Polychlorinated biphenyls (PCBs), polychlorinated camphenes (PCCs) and isomers of DDT and DDE were the predominant organochlorine (OC) hydrocarbons measured in epontic particulate matter, zooplankton, pelagic and benthic amphipods and liver tissue from an abyssal fish collected in the Arctic Ocean. Chlordane, dieldrin and other cyclodienes and hexachlorocyclohexane (HCH) isomers were present at lower concentrations. Levels on a dry weight basis in plankton of various sizes 500 μm) collected in August, dominated by adult copepods and ctenophores, contained concentrations of α-HCH, chlordane isomers and other cyclodienes that were two to four times higher than levels in May. Ratios of α-HCH:γ-HCH (5 to 10) were similar to those in seawater collected simultaneously but there was no difference in ratios in various size categories of planktonic and benthic crustaceans indicating no selective accumulation or metabolic alteration of these isomers. Ratios of cis-chlordane:trans-chlordane concentrations were lower in all sizes of zooplankton (2 to 3) than in shelf amphipods (3 to 6) which corresponded to an increase in the ratio with depth. Higher ratios of DDT:DDE in plankton (2 to 6) than in amphipods (1 to 2) reflects the metabolism of DDT to the more stable DDE isomers in amphipods. Metabolites of trans-chlordane were also measured in plankton and benthic amphipods. Although some OCs are degraded or metabolically transformed, accumulation in lipid-rich tissues results in the highest total concentrations in long-lived large-bodied arctic marine organisms.

Organochlorine pesticides and polychlorinated biphenyls in the Arctic Ocean food web.

The current knowledge about transformation rates and products of pesticides in the atmosphere is reviewed. Reactive species and their concentrations in the atmosphere are presented. Reactions of pesticides with these species (including photolysis) in the gas and the particulate phase are evaluated from available experimental data. The potential of estimation methods is discussed. Experimental techniques for laboratory and outdoor measurements are reviewed. Finally, an estimation is made of uncertainties in atmospheric lifetimes due to chemical or physical reactions. It is concluded that the most important transformation of pesticides in the atmosphere is due to reaction with OH radicals. Very few experimental data for pesticides are available though. The levels of uncertainty in OH radical concentrations are acceptable, however, for a proper estimation of atmospheric removal rates due to reactions with OH radicals of those pesticides for which experimental transformation rates (of homologues) are available.

Transformations of pesticides in the atmosphere : A state of the art

Baseline studies of the global pollution@@@Untersuchungen zur globalen Belastung der Umwelt: III. Trace analysis of polychlorinated biphenyls (PCB) by ECD glass capillary gas chromatography in environmental samples of different trophic levels@@@III. Spurenanalyse der polychlorierten Biphenyle (PCB) mit ECD-Glascapillar-Gas-Chromatographie in biologischen Umweltproben aus unterschiedlichen trophischen Stufen

Assessing the sunlight photoreactivity of new pesticides has become common- place in the last decade in recognition of the effects the sun has on the dissipation rate of organic chemicals and their transformation products in various environmental compartments. Several reviewers have summarized research dealing with both the kinetic aspects (Zepp and Cline 1977, Smith et al. 1977, Zepp 1979 and 1980, Zepp and Baughman 1978) and the photoproduct distributions (Sundstrom and Ruzo 1978, Crosby 1979. Moilanen et al. 1975).

Extrapolating photolysis rates from the laboratory to the environment

Global multi-media box models are used to calculate the fate of persistent organic chemicals in a global environment and assess long-range transport or arctic contamination. Currently, such models assume substances to degrade in one single step. In reality, however, intermediate degradation products are formed. If those degradation products have a high persistence, bioaccumulation potential and / or toxicity, they should be included in environmental fate models. The goal of this project was to gain an overview of the general importance of degradation products for environmental fate models, and to expand existing, exposure-based hazard indicators to take degradation products into account. The environmental fate model CliMoChem was modified to simultaneously calculate a parent compound and several degradation products. The three established hazard indicators of persistence, spatial range and arctic contamination potential were extended to include degradation products. Five well-known pesticides were selected as example chemicals. For those substances, degradation pathways were calculated with CATABOL, and partition coefficients and half-lives were compiled from literature. Including degradation products yields a joint persistence value that is significantly higher than the persistence of the parent compound alone: in the case of heptachlor an increase of the persistence by a factor of 58 can be observed. For other substances, the increase is much smaller (4% for α-HCH). The spatial range and the arctic contamination potential (ACP) can increase significantly, too: for 2,4-D and heptachlor, an increase by a factor of 2.4 and 3.5 is seen for the spatial range. However, an important increase of the persistence does not always lead to a corresponding increase in the spatial range: the spatial range of aldrin increases by less than 50%, although the persistence increases by a factor of 20 if the degradation products are included in the assessment. Finally, the arctic contamination potential can increase by a factor of more than 100 in some cases. Influences of parent compounds and degradation products on persistence, spatial range and ACP are discussed. Joint persistence and joint ACP reflect similar characteristics of the total environmental exposure of a substance family (i.e., parent compound and all its degradation products). The present work emphasizes the importance of degradation products for exposure-based hazard indicators. It shows that the hazard of some substances is underestimated if the degradation products of these substances are not included in the assessment. The selected hazard indicators are useful to assess the importance of degradation products. It is suggested that degradation products be included in hazard assessments to gain a more accurate insight into the environmental hazard of chemicals. The findings of this project could also be combined with information on the toxicity of degradation products. This would provide further insight into the importance of degradation products for environmental risk assessments.

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K.W. Moilanen

Papers

Vapor-phase photodecomposition of DDT

The photodecomposition of dipropylnitrosamine vapor