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C & N isotope analysis of diclofenac to distinguish oxidative and reductive transformation and to track commercial products

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Abstract
Although diclofenac is frequently found in aquatic systems, its degradability in the environment remains imperfectly understood. On the one hand, evidence from concentration analysis alone is inconclusive if an unknown hydrology impedes a distinction between degradation and dilution. On the other hand, not all transformation products may be detectable. As a new approach, we therefore developed GC-IRMS (gas chromatography-isotope-ratio mass-spectrometry) analysis for carbon and nitrogen isotope measurements of diclofenac. The method uses a derivatization step that can be conducted either online or offline, for optimized throughput or sensitivity, respectively. In combination with on-column injection, the latter method enables determination of diclofenac isotope ratios down to the sub-mu gL(-1) range in environmental samples. Degradation in an aerobic sediment-water system showed strong nitrogen isotope fractionation (epsilon(N) = -7.1 parts per thousand), whereas reductive diclofenac dechlorination was associated with significant carbon isotope fractionation (epsilon(C) = -2.0 parts per thousand). Hence dual element isotope analysis bears potential not only to detect diclofenac degradation, but even to distinguish both transformation pathways in the environment. In an explorative survey, analysis of commercial diclofenac products showed significant differences in carbon and nitrogen isotope ratios, demonstrating a further potential to track, and potentially even to authenticate, commercial production batches.
Keywords
MASS-SPECTROMETRY, ACIDIC PHARMACEUTICALS, DRUG DICLOFENAC, WASTE-WATER, FRACTIONATION, BIODEGRADATION, DEGRADATION, PATHWAYS, RIVER, PHARMACEUTICAL RESIDUES

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MLA
Maier, Michael P., et al. “C & N Isotope Analysis of Diclofenac to Distinguish Oxidative and Reductive Transformation and to Track Commercial Products.” ENVIRONMENTAL SCIENCE & TECHNOLOGY, vol. 48, no. 4, 2014, pp. 2312–20, doi:10.1021/es403214z.
APA
Maier, M. P., De Corte, S., Nitsche, S., Spaett, T., Boon, N., & Elsner, M. (2014). C & N isotope analysis of diclofenac to distinguish oxidative and reductive transformation and to track commercial products. ENVIRONMENTAL SCIENCE & TECHNOLOGY, 48(4), 2312–2320. https://doi.org/10.1021/es403214z
Chicago author-date
Maier, Michael P, Simon De Corte, Sebastian Nitsche, Thomas Spaett, Nico Boon, and Martin Elsner. 2014. “C & N Isotope Analysis of Diclofenac to Distinguish Oxidative and Reductive Transformation and to Track Commercial Products.” ENVIRONMENTAL SCIENCE & TECHNOLOGY 48 (4): 2312–20. https://doi.org/10.1021/es403214z.
Chicago author-date (all authors)
Maier, Michael P, Simon De Corte, Sebastian Nitsche, Thomas Spaett, Nico Boon, and Martin Elsner. 2014. “C & N Isotope Analysis of Diclofenac to Distinguish Oxidative and Reductive Transformation and to Track Commercial Products.” ENVIRONMENTAL SCIENCE & TECHNOLOGY 48 (4): 2312–2320. doi:10.1021/es403214z.
Vancouver
1.
Maier MP, De Corte S, Nitsche S, Spaett T, Boon N, Elsner M. C & N isotope analysis of diclofenac to distinguish oxidative and reductive transformation and to track commercial products. ENVIRONMENTAL SCIENCE & TECHNOLOGY. 2014;48(4):2312–20.
IEEE
[1]
M. P. Maier, S. De Corte, S. Nitsche, T. Spaett, N. Boon, and M. Elsner, “C & N isotope analysis of diclofenac to distinguish oxidative and reductive transformation and to track commercial products,” ENVIRONMENTAL SCIENCE & TECHNOLOGY, vol. 48, no. 4, pp. 2312–2320, 2014.
@article{4345453,
  abstract     = {{Although diclofenac is frequently found in aquatic systems, its degradability in the environment remains imperfectly understood. On the one hand, evidence from concentration analysis alone is inconclusive if an unknown hydrology impedes a distinction between degradation and dilution. On the other hand, not all transformation products may be detectable. As a new approach, we therefore developed GC-IRMS (gas chromatography-isotope-ratio mass-spectrometry) analysis for carbon and nitrogen isotope measurements of diclofenac. The method uses a derivatization step that can be conducted either online or offline, for optimized throughput or sensitivity, respectively. In combination with on-column injection, the latter method enables determination of diclofenac isotope ratios down to the sub-mu gL(-1) range in environmental samples. Degradation in an aerobic sediment-water system showed strong nitrogen isotope fractionation (epsilon(N) = -7.1 parts per thousand), whereas reductive diclofenac dechlorination was associated with significant carbon isotope fractionation (epsilon(C) = -2.0 parts per thousand). Hence dual element isotope analysis bears potential not only to detect diclofenac degradation, but even to distinguish both transformation pathways in the environment. In an explorative survey, analysis of commercial diclofenac products showed significant differences in carbon and nitrogen isotope ratios, demonstrating a further potential to track, and potentially even to authenticate, commercial production batches.}},
  author       = {{Maier, Michael P and De Corte, Simon and Nitsche, Sebastian and Spaett, Thomas and Boon, Nico and Elsner, Martin}},
  issn         = {{0013-936X}},
  journal      = {{ENVIRONMENTAL SCIENCE & TECHNOLOGY}},
  keywords     = {{MASS-SPECTROMETRY,ACIDIC PHARMACEUTICALS,DRUG DICLOFENAC,WASTE-WATER,FRACTIONATION,BIODEGRADATION,DEGRADATION,PATHWAYS,RIVER,PHARMACEUTICAL RESIDUES}},
  language     = {{eng}},
  number       = {{4}},
  pages        = {{2312--2320}},
  title        = {{C & N isotope analysis of diclofenac to distinguish oxidative and reductive transformation and to track commercial products}},
  url          = {{http://doi.org/10.1021/es403214z}},
  volume       = {{48}},
  year         = {{2014}},
}

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