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Citation
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HERO ID
2849945
Reference Type
Journal Article
Title
Investigation of humic substance photosensitized reactions via carbon and hydrogen isotope fractionation
Author(s)
Zhang, N; Schindelka, J; Herrmann, H; George, C; Rosell, M; Herrero-Martín, S; Klán, P; Richnow, HH
Year
2015
Is Peer Reviewed?
1
Journal
Environmental Science & Technology
ISSN:
0013-936X
EISSN:
1520-5851
Volume
49
Issue
1
Page Numbers
233-242
Language
English
PMID
25427194
DOI
10.1021/es502791f
Web of Science Id
WOS:000347589300026
Abstract
Humic substances (HS) acting as photosensitizers can generate a variety of reactive species, such as OH radicals and excited triplet states ((3)HS*), promoting the degradation of organic compounds. Here, we apply compound-specific stable isotope analysis (CSIA) to characterize photosensitized mechanisms employing fuel oxygenates, such as methyl tert-butyl ether (MTBE) and ethyl tert-butyl ether (ETBE), as probes. In oxygenated aqueous media, Λ (Δδ(2)H/Δδ(13)C) values of 23 ± 3 and 21 ± 3 for ETBE obtained by photosensitization by Pahokee Peat Humic Acid (PPHA) and Suwannee River Fulvic Acid (SRFA), respectively, were in the range typical for H-abstraction by OH radicals generated by photolysis of H2O2 (Λ = 24 ± 2). However, (3)HS* may become a predominant reactive species upon the quenching of OH radicals (Λ = 14 ± 1), and this process can also play a key role in the degradation of ETBE by PPHA photosensitization in deoxygenated media (Λ = 11 ± 1). This is in agreement with a model photosensitization by rose bengal (RB(2-)) in deoxygenated aqueous solutions resulting in one-electron oxidation of ETBE (Λ = 14 ± 1). Our results demonstrate that the use of CSIA could open new avenues for the assessment of photosensitization pathways.
Tags
IRIS
•
ETBE
Combined Dataset (After duplicates removed electronically)
Excluded / Not on Topic
Biodegradation/environmental fate
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