Shifts in the relative availability of phosphorus and nitrogen along estuarine salinity gradients

Phosphorus (P) availability in estuaries may increase with increasing salinity because sulfate from sea salt supports production of sulfide in sediments, which combines with iron (Fe) making it less available to sequester P. Increased P availability with increased salinity may promote the generally observed switch from P limitation of primary production in freshwater ecosystems to nitrogen (N) limitation in coastal marine waters. To investigate this hypothesis, we analyzed pore water from sediment cores collected along the salinity gradients of four Chesapeake Bay estuaries (the Patuxent, Potomac, Choptank, and Bush Rivers) with watersheds differing in land cover and physiography. At salinities of 1–4 in each estuary, abrupt decreases in pore water Fe²⁺ concentrations coincided with increases in sulfate depletion and PO₄ ^3? concentrations. Peaks in water column PO₄ ^3? concentrations also occur at about the same position along the salinity gradient of each estuary. Increases in pore water PO₄ ^3? concentration with increasing salinity led to distinct shifts in molar NH₄ ⁺:PO₄ ^3? ratios from >16 (the Redfield ratio characteristic of phytoplankton N:P) in the freshwater cores to <16 in the cores with salinities >1 to 4, suggesting that release of PO₄ ^3? from Fe where sediments are first deposited in sulfate-rich waters could promote the commonly observed switch from P limitation in freshwater to N limitation in mesohaline waters. Finding this pattern at similar salinities in four estuaries with such different watersheds suggests that it may be a fundamental characteristic of estuaries generally.