RESIDUE ANALYSIS OF 500 HIGH PRIORITY PESTICIDES:
BETTER BY GCMS OR LCMS/MS?
Lutz Alder,1* Kerstin Greulich,1 Gu
1
Federal Institute for Risk Assessment, Residue Analysis Unit,
Thielallee 88-92, 14195 Berlin, Germany
2
Landesuntersuchungsanstalt fur das Gesundheits- und Veterinarwesen,
Standort Chemnitz, Zschopauer Street 87, D-09111 Chemnitz, Germany
Received 10 October 2005; received (revised) 25 January 2006; accepted 28 January 2006
Published online 3 June 2006 in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/mas.20091
This overview evaluates the capabilities of mass spectrometry
(MS) in combination with gas chromatography (GC) and liquid
chromatography (LC) for the determination of a multitude of
pesticides. The selection of pesticides for this assessment is
based on the status of production, the existence of regulations
on maximum residue levels in food, and the frequency of
residue detection. GCMS with electron impact (EI) ionization
and the combination of LC with tandem mass spectrometers
(LCMS/MS) using electrospray ionization (ESI) are identified
as techniques most often applied in multi-residue methods for
pesticides at present. Therefore, applicability and sensitivity
obtained with GCEIMS and LCESIMS/MS is individu-
ally compared for each of the selected pesticides. Only for one
substance class only, the organochlorine pesticides, GC-MS
achieves better performance. For all other classes of pesticides,
the assessment shows a wider scope and better sensitivity if
detection is based on LCMS. # 2006 Wiley Periodicals, Inc.,
Mass Spec Rev 25:838865, 2006
Keywords: tandem mass spectrometry; gas chromatography;
liquid chromatography; electron impact ionization; electro-
spray ionization; multi-residue method; carbamates; organo-
chlorine pesticides; organophosphorus pesticides; pyrethroids;
sulfonylureas; triazines; triazoles; ureas; food; environmental
samples
I. INTRODUCTION
Pesticides have been widely used throughout the world since the
middle of the 20th century. Based on the compilation of the
British Crop Protection Council, approximately 860 active
substances are formulated in pesticide products currently
(Tomlin, 2003). These substances belong to more than 100
substance classes. Benzoylureas, carbamates, organophosphor-
ous compounds, pyrethroids, sulfonylureas, or triazines are the
most important groups. The chemical and physical properties
of pesticides may differ considerably. There are several
acidic pesticides; others are neutral or basic. Some compounds
contain halogens, others phosphorous, sulfur, or nitrogen. These
heteroatoms may have relevance for the detection of pesticides. A
*Correspondence to: Dr. Lutz Alder, Federal Institute for Risk
Assessment, Fachgruppe 67, Thielallee 88-92, 14195 Berlin, Germany.
E-mail: l.alder@bfr.bund.de
Mass Spectrometry Reviews, 2006, 25, 838 865
# 2006 by Wiley Periodicals, Inc.
nther Kempe,2 and Barbel Vieth1
number of compounds are very volatile, but several do not
evaporate at all. This diversity causes serious problems in the
development of a universal residue analytical method, which
should have the widest scope possible.
But such multi-residue methods are urgently needed.
Probably, no other use of chemicals is regulated more extensively
than that of pesticides. Maximum residue levels (or tolerances)
have been established for pesticides in foodstuffs and drinking
water in most countries to avoid any adverse impact on public
health, and to insist on good agricultural practice. Residues
of systemic herbicides in soil used in the previous season
may influence the growing of succeeding crops. Residues of
insecticides in surface water may cause adverse effects on aquatic
organisms. For these reasons a large number of laboratories
are involved in the surveillance of maximum residue levels or in
the identification and quantification of pesticide residues in
environmental matrices. In this context the use of numerous
single-residue methods is usually too expensive. It has to be noted
that every company which applies for registration of a new
pesticide has to provide residue analytical information. At least in
the EU, this part of a registration package is not confidential.
Depending on the purpose, determination of pesticide
residues may be target analysis or non-target analysis. An
example of target analysis is the inspection of MRLs in food. The
relevant analytes are fixed by the residue definition given in the
MRL regulation. These residue definitions may include relevant
metabolites or degradation products of the pesticides. In contrast,
the EU regulation of residues in drinking water does not contain
detailed residue definitions. Furthermore, residues in soil or
surface water are not regulated at all. In such cases, metabolites or
degradation products may be unknown. Their detection and
identification is part of the analytical task. Both types of analysis
have the need for different analytical schemes and may require
different instrumentation. In this review, we want to focus on the
application of mass spectrometry (MS) in target analysis.
In the past decades, the methods for trace level determina-
tion of pesticides have changed considerably. Since the early
1970s most routine pesticide residue analysis has been conducted
by gas chromatography (GC) in combination with electron
capture, nitrogen-phosphorous, and/or flame photometric detec-
tion. Confirmation of results required the use of a further gas
chromatograph equipped with a different type of column or
detector. Nowadays, using GC combined with MS, simultaneous
determination and confirmation of pesticide residues can be
obtained with one instrument in one analytical run. In most cases,

