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Analyst, July 1996, Vol. 121 (929-938)
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/AN9962100929
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929
Simultaneous Determination of 60 Pesticides
in Water Using Solid-phase Microextraction
and Gas Chromatography-Mass Spectrometry
Anna A. Boyd-Boland, Sonia Magdic and Janusz B. Pawliszyn*
Department of Chemistry and the Waterloo Centi-efor Groundwater Research,
University of Waterloo, Waterloo, Onturio, Canada N2L 3GI
A new method for the simultaneous determination of 60
pesticides by solid-phase microextraction and gas
chromatography-mass spectrometry is presented. The
analyte mixture contains representatives from each of the
organonitrogen,organochlorine and organophosphorus
classes. Both polyacrylate- and polydimethylsiloxane-
coated fibres are used to extract the analytes directly
from the samples over the concentration range
0.1-100 pg 1-1. The performances of the two types of
coating were compared. The limits of detection with both
coatings were determined to be at the ng 1-l to sub-ng I-1
levels, depending on the selectivity of the coating for an
analyte. The method was applied to the analysis of
samples obtained from the Russian and Canadian Arctic.
A contaminated groundwater sample and a contaminated
soil sample, both containing metolachlor, were analysed
by the proposed method and the results were found to be
comparable to those obtained by a liquid-liquid
extraction method. Orange juice was spiked with the 60
pesticides and their recoveries were determined.
Keywords: Solid-phase microextraction; gas
chromatography-mass spectrometry; pesticides;
polydiim4thylsil~~xane;
polyacrylute
Introduction
The need for simple methods for screening water samples for
environmental contaminants is well known. Pesticides represent
an almost universal contaminant in many drinking waters,
ground water and soils.l-18 Total pesticide production in the
USA exceeds 1 X 1O9 pounds per year. Typical concentration
levels of pesticides in contaminated waters range from low
pg 1-1 to low ng mI-l.'-IX.20 The qualitative and quantitative
determination of pesticides in aqueous samples is usually
performed by liquid-liquid extraction (LLE)l-'-' or solid-
phase extraction (SPE)2-3,7,12-14,1732 methods. These two
procedures require several steps for sample preparation and
extraction of the analytes of interest. To achieve the required
limits of detection, a concentration step (solvent evaporation) is
included. It is at this stage in the analysis that the potential for
loss of analytes or contamination of samples is the greatest.
Although this step is less aggressive in SPE methods, where the
amounts of solvent used are smaller than those used for LLE
methods, volatile analytes may still be lost during the
evaporation step, adsorption to vial walls can occur and trace
impurities present in solvents can also become concentrated. It
is therefore desirable to limit the number of sample handling
steps involved in any analytical method.
Solid-phase microextraction (SPME) is an alternative tech-
nique that involves direct extraction of the analytes with the use
' To whom correspondence should be addres\ed.
of a small-diameter optical fibre that has been coated with a
polymeric stationary phase and housed in a syringe assembly
for protection. SPME eliminates the separate concentration step
from the SPE and LLE methods because the analytes diffuse
directly into the coating of the SPME device and are
concentrated there. This device is then transferred directly into
the injection port of' the gas chromatograph where all the
analytes are thermally desorbed and deposited at the head of the
GC column. The SPME process has been described in detail and
will not be fully examined here,2s but one aspect of the SPME
process, the selection of an appropriate coating, will be
discussed in detail in Results.
SPME methods have been developed for a variety of
applications, including drugs in urine and blood, volatile
organic compounds in air, fatty acids and flavours in foods and
beverages.'Sp26 Methods have also been described for the
analysis of some pesticides.377-41 However, none of these
methods has been shown to be applicable to the analysis of more
than 25 analytes from more than two of the main classes of
pesticides. In this paper, an SPME method coupled with GC-
MS for the simultaneous determination of 60 pesticides is
described. The target analytes represent pesticides from three
major classes, i.e., organochlorine, organophosphorus and
organonitrogen pesticides. A list of the analytes and the classes
to which they belong is given in Table 1.
The suitability of the relatively polar pol yacrylate-coated
fibre and the non-polar polydimethylsiloxane-coated fibre was
investigated. The limits of detection and precision data are
given for each coating. The proposed method is shown to be
ideally suited for routine screening of water samples and for the
determination of pesticides in water from mg 1-' to pg 1-I
levels.
Experimental
SPME Fibres
The 100 pm thick polydimethylsiloxane fibres used are
commercially available (Supelco, Mississauga, Canada). The
95 pm thick polyacrylate fibres (purchased from Polymicro
Technologies, Phoenix, AZ. USA) were prepared manually.2s
Tne coated fibres were conditioned according to the manu-
facturers' instructions to ensure that any contaminants that
might be present were removed prior to use. In general, this
involved exposing the fibre to the hot GC injection port (250
"C) for at least 3 h until no peaks were detected in blank
analyses. If the polyacrylate fibre was not successfully
conditioned by that procedure, the procedure of Buchholz and
Pawliszyn,32 which is briefly described here, was used. The
coated fibres were placed inside a stainless-steel tube through
which a stream of helium flowed. The stainless-steel tube was
then placed inside a muffle furnace and held at 300 "C for 4 h.
After mounting the fibres in the needle assembly, further
conditioning under helium at 250 "C in the injection port of a
gas chromatograph was required to remove impurities which
might be present from the epoxy.
 View Online

