Abiotic reduction of 3-nitro-1,2,4-triazol-5-one (NTO) and other munitions constituents by wood-derived biochar through its rechargeable electron storage capacity

Abstract

The environmental fate of 3-nitro-1,2,4-triazol-5-one (NTO) and other insensitive munitions constituents (MCs) is of significant concern due to their high water solubility and mobility relative to legacy MCs. Plant-based biochars...

Pyrogenic Black Carbon Suppresses Microbial Methane Production by Serving as a Terminal Electron Acceptor

“…Globally, 114–383 million tons (Tg) of BC is produced every year, which represents an integral part of the global carbon cycle. Prior work has shown that BC such as plant-derived biochar and wildfire char possesses sizable and regenerable electron storage capacities (ESCs). − The ESC of BC is believed to be composed of redox-facile functional groups such as (hydro)­quinones, which are created through/during pyrolysis . Conceptually, ESC is the sum of the electron-donating capacity (EDC) and electron-accepting capacity (EAC).…”

Unveiling the corrosion mechanism of 3-nitro-1,2,4-triazol-5-one (NTO) toward mild steel from ab initio molecular dynamics: how the “nitro-to-amino” reaction matters

“…7 These energy barriers involved in the "nitro-to-amino" reaction are relatively low, implying that the reaction can easily occur under mild conditions. Although the NTO / ATO reaction is experimentally well documented, 24,30,33,35 this is the rst time that ATO formation on Fe(110) has been observed by AIMD simulations with kinetic information, and we show that this process can be achieved within 4 ps in our simulations.…”

“…Experimentally, NTO anions were veried to be able to complete the "nitro-to-amino" reaction on reducing substances, and the thermodynamic barrier for reducing NTO anions is This journal is © The Royal Society of Chemistry 2023 larger than that for reducing neutral NTO species (cathodic peak potentials, E C = −0.549 and −0.159 eV vs. SHE, respectively). 33,35,69 Therefore, we raise the simulation temperature to 700 K in AIMD to speed up the reaction process of NTO anions on Fe(110), and the corresponding results are shown in Fig. 9(i)-(iv).…”

“…[23][24][25] NTO can be easily released into the environment during production, transportation and use; therefore, it has the potential to cause an acidication of the soil solution, which will negatively impact the aquatic biota and mobilizing metals. 23 Recently, in light of the increasing use of NTO and the inevitable requirement for environmental protection, various methods for treating NTO wastewater have been developed, including chemical degradation, [26][27][28] biodegradation, [29][30][31] abiotic transformation 24,[32][33][34][35] and adsorption. 36,37 Experimentally, NTO has been observed to transform into 3-amino-1,2,4-triazol-5-one (ATO) during these treatments (details of the physico-chemical properties of NTO and ATO can be seen in Table S2 †) abiotically or biologically, through the reduction of nitro to amino.…”

Designing bacterial consortia for the complete biodegradation of insensitive munitions compounds in waste streams

“…Previous investigations have established that DNAN is subject to cometabolic biotransformation or abiotic reduction in soil and waste streams, which generates an array of metabolites of poorly understood toxicity and increased solubility (Berens et al, 2020; Murillo‐Gelvez et al, 2019; Niedźwiecka et al, 2017; Olivares et al, 2013, 2016; Temple et al, 2018; Xin et al, 2022). For example, the complete reduction of DNAN yields the more reactive 2,4‐diaminoanisole (DAAN), a compound that can rapidly react with partially reduced intermediates, forming a wide array of dimeric metabolites with possible consequences for toxicity (Olivares, Abrell, et al, 2016; Olivares, Sierra‐Alvarez, et al, 2016).…”