the sensitivity obtained with GCMS is similar to that of
classical GC detectors. Selectivity of GCMS can be adjusted by
the selection of appropriate molecular and fragment ions to avoid
interferences from co-extracted sample materials. Therefore, the
importance of GC with ECD, NPD, or FPD detection has
decreased in pesticide residue laboratories.
Methods based on liquid chromatography (LC) were applied
more rarely in the past, because traditional UV, diode array, and
fluorescence detectors are often less selective and sensitive than
GC instruments. But in the last few years, the commercial
availability of atmospheric pressure ionization caused a specta-
cular change. Compared to traditional detectors, electrospray
(ESI) or atmospheric pressure chemical ionization (APCI) in
combination with MS instruments have increased the sensitivity
of LC detection by several orders of magnitude. Moreover, HPLC
column switching techniques and extensive sample cleanup
procedures become unnecessary if tandem mass spectrometers
are used and operated in the selected reaction mode (SRM) (Stout
et al., 1998; Hernandez, Sancho, & Pozo, 2005). Due to the
suppression of most interfering signals by LCMS/MS in the
SRM, the signal-to-noise ratio increases distinctly and the full
sensitivity range of LCMS instruments can be utilized.
The applicability of GCMS in pesticide residue analysis is
summarized in pesticide analytical manuals (Thier & Zeumer,
1992; van Zoonen, 1998), applications from instrument produ-
cers (Agilent Technologies, 1999), or scientific studies (Cairns
et al., 1993; Fillion, Sauve, & Selwyn, 2000; Wong et al., 2003).
Several mass spectral databases contain electron impact (EI)
mass spectra of many pesticides (Ehrenstorfer, 2005; NIST/EPA/
NIH, 2005). Analogous presentations of the scope of LCMS/
MS in the area of pesticide residue analysis are missing. Up to
now, the largest overview has been given by Lehotay et al. (2005),
who applied LCMS/MS for the determination of 144 pesticides.
But a complete inventory of all available LCMS/MS informa-
tion does not exist.
Therefore, the aim of this review is to summarize all typical
precursor and product ions appropriate for LCESIMS/MS
determination of 500 pre-selected pesticides (if these pesticides
are adequately ionized by electrospray) and the sensitivity
obtained. The applicability of GCMS with EI MS is checked
for the same list of pesticides. Typical fragment ions are
provided, if their determination is possible. The decision between
two alternatives of quantitative determination also depends on
sensitivity. For this reason, the smallest analyte concentration
required for GCMS and/or LCMS/MS is listed in addition.
Finally, the achievable scope of multi-residue methods based on
GCMS or LCMS/MS is presented.
II. SELECTION OF PESTICIDES
FOR THIS COMPARISON
As noted above, approximately 860 active substances are
currently used in pesticide formulations (Tomlin, 2003). In
addition, several metabolites, degradation products, and old
(persistent) pesticides have to be considered by pesticide residue
analysts. Probably no technique is able to analyze all these >900
analytes completely.
Mass Spectrometry Reviews DOI 10.1002/mas
RESIDUE ANALYSIS OF 500 HIGH PRIORITY PESTICIDES &
For this reason, a selection of important pesticides was
necessary. The selection was started with the exclusion of >140
pesticides, which are not important for the comparison of GC
MS versus LCMS/MS. These pesticides are:
. Nine dithiocarbamates, 48 biological agents (bacteria,
fungi, viruses, etc.), and 29 inorganic compounds, which
cannot be analyzed by multi-residue methods based on GC
MS or LCMS/MS.
. Thirty-five pheromones, which are less important because
residues are not expected.
. Several isomers (e.g., alpha-cypermethrin, beta-cyperme-
thrin, theta-cypermethrin, and zeta-cypermethrin), if one of
these isomers is considered.
The following criteria were taken into account to select the
more important substances from the remaining pesticides:
(1) Status of production: Selected pesticide should be listed in
that part of the 13th edition of the Pesticide Manual that
contains the actually produced pesticides.
(2) Status of residue regulation in the EU or in Germany
(which are completely available for us). Regulated
pesticides are preferred.
(3) Occurrence of residues: Those pesticides are preferred,
which are more often found in food monitoring programs.
(4) Inclusion of important metabolites: Metabolites and/or
degradation products, which are included in the residue
definition, should be considered in addition.
(5) At least one of both detection techniques (GCMS or LC
MS/MS) must be applicable.
Using these criteria, 422 pesticides and 42 important
metabolites were chosen. In addition, 36 pesticides were
selected, because their residues in food are regulated, even
though these compounds are not produced any longer. The
resulting total number of 500 compounds is presented in
Table 1. The compilation contains 81 organophosphorus
pesticides, 43 carbamates, 40 organochlorines, 26 sulfonylur-
eas, 24 triazoles, 23 triazines, 22 other ureas, 19 pyrethroids, 12
aryloxyphenoxypropionates, and 10 aryloxyalkanoic acids. In
the Pesticide Manual, the remaining 207 compounds are assig-
ned to further 90 chemical classes.
The placement of some compounds into categories is
somewhat arbitrary because some pesticides contain several or
more characteristic structural features. If the mode of action is
considered, 172 herbicides, 171 insecticides, 105 fungicides,
and 52 pesticides from other pesticide types (acaricides,
bactericides, herbicide safeners, molluscicides, nematicides,
plant growth regulators, and synergists) are selected. Approxi-
mately 90% of those pesticides that are regulated by the EU
Commission are included in the table. It should be noted that the
majority of the excluded pesticides belongs to the group of
herbicides, which typically causes lower amounts of residues in
food.
By selection of such a large number of pesticides, we tried
to include most analytes being important in pesticide residue
analysis. But without a doubt, every selection must be
incomplete. Several metabolites may be missing, as well as
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TABLE 1. Typical ions selected for GC-EI-MS or transitions used in LC-ESI-MS/MS and the sensitivity obtained with
both techniques