930 Analyst, July 1996, Vol. 121

Reagents Organophosphorus pesticides. Two standard mixtures

Nitrogen-containing herbicides. Two standard mixtures (her-
bicide mix 1 and herbicide mix 2; Supelco Canada, catalogue
numbers 4-9136 and 4-9138, respectively, 100 pg ml-1) were
purchased and used for preparation of the composite standard.
(Supelco Canada, catalogue numbers 4-8391 and 4-8469,2000
pg ml-- I ) were combined with isoxathion, fenitrothion, ipro-
fenfos, EPN and diazinon (Wako, Osaka, Japan; 98-99%
purity) and diluted to contain 200 pg ml-1 of each analyte, with
the exception of disulfoton and methyl parathion, which were

Table 1 Classification of the 60 target analytes

Retention
Pesticide type Target analyte class Analyte Selected ion time/min
Nitrogen-containing herbicides Acetanilide Metolachlor 162 31.34
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/AN9962100929

Diphenyl Ether Oxyfluorofen 36 1 35.52

Nitroanilines Benfluralin 292 25.03
Isopropalin 280 32.44
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Pendimethalin 252 33.02

Profluralin 318 27.22
Trifluralin 306 24.58
Substituted uracils Bromacil 207 3 1.04
Terbacil 161 28.06
Substituted amide Propachlor 120 23.22
Thiocarbamates EPTC 128 17.09
Butylate 146 18.56
Cycloate 154 23.55
Molinate 126 21.32
Pebulate 204 19.43
Vemolate 128 19.19
Triazines Atrazine 216 26.33
Hexazinone 171 38.58
Metribuzin 198 29.23
Propazine 214 26.45
Simazine 202 26.21
Triazole Oxadiazon 258 35.40
Organochlorine pesticides Cyclodienes Aldrin 263 31.29
Dieldrin 79 35.37
Endosulfan I 24 1 34.34
Endosulfan I1 195 & 159 36.48
Endosulfan sulfate 272 38.29
Endrin 263 36.28
Endrin aldehyde 345 37.32
Endrin ketone 317 40.17
Heptachl or 100 30.01
Hetpachlor epoxide 353 33.06
Diphenyl aliphatics Methoxychlor 227 40.48
p,p’-DDD 235 37.08
p,p’-DDE 246 35.31
p,p’-DDT 235 38.38
Hexachlorocyclohexanes a-BHC 181 25.26
0-BHC 181 26.38
6-BHC 181 27.52
Lindane (y-BHC) 181 26.53
Organophosphorus pesticides Phosphate Dichlorvos 109 14.32
Phosphonothioate EPN 157 40.34
Phosphorodithioates Azinphos-methyl 160 41.55
Dimethoate 230 26.02
Disulfoton 89 27.54
Ethoprofos 243 23.53
Phorate 75 25.18
Prothiofos 309 35.15
Phosphorothiolate Iprofenfos (IBP) 91 28.36
Phosphorothionate Chlorpyrifos 3 14 31.44
Diazinon 305 27.44
Ethyl Parathion 292 3 1.46
Famphur 218 38.05
Fenchlorvos 285 30.18
Fenitrothion 125 30.49
Isoxathion 100 31.15
Methyl Parathion 109 29.4 I
O,O,O-Tiethylphos-
phorothiate (O,O,O,-
TEP) I98 12.40
Thionazin 249 23.14
Pyrophosphate Sulfotep 322 25.09
 View Online

