Photo-production of Reactive Oxygen Species and Degradation of Dissolved Organic Matter by Hematite Nanoplates Functionalized by Adsorbed Oxalate

Huang, Xiaopeng; Zhao, Qian; Young, Robert P.; Zhang, Xin; Walter, Eric D.; Chen, Ying; Nakouzi, Elias; Taylor, Sandra D.; Loring, John S.; Wang, Zheming; Hofmockel, Kirsten S.; Rosso, Kevin M.

doi:10.1039/D0EN00365D

Title: Photo-production of Reactive Oxygen Species and Degradation of Dissolved Organic Matter by Hematite Nanoplates Functionalized by Adsorbed Oxalate

Journal Article · Sat Aug 01 00:00:00 EDT 2020 · Environmental Science: Nano

DOI:https://doi.org/10.1039/D0EN00365D· OSTI ID:1668797

^[1];

^[1]; Zhang, Xin ^[1];

^[1];

^[1]; Nakouzi, Elias ^[1]; Taylor, Sandra D. ^[1]; Loring, John S. ^[1];

^[1];

^[1]

BATTELLE (PACIFIC NW LAB)

The geochemical cycling of iron and carbon can couple in unique ways in the euphotic zone of aquatic systems. For example, the prevalence of hematite nanoparticles and low molecular weight organics that can functionalize their surfaces, such as oxalate, creates a solar- photoactive interfacial system capable of generating reactive oxygen species (ROS) that degrade natural organic matter. Here we report a systematic study of this pathway and its efficiency to mineralize model chromophoric dissolved organic matter (DOM) compounds into CO2 under mildly acidic conditions. When illuminated, synthetic hematite nanoplates coated with adsorbed oxalate undergo ligand-to-metal charge transfer yielding Fe(II) via photoreductive dissolution, while oxalate decomposes into the carboxyl anion radical •CO2- as detected by electron paramagnetic spectroscopy using selective spin trap compounds. This important radical quickly reduces molecular oxygen into hydrogen peroxide, which initiates the canonical Fenton reactions that yield hydroxyl radical via Fe(II)/Fe(III) valence cycling. Production of hydroxyl radical in this photocatalytic system is shown to efficiently degrade the pseudo-DOM chromophore RhB, as well as two natural water-extractable chromophoric DOM compounds from agricultural soils, characterized in molecular detail using Fourier transform ion cyclotron resonance mass spectrometry, nuclear magnetic resonance, infrared and fluorescence spectroscopies. The study highlights the photocatalytic interactions that can occur between common iron oxide nanoparticles, low molecular weight dicarboxylic acids, and dissolved organic matter that can couple their steady-state fluxes in the euphotic zone, pointing to the importance of light-induced ROS generation as a key mechanism.

Cite

Export

Save

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1668797

Report Number(s):: PNNL-SA-148918

Journal Information:: Environmental Science: Nano, Vol. 7, Issue 8

Country of Publication:: United States

Language:: English

References (64)

