Iron(II) monosulfide (FeS) minerals reductively transform the insensitive munitions compounds 2,4-dinitroanisole (DNAN) and 3-nitro-1,2,4-triazol-5-one (NTO)

Menezes, Osmar; Yu, Youngjae; Root, Robert A.; Gavazza, Savia; Chorover, Jon; Sierra-Alvarez, Reyes; Field, Jim A.

doi:10.1016/j.chemosphere.2021.131409

Title: Iron(II) monosulfide (FeS) minerals reductively transform the insensitive munitions compounds 2,4-dinitroanisole (DNAN) and 3-nitro-1,2,4-triazol-5-one (NTO)

Journal Article · Fri Jul 02 00:00:00 EDT 2021 · Chemosphere

DOI:https://doi.org/10.1016/j.chemosphere.2021.131409· OSTI ID:1981571

^[1]; Yu, Youngjae ^[2]; Root, Robert A. ^[2];

^[3]; Chorover, Jon ^[2];

^[2]; Field, Jim A. ^[2]

Univ. of Arizona, Tucson, AZ (United States); Universidade Federal de Pernambuco (Brazil)
Univ. of Arizona, Tucson, AZ (United States)
Universidade Federal de Pernambuco (Brazil)

As military applications of the insensitive munitions compounds (IMCs) 2,4-dinitroanisole (DNAN) and 3-nitro-1,2,4-triazol-5-one (NTO) increase, there is a growing need to understand their environmental fate and to develop remediation strategies to mitigate their impacts. Iron (II) monosulfide (FeS) minerals are abundant in freshwater and marine sediments, marshes, and hydrothermal environments. Here, this study shows that FeS solids can reduce DNAN and NTO to their corresponding amines under anoxic ambient conditions. The reactions between IMCs and the FeS minerals were surface-mediated since they did not occur when only dissolved Fe²⁺_(aq) and S^2–_(aq) were present. Mackinawite, a tetragonal FeS with a layered structure, reduced DNAN mainly to 2-methoxy-5-nitroaniline (MENA), which in turn was partially reduced to 2-4-diaminoanisole (DAAN). The layered structure of mackinawite provided intercalation sites likely responsible for partial adsorption of MENA and DAAN. Mackinawite entirely reduced NTO to 3-amino-1,2,4-triazol-5-one (ATO). The reduction of IMCs showed concurrent oxidation of mackinawite to goethite and elemental sulfur. A commercial FeS product, composed mainly of pyrrhotite and troilite, reduced DNAN to DAAN and NTO to ATO. At pH 6.5, DNAN and NTO transformation rates were 667 and 912 μmol h^–1 m^–2, respectively, on the mackinawite surface and 417 and 1344 μmol h^–1 m^–2, respectively, on the commercial FeS surface. This is the first report of the reduction of a nitro-heterocyclic compound (NTO) by FeS minerals. The evidence indicates that DNAN and NTO can be rapidly transformed to their succeeding amines in anoxic subsurface environments and aquatic sediments rich in FeS minerals.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1981571