Analyst, July 1996, Vol. 121 93 1

present in both the standard mixes, and hence were present in
the organophosphorus pesticide mixture at 400 pg ml-1.
Organochlorine pesticides. The standard mixture (Supelco
Canada, catalogue number 4-8913, 2000 pg ml-1) was diluted
in methanol to 200 pg ml-I.
Composite standard. This was prepared by addition of 25 pl
of each of the herbicide mixes and the diluted organophospho-
rus standard and 12.5 pl of the organochlorine standard and
dilution to 100 pl with ethyl acetate. The final standard
contained each analyte at 25 pg ml-l, with the exception of
disulfoton and methyl parathion, which were present at 50
pg ml-1. Stock standard solutions were freshly prepared at least
every 2 weeks and used to prepare 4 ml working standard
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/AN9962100929
spectrometric detector. A 30 m X 0.25 mm id SPB-5 (0.25 pm)
column was used. The column temperature programme was as
follows: 40 "C held for 5 min., ramped to 100 "C at 30
"C min-1, ramped to 275 "C at 5 "C min-1 and ramped to 300
"C at 30 "C min-1, with a final hold for 2 min. The injector, the
transfer line and the ion-trap manifold were held at 250 "C. The
mass spectrometer was tuned to FC-43 (perfluorotri-
butylamine). The electron multiplier and automatic gain control
were set automatically. The mass range scanned was 45-400 u.
The detector was turned off for the first 300 s to prevent
overloading the electron multiplier from the solvents used in the
preparation of the composite standard.
Mass spectra were collected in the total ion current mode for

conditions at the required concentration. each analysis; however, one or two characteristic mass
Aqueous standards. All standard solutions were prepared fragments were chosen for quantification and calibration. The
with NANOpure water (Barnstead ultrapure water system) . ions selected for each analyte are listed in Table 1.
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Blank analyses were performed regularly to ensure that no

herbicides were present in laboratory reagents or fibres.
Russian and Canadian Arctic Samples
Samples were obtained from the Waterloo Centre for Ground-
water Research. The Canadian samples were both core ice and
surface snow samples collected in May 1993 and May 1994.
The Russian samples were collected from ice caps: Acad Navr,
Lenningradski, Alexander, Usha Kova and Graham Bell.
Samples were allowed to melt under refrigeration and stored as
liquids in brown glass bottles.
Contaminated Groundwater and Soil Samples
Groundwater and soil samples were collected from Cambridge,
Ontario, Canada: water from well number 40-9320 and soil
from borehole number BH-50. The water was analysed in
triplicate in 4 ml aliquots by the procedure described in this
section. The soil was analysed by suspending 0.5 g of the
sample in 4 ml of water and exposing the SPME device to the
water-soil mixture.
Instrumentation
All analyses were performed with a Varian Model 3400 gas
chromatograph coupled with a Varian Saturn ion-trap mass
Analytical Procedure
Aqueous standard solutions were prepared by spiking an
appropriate amount of working standard solution into 4.6 ml
clear vials (Supelco Canada) containing 4 ml of NANOpure
water, that were sealed with hole-caps and Teflon-lined septa
(Supelco Canada). After addition of the aliquot and a stirrer bar
to the vial, approximately 0.5 ml of headspace was left into
which the needle was placed to prevent wicking of the sample
during extraction. The fibre was then exposed to the aqueous
phase for 50 min with stirring at room temperature (about 23
"C). After extraction, the fibre was directly exposed to the hot
injector of the gas chromatograph for 5 min and subsequently
analysed.
Sample Analysis
All aqueous samples were directly analysed by taking 4 ml
aliquots with an autopipette (Model 5000, Nichiryo, Japan).
Both standard addition and external calibration methods were
used to quantify the amount of an analyte identified in the
aqueous sample. Samples were first analysed and pesticides
identified if their mass spectra and retention times were the
same as those found for standards. Subsequently, triplicate real
samples, together with triplicate spiked samples or triplicate

4000000
-
- Trifluralin

-
h
v)
3000000

2000000 -
-
Benfluralin

Profluralin

-
C
3

8 lsopropalin
1000000
?? Pendimethalin
v

->
.-
Y

v)
0
0 20 40 60 80 100 120
c
a,
.-C
a,
.-c
- 2 1000000
n:

400000
-
- b-BHC
Lindane

200000

0
0 20 40 60 80 100 120
Extractiontime/min
Fig. 1 Extraction time profiles for ( a )nitroanilines extracted with the polyacrylate fibre and (h) HCHs extracted with the polydimethylsiloxane fibre.
 View Online

932 Analyst, July 1996, Vol. 121

aqueous standard solutions were analysed and the amount of Results and Discussion
any pesticide detected was calculated. The concentrations
Solid-phase microextraction is an equilibrium process. It
spiked were 10 and 20 ng ml-1.
involves the partitioning of analytes between the sample matrix
and a polymeric stationary phase that has been coated on to a
fused-silica fibre, according to the partition coefficients, K, of
Table 2 Limits of detection (LOD), equilibration times and precision* the analytes. These coefficients can be defined by the following
equation:Zs
Equilibration Precision
LODt/ng 1-’ time/min (RSD, %) nJa,
K=- (1)
Target analyte PAC PDMS PAC PDMS PAC PDMS nqvs
O,O,O-TEP 8 3 90 30 3 11 where n, is the amount extracted by the fibre coating at
Dichlorovos 33 30 30 30 16 12 equilibrium, n,, is the amount present in the aqueous phase at
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/AN9962100929