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a
EU regulation can be found on the websites: http://europe.eu.int/eur-lex/en/search/search_lif.html or http://europe.eu.int/eur-
lex/lex/en/repert/035020.htm
b
[M NH4] used as quasimolecular ion.
c
Regulated metabolite in the EU.
d
Analyte requires special HPLC conditions for detection with ESIMS/MS.
e
Quasimolecular ion was [MOH].
f
Reference 2 does not report the product ion.
g
Quasimolecular ion was [(MO)/2].
h
Quantitative degradation of the pesticide occurs in the GC injector.
i
Reference 1 does not report the product ion.
some pesticides, which are important for other reasons not
considered here. Nevertheless, this selection was not put together
to promote a particular analytical technique.
III. SELECTION OF INSTRUMENTS AND
IONIZATION TECHNIQUES
The choice of the most appropriate instruments to handle the
majority of samples and analytes is one of the most important
decisions on investments in residue analytical laboratories. The
same decision was necessary for the comparison presented here.
A. GCMS
Ionization of pesticides in GCMS can be done by EI, and
positive or negative chemical ionization (PCI, NCI). For ion
separation, single quad instruments are used most frequently.
Additionally, GCMS systems with quadrupole ion traps, time-
of-flight (TOF) mass spectrometers or tandem mass spectro-
meters are available.
Most of the published studies on residue analysis by GC
MS report on results obtained by single quadrupole instruments
and EI ionization. Advantages of EI ionization are a low influence
of molecular structure on response, and a large number of
characteristic fragments. Extensive studies describe the simulta-
neous determination of 245400 pesticides by GCEIMS with
single quadrupole mass filters (Cairns et al., 1993; Fillion, Sauve,
& Selwyn, 2000; Stan, 2000; Chu, Hu, & Yao, 2005). The use of
ion traps in scan mode is more simple because no selection of
characteristic ions is necessary during data acquisition. In full
scan mode these instruments are quite sensitive, and confirmation
by library search is possible at lower concentrations. But,
Mass Spectrometry Reviews DOI 10.1002/mas
RESIDUE ANALYSIS OF 500 HIGH PRIORITY PESTICIDES &
compared to single quad instruments running in selected ion
monitoring mode (SIM), identical pesticides are covered and the
sensitivity do not differ significantly (Cairns et al., 1993).
Chemical ionization is used more rarely. Positive or negative
CIMS give better selectivity for several pesticides compared to
EI. This results in chromatograms with reduced matrix
interference (Hernando et al., 2001). But the signal intensity of
different pesticides (if identical amounts are injected) varies
much more compared to EI ionization. Preferentially, GCMS
with chemical ionization is focused on special substance classes
only, for example, organohalogen pesticides (Artigas, Martinez,
& Gelpi, 1988; Chaler et al., 1998), pyrethroids (Ramesh &
Ravi, 2004), and organophosphates (Russo, Campanella, &
Avino, 2002). It is rarely used in multi-residue methods, because
it is not a universal ionization technique. Finally, mass spectra
produced by chemical ionization usually contain a smaller
number of fragments, thus offering less information.
Available GCTOF instruments can be operated in two
different modes. One type offers very high scan rates, allowing
the separation of overlapping peaks by automated mass spectral
deconvolution of overlapping signals (de Koning et al., 2003;
Patel et al., 2004). This can result in up to 30,000 peaks from
cigarette smoke (Dalluge et al., 2002). Another type of GCTOF
instruments offers high mass resolution, allowing data evaluation
with a narrow mass window of 0.02 Da (Cajka & Hajslova, 2004).
However, most TOF instruments suffer from a reduced dynamic
range (Dalluge, Roose, & Brinkman, 2002). For this review, no
sufficient information on multi-analyte GCTOF was available.
In analogy to CIMS and GCTOF, a good suppression of
matrix background is obtained by GCMS/MS systems
(Goncalves & Alpendurada, 2004). Even with extracts of
tobacco, excellent selectivity and sensitivity were observed
(Haib, Hofer, & Renaud, 2003). MS/MS experiments can be
performed using ion trap (Gamon et al., 2001; Aguera et al.,
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& ALDER ET AL.
2002; Martinez Vidal, Arrebola, & Mateu-Sanchez, 2002) and
triple quadrupole mass analyzers (Leandro, Fussell, & Keely,
2005). Some limitations in GCMS/MS arise from the absence
of a universal soft ionization mode, which could be used for the
efficient production of molecular ions of most pesticide classes.
Chemical ionization generates high-intensity ions of only some
pesticides classes. EI ionization is more universal, but often the
total ion current is spread on many fragments, resulting in a low
intensity of parent ions of MS/MS experiments. Up to now, the
prospects of GCMS/MS are not totally clear. GCMS/MS
acquisition parameters are published for a small percentage of
selected pesticides. Therefore, it is too early to choose GCMS/
MS instead of GCMS for a comparison with the most
appropriate LCMS(/MS) approach.
B. LCMS
If pesticides are not amenable to GC, the application of LC is the
best alternative. Likewise, LC may be combined with single
quadrupole instruments, quadrupole ion traps, triple quadrupole
(tandem) mass spectrometers, TOF spectrometers, or hybrid
quadrupole TOF instruments.
