Position-specific isotope effects during alkaline hydrolysis of 2,4-dinitroanisole resolved by compound-specific isotope analysis, 13C NMR, and density-functional theory

Wang, Chunlei; Heraty, Linnea J.; Wallace, Adam F.; Liu, Changjie; Li, Xiaoqiang; McGovern, Gregory P.; Horita, Juske; Fuller, Mark E.; Hatzinger, Paul B.; Sturchio, Neil C.

doi:10.1016/j.chemosphere.2021.130625

Title: Position-specific isotope effects during alkaline hydrolysis of 2,4-dinitroanisole resolved by compound-specific isotope analysis, ¹³C NMR, and density-functional theory

Journal Article · Sat May 01 00:00:00 EDT 2021 · Chemosphere

DOI:https://doi.org/10.1016/j.chemosphere.2021.130625· OSTI ID:1976950

^[1];

^[1]; Wallace, Adam F. ^[1]; Liu, Changjie ^[2]; Li, Xiaoqiang ^[2]; McGovern, Gregory P. ^[3]; Horita, Juske ^[2]; Fuller, Mark E. ^[4]; Hatzinger, Paul B. ^[4];

^[1]

University of Delaware, Newark, DE (United States)
Texas Tech University, Lubbock, TX (United States)
West Texas A & M University, Canyon, TX (United States)
Aptim Federal Services, LLC, Lawrenceville, NJ (United States)

Compound-specific isotope analysis (CSIA), position-specific isotope analysis (PSIA), and computational modeling (e.g., quantum mechanical models; reactive-transport models) are increasingly being used to monitor and predict biotic and abiotic transformations of organic contaminants in the field. However, identifying the isotope effect(s) associated with a specific transformation remains challenging in many cases. We describe and interpret the position-specific isotope effects of C and N associated with a SN₂Ar reaction mechanism by a combination of CSIA and PSIA using quantitative ¹³C nuclear magnetic resonance spectrometry, and density-functional theory, using 2,4-dinitroanisole (DNAN) as a model compound. The position-specific ¹³C enrichment factor of O–C₁ bond at the methoxy group attachment site (ε_C1) was found to be approximately -41‰, a diagnostic value for transformation of DNAN to its reaction products 2,4-dinitrophenol and methanol. Theoretical kinetic isotope effects calculated for DNAN isotopologues agreed well with the position-specific isotope effects measured by CSIA and PSIA. This combination of measurements and theoretical predictions demonstrates a useful tool for evaluating degradation efficiencies and/or mechanisms of organic contaminants and may promote new and improved applications of isotope analysis in laboratory and field investigations.

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Research Organization:: Texas Tech Univ., Lubbock, TX (United States); Univ. of Delaware, Newark, DE (United States)

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

Grant/Contract Number:: SC0016271; SC0018439

OSTI ID:: 1976950

Alternate ID(s):: OSTI ID: 1782009

Journal Information:: Chemosphere, Vol. 280, Issue C; ISSN 0045-6535

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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54 ENVIRONMENTAL SCIENCES
2
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Stable isotopes
13C NMR
density-functional theory

Title: Position-specific isotope effects during alkaline hydrolysis of 2,4-dinitroanisole resolved by compound-specific isotope analysis, 13C NMR, and density-functional theory

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References (43)

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Title: Position-specific isotope effects during alkaline hydrolysis of 2,4-dinitroanisole resolved by compound-specific isotope analysis, ¹³C NMR, and density-functional theory