Solid-phase microextraction (SPME) is a simple, fast, economic, and so
lvent-free sample preparation method, The sensitivity of this techniqu
e for the determination of fatty acids in water can be enhanced with t
he addition of strong acid and salt to the aqueous phase, Under the lo
w-pH and saturated salt conditions, SPME combined with GC-FID can anal
yze less polar acids (C-6-C-10) containing relatively long hydrocarbon
chains directly from aqueous samples with ppt detection limits, The R
SD of the method was 15% for all compounds tested. Under the same cond
itions as above, the detection limits of free short-chain fatty acids
(C-2-C-4) in the aqueous samples are in the high ppb level, However, t
he detection limits can be lowered with in situ derivatization of thes
e acids directly in the SPME polymeric coating doped with a derivatizi
ng reagent. Headspace SPME/derivatization has been investigated, and t
he target analytes can be quantified with GC/MS by comparing the ratio
of the native analytes with that of spiked isotopically labeled analo
gues. For air analysis, quantitative derivatization of short-chain fat
ty acids has been achieved. SPME without derivatization was also used
to extract C-3 and C-4 acids from air samples, demonstrating the poten
tial of SPME to monitor very polar, relatively volatile acids in air.