In contrast to GCMS, single quadrupole mass spectrometers
are not used in the majority of recent studies dealing with LCMS.
A disadvantage of single quadrupole instruments (and ion traps
operated in the SIM mode) is the high intensity of background
signals produced from sample matrix and HPLC solvent clusters.
Due to this chemical noise in real samples very low limits of
quantification cannot be achieved, even if the sensitivity of these
instruments is high (Hernandez, Sancho, & Pozo, 2005).
The chemical background can be reduced significantly if
tandem MS in combination with selected reaction monitoring
(SRM) is applied. Even if a co-extracted matrix component has the
molecular mass of a pesticide, usually both isobaric ions can be
separated in SRM experiments, because their fragmentation in the
collision cell most often results in different product ions. Therefore,
tandem mass spectrometers offer excellent sensitivity and unsur-
passed selectivity. For this reason, triple quadrupole mass analyzers
have been the most often applied MS detectors until now (Pico,
Blasco, & Font, 2004). Quadrupole ion traps may also be operated in
the MS/MS mode, which reduces the background to a level known
from tandem mass spectrometers. However, ion collection,
fragmentation, and mass analysis of fragments is a step by step
process in traps and requires much more time than in triple
quadrupole instruments, which do this in parallel. Furthermore, ion
traps suffer from a limited dynamic range, a smaller potential to
fragment very stable ions and the inefficiency to trap low mass
fragments (Pico, Blasco, & Font, 2004).
Time-of-flight mass spectrometers in combination with LC
are more often used in high-resolution mode (typical mass
error <2 mDa), which provides better discrimination of back-
ground (Hogenboom et al., 1999; Ferrer et al., 2005). The main
advantage of this type of instrument is the identification of
unknown peaks in a sample even if analytical standards are
not available (Garcia-Reyes et al., 2005; Thurman, Ferrer, &
Fernandez-Alba, 2005). But, this advantage is usually not needed
in the enforcement of maximum residue levels. Furthermore,
identification of pesticides in samples is less certain by LC
856
TOFMS than identification of pesticides by GCEIMS
(Maizels & Budde, 2001).
The use of a hybrid quadrupole time-of-flight instrument
(QTOF) allows the most certain confirmation. This confidence
is based on the combination of retention time, mass of the quasi
molecular ion selected by the quadrupole mass filter, and the
complete collision induced mass spectrum obtained by the TOF
analyzer (Hernandez et al., 2004). Unfortunately, the sensitivity
of QTOF instruments in relation to triple quadrupole analyzers
is one order of magnitude lower (Hernandez et al., 2004; Nunez,
Moyano, & Galceran, 2004). Additionally to this drawback, a
smaller linear range restricts the use of QTOF for the
quantification of residues.
All LCMS instruments can be equipped with at least
three types of soft ionization techniques, that is, ESI, APCI, and
photoionization. Up to now, articles on photoionization of
pesticides have been rarely published (Takino, Yamaguchi, &
Nakahara, 2004). ESI and APCI are applied more often.
Comparing the suitability of ESI versus APCI for the ionization
of many pesticides, electrospray was identified as more universal
technique (Thurman, Ferrer, & Barcelo, 2001; Klein & Alder,
2003; Jansson et al., 2004; Hernandez, Sancho, & Pozo, 2005).
C. Final Decision
Any of the instruments discussed above have special merits, but
none of them can detect the full range of all pesticides. However,
if the selection of the most appropriate techniques is focused on
the enforcement of maximum residue levels, simultaneous
identification, and quantification of a very large number of
target analytes will be more important than the detection,
identification, and quantification of non-regulated (non-target)
pesticides and/or metabolites. Under these conditions, EI
ionization and single quadrupole MS was identified as the
preferred GC detection system. If LC is used, most benefits
should be obtained from tandem mass spectrometers operating in
the electrospray mode. Therefore, in the next section scope and
sensitivity of GC-EIMS will be compared to pesticide detection
by LCESItandem MS.
IV. COMPILATION OF EXISTING DATA
Characteristic ions of EI mass spectra, which are applied to the
determination of pesticides by GCMS, as well as typical
transitions from precursor to product ions used for LC/tandem
MS, are presented in Table 1.
Most of the cited articles contain information on the
sensitivity of the instrument or method used. However, a
comparison of such data is difficult. In some cases, sensitivity is
based on the signal-to-noise ratio of peaks in chromatograms of
standards. In other studies, sensitivity is derived from the limit of
quantification (LOQ) of the complete analytical method. In the
latter case, the type of matrix and the concentration of the final
extracts have to be considered. Furthermore, sensitivity of instru-
ments has improved significantly in the last years. Finally, several
parameters of GCMS or LCMS/MS measurement influence the
sensitivity. In GCMS such parameters are the dwell time, but also
the type and length of column or temperature program. If LCMS/
MS is used, chromatography (e.g., type of solvent, buffer),
Mass Spectrometry Reviews DOI 10.1002/mas