Natural, incidental, and engineered nanomaterials and their impacts on the Earth system Hochella, Michael F.; Mogk, David W.; Ranville, James Science, Vol. 363, Issue 6434 https://doi.org/10.1126/science.aau8299	journal	March 2019
Nanominerals, Mineral Nanoparticles, and Earth Systems Hochella, M. F.; Lower, S. K.; Maurice, P. A. Science, Vol. 319, Issue 5870 https://doi.org/10.1126/science.1141134	journal	March 2008
Facet-Dependent Cr(VI) Adsorption of Hematite Nanocrystals Huang, Xiaopeng; Hou, Xiaojing; Song, Fahui Environmental Science & Technology, Vol. 50, Issue 4 https://doi.org/10.1021/acs.est.5b05111	journal	January 2016
The interplay of microbially mediated and abiotic reactions in the biogeochemical Fe cycle Melton, Emily D.; Swanner, Elizabeth D.; Behrens, Sebastian Nature Reviews Microbiology, Vol. 12, Issue 12 https://doi.org/10.1038/nrmicro3347	journal	October 2014
Evolution of the nitrogen cycle and its influence on the biological sequestration of CO2 in the ocean Falkowski, Paul G. Nature, Vol. 387, Issue 6630 https://doi.org/10.1038/387272a0	journal	May 1997
Biogeochemical Controls and Feedbacks on Ocean Primary Production Falkowski, P. G. Science, Vol. 281, Issue 5374 https://doi.org/10.1126/science.281.5374.200	journal	July 1998
The Biogeochemical Cycles of Trace Metals in the Oceans Morel, F. M. M. Science, Vol. 300, Issue 5621 https://doi.org/10.1126/science.1083545	journal	May 2003
Biogeochemical Redox Processes and their Impact on Contaminant Dynamics Borch, Thomas; Kretzschmar, Ruben; Kappler, Andreas Environmental Science & Technology, Vol. 44, Issue 1 https://doi.org/10.1021/es9026248	journal	January 2010
Ascorbate-Promoted Surface Iron Cycle for Efficient Heterogeneous Fenton Alachlor Degradation with Hematite Nanocrystals Huang, Xiaopeng; Hou, Xiaojing; Jia, Falong ACS Applied Materials & Interfaces, Vol. 9, Issue 10 https://doi.org/10.1021/acsami.6b16600	journal	March 2017
Hematite facet confined ferrous ions as high efficient Fenton catalysts to degrade organic contaminants by lowering H2O2 decomposition energetic span Huang, Xiaopeng; Hou, Xiaojing; Zhao, Jincai Applied Catalysis B: Environmental, Vol. 181 https://doi.org/10.1016/j.apcatb.2015.06.061	journal	February 2016
Photochemical cycling of iron in the surface ocean mediated by microbial iron(iii)-binding ligands Barbeau, K.; Rue, E. L.; Bruland, K. W. Nature, Vol. 413, Issue 6854 https://doi.org/10.1038/35096545	journal	September 2001
Ascorbate Induced Facet Dependent Reductive Dissolution of Hematite Nanocrystals Huang, Xiaopeng; Hou, Xiaojing; Song, Fahui The Journal of Physical Chemistry C, Vol. 121, Issue 2 https://doi.org/10.1021/acs.jpcc.6b09281	journal	January 2017
A mesoscale phytoplankton bloom in the polar Southern Ocean stimulated by iron fertilization Boyd, Philip W.; Watson, Andrew J.; Law, Cliff S. Nature, Vol. 407, Issue 6805 https://doi.org/10.1038/35037500	journal	October 2000
Deep carbon export from a Southern Ocean iron-fertilized diatom bloom Smetacek, Victor; Klaas, Christine; Strass, Volker H. Nature, Vol. 487, Issue 7407 https://doi.org/10.1038/nature11229	journal	July 2012
Microheterogeneity of Singlet Oxygen Distributions in Irradiated Humic Acid Solutions Latch, D. E. Science, Vol. 311, Issue 5768 https://doi.org/10.1126/science.1121636	journal	March 2006
Molecular characterization of dissolved organic matter (DOM): a critical review Nebbioso, Antonio; Piccolo, Alessandro Analytical and Bioanalytical Chemistry, Vol. 405, Issue 1 https://doi.org/10.1007/s00216-012-6363-2	journal	September 2012
CHEMISTRY: Enhanced: Dissolved Natural Organic Matter as a Microreactor Hassett, J. P. Science, Vol. 311, Issue 5768 https://doi.org/10.1126/science.1123389	journal	March 2006
Heterogeneous Photodegradation of Pentachlorophenol with Maghemite and Oxalate under UV Illumination Lan, Qing; Li, Fangbai; Liu, Chengshuai Environmental Science & Technology, Vol. 42, Issue 21 https://doi.org/10.1021/es801220n	journal	November 2008
