Mineralization of RDX-derived nitrogen to N₂ via denitrification in coastal marine sediments

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a common constituent of military explosives. Despite RDX contamination at numerous U.S. military facilities and its mobility to aquatic systems, the fate of RDX in marine systems remains largely unknown. Here, we provide RDX mineralization pathways and rates in seawater and sediments, highlighting for the first time the importance of the denitrification pathway in determining the fate of RDX-derived N. ¹⁵N nitro group labeled RDX (¹⁵N-[RDX], 50 atom %) was spiked into a mesocosm simulating shallow marine conditions of coastal Long Island Sound, and the ¹⁵N enrichment of N₂ (δ¹⁵N₂) was monitored via gas bench isotope ratio mass spectrometry (GB-IRMS) for 21 days. The ¹⁵N tracer data were used to model RDX mineralization within the context of the broader coastal marine N cycle using a multicompartment time-stepping model. Estimates of RDX mineralization rates based on the production and gas transfer of ¹⁵N₂O and ¹⁵N₂ ranged from 0.8 to 10.3 μmol d^-1. After 22 days, 11% of the added RDX had undergone mineralization, and 29% of the total removed RDX-N was identified as N₂. These results demonstrate the important consideration of sediment microbial communities in management strategies addressing cleanup of contaminated coastal sites by military explosives.