Application of dual carbon-bromine isotope analysis for investigating abiotic transformations of tribromoneopentyl alcohol (TBNPA).
Many of polybrominated organic compounds, used as flame retardant additives, belong to the group of persistent organic pollutants. Compound-specific isotope analysis is one of the potential analytical tools for investigating their fate in the environment. However, the isotope effects associated with transformations of brominated organic compounds are still poorly explored. In the present study, we investigated carbon and bromine isotope fractionation during degradation of tribromoneopentyl alcohol (TBNPA), one of the widely used flame retardant additives, in three different chemical processes: transformation in aqueous alkaline solution (pH 8); reductive dehalogenation by zero-valent iron nanoparticles (nZVI) in anoxic conditions; oxidative degradation by H2O2 in the presence of CuO nanoparticles (nCuO). Two-dimensional carbon-bromine isotope plots (δ(13)C/Δ(81)Br) for each reaction gave different process-dependent isotope slopes (Λ(C/Br)): 25.2 ± 2.5 for alkaline hydrolysis (pH 8); 3.8 ± 0.5 for debromination in the presence of nZVI in anoxic conditions; ∞ in the case of catalytic oxidation by H2O2 with nCuO. The obtained isotope effects for both elements were generally in agreement with the values expected for the suggested reaction mechanisms. The results of the present study support further applications of dual carbon-bromine isotope analysis as a tool for identification of reaction pathway during transformations of brominated organic compounds in the environment.
†Geological Survey of Israel, 30 Malhei Israel Street, Jerusalem 95501, Israel.|‡Department of Chemistry, The Hebrew University, Jerusalem 91904, Israel.
Anna
A
Kozell
§Department of Earth and Planetary Sciences, Weizmann Institute of Science, Rehovot 7610001, Israel.
Yinon
Y
Yecheskel
∥Zuckerberg Institute for Water Research, Department of Environmental Hydrology and Microbiology, The Jacob Blaustein Institutes for Desert Research, Ben-Gurion University of the Negev, Sede Boqer Campus, Sede Boqer 84990, Israel.
Noa
N
Balaban
§Department of Earth and Planetary Sciences, Weizmann Institute of Science, Rehovot 7610001, Israel.
Ishai
I
Dror
†Geological Survey of Israel, 30 Malhei Israel Street, Jerusalem 95501, Israel.|⊥Biological and Chemical Research Centre, University of Warsaw, 02-089, Poland.
Ludwik
L
Halicz
∥Zuckerberg Institute for Water Research, Department of Environmental Hydrology and Microbiology, The Jacob Blaustein Institutes for Desert Research, Ben-Gurion University of the Negev, Sede Boqer Campus, Sede Boqer 84990, Israel.
Zeev
Z
Ronen
†Geological Survey of Israel, 30 Malhei Israel Street, Jerusalem 95501, Israel.
Faina
F
Gelman
D001966:Bromine / Q000737:chemistry; D002247:Carbon Isotopes / Q000737:chemistry; D002384:Catalysis; D005591:Chemical Fractionation / Q000379:methods*; D003300:Copper / Q000737:chemistry; D005411:Flame Retardants / Q000032:analysis; D054879:Halogenation; D006861:Hydrogen Peroxide / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007501:Iron / Q000737:chemistry; D007554:Isotopes / Q000032:analysis; D053758:Nanoparticles / Q000737:chemistry; D010084:Oxidation-Reduction; D020005:Propanols / Q000032:analysis / Q000737:chemistry*
D002247:Carbon Isotopes; D005411:Flame Retardants; D007554:Isotopes; D020005:Propanols; C545216:tribromoneopentyl alcohol; D003300:Copper; D006861:Hydrogen Peroxide; D007501:Iron; D001966:Bromine; C030973:cupric oxide