Journal Information:: Chemosphere, Vol. 285, Issue C; ISSN 0045-6535

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

Zebrafish embryo toxicity of anaerobic biotransformation products from the insensitive munitions compound 2,4-dinitroanisole Olivares, Christopher I.; Sierra-Alvarez, Reyes; Abrell, Leif Environmental Toxicology and Chemistry, Vol. 35, Issue 11 https://doi.org/10.1002/etc.3446	journal	June 2016
Oxidation of reduced daughter products from 2,4-dinitroanisole (DNAN) by Mn(IV) and Fe(III) oxides Khatiwada, Raju; Olivares, Christopher; Abrell, Leif Chemosphere, Vol. 201 https://doi.org/10.1016/j.chemosphere.2018.03.020	journal	June 2018
Chronic oral toxicity of 3-nitro-1,2,4-triazol-5-one (NTO) in rats Lent, Emily May; Narizzano, Allison M.; Koistinen, Keith A. Regulatory Toxicology and Pharmacology, Vol. 112 https://doi.org/10.1016/j.yrtph.2020.104609	journal	April 2020
Adsorption of novel insensitive munitions compounds at clay mineral and metal oxide surfaces Linker, Billy R.; Khatiwada, Raju; Perdrial, Nico Environmental Chemistry, Vol. 12, Issue 1 https://doi.org/10.1071/EN14065	journal	January 2015
Thermophysical Properties of an Insensitive Munitions Compound, 2,4-Dinitroanisole Boddu, Veera M.; Abburi, Krishnaiah; Maloney, Stephen W. Journal of Chemical & Engineering Data, Vol. 53, Issue 5 https://doi.org/10.1021/je7006764	journal	April 2008
The chemistry of the hydrogen sulfide and iron sulfide systems in natural waters Morse, J.; Millero, F.; Cornwell, J. Earth-Science Reviews, Vol. 24, Issue 1 https://doi.org/10.1016/0012-8252(87)90046-8	journal	March 1987
Reduction of Nitroaromatics Sorbed to Black Carbon by Direct Reaction with Sorbed Sulfides Xu, Wenqing; Pignatello, Joseph J.; Mitch, William A. Environmental Science & Technology, Vol. 49, Issue 6 https://doi.org/10.1021/es5045198	journal	February 2015
Neuromuscular anomalies following oral exposure to 3-nitro-1,2,4-triazol-5-one (NTO) in a one-generation study with Japanese quail (Coturnix japonica) Jackovitz, Allison M.; Koistinen, Keith A.; Lent, Emily M. Journal of Toxicology and Environmental Health, Part A, Vol. 81, Issue 15 https://doi.org/10.1080/15287394.2018.1485123	journal	June 2018
Toxicity and fate of two Munitions Constituents in Spiked Sediment Exposures with the Marine Amphipod Eohaustorius Estuarius Rosen, Gunther; Lotufo, Guilherme R. Environmental Toxicology and Chemistry, Vol. 24, Issue 11 https://doi.org/10.1897/04-611R.1	journal	January 2005
The key role of oxygen in the bioremoval of 2,4-diaminoanisole (DAAN), the biotransformation product of the insensitive munitions compound 2,4-dinitroanisole (DNAN), over other electron acceptors Menezes, Osmar; Melo, Natanna; Paraiso, Matheus Chemosphere, Vol. 267 https://doi.org/10.1016/j.chemosphere.2020.128862	journal	March 2021
Outdoor dissolution of detonation residues of three insensitive munitions (IM) formulations Taylor, Susan; Dontsova, Katerina; Walsh, Marianne E. Chemosphere, Vol. 134 https://doi.org/10.1016/j.chemosphere.2015.04.041	journal	September 2015
Environmental fate of 2,4-dinitroanisole (DNAN) and its reduced products Hawari, J.; Monteil-Rivera, F.; Perreault, N. N. Chemosphere, Vol. 119 https://doi.org/10.1016/j.chemosphere.2014.05.047	journal	January 2015
Effects of Solution Composition and pH on the Reductive Dechlorination of Hexachloroethane by Iron Sulfide Butler, Elizabeth C.; Hayes, Kim F. Environmental Science & Technology, Vol. 32, Issue 9 https://doi.org/10.1021/es9706864	journal	May 1998
Characteristics and products of the reductive degradation of 3-nitro-1,2,4-triazol-5-one (NTO) and 2,4-dinitroanisole (DNAN) in a Fe-Cu bimetal system Kitcher, E.; Braida, W.; Koutsospyros, A. Environmental Science and Pollution Research, Vol. 24, Issue 3 https://doi.org/10.1007/s11356-016-8053-7	journal	November 2016
The adsorption of gold(I) hydrosulphide complexes by iron sulphide surfaces Widler, A. M.; Seward, T. M. Geochimica et Cosmochimica Acta, Vol. 66, Issue 3 https://doi.org/10.1016/S0016-7037(01)00791-8	journal	February 2002