EPTC 16 2 60 30 19 14 equilibrium and V,, and V , are the volumes of the aqueous and
Butylate 1 1 60 60 10 3 stationary phases, respectively. It can be seen that the amount of
Vemolate 2 I 60 60 12 10 an analyte extracted at equilibrium is directly proportional to the
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Pebulate 19 14 60 60 7 10 volume of the stationary phase and the partition coefficient.

Molinate 12 4 60 30 8 14
Hence the sensitivity and limit of detection of the method will
Thionazin 23 17 60 30 14 12
Propachlor 16 13 30 30 13 6 be dependent on the partition coefficient.
Ethoprofos 4 5 90 30 11 13 The most significant factor affecting the magnitude of the
Cycloate 1 1 60 60 11 5 partition coefficient is the affinity of an analyte for the fibre
Trifluralin I 1 60 >I20 6 7
Benfluralin 1 1 60 >120 4 7
Sulfotep 1 1 60 90 5 8
Phorate 2 1 90 60 2 10
a-BHC 1 1 30 60 5 9
Dimethoate 60 50 30 30 17 13
Simazine 15 18 60 30 19 37
Atrazine 11 23 30 30 4 3
(3-BHC 1 1 60 60 5 17
Propazine 6 5 30 30 13 4
Lindane 1 1 90 30 6 7
Profluralin I 1 60 >120 4 7
Diazinon 1 1 90 60 5 10
6-BHC 1 2 90 60 6 6
Disulfoton 2 0.7 90 60 8 6
Terbacil 9 9 30 30 17 17
Iprofenfos 5 6 30 30 12 6 13:ZB 28:EE
Metribuzin 19 4 60 >120 13 31
Methyl parathion 3 3 90 30 5 7
24-26
Heptachlor 1 1 60 >120 5 14 41/42 45/46 u-
Fenchlorovos 1 1 90 >120 15 10 12-16 I 1749
57
I
Fenitrothion 7 9 90 30 4 10
Bromacil 8 10 30 30 9 8
Isoxathion 1 1 90 60 10 7 I
Aldrin I 1 90 >I20 9 2
Metolachlor 8 9 30 30 16 5
Chloropy rifos 1 1 90 120 8 8
Ethyl parathion 1 1 90 60 4 12
Isopropalin 1 1 60 > I 2 0 I1 6
Pendimethalin 1 1 60 >I20 2 6
Heptachlor epoxide 1 1 60 90 2 10
Endosulfan I 1 1 90 >120 6 8
Prothiofos 1 1 60 90 17 7
p,p’-DDE 1 1 60 >120 5 20 I
1688 2888
Dieldrin 1 1 90 120 5 19 888
13:28 28:88 2 6 : ~ 33:28
Oxidiazon 1 1 60 60 8 4
Time/m in
Oxyfluorofen 1 1 90 >120 8 9
Endrin 1 1 90 >120 5 6 Fig. 2 Simultaneous determination of 60 pesticide in a mixture by SPME
Endosulfan I1 1 1 90 > I 2 0 10 12 with GC-MS and (a)polydimethylsiloxane and (b)polyacrylate fibre, with
p.p’-DDD 0.1 1 90 >I20 10 19 a 50 min extraction from 100 ng 1-l solutions. Peak identification: 1,
Endrin aldehyde 0.8 2 60 >I20 14 20 O,O,O-TEP; 2, dichlorovos; 3, EPTC; 4, butylate; 5 , vernolate; 6, pebulate;
Famphur 33 18 30 30 10 10 7, molinate; 8, thionazin; 9, propachlor; 10, ethoprofos; 11, cycloate; 12,
Endosulfan sulfate 1 0.6 90 60 7 6 trifluralin; 13, benfluralin; 14, sulfotep; 15, phorate; 16, a-BHC; 17,
p,p’-DDT 1 1 60 >I20 11 10 dimethoate; 18, simazine; 19, atrazine; 20, P-BHC; 21, propazine; 22,
Hexazinone 15 6 30 30 20 20 lindane; 23, profluralin; 24, diazinon; 25, 6-BHC; 26, disulfoton; 27,
Endrin ketone 1 1 90 60 4 4 terbacil; 28, iprofenfos; 29, metribuzin; 30, methyl parathion; 3 1,
EPN 1 1 30 30 6 4 heptachlor; 32, fenchlorovos; 33, fenitrothion; 34, bromacil; 35, isoxathion;
Methoxychlor I 1 90 >120 10 4 36, aldrin; 37, metolachlor; 38, chloropyrifos; 39, ethyl parathion; 40,
Azinphos-methy 1 19 2 60 30 10 13 isopropalin; 41, pendimethalin; 42, heptachlor epoxide; 43, endosulfan I;
I- PAC is 95 pm polyacrylate and PDMS is 100 Clm POlY - 44, prothiofos; 45, p,p’-DDE; 46, dieldrin; 47, oxadiazon; 48, oxyfluorofen;
dimethylsiloxane. Calcuiated for the line of best fit with a zero intercept, 49, endrin; 50, endosulfan 11; 51, p,p’-DDD; 52, endrin aldehyde; 53,
over the range 0.1-100 pg I-’ (three replicates at each point). famphur; 54, endosulfan sulfate; 55, p,p’-DDT; 56, hexazinone; 57, endrin
ketone; 58, EPN; 59, Methoxychlor; 60, azinphos-methyl.
 View Online

