4.8 Article

Determination of Instinct Components of Biomass on the Generation of Persistent Free Radicals (PFRs) as Critical Redox Sites in Pyrogenic Chars for Persulfate Activation

Journal

ENVIRONMENTAL SCIENCE & TECHNOLOGY
Volume 55, Issue 11, Pages 7690-7701

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.est.1c01882

Keywords

black carbon; in situ chemical oxidation; structure-activity relationship; single-electron transfer; transformation of contaminants

Funding

  1. Australian Research Council (ARC) [FT160100195]
  2. National Natural Science Foundation of China [42007115]
  3. special program of China Postdoctoral Science Foundation [2020T130736]
  4. China Postdoctoral Science Foundation [2019M663245]

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The study investigated the activation of PS on BC derived from various sludges with different organic or inorganic components. Results showed that the properties of SBCs were influenced by the inherent components in the sludges, with higher N-containing content promoting the generation of PFRs and metal content inhibiting this process. A poly-parameter relationship was established to predict the efficiency of PS activation for organic degradation.
Persulfate (PS) activation on biochar (BC) is a promising technology for degrading the aqueous organic contaminants. However, the complexity of activation mechanisms and components in biomass that used to produce BC makes it difficult to predict the performance of PS activation. In this study, we employed eight sludges as the representative biomass that contained absolutely different organic or inorganic components. Results showed that the elemental composition, surface properties, and structures of the sludge-derived BCs (SBCs) clearly depended on the inherent components in the sludges. The intensities of persistent free radicals (PFRs) in the electron paramagnetic resonance (EPR) correlated positively with N-containing content of sludges as electron shuttle, but negatively with the metal content as electron acceptor. Linking with PFRs as crucial sites of triggering a radical reaction, a poly-parameter relationship of predicting PS activation for organic degradation using the sludge components was established (k(obs, PN) = 0.004 x C-protein + 0.16 x C-M(-0.895) -0.118). However, for the PS activation on those SBCs without PFRs, this redox process only relied on the sorption or conductivity-related characteristics, not correlating with the content of intrinsic components in biomass but with pyrolysis temperatures. This study provided insightful information of predicting the remediation efficiency of PS activation on BCs and further understanding the fate of contaminants and stoichiometric efficiency of oxidants in a field application.

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