Degradation of pentaerythritol tetranitrate (PETN) by granular iron

Pentaerythritol tetranitrate (PETN), a nitrate ester, is used primarily as an explosive. It is of environmental concern, posing a threat to aquatic organisms with an estimated EC50 five times greater than that of RDX. This study evaluated the kinetics and products of PETN degradation in the presence of gralar iron. PETN transformation in columns containing 100% granular iron and 30% iron mixed with 70% silica sand followed pseudo first-order kinetics, with average half-lives of 0.26 and 1.58 min, respectively. The reduction pathway was proposed to be sequential denitration, in which PETN was stepwise reduced to pentaerythritol with the formation of pentaerythritol trinitrate and pentaerythritol dinitrate as intermediates. The intermediate of pentaerythritol mononitrate was not detected; however, the nearly 100% nitrogen mass recovery supported complete denitration. Nitrite was released in each denitration step and was subsequently reduced to ammonium by iron. Nitrate was not detected during the experiment suggesting that hydrolysis was not involved in PETN degradation. Batch experiments showed that when solid-phase PETN is present, dissolution is the rate-limiting factor for PETN mass removal. Using 50% methanol as a cosolvent, PETN solubility was enhanced and thus the removal efficiency was improved. The results demonstrate excellent potential of using iron to remediate PETN-contaminated water.