Application of Multiresidue Procedures in Pesticides Residues Analysis

Pure & App!. Chem., Vol. 58, No. 7, pp. 1035—1062, 1986.
Printed in Great Britain.

© 1986 IUPAC
INTERNATIONAL UNION OF PURE

AND APPLIED CHEMISTRY
APPLIED CHEMISTRY DIVISION
COMMISSION ON PESTICIDE CHEMISTRY*
IUPAC Reports on Pesticides (21)
APPLICATION OF MULTIRESIDUE
PROCEDURES IN PESTICIDES
RESIDUES ANALYSIS
Prepared for publication by
A. AMBRUS1 and H-P. THIER2
'Mezogazdasagi és ElelmezesUgyi Miniszterium,
Novenyvedelmi és Agrokemiai Kozpont, Budapest, Hungary
2lnstitut für Lebensmittelchemie der Universität Münster, FRG
*Membership of the Commission during the preparation of this report (1983—85) was as follows:
Chairman: J. A. R. Bates (UK); Secretary: R. Greenhalgh (Canada); Titular Members:
N. Aharonson (Israel); A. Ambrus (Hungary); S. Gorbach (FRG); W. Klein (FRG); Associate
Members: J. Desmoras (France); H. 0. Esser (Switzerland); L. A. Golovleva (USSR); R. J.
Hemingway (UK); R. Hollingworth (USA); N. Kurihara (Japan); W. B. Neely (USA); S. Otto
(FRG); T. R. Roberts (UK); J. Seiber (USA); D. B. Sharp (USA); J. W. Vonk (Netherlands);
National Representatives: A. M. P. D'Angelo (Argentina); W. Lara (Brazil); Zhengming Li
(Chinese Chemical Society); J. Kovacicova (Czechoslovakia); N. Drescher (FRG); F. Dutka
(Hungary); S. K. Mukerjee (India); P. Bracha (Israel); J. Miyamoto (Japan); C. K. Heng
(Malaysia); G. W. Mason (New Zealand); A. Kotarski (Poland); N. Bärbulescu (Romania);
P. C. Kearney (USA).
Correspondence on the report should be addressed to the Secretary (1985—89) of the Commis-
sion: Dr. T. R. Roberts, Shell Research Ltd., Sittingbourne Research Centre, Sittingbourne,
Kent ME9 8AG, UK.
Republication of this report is permitted without the need for formal IUPAC permission on condition that an
acknowledgement, with full reference together with IUPAC copyright symbol (© 1986 IUPAC), is printed.
Publication of a translation into another language is subject to the additional condition of prior approval from the
relevant JUPAC National Adhering Organization.
Application of multiresidue procedures in
pesticides residues analysis
Abstract — The fields of application of nultiresidue procedures and the proper
selection of compounds and samples to be analysed are discussed. The various
processes of well established nultiresidue procedures are reviewed and
critically assessed in order to give guidance for the analysis of compounds
being not included in current methods and to help laboratories to improve
their own methodology.
CONTENTS
1. INTRODUCTION
2. FIELDS OF APPLICATION OF MULTIRESIDUE PROCEDURES (MRPS)
3. SELECTION OF COMPOUNDS AND COMMODITIES FOR REGULATORY ANALYSIS
4. PREPARATION OF SAMPLES FOR ANALYSIS
4.1 Grouping of samples
4.2 Preparation of portion of sample to be analyzed
5. EXTRACTION AND LIQUID—LIQUID PARTITIONING
6. FURTHER CLEAN UP
6.1 Adsorbent column chromatography
6.2 Gel permeation chromatography
6.3 Other clean—up procedures
6.4 No clean—up
7. DETERNINATION OF RESIDUES
7.1 GLC analysis
7.2 Thin—layer chromatographic analysis
7.3 HPLC analysis
8. CONCLUSIONS
I INTRODUCTION
The introduction of new pesticides, the extension of the activities of the field of residue
analysis and the increasing requirements regarding tine, cost and safety necessitate the
regular revision and improvement of the analytical methods available. The main objective
of the use of multiresidue procedures (MRPs) is to determine as many pesticides of different
chemical structure as possible in various types of samples of known or more often of unknown
origin in a single procedure.
The analysis of pesticide residues in samples of unknown origin consists of two phases:
(1) rapid screening of residues possibly present, (2) identification (confirmation) and
quantification of residues present. The requirements regarding the processes applied in
the two phases of the determination may differ significantly. For example at the screening
stage a recovery value as low as 30% may be acceptable if the overall sensitivity of the
method enables the indication of the residue exceeding a certain limit, while for the
quantitation the method is generally considered satisfactory if the recovery is over 70—80%
with a relative standard deviation of 10% for repeatability.
The limits over which the residues should be detected depend on the purpose of the analysis
and should be determined on a case by case basis. For quantitation of those components for
which the recovery is lower than 70% an additional analysis with a specific method may be
considered necessary if an accurate result is required (e.g. the residue detected
approaches the legal limit).
The proper application of MRPs requires knowledge of extractability of different compounds

from various types of samples, the distribution properties in solvent systems of different
polarity, elution patterns in column chromatographic systems, the loadability and
selectivity of chromatographic separation and the specificity and sensitivity of detection.
Information obtained on compounds which are not extractable, not recoverable from
purification steps, or not detectable is as important as the positive results in this regard.
For the determination of pesticide residues such a multitude of methods has been described
that a complete survey of literature is very difficult for the analyst. However, by far
the majority of these methods consist of a few working steps such as extraction with a
1036
Mu/tires/due procedures in pesticides residues ana/ysis 1037
EXTRACTION
PARTITIONING
PURIFICATION Gel Other

Permeation Procedures
Chromatography
DETERMINATION Other
Procedures
FIGURE 1. Very simplified scheme of the working steps in analysis of plant material
limited number of solvents, liquid—liquid partitioning, adsorbent column chromatography or

gel permeation chromatography and the determination, mostly with GLC, TLC, or HPLC. For the
various pesticide groups they differ only in some details (e.g. amount and activity of
adsorbents, composition and polarity of solvent mixtures) selected according to the
attributes of the residues to be analysed and the co—extractives to be separated. For
this reason, an experienced analyst can modify the procedures by interchanging or modifying
the individual steps in order to get the best result for the given purpose of the analysis.
The objective of this paper is to give some guidance on the application of the various
processes used in the general scheme of MRPs (Figure 1) by comparing some well established
methods covering a wide range of pesticides.
2 FIELDS OF APPLICATION OF MULTIRESIDUE PROCEDURES (MRPs)

The regular analysis of pesticide residues in various substrates is necessary to ensure the
safe and efficient use of the parent compounds and to protect the consumers and the
environment.
The main areas of residues analysis are:
(i) Disappearance studies following the application of individual compounds

