α,β-unsaturated sulfophenylcarboxylates as degradation intermediates of linear alkylbenzenesulfonates:: evidence for Ω-oxygenation followed by β-oxidations by liquid chromatography-mass spectrometry

被引:28
作者
Eichhorn, P [1 ]
Knepper, TP [1 ]
机构
[1] ESWE Inst Water Res & Water Technol, D-65201 Wiesbaden, Germany
关键词
linear alkylbenzenesulfonates; biodegradation; sulfophenylcarboxylates; liquid chromatography/mass spectrometry; alpha; beta-unsaturated sulfophenylcarboxylates;
D O I
10.1002/etc.5620210101
中图分类号
X [环境科学、安全科学];
学科分类号
08 ; 0830 ;
摘要
Liquid chromatography with an electrospray interface to a mass spectrometer (LC-ES-MS) and LC-ES coupled to a tandem MS (LC-ES-MS/MS) were used to detect and identify intermediates excreted transiently during the aerobic degradation of linear alkylbenzenesulfonates (LAS) in fixed-bed bioreactors (FBBR). The inoculum for the FBBR was the microflora of the River Rhine, Germany. Two major phenomena were observed on the addition of 100 mg/L LAS to the system, sorption and then biodegradation. Disappearance due to sorption was followed in an inhibited FBBR. Biodegradation of LAS started on day 7 and was accompanied by the transient excretion of intermediates, which were later largely degraded. We detected not only the sulfophenylcarboxylates (SPCs) observed previously but also the alpha,beta -unsaturated SPCs (SPC-2H), which have not been reported before. Experiments with the (4-sulfophenyl)dodecanes (C12-LAS), which had minor contaminants of C11-LAS, showed C12-, C10-, C8-, C6-, and C4-SPCs when LAS was degraded as well as traces of C9-, C7-, and C5-SPCs. Signals from the SPC-2H species were usually some 10% of those from the corresponding SPCs. Samples from these experiments were also examined by gas chromatography-mass spectrometry (GC-MS), but no desulfonated intermediates were detected. We interpret the data to mean that the only attack on LAS was by omega -oxygenation; there was no visible initial desulfonation. The products of omega -oxygenation were oxidized to the corresponding SPC and subject to beta -oxidation, as evidenced not only by the pattern of C-2 units in the excreted SPCs but also in the corresponding series of SPC-2H, representing the intermediates in beta -oxidation.
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页码:1 / 8
页数:8
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