The quick, easy, cheap, effective, rugged, and safe (QuEChERS) sample preparation procedure combined with both gas chromatography–mass
spectrometry (GC–MS) and liquid chromatography–mass spectrometry (LC–MS) was adopted in our laboratory for the analysis of
pesticide residues in food samples as part of the state of Connecticut's regulatory monitoring program. In 2006, data from
a QuEChERS-based sample preparation procedure were compared to data from our previous analytical method. In this article,
these results are further compared to those of the U.S. Food and Drug Administration's pesticide residue monitoring program
and the U.S. Department of Agriculture's pesticide data program.
Since its inception in 1963, the pesticide residue program in the Department of Analytical Chemistry at The Connecticut Agricultural
Experiment Station (CAES) has made major advancements in the analyses of pesticide residues present in food — primarily but
not exclusively produce. In 1992, the method of Pylypiw (1) was used in our laboratory to replace our older methods (2) for
the extraction of organochlorine and organophosphorous pesticides from food samples. At the time, residues were analyzed by
gas chromatography (GC) with element-selective detection. Beginning in 1993, mass spectrometry (MS) was introduced for the
confirmation of violative residues. By 1999, all samples were subjected to MS analysis for the presence of pesticide residues
(3). In 2006, following the acquisition of a ion trap liquid chromatography–mass spectrometry (LC–MS) system, a direct comparison
was made between the Pylypiw method and the then newly published quick, easy, cheap, effective, rugged, and safe (QuEChERS)
method (4). In 2011, an orbital trap LC–MS system (Thermo Scientific Exactive Orbitrap) was added to our program and is currently
used for the exact-mass confirmation of violative pesticide residues.
Figure 1: Flowchart of 2006 sample extract and analysis.
In 2006, we compared the Pylypiw method (1), which offers petroleum ether extracts that are amenable to GC analysis, with
an adaptation of the recently introduced QuEChERS method (4), which offers acetonitrile or toluene extracts that are amenable
to both GC–MS and LC–MS. Approximately 181 samples obtained for analyses in the Connecticut program were tested using a paired
sample blind study protocol (vide infra). The extracts from the Pylypiw method were analyzed by GC–MS and GC with micro electron-capture detection (ECD), and the
QuEChERS extracts were analyzed by GC–MS and LC–MS as outlined in Figure 1.
The Connecticut program is similar to the larger United States (US) Food and Drug Administration (FDA) program in that it
tests a wide variety of samples available to the consumer in the market place. The samples tested in these two surveys can
be comprised of nearly any type of food offered for sale to the consumer. On an average annual basis from 1990 to 2010 the
Connecticut program tested 37 different commodity types of fresh food and 14 different commodity types of processed food.
These two programs contrast to the US Department of Agriculture (USDA) pesticide data program (PDP) which, on average, targets
12 fresh and four processed samples per year. Owing to the fact that the results obtained from the Connecticut and FDA programs
are derived from nontargeted sources (5), as opposed to those in the PDP (6), the results obtained through the Connecticut
program are thought to be more representative of those in the larger FDA program.
Figure 2: Comparison of the Connecticut, FDA, and PDP monitoring programs for pesticide residues in food.
From 1990 through 2005, the results obtained from the Connecticut program closely matched those obtained in the larger FDA
pesticide residue monitoring program (Figure 2). During this timeframe, the FDA program analyzed 167,215 samples (5); the
Connecticut program separately analyzed 4871 food samples (3). The Connecticut program analyzed only about 3% (2.91%) of the
total samples in the FDA program. It is noteworthy that there is not a significant difference in the proportions of pesticide
residue–free samples, 63.3% reported by Connecticut and 64.2% reported by FDA (5) (Figure 2), over the 16-year timeframe (1990–2005)
when the data are compared using a z-test (P = 0.230; z = 1.200). The average violation rate over the same period was similar, 1.5% for the Connecticut program and 2.8% (5) for
the FDA program, but statistically different (P = <0.001; z = 5.114). These results imply that the sampling design in Connecticut closely parallels the larger program of the FDA, that
the analytical methodology used in the two surveys was comparable over the timeframe 1990–2005, and that the smaller Connecticut
subsample is representative of the larger with respect to samples containing pesticide residues.
From the inception of the USDA PDP study in 1992 and through 2005, the results obtained from the Connecticut program contrasted
sharply to those obtained in the PDP study by as much as 38% (Figure 2). During this timeframe the PDP targeted 112,395 samples
(6), and the Connecticut program tested 4150 samples. When compared, the percentages of pesticide residue–free samples over
the inclusive 14-year timeframe (1992–2005), 62.7% reported by Connecticut and 38.8% reported by the PDP, was not similar
nor was it statistically significant (P = <0.001; z =34.117). The average violation rate reported, 3.5% by the PDP (6) and 1.7% by Connecticut, was likewise statistically dissimilar
(P = <0.001; z = 6.208). These results suggested that the sampling designs of the two programs were dissimilar and that the analytical methodology
used in the two studies was likely dissimilar.
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LCGC COLUMNISTS 2014
Sample Prep Perspectives | Ronald E. Majors: LCGC Columnist Ron Majors, established authority on new column technologies, keeps readers up-to-date with new sample preparation trends in all branches of chromatography and reviews developments in existing technology lines.
History of Chromatography | Industry Veterans: With each installment of this column, a different industry veteran covers an aspect of the evolution and continued development of the science of chromatography, from its birth to its eventual growth into the high-powered industry we see today.
MS — The Practical Art| Kate Yu:
Kate Yu is the editor of 'MS-The Practical Art' bringing her expertise in the field of mass spectrometry and hyphenated techniques to the pages of LCGC. In this column she examines the mass spectrometric side of coupled liquid and gas-phase systems. Troubleshooting-style articles provide readers with invaluable advice for getting the most from their mass spectrometers.
LC Troubleshooting | John Dolan: LC Troubleshooting sets about making HPLC methods easier to master. By covering the basics of liquid chromatography separations and instrumentation, John Dolan, Vice President of LC Resources and world renowned expert on HPLC, is able to highlight common problems and provide remedies for them.