Field tracer test for denitrification in a pyrite-bearing schist aquifer

A small-scale artificial tracer test performed on a schist aquifer in Brittany has helped clarify mechanisms and kinetics of in situ autotrophic denitrification. NO3 was injected as a pulse simultaneously with a conservative tracer -Br−. During the test, which lasted 210 h, 73% of the injected Br− was recovered, as against only 47% of the NO3. The 26% difference in the recovery of the two injected species is interpreted as being the result of denitrification, in part due to the direct oxidation of pyrite present in the solid aquifer according to the reaction: 5FeS2+14NO3−+4H+→7N2+10SO42−+5Fe2++2H2O, and in part due to subsequent iron oxidation according to the reaction: NO3−+5Fe2++6H+→1/2N2+5Fe3++3H2O. Despite the potential increase in SO4 and Fe resulting from denitrification through pyrite oxidation, the concentrations of these elements in the groundwater remain moderate due to the precipitation of minerals such as jarosite and/or natroalunite. Tracer transfer takes place in a heterogeneous medium which, according to the breakthrough curves, can be simplified to a dual-porosity aquifer comprising a high-permeability (fractures or large fissures) medium of low porosity from which only minor denitrification of circulating NO3-bearing water was observed and a low-permeability (small fissures) medium of high porosity which induces a higher denitrification rate in the circulating NO3-bearing water. The kinetics of the denitrification reaction are high compared with results obtained for other environments and can be described by a first-order model with a half life of 7.9 days for the low-porosity medium and only 2.1 days for the high-porosity medium.