together with HCHO. Some results of measurements are shown. A future task is the verification of emission cadastres by these inspection measurements.     

Verteilungskoeffizienten chlorierter Kohlenwasserstoffe zwischen Muskulatur und Leber bei Fischen

Zusammenfassung  Lipidbezogene Verteilungskoeffizienten (KL_M/L) zwischen Muskelkonzentrationen-(C_ML) und Leberkonzentrationen (C_LL) zweier Friedfischarten Brassen (Abramis brama) und Aalmutter (Zoarces viviparus) ergeben theoriekonform (KL_M/L=C_ML/C_LL=1) nominale Werte um 1 für persistente (hochchlorierte PCB) und Werte über 1 für metabolisierbare lipophile Umweltchemikalien wie chlorierte Cyclohexane oder DDT.      

Estrogenic and esterase-inhibiting potency in rainwater in relation to pesticide concentrations,sampling season and location

In a year-round monitoring program (1998), pesticide composition and toxic potency of the mix of pollutants present in rainwater were measured. The goal of the study was to relate atmospheric deposition of toxic potency and pesticide composition to each other and to sampling period and local agricultural activity. Rainwater was collected in 26 consecutive periods of 14 days in a background location (BACK) and in two locations representative for different agricultural practices, i.e. intensive greenhouse horticulture (HORT) and flower bulb culture (BULB). Samples were chemically analyzed for carbamate (CARB), organophosphate (OP) and organochlorine (OC) pesticides and metabolites. Esterase inhibiting potency of rainwater extracts was measured in a specially developed bio-assay with honeybee esterases and was expressed as an equivalent concentration of the model inhibitor dichlorvos. Estrogenic potency of the extracts was measured in the ER-CALUX reporter gene assay and was expressed as an equivalent concentration of estradiol. Multivariate principal component analysis (PCA) techniques proved to be valuable tools to analyze the numerous pesticide concentrations in relation to toxic potency, sampling location, and sampling season. Pesticide composition in rainwater depended much more on sampling season than on sampling location, but differences between and were mainly attributed to local differences in agricultural practice. On average, the esterase inhibiting potency exceeded the maximum permissible concentration set for dichlorvos in The Netherlands, and was significantly higher in than in and . Esterase inhibition correlated significantly with OP and CARB concentrations, as expected given the working mechanism of these insecticides. The estrogenic potency incidentally exceeded NOEC levels reported for aquatic organisms and was highest in . Although estrogenic potency of rainwater correlated with OC concentrations, the ER-CALUX responses could not be attributed to any particular pesticides. Besides, the contribution of non-analyzed xeno-estrogens as alkylphenol(-ethoxylates) and bisphenol-A to the estrogenic potency of rainwater could not be excluded. Further research should focus on the chemical identification of estrogenic compounds in rainwater. In addition, more attention should be given to the ecological consequences of atmospheric deposition of individual pesticides and of total toxic potencies that regularly exceed environmental criteria for Dutch surface waters and/or toxic threshold values for aquatic organisms.     

Informing or Empowering? Disclosure in the United States and the Netherlands

This paper studies the emergence of one particular 'new' environmental policy instrument: disclosure of emission and pollution data. Disclosure is part of a relatively new sub-set of regulatory measures, based on monitoring, transparency, citizen-empowerment and accountability. It originated in the United States but has recently attracted international attention. The attractiveness of disclosure is obvious; it promises environmental improvement combined with strengthened environmental democracy and community empowerment. By analysing the experiences in the US, and the developments in the Netherlands, this paper seeks to assess the functioning and effectiveness of disclosure. The available empirical evidence suggests that disclosure has a positive impact on the environmental performance of industrial facilities as well as a democratising effect. It is argued that Dutch policy makers wrongfully assume that disclosure cannot work in the Netherlands. The consequence is that citizens are provided with little specific information that cannot be used to put pressure on polluters.     

Drugs from marine organisms

A modern approach to the search for biologically active substances of potential therapeutic use isolated from marine organisms is illustrated by a presentation of the multidisciplinary project pursued by the Roche Research Institute of Marine Pharmacology near Sydney, Australia. This specialized insitute is part of the world-wide research endeavour of our company and has now been in operation for five years. Following a brief outline of the technical functions the main scientific achievements published by the scientists of the institute are reviewed. This institute is, to our knowledge, the only one of its kind in private industry and we have attempted to demonstrate how its activities should be viewed in the overall context of today's drug or product development.