Heterogeneous photodegradation of pentachlorophenol and iron cycling with goethite, hematite and oxalate under UVA illumination Lan, Qing; Li, Fang-bai; Sun, Cui-xiang Journal of Hazardous Materials, Vol. 174, Issue 1-3 https://doi.org/10.1016/j.jhazmat.2009.09.017	journal	February 2010
The critical role of the surface iron-oxalate complexing species in determining photochemical degradation of norfloxacin using different iron oxides Huang, Mingjie; Xiang, Wei; Zhou, Tao Science of The Total Environment, Vol. 697 https://doi.org/10.1016/j.scitotenv.2019.134220	journal	December 2019
Atrazine Degradation in Irradiated Iron/Oxalate Systems: Effects of pH and Oxalate Balmer, Marianne E.; Sulzberger, Barbara Environmental Science & Technology, Vol. 33, Issue 14 https://doi.org/10.1021/es9808705	journal	July 1999
Evidence for redox cycling of iron in atmospheric water droplets Behra, Philippe; Sigg, Laura Nature, Vol. 344, Issue 6265 https://doi.org/10.1038/344419a0	journal	March 1990
Photochemical Cycling of Iron Mediated by Dicarboxylates: Special Effect of Malonate Wang, Zhaohui; Chen, Xi; Ji, Hongwei Environmental Science & Technology, Vol. 44, Issue 1 https://doi.org/10.1021/es901956x	journal	January 2010
Iron Redox Cycling in Surface Waters: Effects of Humic Substances and Light Voelker, Bettina M.; Morel, François M. M.; Sulzberger, Barbara Environmental Science & Technology, Vol. 31, Issue 4 https://doi.org/10.1021/es9604018	journal	April 1997
Chemical characterization of dissolved organic matter (DOM): A prerequisite for understanding UV-induced changes of DOM absorption properties and bioavailability Sulzberger, Barbara; Durisch-Kaiser, Edith Aquatic Sciences, Vol. 71, Issue 2 https://doi.org/10.1007/s00027-008-8082-5	journal	March 2009
Hydroxyl Radical Photoproduction in the Sea and Its Potential Impact on Marine Processes Mopper, K.; Zhou, X. Science, Vol. 250, Issue 4981 https://doi.org/10.1126/science.250.4981.661	journal	November 1990
Facet-Specific Photocatalytic Degradation of Organics by Heterogeneous Fenton Chemistry on Hematite Nanoparticles Huang, Xiaopeng; Chen, Ying; Walter, Eric Environmental Science & Technology, Vol. 53, Issue 17 https://doi.org/10.1021/acs.est.9b02946	journal	August 2019
Continuous Shape- and Spectroscopy-Tuning of Hematite Nanocrystals Chen, Liqiao; Yang, Xianfeng; Chen, Jian Inorganic Chemistry, Vol. 49, Issue 18 https://doi.org/10.1021/ic100919a	journal	September 2010
Improved WATERGATE Pulse Sequences for Solvent Suppression in NMR Spectroscopy Liu, Maili; Mao, Xi-an; Ye, Chaohui Journal of Magnetic Resonance, Vol. 132, Issue 1 https://doi.org/10.1006/jmre.1998.1405	journal	May 1998
Highly Mobile Iron Pool from a Dissolution−Readsorption Process Loring, John S.; Simanova, Anna A.; Persson, Per Langmuir, Vol. 24, Issue 14 https://doi.org/10.1021/la800785u	journal	July 2008
Adsorption of oxalate and malonate at the water-goethite interface: Molecular surface speciation from IR spectroscopy Persson, Per; Axe, Kristina Geochimica et Cosmochimica Acta, Vol. 69, Issue 3 https://doi.org/10.1016/j.gca.2004.07.009	journal	February 2005
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
Mechanisms of dissolution of iron oxides in aqueous oxalic acid solutions Panias, D.; Taxiarchou, M.; Paspaliaris, I. Hydrometallurgy, Vol. 42, Issue 2 https://doi.org/10.1016/0304-386X(95)00104-O	journal	September 1996
Dissolution of hematite in acidic oxalate solutions: the effect of ferrous ions addition Panias, D.; Taxiarchou, M.; Douni, I. Hydrometallurgy, Vol. 43, Issue 1-3 https://doi.org/10.1016/0304-386X(96)00004-7	journal	November 1996
Hydroxylamine Promoted Goethite Surface Fenton Degradation of Organic Pollutants Hou, Xiaojing; Huang, Xiaopeng; Jia, Falong Environmental Science & Technology, Vol. 51, Issue 9 https://doi.org/10.1021/acs.est.6b05906	journal	April 2017
