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Assessment of ozonation reactivity of aromatic and oxidized naphthenic acids species separated using a silver-ion solid phase extraction method

Huang, Rongfu, Qin, Rui, Chelme-Ayala, Pamela, Wang, Chengjin, Gamal El-Din, Mohamed
Chemosphere 2019 v.219 pp. 313-320
carbon, mass spectrometry, naphthenates, oil sands, oxidation, ozonation, ozone, solid phase extraction, toxicity, ultra-performance liquid chromatography
Owing to the complexity of naphthenic acids (NAs) in oil sands process water (OSPW), previous ozone-treatment studies mainly investigated the removal of classical NAs (aliphatic O₂−NAs) and the understanding of ozonation reactivity of other NA species has been limited. This work utilized a silver-ion solid phase extraction (SPE) approach to separate individual NA species into 20 fractions before subsequent ozone treatment. The ozonation reactivity of aromatic and oxidized NA species in isolated fractions was studied for the first time. Untreated and ozone-treated SPE fractions were characterized using ultra performance liquid chromatography ion mobility time-of-flight mass spectrometry. The removals of aliphatic O₂−NAs (Fraction 3), aromatic O₂−NAs (Fraction 8), O₃−NAs (Fraction 11), and O₄−NAs (Fraction 17) with an applied ozone dosage of 16.8 mg L⁻¹ were 97.2%, 94.7%, 59.4% and 44.7%, respectively. The results showed that aromatic and oxidized NAs with larger carbon number were favorably removed during ozonation treatment. Comparison of the ozone utilization efficiency for different NA species indicated that the degradation of oxidized NAs consumed more ozone in molar ratio than the degradation of classical and aromatic NAs. The reactivity of oxidized NAs was lower than that of classical NAs because the former consumed more ozone in molar ratio during reactions. Knowing the reactivity of different NA species is crucial for the design of ozonation systems targeting species with high toxicity. Moreover, the utilization of silver-ion SPE pre-separation approach has been demonstrated for future studies investigating the degradation mechanism of distinct NA species under other treatment conditions.