Noble gas enrichments in porewater of estuarine sediments and their effect on the estimation of net denitrification rates

The concentration and the isotopic ratios of noble gases He, Ne, Ar, Kr and Xe were measured in porewater trapped in shallow sediments of the estuary of the St-Lawrence River, Québec, Canada. The gases are atmospheric in origin but most samples have gas concentrations 1.7-28 times higher than those expected in solution in water at equilibrium with the atmosphere. Elemental fractionation of heavier noble gases Kr and Xe compared to Ar strongly suggests that noble gases were adsorbed on sediments or organic matter and then desorbed into porewaters due to depressurization, as collected samples were brought to the surface. Atmospheric Ar in porewater is used as a reference to measure the N₂-fluxes at the water-sediment interface. Ignoring the Ar enrichments observed in porewater could lead to a severe underestimation of the denitrification rate in oceans and estuaries.