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Sources and pathways of selected organochlorine pesticides to the Arctic and the effect of pathway divergence on HCH trends in biota: a review

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Abstract

Historical global usage and emissions for organochlorine pesticides (OCPs), including hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethane (DDT), toxaphene and endosulfan, are presented. Relationships between the air concentrations of these OCPs and their global emissions are also discussed. Differences between the pathways of α- and β-HCH to the Arctic Ocean are described in the context of environmental concentrating and diluting processes. These concentrating and diluting processes are shown to control the temporal and spatial loading of northern oceans and that the HCH burdens in marine biota from these oceans respond accordingly. The HCHs provide an elegant example of how hemispheric-scale solvent switching processes can alter the ocean into which an HCH congener partitions, how air–water partitioning controls the pathway for HCHs entering the Arctic, and how the various pathways impact spatial and temporal trends of HCH residues in arctic animals feeding out of marine and terrestrial foodwebs.

Introduction

Interest in persistent organic pollutants (POPs) in Arctic aquatic and terrestrial ecosystems has grown enormously following the discovery of organochlorine (OCs) contamination in arctic marine mammals in the late 1960s. The first report of HCHs (hexachlorocyclohexanes) in arctic air dates from 1979 (Tanabe and Tatsukawa, 1980) where the total HCH concentration was reported at 1000 pg/m3 over the Bering Sea compared to an average of 3600 pg/m3 off China and Japan in 1975–1977. Far from significant pollution sources, the Arctic is obviously a receptor of POPs released elsewhere on the globe. Ottar (1981) suggested that POPs released by human activities (e.g., agriculture and industry) seek cold locations in the global environment and, for this reason, the Arctic may be particularly vulnerable to volatile and semi-volatile substances. Organochlorine pesticides (OCPs), which originate mainly in temperate and warmer areas of the world, can be transported to the Arctic via atmospheric long-range transport (LRT), through ocean currents and through runoff passing through the Arctic's large drainage basin.

Macdonald et al. (2000) reviewed the results from Canadian research on sources, occurrence and pathways of OCPs in the Canadian Arctic. The most discussed compounds were α- and γ-HCH due to the abundant data in the Arctic air and water, and mass budgets for these two chemicals were constructed for the early 1990s. Since that time more data have been collected for other OCPs, and further research on HCHs has deepened our understanding of the pathways to the Arctic and how these have influenced the distributions of HCH within the Arctic.

In this paper, we provide up-to-date inventories of global usage and emissions for α- and β-HCH, dichlorodiphenyltrichloroethane (DDT), toxaphene and endosulfan, and discuss the relationship between global emissions for these OCPs and their air concentrations in the Arctic. We also discuss α- and β-HCH pathways to the Arctic to demonstrate that atmospheric long-range transport (LRT) by itself cannot explain the observed distributions in the upper ocean. Further studies on the spatial and temporal trends of the concentrations for α- and β-HCH in both abiotic and biotic media in the Arctic show that trends reflect the respective pathways of these two compounds into the Arctic.

Section snippets

Global usage

Technical hexachlorocyclohexane (HCH) and lindane are two formulations of HCH, an organochlorine insecticide. While lindane consists almost entirely of γ-HCH, the insecticidal form, technical HCH contains a total of eight HCH isomers, among which only the α, β, γ, δ and ɛ isomers are stable and commonly identified. Generally, technical HCH contains the isomers in the following percentages: α, 60–70%; β, 5–12%; γ, 10–12%; δ, 6–10%; and ɛ, 3–4% (Kutz et al., 1991, Iwata et al., 1993a). Around 10

Linkage between air concentrations of α- and β-HCH, α-endosulfan, DDT and toxaphene in the Arctic and their global emissions

Li et al. (2002) point out that time-series data for organochlorines in the environment should be reported on an individual compound basis (e.g., each isomer or metabolite). Clearly, the common practice of mixing compounds with different physical and chemical properties through the use of, for example, ∑HCH, to produce a trend, makes little sense. In the Canadian Arctic, variation in properties and pathways between HCH isomers has been shown (Li et al., 2002) to lead to dramatic environmental

Pathways of OCPs to the Arctic

Clarification of sources and pathways of pollutants, especially the OCPs, to the Arctic has been a major objective of Arctic research and assessments (Macdonald et al., 2000, Macdonald et al., 2003). Pesticides can be emitted to the atmosphere as gaseous compounds or in the form of liquid or solid particles. Although some degradation may take place in the atmosphere, much of the airborne pesticide burden is removed from the atmosphere through deposition. Part of the deposition takes place close

Summary

This paper provides up-to-date inventories of global usage and emissions for several OCPs. Around 10 Mt of technical HCH has been used since 1940s, of which 4300 kt α-HCH and 230 kt of β-HCH have been emitted to the atmosphere. Overall DDT usage is estimated as around 4.5 Mt; 2.6 Mt for agricultural purposes, 1.5 Mt for public health, and 0.4 Mt for other purposes. The total emissions of DDT through agricultural application are 1030 kt between 1947 and 2000. Total global toxaphene usage is 1.33

Acknowledgements

This study was supported by the Northern Contaminants Program (NCP), under which many new data and ideas have emerged. Valuable comments from T. Bidleman, the guest editor of this special issue, and two anonymous reviewers are gratefully acknowledged. Help from R. McCarthy, M. Fazelipour and M. Latyszewskyj of Environment Canada Library are highly appreciated.

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