C H A P T E R 2 8

PESTICIDES

28.1. CHLORINATED PESTICIDES

A. GC separations
1. Lindane, heptachlor, aldrin, a- and g-chlordane, dieldrin, DDT, and
similar compounds.
a. 30-m CP-Sil 8 CB* column, 60–300 °C at 4 °C min�1. Run for
52 minutes.
b. 30-m DB-5 column, 50 (2 minutes)–140 °C at 20 °C min�1;
140–300 °C at 4 °C min�1.*
c. 15–30-m DB-608 column, 140 (2 minutes)–240 °C at 10 °C min�1;
240 (5 minutes)–265 °C at 5 °C min�1.
d. 50-m CP-Sil 88 column, 60–225 °C at 20 °C min�1.
B. Pesticide extraction procedures
1. For pesticide extraction procedures pertaining to food samples, refer
to U.S. Government Manuals on pesticide residue analysis [1].
2. For pesticide extraction from aqueous samples [2].
3. The Environmental Protection Agency (EPA) has prepared a manual
of pesticide residue analysis dealing with samples of blood, urine,
human tissue, and excreta, as well as water, air, soil, and dust.
Manual of Analytical Methods, edited by Thompson, JF, Quality
Assurance Section, Chemistry Branch EPA, Environmental
Toxicology Division, Pesticides Health Effects Research
Laboratory, Research Triangle Park, NC 27711.
4. Pesticide bulletins are available from Supelco, Inc., Supelco Park,
Bellefonte, PA 16823.
C. Structure of common chlorinated pesticides and abundant ions
The following values reported for the MW of these chlorinated
pesticides are actually the nominal mass values for these molecules. The
nominal mass of Cl is 35. The atomic mass (weight) of Cl is 35.453;
therefore, the integer molecular weight for lindane is 291 Da. Integer
masses reported in mass spectrometry are based on nominal mass

*
The DB-5 column may be used but does not provide enough GC resolution if metabolites
are present.
Gas Chromatography and Mass Spectrometry � 2010 by Academic Press. Inc.
DOI: 10.1016/B978-0-12-373628-4.00028-9 All rights reserved.

373
374 Chapter 28

because mass spectrometry involves the masses of the isotopes of the

elements, not their atomic weights.
1. Lindane
Cl

Cl Cl

Cl Cl

Cl
C6H6Cl6 (MW = 288 Da)

2. Heptachlor
Cl
Cl
C
CL
CL

CL Cl

Cl

C10H7Cl7 (MW = 370 Da)

3. Aldrin
H
Cl Cl H
C Cl C

Cl

Cl Cl

C12H8Cl6 (MW = 362 Da)

4. Chlordane
Cl
Cl
C
CL
CL

Cl
CL Cl

Cl

C10H6Cl8 (MW = 406 Da)

Pesticides 375

100 375
Cl
Cl
Cl

Cl

237
50 Cl
65 Cl Cl 272
Cl 263
39 75 99
109 160 196 301
85 119 143 167 337
51 253 410
27 313
0
20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420

Figure 28.1 EI mass spectrum of chlordane.

The M+• peak for chlordane is discernable in Figure 28.1. Note the
X+2 isotope pattern for eight chlorine atoms. The base peak at m/z
373 is the X+2 isotope peak with a nominal m/z value of 371, which
represents the ion formed by the loss of a •Cl from the molecular ion.
5. Dieldrin
H
Cl Cl H
C Cl C

Cl

Cl Cl
O

C12H8Cl8O (MW = 378 Da)

6. DDT
Cl Cl

C
Cl
C
Cl Cl

C14H8Cl5 (MW = 352 Da)

The M+• peak is apparent in the mass spectrum of DDT at m/z 352
(Figure 28.2) with the classic X+2 isotope pattern for an ion with five
376 Chapter 28

235
100

Cl Cl

50 165
Cl
Cl Cl

199
75 176 212 246
50 63 88 99 123136 150 282 318 354
27 39 183 220 262
0
20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360

Figure 28.2 EI mass spectrum of DDT.