ionization (e.g., ionization voltage, temperature, gas pressure), or
parameters of ion measurement (e.g., dwell time, collision energy)
can influence the sensitivity obtained. Therefore, data on
sensitivity from different studies are often not comparable.
To compare the sensitivity of mass spectrometric determi-
nation of pesticides avoiding these problems, the limits of
quantification presented in Table 1 were estimated by GCMS
and LCMS/MS under identical conditions each.
A. GCMS Data
Gas chromatographymass spectrometry (GCMS) has been
practiced in analyzing pesticides for several decades and
most characteristic ions are available from pesticide analytical
manuals, applications of instrument producers, or spectral
databases supplied by producers of analytical standards. In
addition, some excellent articles covering GCMS analysis of a
broad range of pesticides are published (Fillion, Sauve, &
Selwyn, 2000; Wong et al., 2003; Chu, Hu, & Yao, 2005).
Only for some pesticides, the characteristic ions in Table 1 are
obtained from recent articles or studies conducted by the pesticide
industry.
For estimation of sensitivity, several mixed standards in
solvent containing all pesticides were analyzed. A state-of-the-
art GCMS system (Agilent 6890N GC and 5975 inert MSD)
using a pulsed pressure injection of 1 mL onto a HP-5 MS column
(30 m
0.25 mm
0.25 mm), EI ionization, and a dwell time
of 40 msec were applied for each characteristic ion. The same
GC conditions were used for all injections. Obviously, a longer
dwell time would result in better sensitivity, butat the same
timeit would reduce the number of pesticides analyzed in
one run.
Standard solutions containing 10,000, 1,000, 100, 10, and
1 ng/mL were injected. If a pesticide was not detected at the
highest concentration in the SIM mode, no data were added to
Table 1. In all other cases, characteristic ions are presented. The
LOQ was set to the lowest concentration, which gave a signal-to-
noise ratio of 10 for the most intense peak of the analyte.
B. LCMS/MS Data
Typical transitions from precursor to product ions are taken from
recent publications, since analogous data collections do not
exist for LCMS/MS. SRM transitions from studies conducted
with triple quadrupole or quadrupole ion trap instruments
are preferred. If such studies were not found, data on
those product ions are cited, which are produced in single
quadrupole instruments by increasing the potential between
the entrance capillary and the first skimmer (fragmentor or cone
voltage). Often, transitions for a selected pesticide are published
by more than two authors. In such cases, the citation in Table 1
prefers the first or at least the earlier publications. However, no
transitions were found in published studies for approximately
one-third of the pesticides listed in Table 1. In such cases, typical
transitions are taken from unpublished studies of pesticide
producers or from the world wide web (BfR, 2005).
The sensitivity of LCMS/MS instruments was assessed
using a triple quadrupole mass spectrometer (API 4000,
Mass Spectrometry Reviews DOI 10.1002/mas
RESIDUE ANALYSIS OF 500 HIGH PRIORITY PESTICIDES &
Applied Biosystems) by injection of 20 mL analytical standard
on a short reversed phase column (Phenomenex Aqua,
50 mm
2 mm
5 mm), using a gradient of methanol/water
containing 5 mmol/L ammonium formate. Approximately 100
pesticide transitions were acquired simultaneously after ESI
using an identical dwell time of 20 msec for each SRM transition.
The batch used at the LCMS/MS instrument included
standard solutions with concentrations of 100, 10, 1, and 0.1 ng/
mL. If a pesticide was not detected at the highest concentration in
the SRM mode, no data were added to Table 1. In all other cases,
typical transitions are presented. The LOQ was set to the lowest
concentration, which gave a signal-to-noise ratio of 10 for the
most intense peak of the analyte.
V. CONCLUSIONS FROM COMPILED DATA
A. Comparison of Scope of Both Techniques
The data in Table 1 demonstrate that more pesticides and their
metabolites can be analyzed by LC and ESI than by GCMS. It is
well known that sulfonyl or benzoyl ureas and many carbamates
or triazines can be better or exclusively detected by LCMS/MS
techniques. Furthermore, a wider scope of LCMS/MS was
found for most of the other chemical classes too, for example,
the organophosphorus pesticides. Only 49 compounds out of
500 exhibited no response, if LCMS/MS in combination
with positive and negative ESI was used. On the other
hand, 135 pesticides/metabolites could not be analyzed by GC/
MS using EI ionization, most often because of incompatibility
with evaporation of the intact molecule in the GC injector.
A more detailed overview presenting separate data for
several chemical classes is given in Table 2. The data presented
in this table demonstrate clearly that several pesticides, which
are identified typically by an electron capture detector in
GC measurements, do not show a sufficient LCMS/MS
response. This is well known for organochlorine compounds,
but it is also valid for other pesticides like benfluralin,
chlozolinate, dinobuton, etridiazole, flumethralin, nitrofen, or
vinclozolin. The only exceptions are fenchlorphos, which is
better detected by GC with flame photometric or nitrogen-
phosphorus detection and biphenyl, which can be analyzed by
GCMS, only.
B. Comparison of Sensitivity
Both, GCMS- and LCMS-based methods, reveal a significant
variation of sensitivity, covering at least a range of 34 orders of
magnitude, depending on the pesticide. However, a comparison
of the median of the limits of quantification clearly shows much
higher sensitivity if determinations are based on LC and tandem
MS. Most analytes may be quantified reliably by LCMS/MS
(at least in standard solutions) at concentrations between 0.1 and
1 ng/mL. In contrast, the median of the limits of quantification
observed by GCMS is distinctly higher, that is, at 100 ng/mL.
The distribution of LOQ data from Table 1 is summarized
separately for both techniques in Figure 1. Nearly the same
distribution is found for organophosphorus pesticides, which are
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TABLE 2. Pesticides, which are not covered by GCMS or LCMS/MS

