Reductive biotransformation as a pretreatment to enhance in situ chemical oxidation of nitroaromatic and nitroheterocyclic explosives

Camila L. Madeira, Warren M. Kadoya, Guangbin Li, Stanley Wong, Maria Reye Sierra Alvarez, James A Field

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

In Situ Chemical Oxidation (ISCO) is increasingly being used to remediate a variety of organic contaminants in soil and groundwater. Explosives, such as 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 2,4-dintroanisole (DNAN), and 3-nitro-1,2,4-triazol-5-one (NTO), are not easily oxidized due to the presence of nitro groups in their structures. However, these nitro groups can be reduced to amino groups by soil microorganisms, making them more prone to oxidation. In this study, we propose bioreduction as a pretreatment to ISCO. The oxidation of DNAN, DNT, NTO, and their respective reduced transformation products, 2-methoxy-5-nitroaniline (MENA), 4-amino-2-nitrotoluene (NAT), and 3-amino-1,2,4-triazol-5-one (ATO), by potassium permanganate showed that lower permanganate concentrations and shorter time-scales are needed to oxidize the compounds once they are reduced. Significant fractions of the daughter products were mineralized to CO 2 (30% and 22% for MENA and NAT, respectively, using 2.5 mM permanganate, and 48% for ATO using 1.0 mM permanganate). The bioreductive pretreatment was demonstrated by incubating 1.0 mM NTO anaerobically using soil as inoculum and pyruvate as electron donor. Once NTO was completely reduced to ATO, 1.0 mM permanganate was added, immediately oxidizing 86% of the compound. In controls without pretreatment, no oxidation was observed. NTO and ATO oxidation was tested in soils that differed in organic matter content. The results indicate that natural organic matter decreases the efficiency of NTO oxidation. However, ATO oxidation was not affected by the presence of soil. Our results suggest that the proposed reductive pretreatment followed by ISCO presents a safe and cost-effective alternative for explosives remediation.

Original languageEnglish (US)
Pages (from-to)1025-1032
Number of pages8
JournalChemosphere
Volume222
DOIs
StatePublished - May 1 2019

Fingerprint

biotransformation
Biotransformation
2,4-dinitrotoluene
explosive
Soil
oxidation
Oxidation
4-amino-2-nitrotoluene
Soils
Trinitrotoluene
Potassium Permanganate
Groundwater
Carbon Monoxide
Biological materials
Pyruvic Acid
soil
chemical
in situ
organic matter
trinitrotoluene

Keywords

  • Biotransformation
  • Explosive
  • Insensitive munitions compound
  • ISCO
  • Permanganate

ASJC Scopus subject areas

  • Environmental Engineering
  • Environmental Chemistry
  • Chemistry(all)
  • Pollution
  • Health, Toxicology and Mutagenesis

Cite this

Reductive biotransformation as a pretreatment to enhance in situ chemical oxidation of nitroaromatic and nitroheterocyclic explosives. / Madeira, Camila L.; Kadoya, Warren M.; Li, Guangbin; Wong, Stanley; Sierra Alvarez, Maria Reye; Field, James A.

In: Chemosphere, Vol. 222, 01.05.2019, p. 1025-1032.

Research output: Contribution to journalArticle

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title = "Reductive biotransformation as a pretreatment to enhance in situ chemical oxidation of nitroaromatic and nitroheterocyclic explosives",
abstract = "In Situ Chemical Oxidation (ISCO) is increasingly being used to remediate a variety of organic contaminants in soil and groundwater. Explosives, such as 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 2,4-dintroanisole (DNAN), and 3-nitro-1,2,4-triazol-5-one (NTO), are not easily oxidized due to the presence of nitro groups in their structures. However, these nitro groups can be reduced to amino groups by soil microorganisms, making them more prone to oxidation. In this study, we propose bioreduction as a pretreatment to ISCO. The oxidation of DNAN, DNT, NTO, and their respective reduced transformation products, 2-methoxy-5-nitroaniline (MENA), 4-amino-2-nitrotoluene (NAT), and 3-amino-1,2,4-triazol-5-one (ATO), by potassium permanganate showed that lower permanganate concentrations and shorter time-scales are needed to oxidize the compounds once they are reduced. Significant fractions of the daughter products were mineralized to CO 2 (30{\%} and 22{\%} for MENA and NAT, respectively, using 2.5 mM permanganate, and 48{\%} for ATO using 1.0 mM permanganate). The bioreductive pretreatment was demonstrated by incubating 1.0 mM NTO anaerobically using soil as inoculum and pyruvate as electron donor. Once NTO was completely reduced to ATO, 1.0 mM permanganate was added, immediately oxidizing 86{\%} of the compound. In controls without pretreatment, no oxidation was observed. NTO and ATO oxidation was tested in soils that differed in organic matter content. The results indicate that natural organic matter decreases the efficiency of NTO oxidation. However, ATO oxidation was not affected by the presence of soil. Our results suggest that the proposed reductive pretreatment followed by ISCO presents a safe and cost-effective alternative for explosives remediation.",
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T1 - Reductive biotransformation as a pretreatment to enhance in situ chemical oxidation of nitroaromatic and nitroheterocyclic explosives