atoms of chlorine (see Appendix E). The major fragment ion due to
the loss of CCl3 is represented by the peak at m/z 235.
7. Methoxychlor
CH3 CH3

O O

C
Cl Cl
Cl

C16H15Cl3O3 (MW = 344 Da)

28.2. ORGANOPHOSPHORUS PESTICIDES

A. GC separations
1. Diazinon, malathion, dimethoate, trichlorofon,* and so forth. 30-m
DB-5, SPB-5, or Supelco PTE-5 column, 100–300 °C at 4 °C min�1
or 150 (3 minutes)–250 °C at 5 °C min�1.
2. Dichlorovos, phorate, dimethoate, diazinon, disulfoton, methylparathion,
malathion, parathion, azinphos-methyl, azinphos-ethyl, and so forth.
50-m CP-Sil 13CB column, 75–250 °C at 10 °C min�1.
*
Trichlorofon loses HCl from the molecular ion producing a spectrum identical to that of
dichlorovos. These pesticides can be differentiated by preparing a TMS derivative and/or
their retention times.
Pesticides 377

B. Structures of common organophosphorus pesticides and m/z values

representing the most abundant ions
1. Dichlorovos*
O
H3CO O Cl
P C C
H3CO H Cl

C4H7Cl2O4P (MW = 220 Da)

2. Trichlorofon*
O
H3CO H
P
H3CO C CCl3
HO
C4H8O4Cl3P (MW = 256 Da)
3. Phorate (thimet)
S

P
(C2H5O)2 SCH2SC2H5

C7H17O2PS3 (MW = 260 Da)

4. Dimethoate
S H
P CH2 N
(C2H5O)2 S C CH3
O
C5H12NO3PS2 (MW = 229 Da)
5. Diazinon (dimpylate)
H
H5C2O OCH3
O N C
P
OCH3
H5C2O
O
N

CH3

C12H21N2O3PS (MW = 304 Da)

*
Trichlorofon loses HCl from the molecular ion producing a spectrum identical to that of
dichlorovos. These pesticides can be differentiated by preparing a TMS derivative and/or
their retention times.
378 Chapter 28

6. Disulfoton
S
H5C2O
P S
H5C2O S C2H5

C8H19O2PS3 (MW = 274 Da)

7. Methyl parathion
O OCH3
P
OCH3
S
O2N

C8H10NO5PS (MW = 263 Da)

8. Malathion
O
S H
H3CO C
P C OC2H5
H3CO S
H2C C OC2H5

O
C10H10O6PS2 (MW = 330 Da)

9. Parathion
O OC2H5
P
OC2H5
S
O2N

C10H14NO5PS (MW = 291 Da)

10. Azinphos-methyl
S O
H3CO
P
H3CO S N

N
N

C10H12N3O3PS2 (MW = 317 Da)

Pesticides 379

11. Azinphos-ethyl
S O
H5C2O
P
H5C2O S N

N
N

C12H16N3O3PS2 (MW = 345 Da)