*This calculation/list does not contain four organotin compounds, four quaternary ammonium salts,
glyphosate, and picloram, which require special LC conditions for ESIMS/MS detection.

most often analyzed by GC methods up to now (Fig. 2). An
analogous pattern is found for many other chemical classes of
pesticides.
Another approach that brings to the same conclusion is
presented in Figure 3. In this figure the percentage of those
pesticides that show a better response with GCMS is compared
with the percentage of compounds that are quantified with higher
sensitivity by LCMS/MS. In addition to those 47 pesticides,
which are not detected by LCMS/MS at a level of 100 ng/mL,
only two analytes (acrinathrin and procymidone) are analyzed
with better sensitivity by GC-MS. Finally, 19 pesticides
(bromophos-ethyl, chlormephos, chlorobenzilate, chlorpyrifos-
methyl, cyanofenphos, cyanophos, cycloate, cyhalofop-butyl,
dichlofenthion, diphenylamine, esfenvalerate, fenitrothion, fen-
valerate, lambda-cyhalothrin, methacrifos, parathion-methyl,
phorate, prothiofos, tolclofos-methyl) are detected with an equal
LOQ by GCMS.
The better performance of LCMS/MS is probably
determined by several reasons. Among them the higher injection
volume used in LCMS/MS (20 mL vs. 1 mL) and the lower

