Analysis of methylamine by solid-phase microextraction and HPLC after on-fibre derivatization with 9-fluorenylmethyl chloroformate

A method for the determination of methylamine (MA) in aqueous matrices is reported which uses solid-phase microextraction (SPME) for enrichment and derivatization of the analyte, and high performance liquid chromatography (HPLC). The fluorogenic reagent 9-fluorenylmethyl chloroformate (FMOC) has been used for derivatization. The SPME fibres were successively immersed in the samples and in the derivatization solutions to extract MA and FMOC, respectively. After a defined time of reaction, the derivatized analyte was desorbed into the chromatographic system, and chromatographed in a LiChrosphere 100 RP18, i.d., 5 μm, column under gradient elution. In order to improve the MA-FMOC peak profile, a precolumn ( i.d., packed with Hypersil C₁₈ phase, 30 μm) was connected on-line to the analytical column by means of a switching valve. The experimental conditions (including fibre coating, times of adsorption, reaction and desorption, and concentration of reagent) have been optimised, and the results have been compared with those achieved by using a method previously validated for aliphatic amines in which extraction and derivatization were carried into C₁₈ solid-phase extraction (SPE) cartridges. Although less sensitive, the SPME based method allowed the quantification of MA over the range 2.5-10.0 μg/ml with linearity, reproducibility and accuracy comparable to that of the SPE based method, the limit of detection being 0.75 μg/ml. The main advantages of the proposed SPME procedure are: sample handling involved in the extraction and derivatization steps was considerably reduced, it was free organic solvent and non-destructive. Moreover, the proposed conditions allowed the selective determination of MA in the presence of other primary and secondary short-chain aliphatic amines. The utility of the proposed procedure for the quantification of MA in different types of waters is discussed.