Atlantic Ocean Surface Waters Buffer Declining Atmospheric Concentrations of Persistent Organic Pollutants

Decreasing environmental concentrations of some persistent organic pollutants (POPs) have been observed at local or regional scales in continental areas after the implementation of international measures to curb primary emissions. A decline in primary atmospheric emissions can result in re-emissions of pollutants from the environmental capacitors (or secondary sources) such as soils and oceans. This may be part of the reason why concentrations of some POPs such as polychlorinated biphenyls (PCBs) have not declined significantly in the open oceanic areas, although re-emission of POPs from open ocean water has barely been documented. In contrast, results from this study show that several polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) have undergone a marked decline (2-3 orders of magnitude for some homologues) over a major portion of the remote oligotrophic Atlantic Ocean. The decline appears to be faster than that observed over continental areas, implicating an important role of oceanic geochemical controls on levels and cycling of some POPs. For several lower chlorinated PCDD/Fs, we observed re-emission from surface water back to the atmosphere. An assessment of the effectiveness of the main sink processes highlights the role of degradation in surface waters as potentially key to explaining the different behavior between PCDD/Fs and PCBs and controlling their overall residence time in the ocean/atmosphere system. This study provides experimental evidence that the ocean has a buffering capacity - dependent on individual chemicals - which moderates the rate at which the system will respond to an underlying change in continental emissions.