In June 1999, LCGC published a special supplement that focused on the sample preparation of solids (1). At that time, we covered general methods
— supercritical fluid extraction (SFE), pressurized fluid extraction–accelerated solvent extraction (PFE–ASE), microwave-assisted
extraction (MAE), and automated Soxhlet extraction. In the ensuing six years, these modern extraction techniques have continued
to evolve. In some cases, systems have been further miniaturized and automated. A wider variety of applications has been achieved
in such diverse areas as environmental, pharmaceutical, natural product, food, and polymer chemistry. In this installment
of "Sample Preparation Perspectives," I will update the earlier coverage and make a note of some of the instrumental advances
and a few applications that have spurred the growth of these extraction techniques. Although the literature abounds with applications
examples, this review will focus on the technology. Websites of the various manufacturers, textbooks, and review articles
are great sources of information on applications examples.
Modern liquid–solid extraction has its roots in the shake–filter method. Basically, the shake–filter extraction method involves
the intimate contact between a solid material, usually finely divided, and a solvent that has an optimum solubility for the
analyte of interest and a minimum solubility for the matrix. The technique works well for porous matrices where the solvent
can diffuse into the pores and extract analytes. Sometimes mechanical agitation and heating is used to speed up the extraction
process. At the conclusion of the experiment, insoluble materials are removed by filtration or centrifugation. For some samples,
the extract can immediately be injected into a chromatograph for further separation. More often, there is some additional
sample preparation required to isolate the critical analytes from other extractables that can interfere with the chromatography
step.
For more intimate contact between solvent, the adsorbed (absorbed) analyte and matrix, other sample preparation techniques
might be required. Several methods that can achieve this intimate contact include homogenization, sonication, emulsification,
or vortexing. For biological samples, various cell disruption techniques can be employed. All of these methods require the
application of an additional external force (or forces) to the sample in suspension.
Table I: Most modern solid extraction techniques use increased temperature and pressure
Most modern liquid–solid extraction techniques use increased temperature or pressure to increase the rate of extraction. Table
I summarizes the influence of these parameters on analyte extraction.
Modern Soxhlet Extraction
Soxhlet extraction is by far the most widely used method for solid sample pretreatment. In fact, it is the de facto standard
with which all other extraction procedures are compared and contrasted. Soxhlet extraction is simple, effective, and relatively
inexpensive. Generally, it provides good analyte recovery but its traditional operation is slow and uses copious amounts of
solvent. Although classical Soxhlet extractions can last as long as 18–24 h, once set up and running, the experiment requires
very little user involvement. Small-volume Soxhlet systems are available, but the sample size often is dictated by the analyte
concentration, the necessary mass to obtain a representative sample, and the chromatography detector sensitivity, all of which
could combine to require a larger sample size.