Attenuation of nitrate in aquitard sediments of southern Ontario

To examine nitrate persistence, detailed geochemical profiling, using core-squeezed water and piezometer samples, was carried out at five sites in southern Ontario where groundwater is moving downward in silt-rich aquitard sediments at rates of 16 to more than 20 cm year^?1. Elevated levels of NO₃^?-N (5–50 mg 1^?1) that occur in the shallow groundwater as a result of agricultural activity, were found to be consistently attenuated, generally to very low levels (< 0.05 mg 1^?1-N), at the ‘redoxcline’, the horizon marking the boundary between the surficial weathered (brown) sediments and the underlying unweathered (grey) sediments. Tritium dating suggests that groundwater at the redoxcline depths (3–5 m) was recharged between 1970 and 1980, thus the N03 depletion appears to result from biodegradation reactions since no major landuse changes have occurred during this period. The close association of the nitrate depletion zones with the redoxcline, where, in particular, sediment sulphur contents increase abruptly, and where also porewater SO₄^2? levels increase, suggests that the dominant attenuation reaction is autotrophic denitrification using reduced sulphur compounds present in the unweathered sediment as the electron donor. Mass balance calculations suggest that the increase in the downward rate of migration of the redoxcline, owing to added sulphur consumption from NO₃^? contamination, is only about 1 mm year^?1 at these sites. Review of the literature indicates that most silt- and clay-rich sediments have S contents in the same range, or higher, than those investigated here, thus, in most cases where aquifers are overlain by several metres or more of unweathered confining sediments, it is likely that a high degree of protection is afforded from surficial NO₃^? contamination.