(supervised trials);
(ii) (determination of pesticide residue content of raw agricultural commodities moving

in commerce;
(iii) determination of pesticide residues in food prepared for human consumption

(total diet studies);
(iv) identification and quantitation of residues in environmental elements.
In supervised trials, mainly specific methods are used. These should be suitable for the
determination of the quality and quantity of the parent compound and its major metabolites
and/or degradation products individually in order to provide the necessary data for the
establishment of Maximum Residue Limits (I4RLs) (1).
In total diet studies and in certain environmental monitoring programmes all residue
components of toxicological importance should be determined regardless of the way MRLs are
expressed (metabolites may or may not be included). Therefore, in addition to the MRPs,
which are mostly suitable for the determination of parent compounds only, specific methods
are also needed for the analysis of selected metabolites.
1038 COMMISSION ON PESTICIDE CHEMISTRY
Multiresidue procedures are the preferred methods for the analysis of samples derived from
selective field surveys providing samples of known origin (2) or taken from commodities of
unknown origin which generally form the lots moving in commerce. The residues included in
the MRLs have to be analysed in these two situations as the main objectives of these studies
are either the enforcement of MRLs or the collection of information on the residues in food
items in relation to the MRL. The latter information may be used for the assessment of
possible maximum exposure of consumers to pesticide residues or for setting up priority
lists of pesticides and sampling plans for commodities which should be checked
preferentially.
However, there is no single multiresidue method which could cover the wide variety of
chemical—sample matrices which need to be analysed for regulatory control. In addition
there are many compounds which cannot be recovered by MRPs at all; consequently individual
methods have also to be used for the determination of their residues. Positive results
should be confirmed in each case bearing in mind the various sources of possible
interferences. Every analyst should be aware of the applicability and limitations of the
methods used concerning the type of samples and compounds involved. In order to select
the most suitable procedures, to provide the widest information on the samples within the
shortest time and/or at the lowest cost, the number of active ingredients and metabolites
to be analysed should be limited by careful selection.
3 SELECTION OF COMPOUNDS AND COMMODITIES FOR REGULATORY ANALYSIS

The protection of plants and harvested crops requires a wide range of active ingredients,
the number of which exceeds 200 in many countries. As one pesticide nay be used in/on
several crops the number of possible pesticide/crop combinations is often over 1000.
The Codex Committee on Pesticide Residues has recommended Maximum Residue Limits or is
considering proposals for over 2000 pesticide residue/food combinations regarded as
important in international trade (3). All these and many additional ones may have to be
considered in imported commodities.
Based on the results of a large number of previous analyses and on other considerations,
several countries have set up priority lists of compounds to be looked for in regulatory
analysis. Some of the compounds detected most often or included in priority lists are
given in Appendix 1. The number and kind of active ingredients registered or used in
various countries varies widely, due to the different climatic and economic conditions,
pest situation and growing practices. Therefore each country or group of countries having
similar conditions needs to define their own priority lists. On the selection of compounds
to be included in a priority list for regulatory analysis, information on the extent of
practical application, the frequency of occurrence and level of residue in samples marketed
and the toxicity of the residue has to be taken into account.
The primary source of information on the level and the behaviour of the residue in the
commodities are the reports on supervised trials carried out before registration. A great
number of these and other data are collected in the series of "Pesticide Residues in Foods,
Evaluations" published by FAO yearly (4). The monographs on individual compounds summarize
the most essential toxicological and residue data, metabolic pathway and evaluations of
the results. Those data obtained from trials where the rate of application, the growing
stage and the preharvest intervals were close or similar to the use patterns registered
should be considered first.
The limited number of supervised trials are mainly concentrated on major crops and varieties
and designed to indicate the probable maximum residues level at the time of harvest.
Consequently, the data from such trials cannot generally give sufficient information on the
residue distribution in lots treated on a large scale under average farming practice
conditions. The exceptions are those compounds which can only be applied presowing or at
the beginning of growing season and the use of which does not result in measurable residues
at the time of harvest. For these compounds the results of supervised trials provide
sufficient information and further regulatory control is usually not necessary.
For the other compounds the residue patterns reflecting the practical use and weather
conditions have to be determined during the first few years after the commencement of the
large scale use. Therefore, all these compounds should be included in the priority list
and should be regularly checked in all commodities in which their use is permitted or
proposed.
Having collected sufficient information on the residue distribution further selection can
be made. It is proposed that the priority list should include compounds which
— are sold in large quantities and used extensively;
—
may be applied close to harvest or marketing;
— lead to residues disappearing at an apparent half life of 4 or more days;
Multiresidue procedures in pesticides residues analysis 1039
— themselves or their residues are highly toxic;

— lead either to residue levels at or over MRL with a frequency exceeding 2%, or to
detectable residues in 20% or a higher percentage of the sanples;
— are preferred by farmers and, either their use night be extended to those crops excluded
from the registered uses or they might be applied closer to harvest than the pre—harvest
intervals established permit (possible misuses).
In devising the sampling plans higher priority should be given to crops requiring intensive
plant protection (e.g. apple, citrus fruits, tomato etc.) and which form an appreciable
part of the diet.
4 PREPARATION OF SAMPLES FOR ANALYSIS

4.1 Grouping of samples
Differences in the material and the texture of the samples necesitate somewhat different
processes for the extraction and especially for the cleanup of the concentrated extracts.
Several methods classify samples for extraction into three groups: samples of medium and
high water content, dry samples and fatty samples. Within the first group some methods
(5, 6, 7) distinguish the samples having 5 to 15% or 15 to 30% sugar content. A more
recent approach also takes into account the different cleanup requirements (8). From the
samples of medium and high water content three sub—groups are proposed: root and bulb
vegetables (e.g. carrots, onions); fruits and vegetables of low chlorophyll content (e.g.
pome and stone fruits, berries, fruiting vegetables, citrus fruits); plants and crops
of high chlorophyll content (e.g. leafy and legume vegetables). The universal
applicability of gel column chromatography as a pre—cleanup step for different samples and
compounds permits identification of fatty and non—fatty classes of samples only (19 h).
TABLE 1. Some clean—up procedures used for analysis of organochlorine (OC) and
organosphosphorus (OP) pesticides in plant samples
First author Pesti— Anal. Extraction Au— Dilution Parti— Column Elution
cides sample (ml) quot (ml) tioning Chromatography (ml)
(g)
— 200 PE/Eth 94+6

AOAC (5a). OC OP 100 200 Acnit 600 W 100 PE 10 cm Florisil
PAN (6a) 10 NaClsat. (2 cm i.d.) 200 PE/Eth 85+15
(Mills) 200 PE/Eth 50+50
— 30 Dichlm 120 Bz/Acnit 1+1