Analyst, .luly 1996, Vol. 121 933

coating. The choice of an appropriate stationary phase is thus
extremely important. Two coated fibres available commer-
cially, polydimethylsiloxane and polyacrylate, were tested for
their suitability for the combined pesticide analysis. Organo-
chlorine pesticides are relatively non-polar, Pat-soluble ana-
lytes, whereas organophosphorus pesticides are relatively polar,
highly water-soluble analytes. It is likely, then, that these
compounds will be best extracted with different coatings. The
important factor then becomes the conditions, under which
adequate extraction of both of these classes can be achieved.
One consideration is the choice of an appropriate extraction
time. Since the rate at which the extraction process reaches
equilibrium is primarily dependent on the rate of mass transfer
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/AN9962100929
as that in methods developed for the analytes in separate
mixtures. The equilibration time may be determined experimen-
tally by constructing an extraction time profile (Fig. 1) in which
the extraction time is plotted against the GC area counts. Table
2 shows the equilibration times, determined by this procedure,
for each class of analyte extracted with both fibres. The
equilibration times ranged from 10 to > 120 min, with more
than half of the analytes reaching equilibrium by 50 min. The
optimized GC separation is 44 min in duration, so a 50 min
extraction time provides optimum time efficiency for the SPME
method by ensuring that once the GC run is completed and the
oven has cooled to the initial temperature (approximately 5
min), the next sample is ready for injection.

in the aqueous phase, it is essential that constant rapid stirring is
employed.35 It is also important to maintain a constant
temperature within +2 "C during the extraction since large
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The equilibration times determined for the analytes with this
combined method compare well with those reported using other
methods for the respective a n a l ~ t e s . 3 7This
~ ~ indicates that

fluctuations may affect the rate of mass transfer and thus the
equilibration time. Temperature variations may also lead to
significant reproducibility errors and thus affect the over-all
precision of the method. Therefore, the time for each analyte in
the combined mixture to reach equilibrium should be the same
increasing the number of target analytes from 20 to 60 does not
affect the kinetics of the extraction process. The equilibration
times of each analyte with each fibre are the same or relatively
close. The exceptions are analytes that are very well extracted
by the polydimethylsiloxane fibre ( i . ~ . they, have large K

8.ooO.OOO

6,000,000

4.m.000

2000.000

4.000,OOO t 1

3.000.000

2.000.000

1 .o0O,o0o

dl
mm
0
0 0

x
c 5
w $
4 W

Fig. 3 Effect of addition of salt to the matrix with the polyacrylate fibre for ( a ) nitrogen-containing herbicides, ( h )organophosphorus pesticides and ( c )
organochlorine pesticides.

