Impact of trace metals on denitrification in estuarine sediments of the Douro River estuary, Portugal

Denitrification influences the nitrogen budget in estuaries by removing fixed nitrogen from the inorganic pool; rates are dependent on both geological and geographic conditions as well as increasing anthropogenic impacts. In this study the effects of copper (Cu), chromium (Cr), zinc (Zn), cadmium (Cd) and lead (Pb), on the denitrification pathway were evaluated in subtidal and intertidal sediments of the Douro River estuary. Dinitrogen, N2O and NO2− production rates were measured in triplicate slurries of field samples under different treatments of metal concentrations. Results demonstrated that similar metal amendments led to different site responses for denitrification, suggesting that variations in sediment properties (metal concentrations, grain size, organic matter content, etc.) and/or differences in denitrifying community tolerance modulate the level of metal toxicity. Denitrifying communities in subtidal muddy sediments were not affected by increasing concentrations of metals. In contrast, intertidal sandy sites revealed high sensitivity to almost all trace metals tested; almost complete inhibition by Cr (95%) and Cu (85%) was observed for 98 and 79 μg per gram of wet sediment respectively, and by Zn (92%) at the highest concentration added (490 μg per gram of wet sediment). Moreover, the addition of trace metals stimulated N2O and NO2− accumulation in intertidal sandy (Zn, Cu, Cr and Cd) and muddy sediments (Cu and Zn), demonstrating a pronounced inhibitory effect on specific steps within the denitrification enzymatic system. In summary, the results obtained suggest that, according to the type of estuarine sediment, trace metals cannot only reduce total N removal from an estuary via denitrification but also can enhance the release of N2O, a powerful greenhouse gas.