Common Photo-oxidative Decarboxylation Mechanism in Iron Hydroxy Carboxylate Complexes

Joe-Wong, Claresta; Schaller, Richard D.; Gilbert, Benjamin

doi:10.1021/acs.jpca.3c02656

Title: Common Photo-oxidative Decarboxylation Mechanism in Iron Hydroxy Carboxylate Complexes

Journal Article · Thu Jul 20 00:00:00 EDT 2023 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.3c02656· OSTI ID:2328091

^[1]; Schaller, Richard D. ^[2];

^[1]

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)

Photochemical oxidation of dissolved organic matter is a crucial component of carbon cycling in surface waters. Photo-oxidation of iron(III)-carboxylate complexes is of particular interest because complexation with iron(III) can sensitize this functional group to photodecarboxylation. Further, the photo-oxidation mechanism of ferrioxalate has been extensively characterized, but it is unclear whether the mechanism or timing is similar for other more complex carboxylates. In this study, we use time-resolved infrared spectroscopy to demonstrate that Fe(III)-citrate, an aliphatic carboxylate, and Fe(III)-salicylate, an aromatic carboxylate, follow the same photo-oxidation kinetics as ferrioxalate. Hence the data suggest a common mechanism for decarboxylation of iron hydroxy carbonates. Differences in the CO₂ yield within 50 ps are qualitatively similar to the long-time-scale quantum yield for Fe(II) production.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 2328091

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 127, Issue 30; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (24)