934 Analyst, July 1996, Vol. 121
values). The polydimethylsiloxane coating has a slightly larger
volume than the polyacrylate coating and hence a slightly larger
capacity for an analyte even when the K values of the analyte for
each coating are similar. When the K values are much larger for
an analyte with the polydimethylsiloxane fibre than they are
with the polyacrylate, the time to reach equilibrium is expected
to be longer. This was observed for some analytes from the
nitroaniline, cyclodiene and diphenyl aliphatic classes of
pesticide. The polydimethylsiloxane coating is almost capable
of completely extracting these analytes from an aqueous sample
at low concentration and volume.
The two factors that have the potential to be affected by
choosing an extraction time that is less than the time required for
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/AN9962100929
equilibrium are precision and sensitivity. The former could be
adversely affected if the extraction time is not carefully
monitored, since slight deviations in the extraction time may
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imply large variations in the amount extracted when equilibrium
has not been established. The precision of the method was
determined using a 50 min extraction time with a set of seven
replicates using both of the coated fibres with MS detection
(Table 2). Most analytes were extracted with relative standard
deviations (RSDs) ranging from 2 to 20%. Although this
precision is more than adequate for US EPA requirements, if the
I w
Fig. 4 Effect of addition of salt to the matrix with the polydimethylsiloxane fibre for ( a )nitrogen-containing herbicides, (b)organophosphorus pesticides
and (c) organochlorine pesticides.
View Online
time is not carefully monitored, the precision could be
unacceptable. It is therefore recommended that all extractions
be performed for 50 k 2 min. Fortunately, the SPME extraction
procedure can be easily automated. The autosampler used for
SPME is a modified syringe injection system. The autosamplers
fit directly on to most conventional gas chromatographs with no
modification required, and provide a simple way of controlling
the extraction time.
The sensitivity of SPME methods is primarily dependent on
the K value of an analyte. If extractions are performed before
equilibrium has been reached, the method is generally being
operated at less than optimum sensitivity. Fortunately, the
analytes with smaller K values generally have the shortest
equilibration times (typically less than the 50 min selected
here), so the overall sensitivity of the method is not adversely
affected. Fig. 2 shows a chromatogram obtained from a 50 min
extraction of a 100 pg 1-l sample of the 60 pesticide mixture
with ( a ) polydimethylsiloxane and ( h )polyacrylate.
The chromatograms in Fig. 2 show the successful extraction
of the 60 pesticides. The retention times of the analytes are
listed in Table 2, together with the relevant mass ion used for
quantification. Of the 60 analytes, only five pairs of analytes
completely overlap: ethoprofos and cycloate; atrazine and
L3g
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Analyst, July 1996, Vol. 121 935

CJ-BHC; 6-BHC and disulfoton; chlorpyrifos and ethyl para-
thion; and pendimethalin and heptachlor. If the analysis of all 60
pesticides was attempted with the use of flame ionization
detection, quantification would be very difficult. In some cases,
the use of dual detection with nitrogen-phosphorus detection
(NPD) and electron-capture detection (ECD) would permit the
resolution of the components. However, these analytes are
easily detected and quantified by MS by selecting an appro-
priate quantification mass. Fortunately, those analytes which do
overlap have sufficiently different mass spectra so that selecting
several quantification ions is possible. The use of MS detection
also allows the confirmation of the identity of target analytes
detected in real samples.
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/AN9962100929
even under neutral conditions, the limits of detection (Table 2)
are sufficiently low with GC-MS to allow the determination of
all the analytes at low- to sub-ng 1-1 levels. All the analytes
exhibit detection limits that are significantly lower than those
required by the US EPA drinking water and waste water
methods.
The calculated limits of detection are presented in Table 2.
The values were calculated from 10 pg 1- extractions using the
recommended procedure for each coated fibre and detection by
MS. The limits of detection are calculated as the concentration
in the aqueous sample that produces a peak that has a signal-to-
noise ratio of 3. However, even at this low concentration,
several analyte peaks have signal-to-noise ratios well in excess

The effect of varying the ionic strength was tested for the of 100, and even up to 1000. This occurred as a result of the
analytes with both coatings by comparing the results obtained extremely low abundance of the ion selected for quantification
for unsalted and 25% NaCl solutions. The results are shown in in the background noise. For these analytes, the limit of
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Figs. 3 and 4.The 25% salt concentration was found to affect detection was estimated to be at least 1 ng 1-1. The linearity of
the extraction of target analytes differently depending on the the method was investigated over the range 0.1-100 pg 1-1,
class to which the analyte belongs. These findings are generally with both fibres and GC-MS. The correlation coefficients and
in agreement with previously published results for the same slopes of the line of best fit (forced through the origin) are also
analytes with different methods.37~38Interestingly, the addition
of salt showed the same influence (i.e., either a positive or
negative effect) for each analyte independent of the type of
coating used. This indicates that the addition of salt primarily Table 3 Results of the analysis of Russian Arctic Samples
affects an analyte's affinity for the aqueous phase rather than its
Concentration in sample/ng 1-1
affinity for the coating. The polarities of the two phases,
although different, are not sufficiently different to overcome the Target analyte Acad Lennin- Graham Usha
influence of the salt on the polarity and ionic strength of the detected Navr gradski Alexander Bell Kova
aqueous phase. There were a few exceptions to this general Dichlorovos 500 700 1500 600 ND*
observation, viz., endrin aldehyde, heptachlor epoxide and EPTC 440 140 120 ND 180
diazinon. Butylate ND ND ND 110 ND
Not surprisingly, different classes of analytes have different Vernolate 470 96 94 ND 170
conditions under which optimum extraction occurs; however, Molinate 150 14 ND 38 36
Thionazin ND 430 630 480 320
Propachlor 300 70 90 200 260
C ycloate 20 50 40 80 140
Trifluralin 2200 950 870 2200 1900
Sulfotep ND 2.3 2.1 4.3 5.7
f Phorate ND 24 ND ND 20
a-BHC 1000 380 690 200 220
Simazine ND ND 1100 2500 1100
Lindane 170 20 97 78 36
Profluralin 1300 700 520 1400 1090
6-BHC 98 ND 110 74 40
Disulfoton 5.8 7.7 7.2 8.5 7.9
Iprofenfos 52 95 83 76 110
Methyl parathion ND 84 ND 110 79
Heptachlor 58 160 99 280 210
Fenchlorvos 320 160 100 330 350
1688 2000 2400 Fenitrothion ND ND 180 240 320
26 :40 m:ze 48 :88
Isoxathion 43 45 43 82 92
Aldrin 280 310 220 3 10 290
Metolachlor 24 45 23 34 110