Nanostructured hematite: synthesis, characterization, charge carrier dynamics, and photoelectrochemical properties Wheeler, Damon A.; Wang, Gongming; Ling, Yichuan Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee00001f	journal	January 2012
Facile synthesis of carbon-coated hematite nanostructures for solar water splitting Deng, Jiujun; Lv, Xiaoxin; Gao, Jing Energy & Environmental Science, Vol. 6, Issue 6 https://doi.org/10.1039/c3ee00066d	journal	January 2013
Intermediate free radicals in the oxidation of wastewaters Bianchini, Roberto; Calucci, Lucia; Lubello, Claudio Research on Chemical Intermediates, Vol. 28, Issue 2-3 https://doi.org/10.1163/156856702320267154	journal	April 2002
Theoretical and Experimental Studies of the Spin Trapping of Inorganic Radicals by 5,5-Dimethyl-1-Pyrroline N -Oxide (DMPO). 1. Carbon Dioxide Radical Anion Villamena, Frederick A.; Locigno, Edward J.; Rockenbauer, Antal The Journal of Physical Chemistry A, Vol. 110, Issue 49 https://doi.org/10.1021/jp064892m	journal	December 2006
Analysis of the oxidant in photooxidation reactions Cohen, Israel R.; Purcell, Thomas C.; Altshuller, Aubrey P. Environmental Science & Technology, Vol. 1, Issue 3 https://doi.org/10.1021/es60003a006	journal	March 1967
Iron(III) Catalyzed Photochemical Reduction of Chromium(VI) by Oxalate and Citrate in Aqueous Solutions Hug, Stephan J.; Laubscher, Hans-Ulrich; James, Bruce R. Environmental Science & Technology, Vol. 31, Issue 1 https://doi.org/10.1021/es960253l	journal	January 1997
Reduction potential of the carboxyl radical anion in aqueous solutions Surdhar, Parminder S.; Mezyk, Stephen P.; Armstrong, David A. The Journal of Physical Chemistry, Vol. 93, Issue 8 https://doi.org/10.1021/j100345a094	journal	April 1989
Yield of Carboxyl Anion Radicals in the Photocatalytic Degradation of Formate over TiO ₂ Particles Perissinotti, Laura L.; Brusa, Marta A.; Grela, María A. Langmuir, Vol. 17, Issue 26 https://doi.org/10.1021/la0155348	journal	December 2001
Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications Warren, Jeffrey J.; Tronic, Tristan A.; Mayer, James M. Chemical Reviews, Vol. 110, Issue 12 https://doi.org/10.1021/cr100085k	journal	December 2010
Role of Proton-Coupled Electron Transfer in O–O Bond Activation Rosenthal, Joel; Nocera, Daniel G. Accounts of Chemical Research, Vol. 40, Issue 7 https://doi.org/10.1021/ar7000638	journal	July 2007
Formation of hydrogen peroxide and depletion of oxalic acid in atmospheric water by photolysis of iron(III)-oxalato complexes Zuo, Yuegang; Hoigne, Juerg Environmental Science & Technology, Vol. 26, Issue 5 https://doi.org/10.1021/es00029a022	journal	May 1992
Evidence for Photochemical Formation of H2O2 and Oxidation of SO2 in Authentic Fog Water Zuo, Y.; Hoigne, J. Science, Vol. 260, Issue 5104 https://doi.org/10.1126/science.260.5104.71	journal	April 1993
On some fundamental reactions in radiation chemistry: Nanosecond pulse radiolysis Ilan, Yael; Rabani, Joseph International Journal for Radiation Physics and Chemistry, Vol. 8, Issue 5 https://doi.org/10.1016/0020-7055(76)90030-9	journal	January 1976
An in vivo ESR spin-trapping study: Free radical generation in rats from formate intoxication-- role of the Fenton reaction Dikalova, A. E.; Kadiiska, M. B.; Mason, R. P. Proceedings of the National Academy of Sciences, Vol. 98, Issue 24 https://doi.org/10.1073/pnas.251091098	journal	November 2001
Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O ⁻ in Aqueous Solution Buxton, George V.; Greenstock, Clive L.; Helman, W. Phillips Journal of Physical and Chemical Reference Data, Vol. 17, Issue 2 https://doi.org/10.1063/1.555805	journal	April 1988
What happens to terrestrial organic matter in the ocean? Hedges, J. I.; Keil, R. G.; Benner, R. Organic Geochemistry, Vol. 27, Issue 5-6 https://doi.org/10.1016/S0146-6380(97)00066-1	journal	November 1997
Spatial distribution of riverine DOC inputs to the ocean: an updated global synthesis Dai, Minhan; Yin, Zhiqiang; Meng, Feifei Current Opinion in Environmental Sustainability, Vol. 4, Issue 2 https://doi.org/10.1016/j.cosust.2012.03.003	journal	May 2012
