US Army and the Department of Defense (DoD) facilities generate perchlorate (ClO(4)(-)) from munitions manufacturing and demilitarization processes. Ammonium perchlorate is one of the main constituents in Army's new main charge melt-pour energetic, PAX-21. In addition to ammonium perchlorate, hexahydro-1,3,5-trinitro-1.3,5-triazine (RDX) and 2,4-dinitroanisole (DNAN) are the major constituents of PAX-21. In order to evaluate microbial perchlorate reduction as a practical option for the treatment of perchlorate in PAX-21 wastewater, we conducted biodegradation experiments using glucose as the primary sources of electrons and carbon. Batch experiments showed that negligible perchlorate was removed in microbial reactors containing PAX-21 wastewater while control bottles containing seed bacteria and glucose rapidly and completely removed perchlorate. These results suggested that the constituents in PAX-21 wastewater may be toxic to perchlorate reducing bacteria. A series of batch toxicity test was conducted to identify the toxic constituents in PAX-21 and DNAN was identified as the primary toxicant responsible for inhibiting the activity of perchlorate reducing bacteria. It was hypothesized that pretreatment of PAX-21 by zero-valent iron granules will transform toxic constituents in PAX-21 wastewater to non-toxic products. We observed complete reduction of DNAN to 2,4-diaminoanisole (DAAN) and RDX to formaldehyde in abiotic iron reduction study. After a 3-day acclimation period, perchlorate in iron-treated PAX-21 wastewater was rapidly decreased to an undetectable level in 2 days. This result demonstrated that iron treatment not only removed energetic compounds but also eliminated the toxic constituents that inhibited the subsequent microbial process. (C) 2011 Elsevier B.V. All rights reserved.