AOAC (5b), OP 100 200 Acnit 1/10 6 g C/MgO/Celite
PAN (6b) 1+2+4
(Storherr)
— —
Panel (18) OP 20 3xSO Acnit —
500 Na2SO4 3x50 Dhlfm
(2.5%)
Becker (19a) OC, OP 100 200 Ac 1/5 250 W, 2x50 Dichlm 15 g Silica gel 140 Dichlm/Tol/
others 25 NaClsat. + I g C, 5 g Ac 10+2+2
Silica gel
150 Ac — 150 Dichim

Ambrus (8) OC, OP 50 450 Na2SO4 100, 2xSO 7 g C/MgO/Cel.
others (0—4%) Dichlm 1+2+4
8 g Alumina N 30 Hex
(19% W) 30 Hex/Eth 7+3
25 g Alumina B 80 Hex
(16% W) 75 Hex/Eth 2+1
100 200 Ac 80 — 200 PE/Dichlm

Luke (13,20) OC, OP. (10 cm Florisil, (200 PE/Eth 85+
others ml 1+1, 2x100 2 cm i.d.) 15)
Dichlm
100 200 Ac 200 — 100 Dichlm 32 cm Bio Beads

Specht (19j) OC, OP 175 Cyclh/EtAc
nthers ml S—X3 1+1
Ebing (19b,c) OP 100 200 Ac 1/5 250 W, 2x5O 375 ml Sephadex 450 Ethanol
35 NaClast. Dichlm LH—20
Ebing (19d,e,f) OC, OP 100 200 Ac 1/5 250 W, 2xSO Sweep—Co—

35 NaClsat. Dichlm Distillation
— — —
AOAC (Sc). OC, OP 25 125 EtAc Sweep—Co—
Distillation
— — — 150 Tol/Ac/EtAc
Watts (18,21) OP 50 250 EtAc 10 gC/MgO/Cel.
1+2+4 2+1+1
It should be emphasized that none of the subgroups is sufficiently uniform for the various
samples to be treated similarly at cleanup. Depending on the method of detection some of
the materials require additional procedures in order to remove interfering constituents.
For instance the sulfur—containing compounds which interfere with the ECD determination
must be removed from extracts of onion, leek, certain cabbages etc. with a specific
procedure such as the silver nitrate/aluminium oxide column chromatographic method (9).
4.2 Preparation of portion of sample to be analysed

An analytical sample is that part of a laboratory sample which is analysed to provide
information on the quality (the residue content) of the entire sample. The analytical
sample has to be a fully representative portion of laboratory sample or a certain part of
it depending on the purpose of the analysis. Thus the first step in the preparation of an
analytical sample is to separate the appropriate portions of individual items to be
analysed from the laboratory sample. As the residues are unevenly distributed in/on crops
the portion of sample selected for the analysis should always be consistent if comparable
results are sought. In order to enable the results obtained in various countries to be
widely utilized the procedures recommended by the Codex Committee on Pesticide Residues
(10,11) should be used as far as applicable for the objective of the analysis.
5 EXTRACTION AND LIQUID-LIQUID PARTITIONING
In the case of MRPs the extracting solvent must be suitable for the extraction of compounds
with a wide range of polarity from various matrices containing different amount of water,
fat, sugar and other substances. In order to provide suitable conditions for the transfer
of residues from the samples to the extracting solvent the analytical sample needs to be
disintegrated in high speed homogenizers or choppers in the presence of one solvent or a
solvent mixture. The type of solvent and the blender used in extraction may influence
materially the efficiency of extraction. The differences caused by the use of various
equipment can be reduced by shaking the solvent sample mixture for an hour after
homogenization (8). For the extraction of systemic and contact pesticide residues
simultaneously the differences in the hydrolytic stability of the compounds, especially
the sensitivity of some contact pesticides, have to be considered (12).
In MRPs the most widely used solvents are acetonitrile and acetone. Both ae miscible with
water, consequently the actual extracting agent is their mixture with the water derived
from the sample. Methods based on the extraction of plant materials with acetonitrile and
acetone are summarized in Table 1. The cleanup procedures mainly used for fats are given in
Table 2. Table 3 lists the compounds reported to be covered by the most widely used methods.
TABLE 2. Some clean—up procedures used for analysis of organochlorine

pesticides in fats or lipid extacts from fatty foods
Abbreviations for solvents
First author g fat Extraction, Column Elution used in all tables:
max. Partitioning Chromatography (ml)
Ac : Acetone
Acnit : Acetonitrile
ADAC (5a), 3 PE/Acnit 10 cm Florisil 200 PE/Eth 94+6 Bz : Benzene
PAM (6d) (2 cm i.d.) 200 PE/Eth 85+15 Chlfm : Chloroform
Cyclh : Cyclohexane
de Faubert 5 Hex/DMF 5 g Alumina N 50 Hex Dichlm : Dichloromethane
Maunder (22) (7% W) DMF : Dimethylformamide
DM50 : Dimethylsuphoxide
Specht (19h) 5 PE/DMF 30 g Florisil 200 PE/Eth 94+6 EtAc : Ethyl acetate
(5% W) Eth : Diethyl ether
Hex : Hexane
Wood (23) 1 Column extr. 5 g Alumina N 100 Hex Meth : Methanol
with DMSO (7% W) + PE : Petroleum
ether
5 g Florisil
Propc : Popylene
(15% W)
carbonate
Schulte (24) 1.5 Column extr. 10 g Alumina N 30 FE Tol : Toluene
with Propc (17.5% W)
W : Water
Stijve (19i) 1 (Soln in FE) 25 g Florisil 300 PE/Dichim 8+2 Bz can be mostly replaced
(3% W) by Tol, Chlfm by Dichlm.
Telling (25,26) 0.5 (Soln in Hex) 22 g Alumina N 150 Hex

(10% W)
Steinwandter 0.5 (Soln in PE) 20 g Silica gel 250 PE

(27,32) (30% W)
Specht (19j) 0.3 (Soln in GPC 32 cm BioBeads 100+65 Cyclh/EtAc

solvent S—X3 1+1
Stijve (28) 0.1 (Soln in PE) 3 g Florisil 30 PE/Dichlm 8+2

(3% W)
Greve (29) 0.05 (Soln in Hex) 2 g Alumina B 15 Hex

(10% W)
Notes: N — neutral, B — basic

TABLE 3. Applicability of multiresidue procedures
Explanation of columns 1—7 in Table

1 AOAC/FDA: Acnit/water/PE, Florisil, PE/Eth mixtures, 3 eluates
2 AOAC/FDA: Acnit/water/PE, Florisil, Dichlm/Hex/Acnit mixtures 3 eluates
3 Becker: Ac/water/Dichim, Silica/carbon, 1 eluate
4 Anibrus: Ac/water/Dichlm, mixed adsorbent, 1 eluate
5 Ambrus: Ac/water/Dichlm, Alumina N, 2 eluates
6 Luke: Ac/Dichlm, no clean—up (AOAC 1984 + PAM Table 2011 + PAN Section 232.4)
7 Specht: Ac/Dichlm, GPC, Silica, 5 eluates
Explanation of signs: Detectors used:

Pesticide can be determined according H ECD
to author's publication, other references F FPD (P—mode)
or unpublished work: P thermionic (P—mode)
N thermionic (N—mode)
++ well recovered, >70% 1, 2, 3, 4, 5 S FPD (S—mode)
H Hall Electrol.Cond.Det.
+ partially recovered, 40—70% Number of eluate
/ hardly recovered, >40% applies only to L by HPLC only
— not recovered T by TLC only
procedure 1, 2, 5, 7)
Structural analogies indicate that pesticide can probably be determined with the procedure
(including column clean—up).
e, f, p, n, s, h corresponds to detectors E, F, P, N, 5, H.
c from crude extract only (no column clean—up)
from GPC eluate only (applies only to procedure 7)
x probably no recovery
1 2 3 4 5 6 7
Organohalogen pesticides
Aidrin -H-El -H-El ++E -I-I-E ++El ++H -H-El
—
Brompropylate -H-E23 -f-i-H ++E34
Captafol /E3 -H-H3 ++E -H-E -H-H -H-E3
Captan /H3 -H-H3 ++E ++E +1-H -H-E3
Chiorbenside -H-El -H-El e -f-I-H /E3
Chlorbenzilate -H-E23 -H-El -H-H -H-E34
Camphechior -H-Hi -H-El e h -H-El
Chiordane -H-El -H-El e -1--I-H -H-El
Chiordecone +E23 — — h ++E4
Chlorfenprop—methyl h -H-E23
Chlorfenson ++E2 -H-E2 e h -H-E12
Chlorfensulphide -H-H e
Chloroneb -H-Hi -H-E2 e h -H-H2
Chlorpropylate -H-H23 /E3 +1-H h ++E34
Chiorthal -H-H -H-H -H-El h -H-H2
Chiorthalonil -H-El -H-H -H-H2
Chiorthiamid
Cymoxanil -H-H -1-1-4
DDD (TDE) -H-El -H-El -H-H -H-El -H-H -H-El
DDE -H-El -H-El -H-H - -H-El -H-H -H-El
DDT -H-El -H-El -H-H -H-Hi -H-H -H-El
Dichlobenil +E2 +H2 -H-H -H-El -H-E2
Dichlofluanid -H-H -H-H ++E23
Dichloran +H23 ++E2 /E +El -H-H -H-H2
Dichlorbenzamid -H-E4
Diclof op—methyl h -H-E3
Dicofol +El2 -H-E12 -H-H -H-H +H -H-H -H-Hl2
Dieldrin -I-I-/2 -H-E2 ++H -H-El -H-H -H-E2
n—Endosulfan -H-H2 -H-H2 -H-H -H-El h -H-Hl2
5—Endosulfan -H-H23 — e
Endosulf ansuif ate -H-E3
-H-Hw
-H-E2 - -H-H
-H-H
-H-E2
-H-H2
Endrin -H-E2 -H-H2 -H-El -H-H -H-E2
TABLE 3. (contInued)
1 2 3 4 5 6 7
Organohalogen pesticides (continued)

Fenson e e e h -i-i-E2
Fluorodlf en h e
Folpet +E23 ++E23 -H-E -H-E -H-H -H-23
Halacrinate
Heptachior ++El -H-El +-I-E e h -H-El
Heptachior—epoxlde -H-El ++E2 ++E -H-El -H-H -H-E12
HCB -H-El -H-El — e h -H-El
cz-HCH -H-El ++El -H-E -H-E -H-El H-H -H-El
B-HCH -H-El -H-El ++E -H-E -H-El -H-H -H-El
)'—HCH (Lindane) -H-El -H-El -H-E -H-E -H-El -H-H +EE1
-HCH -H-E12 -H-El h -H-El
Isobenzan e e e h -H-El
Isodrin -H-El -H-El e h -H-El
Kelevan -H-E34
Methoxychior -H-El -H-E2 ++E -H-E -H-El -H-E2
Mirex -H-El -H-El e -H-H -H-El
Nitrofen -H-E2 -H-E2 -H-El -H-E12
Nitrothal—isoprop. -H-E -H-El +E234
Oxyclordane -H-El -H-El -H-E12
Pentachioranilin -H-El -H-El — -H-El
Perthane -H-El -H-El -H-E e h -H-E12
Tecnazene -H-El -H-El ++E e h -H-El
Quintozene -H-El -H-El -H-E e -H-H -H-El
Tetradif on -H-E2 -H-E2 -H-E -H-El -H-H -H-E2
Tetrasul -H-El -H-El -H-E -H-E -H-El -H-El
Tolyfluanld -H-E -H-E23
Binapacryl -H-E2 e -H-E2

Dinobuton e -H-E -H-El -H-E23
Dinocap -H-E2 -H-E2 -H-E -H-El -H-E2
Dinocton e
Dinofenate e
Dinoseb acetate ++E ++E2
Benfluralin -H-El +-I-E2 -H-E -H-El -H-El

Butralin e
Fluchoralin ++E12
Isopropalin ++E1
Nitralin +E3 ++E3 -f+E23
Pedirnethalin ++E2
Prof luarlin -H-El
Trifluralin -H-El ++E2 -H-E -H-El -H-El
Organophosphorus pesticides
Acephate -H- ++F5

Azinpohos—ethyl +P3 ++P3 -H-P -H-F -H-P3
— —
++P +P +Pl ++F ++P3
Azinphos—rnethyl
Bensulide -H-P3 /P3 +El23
Brornophos* ++Pl -H-P -H-P -H-Pl -H-? -H-Pl2
Brornophos_ethyl* -H-Pl -H-P P -H-Pl2
Butonate +P +Pl
Carbophenothion -H-Pl
—
+P2
—
-H-P p -H-F +P2
Chlorfenvinphos* -H-P -H-P p -H-F -H-P34
Chiormephos -H-Pl2
Chiorpyrif08* -H-Pl +P2 -H-P -H-P -H-Pl -H-F -H-Pl2
Chlorpyrifos_rnethyl* p p -H-P -H-P -H-P -H-Pl2
Chlorthion* ++Pl
Chlorthiophos* -H-P PPF -H-P2
Cournaphos -H-P3 -H-gF
—
Crotoxyphos -H-F4
Cruf ornate —
-H-F45
Cyanofenphos -H-P -H-F23
Cycloate -H- -H- 12
Derneton — -H- -H-gF
Dialifos +4-P2 ++P2 +P -H-F ++F23
Diazinon* -H-P2 -H-P3 -H-P -H-P -H-Pl -H- -H-P3
Dichlofenthion* ++Pl ++P +H-l2
Dichlorvos* — — -H-P -H-P +Pl -H-F +F34
Dicrotopho8 +1-F -H-PS
Dirnef ox -H-P5
Dirnethoate — — -H-P -H-P — -H- -H-P45
Dioxathion — +P2 -H-PO +-H-F234
Disulfoton* +pl — -H-P -H-P -H-Pl +F2
Ditalirnfos -H-P -H-P -HP1 -H-P3
TABLE 3. (continued)
1 2 3 4 5 6 7
Organophosphorus pesticides (continued)