28.3. MASS SPECTRA OF PESTICIDES

Pesticides have widespread health and environmental considerations. GC/MS
analyses of this class of compounds are extensive for a wide variety of matrices
from soil and water to commodities and living plants to biological fluids such
as blood plasma and urine. The challenge often is how to get the pesticide
from the sample into a form that can be injected into the GC. The mass
spectra of this class of compounds can be very complex due to the often high
number of atoms of X+2 elements that are present and due to the fact that the
EI mass spectra of many pesticides do not exhibit a M+• peak. The signifi­
cance of the analyses of pesticides by GC/MS is evident by the large number
of EI mass spectral databases of these compounds.
Some of these databases are only available in a hardcopy format, although
many of the actual spectra are now included in the NIST08 Mass Spectra
Database and/or the Wiley Registry of Mass Spectra, 9th ed. The authors of the
first edition of this book recommended Mass Spectrometry of Pesticides and
Pollutants, (Safe S, Hutzinger O. Boca Raton, FL: CRC Press; 1973, with
two additional printings in 1976, and one each in 1977, 1979, and 1980,
indicating its popularity; ISBN: 08493-5033-6; contains 275 spectra). Unfor­
tunately, this book has been out of print for many years and finding copies is
very difficult. Another hardcopy-only publication are the first and second
editions of Handbook of Mass Spectra of Environmental Contaminants (Hites RA.
CRC Press: 2nd ed., 1992, ISBN:0873715349; 533 spectra (reviewed JASMS
5:598); 1st ed., 1985, ISBN:084930537; 394 spectra). In addition to these
three hardcopy-only collections, Agilent Technologies has three different
electronic databases of pesticide EI mass spectra for use with their GC/MS
ChemStation: Stan Pesticide Mass Spectral Library (340 spectra); the Agilent
Pesticide RTL (retention time locking) Library (926 spectra including spectra
of endocrine disrupters); and the Japanese Positive List Pesticide RTL Library
(431 spectra). John Wiley & Sons has announced Mass Spectra of Pesticides
2009, a database available in electronic format for the NIST11 MS Search
Program and other proprietary instrument manufacturers’ data systems that
380 Chapter 28

contains 1,238 spectra and is authored by Rolf Kühnle. The Wiley database
includes structures; however, none of the Agilent databases do.
The challenge in a GC/MS pesticide analysis can be in achieving the
desired limit of detection or limit of quantitation. It may be necessary to use
electron capture negative ionization (ECNI), which will be highly specific for
the halogenated target analytes and will ignore the presence of nonhalogenated
matrix compounds. The importance of the role of retention indices (RI values)
in the confirmation of the identity of pesticides should not be forgotten.
If pesticide analyses are a major function of the laboratory, a mass spectral
database should be created of pure standards and standards at different
concentration levels (down to the desired limit of detection) in usually
encountered matrices using the instrument(s) that is(are) normally used for
these analyses. When using EI with sample having complex matrices, the
use of AMDIS for data processing can be very helpful.
A list of the most abundant ions for a few pesticides is found in Table 28.1.
The use of this list and/or a computer library search will often be sufficient to

Table 28.1 Ions for identifying pesticides

Base Four next most Compound Highest m/z

peak intense peaks peak >1%

66 263 265 79 261 Aldrin 362

75 121 260 97 – Phorate (thimet) 260
77 32 160 93 76 Azinphos-methyl 317
79 82 263 81 277 Dieldrin 378
81 100 61 60 59 Methyldemeton 230
87 75 55 – – Aldicarb 190
87 93 125 229 – Dimethoate 229
88 89 97 274 – Disulfoton 274
97 197 199 314 – Chlorpyrifus 349
100 272 274 65 270 Heptachlor 370
109 79 185 145 – Dichlorovos 220
109 79 185 145 – Trichlorofon 256
109 81 149 99 – Paraoxon 275
109 97 137 291 – Parathion 291
109 263 125 – – Methyl parathion 263
110 152 81 – – Propoxur 209
132 160 77 – – Azinphos-ethyl 345
173 127 125 93 158 Malathion 330
179 137 152 199 304 Diazinon (dimpylate) 304
181 183 109 217 – Lindane 288
227 274 308 – – Methoxychlor 344
235 237 165 236 239 DDT 352
373 375 377 – – Chlordane 404
Pesticides 381

identify many of the most encountered commercial pesticides. Also, see

Chapters 20, 29, and 30.
In addition to compounds listed here, there may be many others. Many
of the other compounds contain Br instead of Cl. It is important to be
careful in the evaluation of X+2 isotope peak patterns.

REFERENCES
1. Food and Drug Administration (1994). Pesticide Analytical Manual, Volumes I and II,
Washington, DC: U.S. Department of Health and Human Services, Food and Drug
Administration, U.S. Government Printing Office.
2. Eisert, R., Leusen, K. (1995). Determination of pesticides in aqueous samples by
solid-phase microextraction coupled to gas chromatography-mass spectrometry.
J. Am. Soc. Mass Spectrom., 6, 11-19.