Triplet Photochemistry of Dissolved Black Carbon and Its Effects on the Photochemical Formation of Reactive Oxygen Species

Abstract

Dissolved black carbon (DBC) is an important component of dissolved organic matter pool; however, its photochemical properties are not fully understood. In this study, we determined the excited triplet-state quantum yields of DBC (³DBC*) and ¹O₂ quantum yields (Φ_¹O₂) of six diverse DBCs using sorbic alcohol, 2,4,6-trimethylphenol (TMP), and furfuryl alcohol and compared the results with quantum yields of reference natural organic matters (NOMs). The average Φ_¹O₂ of six DBCs (4.2 ± 1.5%) was greater than that of terrestrial NOM (2.4 ± 0.3%) and comparable to autochthonous NOM (5.3 ± 0.2%). Using TMP as a probe for oxidizing triplets, DBC presented significantly higher apparent quantum yield coefficients for degrading TMP (<i>f</i>_TMP) than the reference NOM, reflecting that the <i>f</i>_TMP values of low-energy ³DBC* were approximately 12-fold greater than those of low-energy ³NOM*. The differences in the <i>f</i>_TMP and Φ_¹O₂ trends among the DBCs indicated that the ³DBC* responsible for these reactions may be from different sources. In addition, DBC was much more effective than NOM, on a carbon-normalized basis, during photodegradation of pharmaceutically active compounds. This result confirms that the presence of DBC can accelerate the photodegradation of contaminants that are susceptible to one-electron oxidation by triplets.