EPN +4-P2 +4-P2 ++F ++FP2
Ethion* +4-Pi +-I-P2 +4-P ++ +-l-P2
E thoprophos +4-P +4-P +4-P1 +4-F34
Etrimfos -H-P -H-P +P1 +4-F3
Famophos +-I-F3
Fenamiphos -H-F +4-gF
Fenchlorphos* ++Pl +4-P2 -H-P p -H-F -H-P12
Fenitrothion* -H-P2 -H-P2 -H-P -H-P +4-P1 -H-F -H-P2
Fensulfothion — +4-P +4-F ++F45
Fenthion* +P12 — -H-P -H-P ++P1 -H-F +F2
Fonofos +4-Pi +P2 -H-P -H-P +4-Pi +4-F ++F23
Formothion -H-P -H-P3
Heptenophos +4-P -H-P +4-F34
Iodfenphos* p p -I-4-P12
I sofenphos -H-P ++gF
Leptophos ++Pl -H-P2 +4-F ++F12
Malathion* +4-P23 -H-P3 -H-P -H-P +P1 -H- -H-P3
Malaoxon* — +4-P +4-F ++P4
Menazon
Mephosfolan +4-F ++F45
Methacrifos -H-P
Methamidophos — +4- +4-Ps
Methidathion 'P3 -H-P3 -H-P +4-P ++P1 +4-F +4-P3
Mevinphos +4-P -H- ++P4
Monocrotophos +4-P +4- ++F5
Naled* — -H-P +4-F +4-F34
Omethoate +4-F +4-PS
Parathion* -H-P2 ++P2 -H-P -H-P +4-P +4- ++P23
Paraoxon* — -H-P +4-F +4-P4
Parathion_methyl* ++P2 -H-P2 -H-P -H-P +4-Pl +4- ++P23
Paraoxon_methyl* +4-FP234
Phenkapton* ++Pl +4-P +4-P +4-Pl ++FP12
Phenthoate -H-P -H-Pl +4-S +4-P23
Phorate -H-Pl +4-P -H-P ++Pl +4- -H-gF
Phosalone +4-P3 -H-P23 -H-P +1-F +-I-P3
Phosmet +P3 +P ++Pl +4-F ++P3
Phosphamidon — -H-P — +4-? ++F45
Phoxim +4-P +4-F +4-F2
Pirimiphos—ethyl -l--I-F3
Pirimiphos—methyl ++P /P -H-P1 +4-P3
Prof enophos* -H-P +4-F +4-F34
Prothiofos* -H-P ++P1
Prothoate f
Pyrazophos -H-P +4-P +P1 +4-F ++P3
Quinalphos +4-F34
Sulfotep -H-P12 +P2 -H-P +4-P23
Sulprofos +4-F -H-gF
Temephos
TEPP
Terbufos +Pl 1-l-gN
— -H-P +4-P ++P1
Tetrachlorvinphos* +4-F +4-FP34
Thiometon ++gF
Thionazin +P23 -H-P -H-F +4-P3
Triamiphos -H-FP3
Triazophos -H-P PPF +4-P34
Trichloronat* +4-P12
Trichlorfon* +4-P —
+4-F +4-F5
Vamidothion +gF
Pyrethrins, Pyrethroids
Pyrethrins +4-E +4-E34
Cypermethrin +4-El +4- -H-E2

Decamethrin -H-El +4-E2
Fenvalerate +4-El +4- ++E23
Permethrin +4-El -H-H ++E23
Resmethrin +4-2
Tetramethrin 1-4-E3
*Pesticide can also be determined by E.