Influence of vegetation on low-molecular-weight carboxylic acids in soil solution—a review Strobel, Bjarne W. Geoderma, Vol. 99, Issue 3-4 https://doi.org/10.1016/S0016-7061(00)00102-6	journal	February 2001
Photolysis of Fe(III) carboxylato complexes: Fe(II) quantum yields and reaction mechanisms Weller, Christian; Horn, Sabrina; Herrmann, Hartmut Journal of Photochemistry and Photobiology A: Chemistry, Vol. 268 https://doi.org/10.1016/j.jphotochem.2013.06.022	journal	September 2013
Sunlight controls water column processing of carbon in arctic fresh waters Cory, R. M.; Ward, C. P.; Crump, B. C. Science, Vol. 345, Issue 6199 https://doi.org/10.1126/science.1253119	journal	August 2014
Photochemical Aging of Guaiacol by Fe(III)–Oxalate Complexes in Atmospheric Aqueous Phase Pang, Hongwei; Zhang, Qi; Wang, Hongli Environmental Science & Technology, Vol. 53, Issue 1 https://doi.org/10.1021/acs.est.8b04507	journal	November 2018
Ligand exchange and fluorescence quenching studies of the fulvic acid-iron interaction Waite, T. David; Morel, Francois M. M. Analytica Chimica Acta, Vol. 162 https://doi.org/10.1016/S0003-2670(00)84247-6	journal	August 1984
Photochemical and spectroscopic studies of complexes, of iron(III) with citric acid and other carboxylic acids Abrahamson, Harmon B.; Rezvani, Ahmad B.; Brushmiller, J. George Inorganica Chimica Acta, Vol. 226, Issue 1-2 https://doi.org/10.1016/0020-1693(94)04077-X	journal	November 1994
Mechanism of Ferric Oxalate Photolysis Mangiante, David. M.; Schaller, Richard D.; Zarzycki, Piotr ACS Earth and Space Chemistry, Vol. 1, Issue 5 https://doi.org/10.1021/acsearthspacechem.7b00026	journal	June 2017
Vibrational spectrum of CO2− in an argon matrix Jacox, Marilyn E.; Milligan, Dolphus E. Chemical Physics Letters, Vol. 28, Issue 2 https://doi.org/10.1016/0009-2614(74)80043-6	journal	September 1974
Photochemical transformation of dissolved organic matter in lakes Bertilsson, Stefan; Tranvik, Lars J. Limnology and Oceanography, Vol. 45, Issue 4 https://doi.org/10.4319/lo.2000.45.4.0753	journal	June 2000
Transient Structures and Kinetics of the Ferrioxalate Redox Reaction Studied by Time-Resolved EXAFS, Optical Spectroscopy, and DFT ^† Chen, Jie; Zhang, Hua; Tomov, Ivan V. The Journal of Physical Chemistry A, Vol. 111, Issue 38 https://doi.org/10.1021/jp0733466	journal	September 2007
Mechanistic insights into iron redox transformations in the presence of natural organic matter: Impact of pH and light Garg, Shikha; Jiang, Chao; David Waite, T. Geochimica et Cosmochimica Acta, Vol. 165 https://doi.org/10.1016/j.gca.2015.05.010	journal	September 2015
Complexation and Redox Buffering of Iron(II) by Dissolved Organic Matter Daugherty, Ellen E.; Gilbert, Benjamin; Nico, Peter S. Environmental Science & Technology, Vol. 51, Issue 19 https://doi.org/10.1021/acs.est.7b03152	journal	September 2017
Factors Influencing Photoreactions of Dissolved Organic Matter in a Coastal River of the Southeastern United States Gao, Huizhen; Zepp, Richard G. Environmental Science & Technology, Vol. 32, Issue 19 https://doi.org/10.1021/es9803660	journal	October 1998
New Trends in the Chemistry of Iron(III) Citrate Complexes: Correlations between X‐ray Structures and Solution Species Probed by Electrospray Mass Spectrometry and Kinetics of Iron Uptake from Citrate by Iron Chelators Gautier‐Luneau, Isabelle; Merle, Claire; Phanon, Delphine Chemistry – A European Journal, Vol. 11, Issue 7 https://doi.org/10.1002/chem.200401087	journal	March 2005
Complete and Partial Photo-oxidation of Dissolved Organic Matter Draining Permafrost Soils Ward, Collin P.; Cory, Rose M. Environmental Science & Technology, Vol. 50, Issue 7 https://doi.org/10.1021/acs.est.5b05354	journal	March 2016
Photochemical degradation of dissolved organic carbon and its impact on the oceanic carbon cycle Mopper, Kenneth; Zhou, Xianliang; Kieber, Robert J. Nature, Vol. 353, Issue 6339 https://doi.org/10.1038/353060a0	journal	September 1991
Photochemical release of humic and fulvic acid-bound metals from simulated soil and streamwater Porcal, Petr; Amirbahman, Aria; Kopáček, Jiří Journal of Environmental Monitoring, Vol. 11, Issue 5 https://doi.org/10.1039/b812330f	journal	January 2009
Molecular investigation of the multi-phase photochemistry of Fe(iii)–citrate in aqueous solution West, Christopher P.; Morales, Ana C.; Ryan, Jackson Environmental Science: Processes & Impacts, Vol. 25, Issue 2 https://doi.org/10.1039/D1EM00503K	journal	January 2023
Infrared spectra of the CO2− and C2O4− anions isolated in solid argon Zhou, Mingfei; Andrews, Lester The Journal of Chemical Physics, Vol. 110, Issue 5 https://doi.org/10.1063/1.477947	journal	February 1999
New Insight into Photochemistry of Ferrioxalate Pozdnyakov, Ivan P.; Kel, Oksana V.; Plyusnin, Victor F. The Journal of Physical Chemistry A, Vol. 112, Issue 36 https://doi.org/10.1021/jp8040583	journal	September 2008
Large Transient Optical Modulation of Epsilon-Near-Zero Colloidal Nanocrystals Diroll, Benjamin T.; Guo, Peijun; Chang, Robert P. H. ACS Nano, Vol. 10, Issue 11 https://doi.org/10.1021/acsnano.6b05116	journal	October 2016
Characterization of Iron(III) in Organic Soils Using Extended X-ray Absorption Fine Structure Spectroscopy Karlsson, Torbjörn; Persson, Per; Skyllberg, Ulf Environmental Science & Technology, Vol. 42, Issue 15 https://doi.org/10.1021/es800322j	journal	August 2008
Photochemistry of aqueous iron(III)-polycarboxylate complexes: roles in the chemistry of atmospheric and surface waters Faust, Bruce C.; Zepp, Richard G. Environmental Science & Technology, Vol. 27, Issue 12 https://doi.org/10.1021/es00048a032	journal	November 1993
Photophysics of Fe(III)–tartrate and Fe(III)–citrate complexes in aqueous solutions Pozdnyakov, Ivan P.; Kolomeets, Alexander V.; Plyusnin, Victor F. Chemical Physics Letters, Vol. 530 https://doi.org/10.1016/j.cplett.2012.01.051	journal	March 2012

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