Iron and Electron Shuttle Mediated (Bio)degradation of 2,4-Dinitroanisole (DNAN) Niedźwiecka, Jolanta B.; Drew, Scott R.; Schlautman, Mark A. Environmental Science & Technology, Vol. 51, Issue 18 https://doi.org/10.1021/acs.est.7b02433	journal	September 2017
Iron Sulfides Formed from Aqueous Solution at Low Temperatures and Atmospheric Pressure Berner, Robert A. The Journal of Geology, Vol. 72, Issue 3 https://doi.org/10.1086/626987	journal	May 1964
Abiotic reduction of insensitive munition compounds by sulfate green rust Khatiwada, Raju; Root, Robert A.; Abrell, Leif Environmental Chemistry, Vol. 15, Issue 5 https://doi.org/10.1071/EN17221	journal	January 2018
Characterization of synthetic nanocrystalline mackinawite: Crystal structure, particle size, and specific surface area Jeong, Hoon Y.; Lee, Jun H.; Hayes, Kim F. Geochimica et Cosmochimica Acta, Vol. 72, Issue 2 https://doi.org/10.1016/j.gca.2007.11.008	journal	January 2008
Bacteria Make a Living Breathing the Nitroheterocyclic Insensitive Munitions Compound 3-Nitro-1,2,4-triazol-5-one (NTO) Madeira, Camila L.; Menezes, Osmar; Park, Doyoung Environmental Science & Technology, Vol. 55, Issue 9 https://doi.org/10.1021/acs.est.0c07161	journal	April 2021
Insensitive Munitions – Design Principles and Technology Developments Powell, Ian J. Propellants, Explosives, Pyrotechnics, Vol. 41, Issue 3 https://doi.org/10.1002/prep.201500341	journal	February 2016
Kinetics of FeS precipitation: Part 1. Competing reaction mechanisms Rickard, David Geochimica et Cosmochimica Acta, Vol. 59, Issue 21 https://doi.org/10.1016/0016-7037(95)00251-T	journal	November 1995
Chemistry of Iron Sulfides Rickard, David; Luther, George W. Chemical Reviews, Vol. 107, Issue 2 https://doi.org/10.1021/cr0503658	journal	February 2007
Ecotoxicity of the insensitive munitions compound 3-nitro-1,2,4-triazol-5-one (NTO) and its reduced metabolite 3-amino-1,2,4-triazol-5-one (ATO) Madeira, Camila L.; Field, Jim A.; Simonich, Michael T. Journal of Hazardous Materials, Vol. 343 https://doi.org/10.1016/j.jhazmat.2017.09.052	journal	February 2018
The HighScore suite Degen, Thomas; Sadki, Mustapha; Bron, Egbert Powder Diffraction, Vol. 29, Issue S2 https://doi.org/10.1017/S0885715614000840	journal	October 2014
Assessment of 2,4-Dinitroanisole Transformation Using Compound-Specific Isotope Analysis after In Situ Chemical Reduction of Iron Oxides Berens, Matthew J.; Hofstetter, Thomas B.; Bolotin, Jakov Environmental Science & Technology, Vol. 54, Issue 9 https://doi.org/10.1021/acs.est.9b07616	journal	April 2020
The ecology and biotechnology of sulphate-reducing bacteria Muyzer, Gerard; Stams, Alfons J. M. Nature Reviews Microbiology, Vol. 6, Issue 6 https://doi.org/10.1038/nrmicro1892	journal	May 2008
Remediating Munitions-Contaminated Soil with Zerovalent Iron and Cationic Surfactants Park, J.; Comfort, S. D.; Shea, P. J. Journal of Environment Quality, Vol. 33, Issue 4 https://doi.org/10.2134/jeq2004.1305	journal	January 2004
Trace Explosives Signatures from World War II Unexploded Undersea Ordnance Darrach, M. R.; Chutjian, A.; Plett, G. A. Environmental Science & Technology, Vol. 32, Issue 9 https://doi.org/10.1021/es970992h	journal	May 1998
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 Khatiwada, Raju; Abrell, Leif; Li, Guangbin Environmental Pollution, Vol. 240 https://doi.org/10.1016/j.envpol.2018.04.034	journal	September 2018
A review on pyrrhotite oxidation Belzile, Nelson; Chen, Yu-Wei; Cai, Mei-Fang Journal of Geochemical Exploration, Vol. 84, Issue 2 https://doi.org/10.1016/j.gexplo.2004.03.003	journal	September 2004
Adsorption of Gases in Multimolecular Layers Brunauer, Stephen; Emmett, P. H.; Teller, Edward Journal of the American Chemical Society, Vol. 60, Issue 2, p. 309-319 https://doi.org/10.1021/ja01269a023	journal	February 1938