1 2 3 4 5 6 7
Carbamate insecticides and herbicides

Aldicarb x x +4-cL ++T +4-Ti
Aminocarb +4-cL
Barban ++EN23
Bufencarb
Butocarboxim
Carbanolate
Carbaryl -H-c: +N ++N1 n
Carbetamide
Carbofuran ++N +4-N12 n
Chiorbufam -H-N12
Chiorpropham +4-E2 +4-E2 +4-cL +4-N +4-N +4-Ni +4-EN23
Desmedipham — +4-Ti
Dioxacarb +4-N +4-N2 -H-N4
Ethiofencarb +4-N
Formetanate
Landrin
Mercaptodimethur +4-cL
Methomyl x x +4-cL - +4-H
Oxamyl x x -
Phenmedipham x x +1-cL - ++T2
Pirimicarb -I-I-N /N3 -1-4- ++N4
Promecarb +4-cL
Propham +4-cL +4-N
Propoxur -H-cL -H-N -H-N ++N34
Thiofanox
Butylate +4-N -H-N12 n
Diallate ++E23
Eptam + 2 +4-N ++N12 n
Ethiolate
Pebulate
Sulfallate -H- 1 -H- 2 +4-gE
Thiobencarb +N +4-Ni na
Vernolate + 2 n
Urea herbicides
Benzthiazuron x x
Buturon x x +4-cL +4- 23
Chlorbromuron x x -I--I-cL ++N +4-gE
Chioroxuron x x ci +4-N ++N12 ++E34
Chiortoluron x x ci + -H- 12 n
Cycluron x x +4-N45
Difenoxuron x x ci -H-N2 n
Diflubenzuron x x
Dimefuron x x
Diuron — — ci +N n n
Fenuron x x +4-cL n n
Isonoruron x x
Isoproturon x x ci +N +N
Linuron x x ci +4-N ++Ni2 -H-N +4-N34
Methabenzthiazuron x x +4-N +4-Ni ++N4
Metmercapturon x x +4-N +4-N2 N
Metobromuron x x +4-cL +4-N ++Ni2 ++N234
Metoxuron x x -I-I-cL
—
Monolinuron x x +4-cL +4- +4- 12 ++N34
Monuron — — +4-cL n n
Neburon — — +4-cL n ++E4
Triazine herbicides
—
Ametryne -H-N ++N12 +4-S -H-gN
Atrazine /N3 — -H-N -H-N ++N2 +4-N34
Aziprotryne ++N -H-N -H-Ni2 a -H-gN
Cyanazine - -H-N ++N2 +4-N4
Cyprazine n n
Desmetryn +4-N n a +N45
Dipropethryn n a +4-gN
Methoprotryn +4-N n +-I-N45
+N3 —
Prometryn -H-N +4-N -H-N12 -H-S -H-gN
Propazine +N23 — -H-N n +4-N34
Simazine — - -H-N IN -H-N2 +4-N34
Terbumeton +4-N +4-N2 n
Terbuthylazine +N23 -H-N -H-Ni2 -H-N34
Terbutryn +1-N +4-N ++Ni2 a ++gN
Trietazine n +4-N34
TABLE 3. (contInued)
1 2 3 4 5 6 7
Other pesticides
Alachior — /E3 ++EN3
Allidochior — —
+-I-E3
4—Aininopyridin
Amitraz ++gN
Anilazine ++E2 ++E2 ++E3
Benodanil -H-gE
Bentazon —
Benzoylpropethyl ++E23
Benzoxlmate —
Bifenox ++E23
Bitertanol -H-N4
Bromacil — — ++E ++E4
Bromofenoxiin
Brompyrazon ++N45
Bupirimate ++N ++N -H-N
Carboxin -H- -H- 1 +N12
Chinomethionate -H- 1 -H-S -H- 23
Chioridazone
Dazomet
Dimethachior -H-N34
Diphenaniid ++ 1 -H-N34
Diphenylainine +-I-gN
Dithianon
Drazoxolon
Endothal
Ethiritnol —
Ethofumesate -H- -H- 23
Fenarimol -H- + -H-EN4
Fenazaflor -H-E2
Fenfuram
Flamprop—Isopropyl
Flamprop—inethyl
Fluotrimazol -H-EN34
Imazalil -H-N5
Iprodione -H-E -H-E -H-E -H- -H-E3
Isocarbamid
Isomethiozin -H-gN
Lenacil -H-N4
Metalaxyl -H-N -H- -H-N4
Metamitron -H-N45
Methazole
Methfuroxam
Metolachior -H-E34
Metribuzin -H- -H- 12 -H-S -H-gN
Molinate -H- / 1 -H-gN
Napropamid -H- -H-N34
Nitrapyrin -H-El
Norfiurazon -H-E4
Nuarimol +E +E
Oxadiazon -H-E2 -H- -H- 1 -H-EN3
Oxycarboxin
Procymidon -H-E -H-EN3
Propachior -H- 1 -H-E3
Propanil +E3 -H-E -H-E34
Propargite -H- 1 -H-S -H-E23
Propiconazol +E -H-N45
Propyzaniid -H-E + +1 -H-N ++E3
Pyridinitril
Rabenzazol -H-N3
Terbacil — /E23 -H-N4
Thiochinox
Triadimef on -H- -H- -H- 12 -H-FN34
Triadimenol -H-N45
Trichiophenidin
Triforine
Vinclozolin -H- -H- -H- 1 -H-H -H-EN23
Pesticides which cannot be recovered by the multiresidue procedures cited
Azocyclotin Bromoxynil Chiormequat Amitrole

Cyhexatin 2,4—D Diquat Antrachinon
Fenbutatin oxide 2,4—D Difenzoquat Aramite
Fentin Dalapon Morfamquat Asulani
Benouiyl Dicamba Paraquat Benzadox
Carbendazim Dichiorprop Chiorfiurenol
Fuberidazol Dinoseb Ferbain Daininozide
Thiabendazol Dinoterb Mancozeb Dodine
Thiophanate—methyl DNOC Maneb Etephon
Fenoprop Metani Flurenol
loxynil Metiram Glyodin
MCPA Methylmetiram Glyphosate
MCPB Nabam Guazatine
Mecoprop Nema Maleic hydrazide
Medinoterb Propineb Metaladehyde
Naphthylacetic acid Thiram Methyl bromide
Naphthylacetamide Vondozeb Nicotine
Pentachlorophenol Zineb Piperonyl butoxide
2,4,5—T Ziram Rotenone
2 ,3,6—TBA Sethoxydim
TCA Sulphur
Tridemorph
Trifenmorph
It should be borne in mind that many of the methods are suitable for the determination of
additional pesticides which were not in use at the time of the publication of the methods.
Using the tabulated data an estimation can be made on the applicability of certain methods
or processes for the analysis of new compounds based on the similarities of chemical
structure and physico—chemical properties.
The merit of acetonitrile is that much lipophilic plant material such as fats and waxes is
not extracted. The extract therefore contains only a minor load of co—extractives.
Disadvantages are high cost, toxicity, difficulties in purification and some difficulty in
removing it, if necessary, before the final determination.
In comparison, acetone can be obtained commercially in higher purity grades, is more