Molecular Signatures of Biogeochemical Transformations in Dissolved Organic Matter from Ten World Rivers Riedel, Thomas; Zark, Maren; Vähätalo, Anssi V. Frontiers in Earth Science, Vol. 4 https://doi.org/10.3389/feart.2016.00085	journal	September 2016
Changes in the compound classes of dissolved organic matter along an estuarine transect: A study using FTIR and 13C NMR Abdulla, Hussain A. N.; Minor, Elizabeth C.; Dias, Robert F. Geochimica et Cosmochimica Acta, Vol. 74, Issue 13 https://doi.org/10.1016/j.gca.2010.04.006	journal	July 2010
HPLC-SEC-FTIR characterization of the dissolved organic matter produced by the microbial carbon pump Daoud, Abdou Ben Ali; Tremblay, Luc Marine Chemistry, Vol. 215 https://doi.org/10.1016/j.marchem.2019.103668	journal	September 2019
Fluorescence analysis of dissolved organic matter in natural, waste and polluted waters—a review Hudson, Naomi; Baker, Andy; Reynolds, Darren River Research and Applications, Vol. 23, Issue 6 https://doi.org/10.1002/rra.1005	journal	January 2007
High-field NMR spectroscopy and FTICR mass spectrometry: powerful discovery tools for the molecular level characterization of marine dissolved organic matter Hertkorn, N.; Harir, M.; Koch, B. P. Biogeosciences, Vol. 10, Issue 3 https://doi.org/10.5194/bg-10-1583-2013	journal	January 2013
Proposed Guidelines for Solid Phase Extraction of Suwannee River Dissolved Organic Matter Li, Yan; Harir, Mourad; Lucio, Marianna Analytical Chemistry, Vol. 88, Issue 13 https://doi.org/10.1021/acs.analchem.5b04501	journal	June 2016
Major Structural Components in Freshwater Dissolved Organic Matter Lam, Buuan; Baer, Andrew; Alaee, Mehran Environmental Science & Technology, Vol. 41, Issue 24 https://doi.org/10.1021/es0713072	journal	December 2007
Characterization of a major refractory component of marine dissolved organic matter Hertkorn, Norbert; Benner, Ronald; Frommberger, Moritz Geochimica et Cosmochimica Acta, Vol. 70, Issue 12 https://doi.org/10.1016/j.gca.2006.03.021	journal	June 2006
Oxidized sterols as a significant component of dissolved organic matter: Evidence from 2D HPLC in combination with 2D and 3D NMR spectroscopy Woods, Gwen C.; Simpson, Myrna J.; Simpson, André J. Water Research, Vol. 46, Issue 10 https://doi.org/10.1016/j.watres.2012.03.040	journal	June 2012
Organic acids in the rhizosphere – a critical review Jones, David L. Plant and Soil, Vol. 205, Issue 1, p. 25-44 https://doi.org/10.1023/A:1004356007312	journal	August 1998
Iron Dissolution of Dust Source Materials during Simulated Acidic Processing: The Effect of Sulfuric, Acetic, and Oxalic Acids Chen, Haihan; Grassian, Vicki H. Environmental Science & Technology https://doi.org/10.1021/es401285s	journal	August 2013
Quantitative Relationships Between soil Color and Hematite Content Torrent, J.; Schwertmann, U.; Fechter, H. Soil Science, Vol. 136, Issue 6 https://doi.org/10.1097/00010694-198312000-00004	journal	January 1983

Similar Records

Photolysis of Dissolved Organic Matter over Hematite Nanoplatelets

Journal Article · Wed Jan 31 00:00:00 EST 2024 · Environmental Science and Technology · OSTI ID:1668797

Huang, Xiaopeng; Song, Duo; Zhao, Qian; +10 more

Facet-Dependent Photodegradation of Methylene Blue by Hematite Nanoplates in Visible Light

Journal Article · Tue Jan 05 00:00:00 EST 2021 · Environmental Science & Technology · OSTI ID:1668797

Zong, Meirong; Song, Duo; Zhang, Xin; +3 more

Photocatalyzed electron exchange between organic chromophores and hematite nanoparticles and the role of solid-state charge transport

Journal Article · Mon Oct 03 00:00:00 EDT 2022 · Environmental Science: Nano · OSTI ID:1668797

Boamah, Mavis D.; Huang, Xiaopeng; Joly, Alan; +2 more

Title: Photo-production of Reactive Oxygen Species and Degradation of Dissolved Organic Matter by Hematite Nanoplates Functionalized by Adsorbed Oxalate

Citation Formats

References (64)

Similar Records

Related Subjects