Solid‐phase microextraction liquid chromatography/tandem mass spectrometry for the analysis of chlorophenols in environmental samples

Abstract

Liquid chromatography with atmospheric pressure chemical ionisation mass spectrometry (LC/APCI-MS), using negative ion detection in a triple quadrupole instrument, was used for the determination of chlorophenols (CPs) in environmental samples. In-source collision-induced dissociation (CID) was compared with MS/MS fragmentation. In general, less fragmentation was observed in MS/MS as compared with in-source CID, with the latter providing more intense fragment ions due to chemical ionisation. Under MS/MS conditions [M - H - HCl](-) was the main fragment ion observed for all compounds except for pentachlorophenol, which showed no fragmentation. For multiple reaction monitoring (MRM) acquisition mode, the transition from [M - H](-) to [M - H - HCl](-) was selected, leading to detection limits down to 0.3 ng injected. Direct and headspace-solid-phase microextraction (HS-SPME) were used as preconcentration procedures for the analysis of CPs in wood and in industrially contaminated soils. CPs were quantified by standard addition, which led to good reproducibility (RSD between 4 and 11%) in both SIM and MRM modes, and detection limits down to ng/g. The combination of MS/MS and in-source CID allowed confirmation of the presence of CPs in environmental samples.

1,2-Dimethylimidazole-4-sulfonyl chloride, a novel derivatization reagent for the analysis of phenolic compounds by liquid chromatography electrospray tandem mass spectrometry: Application to 1-hydroxypyrene in human urine

“…Compounds with phenolic groups have been determined by a variety of methods including gas chromatography/mass spectrometry (GC/MS) after solid phase extraction (SPE) and derivatization by trimethylsilation [5][6][7] and high-performance liquid chromatography (HPLC) with fluorescence detection [8]. Recently, liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS) and tandem mass spectrometry (LC-ESI-MS/MS) in the negative ion mode have been employed to analyze these compounds [9][10][11][12]. However, many phenols are not strong acids and therefore show low ionization efficiency in ESI-MS, leading to higher detection limits compared with the limits that are obtained for many highly ionizable compounds.…”

Dechlorane Plus and decabromodiphenyl ether in atmospheric particles of northeast Asian cities

“…The loss of carbon monoxide following the desorption of hydrochloric acid was reported in the case of dichloro catechol, which also has chlorine and hydroxyl in the same benzene ring (Ziagova and Liakopoulou-Kyriakides, 2007). The loss of hydrochloric acid was also reported in LC-MS/MS analysis as being involved in the main fragmentation pathway of chlorophenol (Sarrión et al, 2003). To determine the precise structures of M1, M2, and M3, we synthesized these metabolites by chlorination of 1-hydroxypyrene, purified them using LC fractionation, and analyzed by NMR.…”

Accurate analysis of trace pentachlorophenol in textiles by isotope dilution liquid chromatography‐mass spectrometry

“…LC tandem MS (LC/MS/ MS) was a newly developed technique in recent years and has been widely used for the measurement of PCP in environmental samples [10,11]. To demonstrate traceability of the results of these methods, control samples for internal and external quality control must be available with PCP concentration values assigned by a method of higher metrological order.…”