TY - JOUR
T1 - Electron exchange capacity of pyrogenic dissolved organic matter (pyDOM)
T2 - complementarity of square-wave voltammetry in DMSO and mediated chronoamperometry in water
AU - Cao, Han
AU - Pavitt, Ania S.
AU - Hudson, Jeffrey M.
AU - Tratnyek, Paul G.
AU - Xu, Wenqing
N1 - Publisher Copyright:
© 2023 The Royal Society of Chemistry.
PY - 2023/3/9
Y1 - 2023/3/9
N2 - Pyrogenic dissolved organic matter (pyDOM) is derived from black carbon, which is important in the global carbon cycle and other biogeochemical redox processes. The electron-exchange capacity (EEC) of pyDOM has been characterized in water using mediated chronoamperometry (MCA), which gives precise results under specific operational conditions, but the broader significance of these EECs is less clear. In this study, we described a novel but complementary electrochemical approach to quantify EECs of pyDOM without mediation using square-wave voltammetry (SWV) in dimethyl sulfoxide (DMSO). Using both the SWV and MCA methods, we determined EECs for 10 pyDOMs, 6 natural organic matter (NOM) samples, and 2 model quinones. The two methods gave similar EECs for model quinones, but SWV gave larger EECs than MCA for NOM and pyDOM (by several-fold and 1-2 orders of magnitude, respectively). The differences in the EECs obtained by SWV and MCA likely are due to multiple factors, including the potential range of electrons sampled, kinetics of electron transfer from (macro)molecular structures, and coupling of electron and proton transfer steps. Comparison of the results obtained by these two methods should provide new insights into important environmental processes such as carbon-cycling, wildfire recovery, and contaminant mitigation using carbon-based amendments.
AB - Pyrogenic dissolved organic matter (pyDOM) is derived from black carbon, which is important in the global carbon cycle and other biogeochemical redox processes. The electron-exchange capacity (EEC) of pyDOM has been characterized in water using mediated chronoamperometry (MCA), which gives precise results under specific operational conditions, but the broader significance of these EECs is less clear. In this study, we described a novel but complementary electrochemical approach to quantify EECs of pyDOM without mediation using square-wave voltammetry (SWV) in dimethyl sulfoxide (DMSO). Using both the SWV and MCA methods, we determined EECs for 10 pyDOMs, 6 natural organic matter (NOM) samples, and 2 model quinones. The two methods gave similar EECs for model quinones, but SWV gave larger EECs than MCA for NOM and pyDOM (by several-fold and 1-2 orders of magnitude, respectively). The differences in the EECs obtained by SWV and MCA likely are due to multiple factors, including the potential range of electrons sampled, kinetics of electron transfer from (macro)molecular structures, and coupling of electron and proton transfer steps. Comparison of the results obtained by these two methods should provide new insights into important environmental processes such as carbon-cycling, wildfire recovery, and contaminant mitigation using carbon-based amendments.
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U2 - 10.1039/d3em00009e
DO - 10.1039/d3em00009e
M3 - Article
C2 - 36891820
AN - SCOPUS:85150183665
SN - 2050-7887
VL - 25
SP - 767
EP - 780
JO - Environmental Science: Processes and Impacts
JF - Environmental Science: Processes and Impacts
IS - 4
ER -