volatile and can be used with commodities of high sugar content because it does not form a
two phase system with water in the presence of sugar (13). However, it yields extracts
containing appreciably more co—extracted plant substances which have to be removed during
the cleanup.
With both solvents, crude extracts are obtained which contain the water extracted from the
plant matrix. The extracts cannot be evaporated directly to dryness, as pesticide residues
would be lost via distillation with water. Residues are therefore transferred into a low
boiling solvent immiscible with water. The low polarity petroleum ether or the moderately
polar methylene chloride are used almost exclusively for this purpose, with or without
previous dilution of the crude extract with additional water.
Partitioning with petroleum ether is an excellent cleanup step for analysis of non—polar
residues (e.g. organochlorines, PCBs, some low polarity fungicides and herbicides), for
only low polarity co—extractives (fats, waxes, carotenoids) are transferred into the
petroleum ether with the pesticides.
Partitioning with methylene chloride is much less effective for cleanup, but will be
necessary for sufficient recovery of the more polar pesticides which are not soluble in
petroleum ether. In more recent methods, the crude extract is not diluted with water, but
is diluted with methylene chloride only, yielding the co—extracted water as a separate
aqueous layer. This is optimal for maximum recovery of nearly all (even highly water—
soluble) pesticides, but has little if any cleanup effect.
Some other solvents have been used, mainly for the extraction of organophosphorus compounds.
The major advantage of ethyl acetate (21) and butanol is the fact that one can directly use
an aliquot of dried extract because of the limited solubility of water in ethyl acetate.
The extraction procedure is therefore extremely quick, no partition step is required and
it gives cleaner extracts than with acetone (15). Benzene, methanol (14) and chloroform
have also been used in some methods but their use is limited by their toxicity.
Although the efficiency of the extraction with mixtures of water—immiscible and water—
miscible solvents is very good, they are not widely used, possibly because of emulsion
problems and difficulties in obtaining representative aliquots for the analysis (16).
Techniques for dry crops after they have been ground to powder include extraction with
acetonitrile containing 35% water (5,6) or with dichlornethane (8). Powdered naterial can
be efficiently extracted with chloroforni/nethanol 1+1 in a colunn after nixing it with
Celite 545 but the adoption of the nethod is limited by the toxicity of the solvents.
Extraction in a chromatographic colunn was also found to be very efficient for a wide range
of conpounds and samples with medium and high water content (17). The sample is homogenized
with the addition of a small amount of water, if required. A portion of the pulp is mixed
with Florisil, activated at 450°C, to provide a constant ratio of Florisil to water of
1.67. The free-flowing dry mixture of sample pulp and Florisil is transferred onto a column
over a 5 mm layer of anhydrous sodium sulphate. The pesticides are extracted with 100 ml
of dichloromethane/acetone mixture, 9+1. The concentrated extract is clean enough to
determine organophosphorus compounds directly with the phosphorus selective TID, although
in other cases additionally cleanup is necessary.
For the extraction of acidic pesticides (e.g. chlorphenoxy herbicides or phenols), the use
of a slightly alkaline solution is the best. Partitioning from organic phase into a
slightly alkaline aqueous solution, acidification and re—extraction into an organic layer
is a very efficient tool for separating residues from co—extractives.
The efficiency of extraction is a very important parameter of any method. Special attention
should be paid to testing the extraction efficiency for any new compounds which are
intended to be analysed by a given method. It must be emphasised that the recovery of a
pesticide from fortified samples does not give accurate information on the extraction
efficiency and can only be used for testing the percentage loss of the compound added to
the sample. The efficiency of extraction may be checked by analysing field—treated samples
with a specific method of known efficiency and with the method to be tested.
6 FURTHER CLEANUP
6.1 Adsorbent column chromatography
Most multiresidue methods include a cleanup using adsorption columns, in particular
Florisil, alumina and carbon. Reproducible results depend both on the material used and
on some external conditions. For example, separation is influenced by quality, quantity
and particle size of the sorbent and its activity, the relative humidity of the air,
polarity and composition of the eluting mixture, activation or deactivation of the sorbent
by the solvents, temperature, nature of the residues and the co—extractives and loading of
the column. Host adsorbent columns will achieve a good cleanup only when they are eluted
with solvent mixtures of low polarity, eluting less polar residues and leaving more polar
co—extractives behind on the column. The more the eluting solvent polarity is increased,
the greater will be the portion of interfering substances eluted and the less effective
the cleanup. Solvents of high polarity used for carrying the sample into the column can
deactivate the adsorbent immediately and may change the elution profile of some compounds
(12). Therefore the type and amount of solvent applied in a method should not be altered
without adequate checking if similar results are sought.
6.1.1 Florisil
Of all the sorbents used in residue analysis, Florisil has gained the greatest attention.
Although it is sometimes used as activated material (130°C), it is more often used in
deactivated form (addition of 2—7% water). As Florisil retains some lipids preferentially
(25 g Florisil with 3% water will retain 1 g fat), it is particularly well suited for the
cleanup of fatty foods. When a Florisil column is eluted with solvent mixtures of low
polarity, non—polar residues are recovered almost quantitatively. The eluates are very
clean for GLC with ECD as well as for TLC detection on silver nitrate coated plates. The
most widely used eluants are mixtures of petroleum ether with a low percentage of diethyl
ether or dichloromethane. There have been many attempts to improve cleanup efficiency by
more complex solvent mixtures, but without particular success. Florisil is one of the
most useful absorbents for cleanup in the analysis of organochlorines and PCBs in fatty
foods. Miniaturization is readily possible. A major disadvantage is, however, that
activity may vary from one batch to another, so that Florisil needs always to be
standardized very carefully, otherwise poor cleanup or recovery will result.
For the analysis of plant material, Florisil is of minor importance, although it has been
often recommended in the framework of multiresidue procedures for fruits and vegetables.
The main reason is that the cleanup is poor when more polar pesticides need to be eluted
from the column and, in addition, even well—deactivated Florisil will decompose several
pesticides (e.g. the phthalimide fungicides); will oxidise organophosphates with thio—ether
groups or will adsorb the oxons of some organophosphates irreversibly. Examples of
elution possibilities of some organochlorine and organophosphorus compounds are given in
Tables 4 and 5.
Table 4. Elution behaviour of some organochlorine compounds on Florisil
Author AOAC Specht Mestres Stijve

(5a) (19h) (30) (191)
Florisil quantity 20 g 30 g 5 g 25 g
Water content — 5 5 3
(g/100 g)
Solvents PE/Eth PE/Eth PE/Eth PE PE/Eth PE/Dichlm

94+6 85+15 94+6, 8+2 8+2
Quantity (ml) 200 200 200 50 50 300
HCB + + + +
Lindane + + + +
Aldrin + + + +
Heptachlor + + + +
p,p'—DDE + + + +
p,p'—DDT + + + +
PCB + + + +
Heptachlor—epoxide + + + +
Methoxychlor + + + +
Dieldrin + + + +
Endrin + + + +
Notes: + : quantitative recovery
TABLE 5. Elution behaviour of some organophosphorus compounds on 20 g activated

Florisil
Author AOAC (Sa) Mills (5a) Backman (65)
Solvents PE/Eth Dichlm/Hec/Acnit Bz/Eth Ac

94+6 85+15 94+6 50+ 50+ 2+1
49.65 48.5
+0.35 +1.5
Quantity (ml) 200 200 200 200 200 50 100
Carbophenothion + (+) +
Ethion + + +
Fenchiorphos + + +
— — +
Disulfoton (+)
Chlorpyrif Os + + +
Fenthion (+) (+)

— — +
Parathion + + +
Fenitrothion + + (+) (+)
Parathion—methyl + + (+) +
Diazinon + + (+) +
Malathion (+) + + +
Azinphos—ethyl (+) + +
Dimethoate — — +
— — — — —
Dichlorvos (+)
— —
Paraoxon
— —
Malaoxon
Notes: Recovery + : quantitative

(+) : only partially
— : no
6.1.2 Alumina
In many cases, Florisil can be replaced by alumina, particularly for the analysis of fatty
foods. Basic alumina shows similar elution and cleanup characteristics for the removal
of lipids but does not exhibit the problems of varying activity to the sane degree.
Miniaturized nethods are also available. As with Florisil, experience has shown that
alumina can remove some special types of plant co—extractives but it cannot be unequivocally
recommended for cleanup of plant material. Basic alumina will readily decompose some
organophosphates, and some more polar pesticides are not or only partially recovered from
neutral or acidic alumina (Table 6). To achieve maximum efficiency, one should carefully
consider optimum conditions in relation to both substrates and pesticides to be analysed.
Silver nitrate coated alumina can be of special value for eliminating interfering sulfur—
containing substances from kale, onions etc. for ECD detection. In this case alumina acts
mainly as support for reactive silver nitrate (9).
TABLE 6. Elution behaviour of different pesticides on neutral alumina (8)

