Abstract

Chromophoric dissolved organic matter (CDOM) is the main photosensitizer in seawater. CDOM can absorb solar radiation extensively and generate reactive intermediates (RIs), including singlet oxygen (1O2), hydroxyl radicals (HO·), and CDOM triplet states (3CDOM*), that are favorable for indirect photodegradation of organic pollutants. In the current study, the effect and mechanism of CDOM components on zinc pyrithione (ZnPT) indirect photodegradation were studied. Among the three CDOM isolates (humic acid (JKHA), Suwannee River humic acid (SRHA), and Suwannee River natural organic matter (SRNOM)), JKHA had the highest fluorescence intensity per gram of carbon and the fastest indirect photodegradation rate for ZnPT. Furthermore, the fluorescent components were divided into four terrestrial humic-like components: C1, C2, C3, and C4, by using excitation–emission matrix spectroscopy combined with parallel factor analysis. A notable relationship was found between the four fluorescent components of CDOM and ZnPT indirect photodegradation. The indirect photodegradation rate of ZnPT varied in different types of CDOM solutions, which may be attributed to the different compositions of CDOM. The relative contents of C1 and C4 were significantly higher in JKHA than in the other two CDOMs, and they were the major contributors to the production of 3CDOM* and 1O2, which promoted ZnPT indirect photodegradation. The impact of seawater factors on ZnPT indirect photodegradation was also investigated. The ZnPT indirect photodegradation rate initially decreased and then increased as the pH increased from 5.00 to 11.00. The lowest rate of indirect photodegradation of ZnPT was observed at pH = 9.00. As the salinity was <25‰, in salinity the ZnPT indirect photodegradation rate increased concomitantly with an increase, and pronounced inhibition of ZnPT indirect photodegradation was observed when the salinity was >25‰. Nitrate had a promoting influence on ZnPT indirect photodegradation, whereas HCO3−, halogen ions, and metal ions all inhibited it.

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