The effects of sea salts on the forms of nitrogen released from estuarine and freshwater sediments: Does ion pairing affect ammonium flux?

In sediments with oxidized surface layers, the percentage of mineralized nitrogen that is nitrified/denitrified, compared with that released directly as ammonium, appears to be affected by the presence of sea salts. In estuarine systems, a significant portion of the nitrogen is released as ammonium, whereas in freshwater systems, most of the mineralized nitrogen is often released from the sediments as nitrogen gas. We hypothesized that this discrepancy is caused by differential competition between physical diffusion and nitrification/denitrification in the two systems. The vertical migration (by Fickian diffusion) of ammonium out of the oxic layer may be hindered by cation exchange (or sorption) interactions with sediment particles to a greater extent in fresh water than in estuarine systems. The resulting relatively long residence time, and potentially high levels of particle-bound ammonium in the freshwater sediments, would favor nitrification as the major ammonium removal process. By contrast, ion pair formation of ammonium with seawater anions and blockage of sediment cation exchange sites with seawater cations may allow a sizable fraction of the ammonium to diffuse out of estuarine sediments before it is nitrified. A salt effect, consistent with this hypothesis, has been demonstrated in experimental systems by changing the ionic composition of water flowing above intact cores of freshwater and estuarine sediments. Steady-state ammonium release from Lake Michigan sediments was substantially enhanced in the presence of 30% seawater over that in the presence of lake water alone. Likewise, steady-state ammonium release, from Ochlockonee River and Bay sediments (Florida) and from Toms River and Barnegat Bay sediments (New Jersey), was usually higher in the presence of diluted synthetic seawater than it was in the presence of fresh water.