FIGURE 1. Distribution of limit of quantification (LOQ) data of all FIGURE 2. Distribution of LOQ data of all organophosphorus pesti-
pesticides/metabolites. cides.

858 Mass Spectrometry Reviews DOI 10.1002/mas


FIGURE 3. Comparison of GCMS sensitivity versus LCMS/MS sensitivity of individual pesticides
summarized for different pesticide classes.
amount of fragmentation during ionization (ESI vs. EI) may
explain some of these differences.
C. Conclusions and Perspectives for
Multi-Residue Methods
Gas chromatography (GC) coupled to EI-MS and LC combined
with tandem MS are the most important detection techniques in
pesticide residue analysis today. The comparison of scope and
sensitivity of both techniques presented above has illustrated the
better performance of LCMS/MS.
While establishing the measurements of hundreds of LOQs,
another important advantage of LCMS/MS became clear. Due
to the small peak width in GC, the cycle time in GCMS methods
must be 1 sec or shorter. Since all ions are recorded using a dwell
time of 40 msec, not more than 25 characteristic ions can be
recorded in one time window. Assuming 10 time windows in one
GC run, 250 ions or 83 pesticides with 3 characteristic ions each
can be analyzed in parallel theoretically. The peak width in LC
measurements is usually higher, often allowing a typical cycle
time of 2.5 sec. Based on the dwell time of 20 msec used for
the data in Table 1, approximately 125 SRM transitions can
be acquired simultaneously in one time window. Assuming
5 time windows per LC run in that case, 625 SRM transitions are
obtained with one injection. Since two SRM transitions are often
sufficient to quantify and confirm a result, up to 312 pesticides
can be analyzed theoretically in one run. In practice, the
theoretical numbers calculated above cannot be reached because
usually more pesticides elute in the middle than in the beginning
or end of the chromatograms. However, irrespective of this
limitation, the number of analytes covered in one LCMS/MS
run is at least two or three times higher than the number of
pesticides measured in parallel by GCMS in the SIM mode.
The comparison of both techniques would remain incom-
plete, if the influence of matrix on the determination is not
Mass Spectrometry Reviews DOI 10.1002/mas
RESIDUE ANALYSIS OF 500 HIGH PRIORITY PESTICIDES &
considered. Matrix effects on the analyte transmission from the
GC injector to the column (Hajslova & Zrostlikova, 2003) or
inhibition of ESI (Bester et al., 2001; Stuber & Reemtsma, 2004)
are well known phenomena. In both cases the use of matrix
matched standards can reduce the problem, but preparation of
such standards is laborious and appropriate sample materials
without any residues are not generally available. Therefore, the
use of surface protectants is an interesting alternative (Anastas-
siades, Mastovska, & Lehotay, 2003), which is applicable for GC
methods but not for LCMS/MS. In several cases, the influence
of coeluting matrix peaks on the atmospheric pressure ionization
can be reduced by the ECHO technique (Zrostlikova et al., 2002),
but a general compensation of matrix effects is not obtained
(Alder et al., 2004). Using LCMS/MS, the simplest alternative
is the dilution of extracts. However, such dilution requires residue
concentrations distinctly above the LOQ. If no other
choice exists, the method of standard addition will solve this
problem of accurate quantification.
In addition to the effect on response, matrix components
produce several additional signals in chromatograms. Such
interferences are not seldom if extracts of complex matrices (i.e.,
herbs or tea) are analyzed by GCMS. False positive identifica-
tions of pesticides may be a consequence. Matrix interference is
significantly reduced if tandem MS is used. From that reason, LC
