TY - JOUR
T1 - Adsorption and oxidation of 3-nitro-1,2,4-triazole-5-one (NTO) and its transformation product (3-amino-1,2,4-triazole-5-one, ATO) at ferrihydrite and birnessite surfaces
AU - Khatiwada, Raju
AU - Abrell, Leif
AU - Li, Guangbin
AU - Root, Robert A.
AU - Sierra-Alvarez, Reyes
AU - Field, James A.
AU - Chorover, Jon
N1 - Funding Information:
We thank Paul Lee at The Laboratory for Electron Spectroscopy and Surface Analysis (LESSA) , The University of Arizona for assistance with XPS data collection. We would also like to thank Mary Kay Amistadi, Arizona Laboratory for Emerging Contaminants (ALEC) for ICP-MS sample analysis. The comments of three anonymous reviewers are greatly appreciated. This research was supported by the USA Department of Defense , Strategic Environmental Research and Development Program (SERDP) grant number ER 2221 and NSF CBET 0722579 . Portions of this research were carried out at the Stanford Synchrotron Radiation Laboratory (SSRL) . Use of the SSRL, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515.
Funding Information:
We thank Paul Lee at The Laboratory for Electron Spectroscopy and Surface Analysis (LESSA), The University of Arizona for assistance with XPS data collection. We would also like to thank Mary Kay Amistadi, Arizona Laboratory for Emerging Contaminants (ALEC) for ICP-MS sample analysis. The comments of three anonymous reviewers are greatly appreciated. This research was supported by the USA Department of Defense, Strategic Environmental Research and Development Program (SERDP) grant number ER 2221 and NSF CBET 0722579. Portions of this research were carried out at the Stanford Synchrotron Radiation Laboratory (SSRL). Use of the SSRL, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515.
Publisher Copyright:
© 2018
PY - 2018/9
Y1 - 2018/9
N2 - The emerging insensitive munitions compound (IMC) 3-nitro-1,2,4-triazole-5-one (NTO) is currently being used to replace conventional explosives such as 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), but the environmental fate of this increasingly widespread IMC remains poorly understood. Upon release from unexploded solid phase ordinances, NTO exhibits high aqueous solubility and, hence, potential mobilization to groundwater. Adsorption and abiotic transformation at metal oxide surfaces are possible mechanisms for natural attenuation. Here, the reactions at ferrihydrite and birnessite surfaces of NTO and its biotransformation product, 3-amino-1, 2, 4-triazol-5-one (ATO), were studied in stirred batch reactor systems at controlled pH (7.0). The study was carried out at metal oxide solid to solution ratios (SSR) of 0.15, 1.5 and 15 g kg−1. The samples were collected at various time intervals up to 3 h after reaction initiation, and analyzed using HPLC with photodiode array and mass spectrometric detection. We found no detectable adsorption or transformation of NTO upon reaction with birnessite, whereas ATO was highly susceptible to oxidation by the same mineral, showing nearly complete transformation within 5 min at 15 g kg−1 SSR to urea, CO2(g) and N2(g). The mean surface-area-normalized pseudo-first order rate constant (k) for ATO oxidation by birnessite across all SSRs was 0.05 ± 0.022 h−1 m−2, and oxidation kinetics were independent of dissolved O2 concentration. Both NTO and ATO were resistant to oxidation by ferrihydrite. However, NTO showed partial removal from solution upon reaction with ferrihydrite at 0.15 and 1.5 g kg−1 SSR and complete loss at 15 g kg−1 SSR due to strong adsorption. Conversely, ATO adsorption to ferrihydrite was much weaker than that measured for NTO. Insensitive munitions compound NTO is strongly adsorbed by the hydrous ferric oxide, ferrihydrite, whereas the reduced daughter product ATO is rapidly oxidized to innocuous products by the common Mn(IV) soil mineral birnessite.
AB - The emerging insensitive munitions compound (IMC) 3-nitro-1,2,4-triazole-5-one (NTO) is currently being used to replace conventional explosives such as 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), but the environmental fate of this increasingly widespread IMC remains poorly understood. Upon release from unexploded solid phase ordinances, NTO exhibits high aqueous solubility and, hence, potential mobilization to groundwater. Adsorption and abiotic transformation at metal oxide surfaces are possible mechanisms for natural attenuation. Here, the reactions at ferrihydrite and birnessite surfaces of NTO and its biotransformation product, 3-amino-1, 2, 4-triazol-5-one (ATO), were studied in stirred batch reactor systems at controlled pH (7.0). The study was carried out at metal oxide solid to solution ratios (SSR) of 0.15, 1.5 and 15 g kg−1. The samples were collected at various time intervals up to 3 h after reaction initiation, and analyzed using HPLC with photodiode array and mass spectrometric detection. We found no detectable adsorption or transformation of NTO upon reaction with birnessite, whereas ATO was highly susceptible to oxidation by the same mineral, showing nearly complete transformation within 5 min at 15 g kg−1 SSR to urea, CO2(g) and N2(g). The mean surface-area-normalized pseudo-first order rate constant (k) for ATO oxidation by birnessite across all SSRs was 0.05 ± 0.022 h−1 m−2, and oxidation kinetics were independent of dissolved O2 concentration. Both NTO and ATO were resistant to oxidation by ferrihydrite. However, NTO showed partial removal from solution upon reaction with ferrihydrite at 0.15 and 1.5 g kg−1 SSR and complete loss at 15 g kg−1 SSR due to strong adsorption. Conversely, ATO adsorption to ferrihydrite was much weaker than that measured for NTO. Insensitive munitions compound NTO is strongly adsorbed by the hydrous ferric oxide, ferrihydrite, whereas the reduced daughter product ATO is rapidly oxidized to innocuous products by the common Mn(IV) soil mineral birnessite.
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U2 - 10.1016/j.envpol.2018.04.034
DO - 10.1016/j.envpol.2018.04.034
M3 - Article
C2 - 29738948
AN - SCOPUS:85052963587
VL - 240
SP - 200
EP - 208
JO - Environmental Pollution
JF - Environmental Pollution
SN - 0269-7491
ER -