r Isopropalin
Pendimethalin
4200 1600
910 470
100
310
3700
920
2600
790
162 t Heptachlor epoxide 98 42 11 67 58
I
I
238
t Endosulfan I
Prothiofos
240
2300 1000
130 140
660
140
2100
100
1800
5 1 91 , 284 328 p,p'-DDE 4000 2000 900 2300 2000
Oxadiazon 65 93 72 150 130
Oxy fluorofen 950 620 480 1900 1500
Endrin 10 38 2.1 83 60
Endosulfan I1 120 89 60 99 97
p,p'-DDD 1100 370 270 120 840
Endrin aldehyde 5.3 150 9.9 96 95
Famphur 70 99 110 350 180
Endosulfan sulfate 1.5 ND ND ND ND
p,p'-DDT ND 290 240 750 620
Endrin ketone 69 24 20 27 33
EPN 700 55 24 150 140
Time/min
Methoxychlor 2100 160 72 590 370
Fig. 5 Chromatograms obtained for extraction of (a)contaminated ground * ND = not detected or detected below the limit of quantification.
water and (b)contaminated soil.
 View Online

936 Analyst, July 1996, Vol. 121

provided in Table 2. Most of the analytes had correlation presence of the target analytes. The water sample (60 ml) had
coefficients ranging from 0.990 to 1.000 with polydimethylsi- been previously analysed for the presence of metolachlor using
loxane and from 0.997 to 1.000 with polyacrylate when three LLE, while the soil sample ( 5 g) had been analysed using
significant figures are used. Soxhlet extraction. Similar concentrations of metolachlor were
The method was then applied to the analysis of real samples. detected in the water samples by SPME (1.16 mg 1-1) and
Contaminated ground water and soil were screened for the conventional LLE42 (0.95 mg 1-1). The soil was analysed by
stirring 0.5 g of the soil in 4 ml of water and exposing the SPME
device directly to the resultant slurry for the recommended SO
Table 4 Target analytes detected in Canadian Arctic samples min. The concentrations of metolachlor were determined to be
I .84 and 1.85 mg kg-1 (Ref. 42) when the sample was analysed
Ice core/ Surface using SPME and Soxhlet extraction, respectively. The results
Target analyte detected ng I-' snowfng 1-1 indicate that for metolachlor, a relatively water-soluble com-
Dichlorovos 14 8 pound (solubility = 530 mg 1- l ) , extraction from soil by the
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/AN9962100929

Butylate ND* 6 addition of water is as effective as traditionally accepted LLE

Vernolate 3 ND methods. However, the extraction from soil is likely to be
Ethoprofos 5 5 incomplete if the analyte is not very water soluble or is bound to
Downloaded by University of Wisconsin - Madison on 04 October 2012