Ecotoxicological assessment of a high energetic and insensitive munitions compound: 2,4-Dinitroanisole (DNAN) Dodard, Sabine G.; Sarrazin, Manon; Hawari, Jalal Journal of Hazardous Materials, Vol. 262 https://doi.org/10.1016/j.jhazmat.2013.08.043	journal	November 2013
Degradation of 2,4-dinitrotoluene by persulfate activated with iron sulfides Oh, Seok-Young; Kang, Seung-Gu; Kim, Dong-Wook Chemical Engineering Journal, Vol. 172, Issue 2-3 https://doi.org/10.1016/j.cej.2011.06.023	journal	August 2011
Analysis of Bacterial Community Diversity in Anaerobic Fluidized Bed Bioreactors Treating 2,4-Dinitroanisole (DNAN) and n-Methyl-4-nitroaniline (MNA) Using 16S rRNA Gene Clone Libraries Arnett, Clint M.; Rodriguez, Giselle; Maloney, Stephen W. Microbes and Environments, Vol. 24, Issue 1 https://doi.org/10.1264/jsme2.ME08556	journal	January 2009
Reduction of 3-Nitro-1,2,4-Triazol-5-One (NTO) by the Hematite–Aqueous Fe(II) Redox Couple Cárdenas-Hernández, Paula A.; Anderson, Katelyn A.; Murillo-Gelvez, Jimmy Environmental Science & Technology, Vol. 54, Issue 19 https://doi.org/10.1021/acs.est.0c03872	journal	September 2020
Complete Reduction of TNT and Other (Poly)nitroaromatic Compounds under Iron-Reducing Subsurface Conditions Hofstetter, Thomas B.; Heijman, Cornelis G.; Haderlein, Stefan B. Environmental Science & Technology, Vol. 33, Issue 9 https://doi.org/10.1021/es9809760	journal	May 1999
Reactivity of Fe(II)-Bearing Minerals toward Reductive Transformation of Organic Contaminants Elsner, Martin; Schwarzenbach, René P.; Haderlein, Stefan B. Environmental Science & Technology, Vol. 38, Issue 3 https://doi.org/10.1021/es0345569	journal	February 2004
Reduction of Substituted Nitrobenzenes by Fe(II) in Aqueous Mineral Suspensions Klausen, Joerg.; Troeber, Serge P.; Haderlein, Stefan B. Environmental Science & Technology, Vol. 29, Issue 9 https://doi.org/10.1021/es00009a036	journal	September 1995
Covalent binding with model quinone compounds unveils the environmental fate of the insensitive munitions reduced product 2,4-diaminoanisole (DAAN) under anoxic conditions Menezes, Osmar; Kadoya, Warren M.; Gavazza, Savia Journal of Hazardous Materials, Vol. 413 https://doi.org/10.1016/j.jhazmat.2021.125459	journal	July 2021
Enhanced reductive transformation of 2,4-dinitroanisole in a anaerobic system: the key role of zero valent iron Ou, Changjin; Zhang, Shuai; Liu, Jianguo RSC Advances, Vol. 5, Issue 92 https://doi.org/10.1039/C5RA11197H	journal	January 2015
Microbial toxicity of the insensitive munitions compound, 2,4-dinitroanisole (DNAN), and its aromatic amine metabolites Liang, Jidong; Olivares, Christopher; Field, Jim A. Journal of Hazardous Materials, Vol. 262 https://doi.org/10.1016/j.jhazmat.2013.08.046	journal	November 2013
Combined Biotic–Abiotic 2,4-Dinitroanisole Degradation in the Presence of Hexahydro-1,3,5-trinitro-1,3,5-triazine Niedźwiecka, Jolanta B.; McGee, Kameryn; Finneran, Kevin T. Environmental Science & Technology, Vol. 54, Issue 17 https://doi.org/10.1021/acs.est.0c02363	journal	July 2020

Similar Records

NTO decomposition studies

Book · Mon Jul 01 00:00:00 EDT 1996 · OSTI ID:1981571

Oxley, J C; Smith, J L; Yeager, K E; +2 more

Mechanisms and Kinetics of Alkaline Hydrolysis of the Energetic Nitroaromatic Compounds 2,4,6-Trinitrotoluene (TNT) and 2,4-Dinitroanisole (DNAN)

Journal Article · Tue Jul 02 00:00:00 EDT 2013 · Environmental Science and Technology · OSTI ID:1981571

Salter-Blanc, Alexandra J.; Bylaska, Eric J.; Ritchie, Julia J.; +1 more

Free radicals from photolysis of (NTO) 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one studied by EPR spin trapping

Conference · Mon Jul 01 00:00:00 EDT 1996 · OSTI ID:1981571

Pace, M D; Fan, L; Burkey, T J

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
mackinawite
pyrrhotite
troilite
insensitive high explosive
nitroaromatic
nitro-heterocyclic

Title: Iron(II) monosulfide (FeS) minerals reductively transform the insensitive munitions compounds 2,4-dinitroanisole (DNAN) and 3-nitro-1,2,4-triazol-5-one (NTO)

Citation Formats

References (43)

Similar Records

Related Subjects