Details zur Publikation
Kategorie Textpublikation
Referenztyp Zeitschriften
DOI 10.1016/j.watres.2024.122956
Lizenz creative commons licence
Titel (primär) Carbon, hydrogen, nitrogen and chlorine isotope fractionation during 3-chloroaniline transformation in aqueous environments by direct photolysis, TiO2 photocatalysis and hydrolysis
Autor Min, N.; Yao, J.; Li, H.; Kümmel, S. ORCID logo ; Schaefer, T.; Herrmann, H.; Richnow, H.H.
Quelle Water Research
Erscheinungsjahr 2025
Department TECH
Band/Volume 273
Seite von art. 122956
Sprache englisch
Topic T7 Bioeconomy
Supplements https://ars.els-cdn.com/content/image/1-s2.0-S0043135424018566-mmc1.docx
Keywords 3-Chloroaniline; Compound-specific isotope analysis; Multi-element isotope fractionation; Degradation pathways; Photolysis; Hydrolysis
UFZ Querschnittsthemen ProVIS;
Abstract This study investigates carbon, hydrogen, nitrogen and chlorine isotope fractionation during the transformation of 3-chloroaniline (3-CA) via direct photolysis, TiO2 photocatalytic degradation at neutral condition and hydrolysis at pH 3, pH 7 and pH 11. Direct photolysis and ∙OH reaction (UV/H2O2) showed similar inverse isotope fractionation (ε) for carbon (1.9 ± 0.4 ‰ and 1.9 ± 0.6 ‰), for hydrogen (6.9 ± 1.6 ‰ and 5.0 ± 2.6 ‰), and inverse chlorine (13.9 ± 3.8 ‰ and 11.9 ± 2.9 ‰) and no nitrogen isotope fractionation, respectively. In contrast, significantly different normal carbon (-0.5 ± 0.1 ‰), inverse hydrogen (6.6 ± 1.5 ‰), and normal nitrogen (-0.8 ± 0.2 ‰) and inverse chlorine (5.2 ± 3.7 ‰) isotope fractionations were observed for the photocatalysis of 3-CA by TiO2 indicating a different degradation pathway as expected from ∙OH. For hydrolysis, inverse carbon (0.7 ± 0.3 ‰) and hydrogen (12.5 ± 3.3 ‰) isotope fractionation have been found at pH 3 while a normal carbon isotope fractionation was observed at pH 7 (-0.9 ± 0.3 ‰) and pH 11 (-1.3 ± 0.4 ‰), respectively. The correlation of 2H and 13C, 15N and 13C, and 37Cl and 13C isotope fractionation (Λ) allowed to distinguish direct photodegradation (ΛHsingle bondC = -4.6 ± 1.7 (ΛHsingle bondC-YORK=-5.2 ± 1.0) and ΛCl-C = 8.7 ± 0.9 (ΛCl-C-YORK=8.0 ± 0.3)), UV/H2O2 oxidation (ΛHsingle bondC = -4.7 ± 1.0 (ΛHsingle bondC-YORK=-4.5 ± 0.6) and ΛCl-C = 6.7 ± 0.8 (ΛCl-C-YORK=7.0 ± 1.0)), UV/TiO2 photocatalysis (ΛHsingle bondC = -9.2 ± 3.1 (ΛHsingle bondC-YORK=-9.3 ± 1.4), ΛCl-C = -10.2 ± 1.5 (ΛCl-C-YORK=-12.4 ± 1.7) and ΛNsingle bondC -2.2 ± 0.3 (ΛNsingle bondC-YORK=-2.3 ± 0.4)) and the modes of hydrolysis (ΛHsingle bondC = 15.2 ± 5.3 (ΛHsingle bondC-YORK=17.9 ± 2.9) and ΛCl-C = 0.9 ± 0.2 (ΛCl-C-YORK=1.1 ± 0.1) at pH 3) of 3-CA. The results were mechanistically interpreted highlighting the potential of CSIA to elucidate chemical oxidation and hydrolysis mechanisms of 3-CA.
dauerhafte UFZ-Verlinkung https://www.ufz.de/index.php?en=20939&ufzPublicationIdentifier=30203
Min, N., Yao, J., Li, H., Kümmel, S., Schaefer, T., Herrmann, H., Richnow, H.H. (2025):
Carbon, hydrogen, nitrogen and chlorine isotope fractionation during 3-chloroaniline transformation in aqueous environments by direct photolysis, TiO2 photocatalysis and hydrolysis
Water Res. 273 , art. 122956 10.1016/j.watres.2024.122956