The individual and Co-exposure degradation of benzophenone derivatives by UV/H2O2 and UV/PDS in different water matrices
Graphical abstract
Introduction
To protect humans from the harmful effects of ultraviolet radiation, UV filters are used in a diverse range of personal care products (PCPs), including sunscreens, cosmetics and shampoo (Fent et al., 2010; Jansen et al., 2013). UV filters are used in combinations and can exceed 10% of the product's mass (Brausch and Rand, 2011; Schreurs et al., 2002). Among UV filters, benzophenone derivatives are commonly used due to their high photo/biostability, resulting in their general occurrence in environment media, especially aqueous environments (Brausch and Rand, 2011; Kasprzyk-Hordern et al., 2008; Poiger et al., 2004; Tsui et al., 2017). Due to their endocrine disrupting potential and carcinogenic effects, benzophenone derivatives are considered to the emerging contaminants in recent decades (Schlumpf et al., 2001; Schreurs et al., 2005; Suzuki et al., 2005; Tang et al., 2013). The most detected UV filters families in surface water were benzophenone derivatives with concentrations up to 0.4 mg/L (Kasprzyk-Hordern et al., 2009). Meanwhile, benzophenone-1 (C13H10O3, BP1) and benzophenone-8 (C14H12O4, BP8) in the influent of urban sewage treatment plants have reached maximum concentrations of 245 and 10 ng/L, respectively (Negreira et al., 2009; Wu et al., 2013). Benzophenone-3 (C14H12O3, BP3) has been reported to occur in surface waters in Switzerland, at a concentration range of <2–35 ng/L (Balmer et al., 2005), and in wastewater from China, at concentration ranging from 68 to 722 ng/L (Li et al., 2007). Besides, UV filters were also detected in seawater (Tsui et al., 2017; Manasfi et al., 2017), even in human urine because of dermal exposure (Kunisue et al., 2012; Wang et al., 2013). Hence, an efficient and economical approach to removing these pollutants from aquatic environments is highly needed.
Advanced oxidation processes (AOPs), which can generate reactive species, are becoming increasingly popular technologies for contaminants degradation in water (Oller et al., 2011; Oturan and Aaron, 2014). Radical-based AOPs, in particular those with hydroxyl radical (HO∙) or sulfate radical (SO4∙-), have been successfully applied to decompose micropollutants (Keen and Linden, 2013; Luo et al., 2015, 2017; Nfodzo and Choi, 2011; Yang et al., 2019; Liu et al., 2018). Meanwhile, AOPs were also used in human urine and seawater to obtain the pharmaceuticals removal, toxicity elimination and disinfection (Zhang et al., 2015, 2016b; Rubio et al., 2013). Reports have shown that many micropollutants can react rapidly with HO∙ (108 ≤ k ≤ 1010 M−1 s−1) (Wols and Hofman-Caris, 2012), whereas the reaction rates of PCPs with HO∙ and SO4∙- have not been extensively studied, especially for secondary reactive species (i.e., carbonate radical-CO3∙-). Additionally, one critical issue is that micropollutants, such as PCPs, normally occur in a co-exposure pattern rather than individual existence in aqueous environments. The degradation behaviors of PCPs in co-exposure pattern are likely different from individual pattern using AOPs. However, the specific difference of degradation behaviors and its related factors for triggering are still unknown. Furthermore, constituents in various water matrices make micropollutants degradation even more complex because of conversions of reactive species (Yang et al., 2014; Zhang et al., 2015). To the best of our knowledge, degradation behaviors of multiple PCPs (i.e., UV filters) by AOPs in various aqueous environments have not been investigated.
In this study, the degradation of benzophenone derivatives in both individual and co-exposure patterns by UV/H2O2 and UV/PDS in the presence of different water matrices (surface water, hydrolyzed urine and seawater) was comprehensively investigated. The degradation kinetics were also experimentally and mathematically determined. For the first time, the reaction rate constants of benzophenone derivatives toward HO∙, SO4∙- and CO3∙- were determined, which can largely benefit the future work regarding on the kinetic simulation of radical-based degradation in other water matrices. An energy-cost evaluation (i.e., electrical efficiency per log order (EE/O)) was also conducted to compare the energy cost of UV-based AOPs in different water matrices.
Section snippets
Chemicals and reagents
Sources of chemicals, reagents and synthetic matrices were provided in the Supporting Information Text S1 and Tables S1-S2.
Kinetics of UV filter oxidation by UV/H2O2 and UV/PDS in different water matrices
A semi-collimated beam apparatus (Figure S1) consisting of one 15-W low-pressure mercury lamp above a quartz reactor (6 cm diameter × 5 cm height) was employed for batch studies. Kinetics experiments were conducted at room temperature (25 ± 1 °C) in aqueous solutions, including ultrapure water with phosphate buffer solution (PBS), surface water, hydrolyzed urine and
Direct photolysis
Direct photolysis (UV alone) of individual (BP1, BP3 and BP8 for individual substance, hereafter referred to as BP) and co-exposure (referred to BPs) benzophenone derivatives were studied in ultrapure water with PBS. After 60 min irradiation, the degradation of BP and BPs were not evidently observed (Figure S2), confirms their photo-stability. These results were consistent with previous study, which also did not observe BP3 photo-degradation under UV irradiation (Liu et al., 2011). Meanwhile,
Conclusions
The individual and co-exposure patterns of benzophenone derivatives degradation using UV/H2O2 and UV/PDS were investigated under various water matrices. The following conclusions were obtained:
- (1)
Benzophenone derivatives could be degraded by HO∙, SO4∙- and CO3∙-, and the second-order rate constants were determined (Table 2).
- (2)
In surface water, attack of BP3 by HO∙ and CO3∙- in UV/H2O2 can generate BP8, which was responsible for the relatively high degradation rate of BP3. Intermediates generated
Acknowledgments
This work was supported by the National Natural Science Foundation of China (51478171, and 51778218). The authors appreciate the support from the Brook Byers Institute for Sustainable Systems, Hightower Chair and Georgia Research Alliance at the Georgia Institute of Technology. The views and ideas expressed herein are solely those of the authors and do not represent the ideas of the funding agencies in any form. We also thank ChemWorx for English editing.
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