Cycloate 3 1 the soil, as has been observed previously for LLE methods. The
Trifluralin 8 7 need for a more vigorous extraction procedure to ensure total
Benfluralin 9 13
extraction of many analytes from a soil matrix is generally
Phorate 3 ND
a-BHC 3 5 necessary. Supercritical fluid extraction and Soxhlet extraction
(3-BHC ND 2 provide alternatives that can be coupled with SPME to provide
Heptachlor 18 12 complete information about the interaction between target
Propazine ND 16 analytes and the soil matrix.
Lindane 5 ND Chromatograms of the water and soil extractions are shown
Profluralin 10 11 in Fig. 5(a) and (b),respectively. The dominant peak in both
6-BHC 402 49 1 chromatograms is the metolachlor peak at 29 min 13 s. It is
lprofenfos 8 6 obvious that the soil sample contains more extracted species
Fenchlorvos 7 6
that have peak heights close to that of the metolachlor peak.
B romac il 10 10
Isoxathion 14 3
This is a reflection of the more complex matrix of soil compared
Aldrin 21 3 with water, and shows the ability of the SPME method to detect
Chlorpyrifos 10 6 various components of the sample.
Ethyl parathion 2 I Surface snow and ice-core samples from the Russian and
Isopropalin 21 12 Canadian Arctic were analysed in triplicate. The analytes
Pendimethalin 24 13 detected in the Russian and Canadian samples are given in
Heptachlor epoxide 18 6 Tables 3 and 4, respectively. The relative standard deviations
Endosulfan 1 ND 12 were estimated to be 2-2096, based on triplicate analyses. Only
p,p'-DDE 50 46
those target analytes that were detected above the limit of
Dieldrin 199 203
Oxadiazon 37 11
quantification are reported. Many of the 60 target analytes were
Oxyfluorofen 62 27 detected in the samples and their presence was confirmed by
Endrin 35 14 comparing the mass spectra and retention times of detected
Endosulfan I1 567 323 peaks with those of the standards. The Canadian Arctic samples
p 9'-DD D 59 48 were previously analysed for the presence of organochlorine
Endrin aldehyde 58 29 pesticides by SPME with a polydimethylsiloxane-coated fibre
Fdmphu r 53 39 and GC-ECD.38 Generally, the results of these analyses were in
Endosulfan sulfate 12 5 agreement .
p,p'-DDT 19 14
The results obtained for the Arctic samples are indicative of
Endrin ketone 29 11
EPN 6 6 the environmental persistence of organochlorine pesticides that
Methoxy chlor 41 17 have been banned from use in North America and Western
Europe for close to 10 years. The concentrations of the other
* ND = not detected or detected below the limit of quantification.
classes of pesticides are lower than the organochlorine levels
detected, even though the other classes are produced and
applied in much greater quantities throughout the world. The
results reflect the persistence of organochlorines that can be
transported through the atmosphere without significantly de-
grading. The other pesticides can be degraded more readily and
24-26 therefore the amount of the parent compound available for
I 34.37
transport is reduced. Generally, the results of the Arctic
sampling show that pollution by pesticides and herbicides is a
- serious environmental concern.
c
As a final example of the use of the method for screening
samples, an orange juice sample was spiked with the target
analytes to produce a concentration of 2 pg 1- I of each analyte
in the juice (4 pg 1-1 of disulfoton and methyl parathion). When
the samples were analysed by comparison with a calibration
1288 1688 20B0
curve prepared from extraction of standard aqueous solutions,
13 :zB m:m 26:48 33:tB the concentration detected was generally lower than the true
Time/min value. This is obviously due to the interference of the matrix,
Fig. 6 Detection of spiked analytes in orange juice. For peak identification which may compete with the coating and retain analytes. This
see Fig. 2. has the effect of raising the limit of detection of the analytes,

however, at the 2 pg 1 - 1 level all 60 of the analytes were
detected by the method (see Fig. 6). It is also obvious from this
analysis that if complex matrices are to be analysed, the
standard addition or isotope spiking methods are required for
accurate calibration of analytes. The advantage of this method is
the relative ease with which analytes can be screened even at
low ng 1-1 concentrations.
Conclusions
A method for the simultaneous determination of 60 pesticides in
water has been developed. Either a polydimethylsiloxane- or a
polyacrylate-coated fibre may be used to achieve detection
limits in the low pg 1- 1 range for aqueous samples. The method
Published on 01 January 1996 on http://pubs.rsc.org | doi:10.1039/AN9962100929
has been shown to exhibit adequate precision and good linearity
over the range 0 . 1 - 100 pg 1 - I . The application of the method to
Downloaded by University of Wisconsin - Madison on 04 October 2012
the analysis of water samples from ice cores, snow samples and
ground water has been shown. The method has been used to
analyse samples obtained from both the Russian and Canadian
Arctic. The results of the determination of metolachlor from soil
were shown to be comparable to those obtained by LLE, by
simply adding water to soil and extracting with the SPME
device. Finally, the qualitative detection of the target aiialytes in
orange juice demonstrated the applicability of the method to the
beverage industry.
The authors gratefully acknowledge financial support from the
Natural Sciences and Engineering Research Couiicil of Canada,
Varian and Supelco. A. Steffen is acknowledged for her help
with the orange juice analysis. Finally, thanks are extended to
M. McMaster for contributing the LLE and Soxhlet extraction
results .
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Paper 51082431
Received December 19,1995
Accepted March 19, I996