MS/MS methods do not require such an extensive cleanup and
sophisticated chromatographic separation (Stout et al., 1998).
Different molecules that share the same transition are more rarely
found than molecules producing fragments of identical mass. As a
consequence, peak identification, integration, and data processing
are much easier and faster in LCMS/MS, and require less manual
corrections compared to GCMS (Lehotay et al., 2005).
The discussion of many aspects of determination of pesticide
residues by GCMS and LCMS/MS clarified that neither MS in
combination with GC nor the LC-based technique may solve all
problems of residue analysts. Both techniques and additional
ones are needed today and will be needed in future. However, the
859
& ALDER ET AL.
benefits of LCMS/MS in terms of wider scope, increased
sensitivity, and better selectivity are obvious. These character-
istics, together with the ability to perform most determinations
without derivatization, make LCMS/MS the preferred techni-
que currently available for the determination of pesticide
residues.
ACKNOWLEDGMENTS
We thank Volker Happel and Marilyn Menden for their support
needed for the determination of limits of quantification. Natasa
Markovic, Birgit Mueller, and Annamaria Melcher provided
important technical assistance throughout this work.
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Lutz Alder studied chemistry in Berlin/Germany with a focus on organic and analytical
chemistry. After his Ph.D. in 1978, he managed the mass spectrometry laboratory at
Humboldt University for several years. He has been employed by the Federal Health
Office, which is now the Federal Institute for Risk Assessment (BfR) since 1991. Most of
his research has been concerned with residue analytical methods and its standardization
for official use. He has published 50 scientific journal articles and book chapters.

Kerstin Greulich studied chemistry at Dresden Technical University focusing on

environmental chemistry. She received her Ph.D. at Humboldt University in 2004. At
present she is employed at the Federal Institute for Risk Assessment (BfR). Her research
interests involve residue analytical methods, environmental analysis, ecotoxicology, and
herpetology. She has published 12 scientific journal articles and book chapters.

Baerbel Vieth studied chemistry at the Humboldt University in Berlin. After finishing the
Ph.D. in 1981, her research has been focused on the development and application of HPLC
methods in trace analysis of drugs, enzyme activities, and of pesticides. In 1991, she joined
the former Federal Health Office of Germany, which is now the Federal Institute for Risk
Assessment (BfR). Besides residue analytical methods for pesticides, she has been
responsible for evaluation of residues in human milk with special focus on POPs. She has
published about 30 articles in scientific journals.

At present, Lutz Alder, Kerstin Greulich, and Baerbel Vieth are responsible for the
evaluation of residue analytical methods provided for registration of new pesticides in
Germany and contribute to authorization of plant protection products in Europe.

Guenther Kempe studied food chemistry and analytical chemistry in Dresden/Germany.

He started his career in the Hygiene Institute Chemnitz, which became the State Institute
for Food and Health Protection of Saxony/Germany in 1991. Most of his research has been
concerned with pesticide residue analysis in food. Today he is the head of the residue
laboratory of the State Institute and chairmen of the Working Group Pesticides of the
Gesellschaft Deutscher Chemiker (Chemical Society of Germany). His publication list
contains 20 scientific articles and book chapters.

Mass Spectrometry Reviews DOI 10.1002/mas 865