Measuring and simulating atmospheric concentration trends of polychlorinated biphenyls in the Northern Hemisphere

Temporal trend analysis of polychlorinated biphenyls (PCB) air concentration data measured in the Canadian Arctic and around the Great Lakes in the 1990s has shown that individual PCB congeners decline at different rates in air. The atmospheric decline rate of the same congener also varied from site to site. To determine whether these site-specific variations in atmospheric trends of PCB concentrations are controlled by changes in primary emissions or various removal processes in the environment (transfer to deep sea, freshwater sediment burial, reaction with OH radicals, degradation in media other than air), the measured trends are compared to those simulated by a zonally averaged global fate and transport model using historical emission estimates and realistic and hypothetical environmental scenarios. The modelled decline rates of a specific congener in both the North Polar and the North Temperate zones are similar and mimic closely those of the historical emission estimates fed into the model, suggesting that the rate of decline of PCB air concentrations during the 1990s was mostly driven by declines in primary emission. This implies that measured air concentration data reflect primary PCB emissions as long as these continue. Under the assumption that primary emission completely ceased after 2001, the model predicted that the terrestrial surface media would eventually become the only major global PCB reservoir, and the rate of concentration decline in air then depends solely on that in soil. Also, primary emissions and volatilization from soil, respectively, are the primary input to the atmosphere before and after primary emissions stopped. The model further illustrates that even during periods when primary emissions still dominate PCB air concentrations temperature-driven cycles of air/surface exchange may be observed. Large scale re-distribution of PCBs by the grass-hopper effect can thus also occur while primary emissions are still dominant.