In situ analysis of microbial reduction of a nitrate plume in Opalinus clay

Document available in extended abstract form only. In several countries, such as Belgium, France and Switzerland, clay formations are foreseen as the host rock for geological disposal of bituminized low-level and intermediate-level long-lived radioactive waste. Suitable clay formations exhibit favorable hydro-mechanical and geochemical characteristics, which are expected to retard the migration of leached radionuclides. Along with radionuclides, certain classes of bituminized radioactive waste may also contain high concentrations of NaNO3, dispersed into the hydrophobic bitumen matrix used to stabilize the waste. During and after saturation of the disposal gallery, this bituminized waste will start to take up water due to osmosis, resulting in the leaching of significant amounts of NaNO3 and soluble organic bitumen degradation products (BDP) into the clay pore water. This nitrate plume could cause several geochemical and biochemical processes in the clay surrounding the waste disposal gallery, potentially affecting the barrier function of the host rock. To study these processes, an in situ experiment in the Opalinus Clay, named the Bitumen-Nitrate-Clay interaction (BN) experiment, is being performed at the Mont Terri Rock Laboratory (CH). The experiment consists of a vertical borehole rigged with a downhole equipment containing three packed-off intervals, each lined with a cylindrical sintered stainless steel filter screen to allow contact with the surrounding clay. Prior to the start of the tests, the intervals were injected with an artificial Opalinus Clay pore water, containing all major ions at pore water concentrations at Mont Terri, but no organic matter, and were equilibrated with the surrounding clay for ∼8 months. To ensure a continuous water flow during the tests, each interval is connected to a stainless steel water circulation unit, equipped with water sampling containers, circulation pumps and flow meters. In addition, to continuously monitor the nitrate and nitrite concentrations and pH, an on-line UV spectrophotometer and pH electrode are installed in the water circuit of one of the intervals. In a first series of tests, the biogeochemical evolution of the artificial Opalinus Clay pore water in the intervals was investigated after injection of low concentrations of nitrate or nitrate and acetate, simulating the BDP. The results of these tests indicate that microbial reduction of nitrate and nitrite can occur in the Opalinus Clay artificial water in the borehole, using acetate and/or clay components as electron donors. In these tests, nitrate was reduced to nitrite, ammonium and/or nitrogenous gases. Comparing the evolution in nitrate and nitrite concentrations in the absence or presence of acetate, clearly indicates faster reaction rates of microbial nitrate reduction when the system is fueled with acetate. When easily degradable organic compounds like acetate were added to the nitrate containing artificial pore water, these compounds were preferentially used as electron donors for nitrate reduction by heterotrophic microorganisms. Afterwards, alternative electron donors have been used originating either from the clay rock, e.g. pyrite, siderite, clay minerals, and/or dissolved natural organic matter, or from the stainless steel equipment, i.e. Fe0 and/or Fe2+. Furthermore, high concentrations of nitrate reducing prokaryotes were detected after injection of the intervals with nitrate, indicating that the nitrate and nitrite reduction, observed during all tests, was microbially mediated. Based on the results of the microbiological analyses, these nitrate reducers have most likely been introduced during the first injection or installation of the downhole equipment. The nature of the nitrate reduction reaction prevailing in the system appears to be depending on the microbial populations active in the borehole and on the electron donors and carbon sources present in the interval. Furthermore, the history of the interval is also of importance, as microbial populations grown and activated in interval 2 during the first injection test were able to remain in a stationary state for several months after complete consumption of the electron donors and acceptors. These microbial populations started to grow and become active very soon once the interval was injected again with nitrate and acetate, without needing a clear adaptation phase. In conclusion, these results suggest that when sufficient water and space are available in the clay to allow microbial growth and activity in the near field of a geological repository for bituminized radioactive waste, microbial nitrate reduction using clay components could occur. However, in the presence of easily degradable organic compounds leached from the bituminized waste, microbes are expected to preferentially use these electron donors