AU - Madeira, Camila L.

AU - Kadoya, Warren M.

AU - Li, Guangbin

AU - Wong, Stanley

AU - Sierra Alvarez, Maria Reye

AU - Field, James A

PY - 2019/5/1

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N2 - In Situ Chemical Oxidation (ISCO) is increasingly being used to remediate a variety of organic contaminants in soil and groundwater. Explosives, such as 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 2,4-dintroanisole (DNAN), and 3-nitro-1,2,4-triazol-5-one (NTO), are not easily oxidized due to the presence of nitro groups in their structures. However, these nitro groups can be reduced to amino groups by soil microorganisms, making them more prone to oxidation. In this study, we propose bioreduction as a pretreatment to ISCO. The oxidation of DNAN, DNT, NTO, and their respective reduced transformation products, 2-methoxy-5-nitroaniline (MENA), 4-amino-2-nitrotoluene (NAT), and 3-amino-1,2,4-triazol-5-one (ATO), by potassium permanganate showed that lower permanganate concentrations and shorter time-scales are needed to oxidize the compounds once they are reduced. Significant fractions of the daughter products were mineralized to CO 2 (30% and 22% for MENA and NAT, respectively, using 2.5 mM permanganate, and 48% for ATO using 1.0 mM permanganate). The bioreductive pretreatment was demonstrated by incubating 1.0 mM NTO anaerobically using soil as inoculum and pyruvate as electron donor. Once NTO was completely reduced to ATO, 1.0 mM permanganate was added, immediately oxidizing 86% of the compound. In controls without pretreatment, no oxidation was observed. NTO and ATO oxidation was tested in soils that differed in organic matter content. The results indicate that natural organic matter decreases the efficiency of NTO oxidation. However, ATO oxidation was not affected by the presence of soil. Our results suggest that the proposed reductive pretreatment followed by ISCO presents a safe and cost-effective alternative for explosives remediation.

AB - In Situ Chemical Oxidation (ISCO) is increasingly being used to remediate a variety of organic contaminants in soil and groundwater. Explosives, such as 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 2,4-dintroanisole (DNAN), and 3-nitro-1,2,4-triazol-5-one (NTO), are not easily oxidized due to the presence of nitro groups in their structures. However, these nitro groups can be reduced to amino groups by soil microorganisms, making them more prone to oxidation. In this study, we propose bioreduction as a pretreatment to ISCO. The oxidation of DNAN, DNT, NTO, and their respective reduced transformation products, 2-methoxy-5-nitroaniline (MENA), 4-amino-2-nitrotoluene (NAT), and 3-amino-1,2,4-triazol-5-one (ATO), by potassium permanganate showed that lower permanganate concentrations and shorter time-scales are needed to oxidize the compounds once they are reduced. Significant fractions of the daughter products were mineralized to CO 2 (30% and 22% for MENA and NAT, respectively, using 2.5 mM permanganate, and 48% for ATO using 1.0 mM permanganate). The bioreductive pretreatment was demonstrated by incubating 1.0 mM NTO anaerobically using soil as inoculum and pyruvate as electron donor. Once NTO was completely reduced to ATO, 1.0 mM permanganate was added, immediately oxidizing 86% of the compound. In controls without pretreatment, no oxidation was observed. NTO and ATO oxidation was tested in soils that differed in organic matter content. The results indicate that natural organic matter decreases the efficiency of NTO oxidation. However, ATO oxidation was not affected by the presence of soil. Our results suggest that the proposed reductive pretreatment followed by ISCO presents a safe and cost-effective alternative for explosives remediation.

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KW - Insensitive munitions compound

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