Isolation and characterization of dissolved organic matter from the Callovo–Oxfordian formation

Characterizing dissolved organic matter (DOM) in the pore water of the Callovo–Oxfordian formation, a potential host rock for the disposal of radioactive waste, is important to estimate its potential influence on the mobility of radionuclides in the rock. To isolate DOM, crushed rock material was extracted under anoxic conditions with deionized water, 0.1 M NaOH and synthetic pore water (SPW, water containing all major ions at pore water concentrations but no organic matter), respectively. The effects of extraction parameters on the extracted DOM including the solid-to-liquid ratio, extraction time, exposure to O2 and acid pretreatment of the rock material prior to the anoxic extraction were evaluated. In addition, DOM in one of the first pore water samples collected in the underground rock laboratory at Bure (France) was characterized for comparison. The size distribution and the low molecular weight organic acid contents of the extracts and pore water DOM were determined by liquid chromatography coupled with an organic C detector (LC-OCD) and by ion chromatography. The results revealed that only a fraction of less than 1.2% of the total organic C present in the rock was extractable. Maximum dissolved organic C (DOC) concentrations in the anoxic extracts ranged from 5.5 ± 0.3 mg/L for SPW extracts to 14.2 ± 1.1 mg/L for 0.1 M NaOH extracts. The major portion of the DOC in the anoxic extracts consisted of hydrophilic compounds (48–78%) having a molecular weight of less than 500 Da. Up to 21% of DOC in the anoxic extracts was identified as acetate, formate, lactate and malate. The short-term exposure of rock material to O2 during rock crushing strongly increased DOC concentrations and led to a shift towards smaller molecular weight compounds and to a higher low molecular weight organic acid (LMWOA) content as compared to the strictly anoxic extraction. The pore water sampled from a packed-off borehole exhibited a higher DOC concentration (56.7 mg/L) than the rock extracts. The pore water DOM was almost exclusively composed of acetate and propionate (88% of the DOC). The predominance of LMWOA in the pore water compared to the anoxic extracts may arise from the heterogeneity of the rock material, a more effective DOM filtration by the rock formation compared to laboratory extractions, or possibly, bacterial activity in the pore water induced by the borehole disturbance.