Trace element determination by combining solid-phase microextraction hyphenated to elemental and molecular detection...

The state of the art of analytical procedures based on solid-phase microextraction (SPME) and its applications to tin, mercury, arsenic, antimony, chromium, selenium, and lead determination in abiotic and biotic matrixes are critically reviewed from 1994 to present. First, sample pretreatment prior to SPME is evaluated, including a description of the most usual leaching procedures for sediment, soil, and biological samples. Because most organometallic species lack volatility, a derivatization step is mandatory prior to gas chromatographic (GC) determination, except for the volatile organometallics that can be directly extracted from the sample headspace or liquid phase by SPME. The most common derivatization procedures used in alkylation and hydridization reactions used for mercury, lead, and tin, as well as other procedures for the determination of total chromium and arsenic [i.e., trifluoroacetylacetonates for chromium (III) and thioglycol methylate for organic arsenic species] are reviewed. Critical variables usually evaluated along with the method development to improve the sensitivity of the extraction methods based on SPME, such as sampling size, stirring procedures, sampling temperature and pressure, polymer coating, and thermal desorption are reviewed. In addition, figures of merit of the different detection systems used in SPME combined with GC are evaluated. The validation of the reported analytical procedures with reference materials are also discussed in terms of precision and accuracy. Finally, future developments in the application of SPME to speciation are highlighted. Moreover, the capability of SPME automation for the derivatization-extraction procedures are also presented.