8 g alumina (19% water): eluents: 1: 30 ml hexane, 2: 30 ml hexane—diethylether
7+3
0r&anochlorines Organophosphates Methylcarbamates Other compounds
Aldrin Bromophos Carbaryl Butylatea
DDT, DDD, DDE Chlorpyrifos Carbofurana Carboxin
Dieldrin Diazinon Dioxacarb' Chinomethionate
Endosulfan Disulfoton Xpirimicarb Chiorpropham
Endrin Ditalimfos Chlorthal
Heptachlor—epoxide Fenitrothion lJreas Cycloatea

cz—HCH Fenthion Chloroxurona Desmedipham
—HCH Fonofos Chlortolurona Dichlobenil
Lindane Parathion—methyl Linurona Diphenamid
Tetradifon Phecapton Metobromurona EpTCa
Tetrasul Phorate Monolinurona Ethofumesatea
Phosmet XMethabenzthiazuron Metribuzina
Pyrethroids Piriniiphos—methyl Nitrothal—isopr.
Cypermethrin Tetrachlorvinphos Triazines Oxadiazon
Decamethrin XAzinphosmethyl Ametryntm Phenmedipham
Fenvalerate XButonate Atrazineb Piperonyl butoxide
Permethrin XDichlorvos Cyanazineb Propachlor
°Dimethoate Prometryna Propargite
Dinitro—compounds XEtrimfos Simazineb Trifluralin
Dinobuton Xlathion Terbumetonb Vinclozolin
Dinocap 'Methidathion Terbuthylazina xAldicarb
°Dinoseb °Phosphamidon Terbutryn5 °Benomyl
°DNOC Xpyrazophos XDichloran
°Trichlorf on °Difenzoquat
XTriadimef on
Notes: No mark: the pesticide elutes in fraction 1 with recovery higher than 80%
a : the pesticide appears in both fractions x : recovery lower than 80%
b : the pesticide elutes in fraction 2 0 : recovery lower than 40% or not recovered
6.1.3 Silica gel

In general, silica gel is less efficient than alumina as a cleanup adsorbent and will not
adequately separate pesticides from plant co—extractives. Its importance in the analysis
of plant material lies in its use for the fractionation of certain residues according to
their polarity without appreciable losses (10), thus yielding additional information to GLC
data (Tables 7 and 8). Low polarity eluates are simultaneously cleaned up, so that GLC
detection with the ECD is possible. Special attention is drawn to the use of silica gel
deactivated with 10—30% of water for the removal of lipids from organochlorine compounds
in fat analysis. Eluates obtained with petroleum ether are very clean and may even be
suitable for TLC estimation.
TABLE 7. Examples for the separation of pesticides having similar GLC relative
retention times (RRT) on a silica gel column (31).
GLC column: 3% OV—22 on Gas Chrom Q (100—120 mesh), temp. 180°C. Column
chromatography: 5 g Silica gel (Woelm no. 02747), containing 5% water.
Elution fractions: I: 10 ml Hex; II: 16 ml Hex/Bz 4+6; III: 16 ml Bz;
IV: 20 ml Bz/EtAc 1+1; V: 50 ml EtAc.
Compound Relation Silica gel Compound Relation Silica gel

pairs or RRTs column fraction pairs or RRT5 column fraction
Bromophos 1.06 It Dioxacarb 1.06 IV (10%) + V (90%)

Malathion IV Bromophos II
V
Carbaryl
Fenitrothion
1.05
i
IV Phosphamidon II
Parathion—methyl
1.01
III
Fenthion 1.06 III Prometryne 1.0 IV (90%) + V (10%)

Bromophos II Parathion—methyl III
Dioxacarb 1.01 IV (10%) + V (90%) Propachlor 1.03 IV

Fenthion III Chlorpropham III
TABLE 8. Elution behaviour of some organochlorines on silica gel (32).

Adsorbent: 15 g Silica gel (Merck no. 7734) containing 10% water.
Elution: 10 ml fractions of PE/Dichlni 8+2
Pesticide % Recovery in fract ions
1 2 3 4 5 6 7 8 9 10
HCB 95 5
a—HCH — 25 75
— — 26
8—HCH 54 20
°-HCH - 40 60
f—HCH — — — — 5 35 45 15 — —
Heptachlor 36 64
— — 50 50
Heptachlor—epoxide
Dieldrin 9 37 41 13 —
Endrin 7 26 47 20 —
o,p'—DDT 30 70
p,p'—DDT 20 80
p,p'—DDE 41 59
— 70 30
p,p'—DDD
6.1.4 Magnesia
Magnesium oxide is valuable in some situations for removing some interfering co—extractives
from plant extracts known to contain sulfurous material. It is not used as such for basic
cleanup but only for additional cleanup (see also mixed adsorbents).
6.1.5 Carbon
Unlike other adsorbents mentioned above, carbon shows different elution characteristics due
to its lipophilic nature. It adsorbs preferentially non—polar, lipophilic and high
molecular weight substances. It is particularly suitable for cleanup of extracts with
high chlorophyll content (vegetables) but no so effective for the removal of plant wax in
the analysis of organophosphates. Efficiency is, however, affected by type and pre-
treatment of the carbon, so that results reported in the literature are often not directly
comparable. As finely—divided carbon columns have poor flow characteristics, the material is
diluted with diatomaceous earth used in granular form or is used in adsorbent mixtures.
6.1.6 Mixed adsorbents

There have been many attempts to combine the different properties of the hydrophilic
adsorbents and the lipophilic carbon. Some of them have gained some (mostly national)
importance, such as the silica/carbon column or mixtures of carbon with magnesia and celite
etc. Choice of eluting mixtures appears to be rather accidental and without systematic
approach other than observation and experience (Table 9).
6.2 Gel permeation chromatography (GPC)

The most universally applicable cleanup step is GPC. In the analysis of plant extracts it
separates efficiently the relatively small pesticide molecules from the surplus of natural
and higher molecular weight plant constituents. Searation is generally performed by using
DVB—linked polystyrene gels, mostly Bio Beads S—X2 or S—X3. It is suitable for organo—
chlorine, organophosphorus and nearly all other types of pesticides and does not involve
any losses by adsorption. For elution several solvent mixtures have been recommended
(Table 10) among which cyclohexane/ethyl acetate 1+1 has proved to be suitable for cleanup
TABLE 9. Examples for clean—up of organophosphates with mixed adsorbants
Adsorbent Char— MgO Celite Others Eluting Ref.

mass coal 545 solvent
(g) (ml)
— — 57
2.9 0.7 2.2 cellulose 200 Chlfm,
200 Bz
4 — 200 Dichlm/Ac 2+1 13

6.0 1 2
6.0 1 2 4 — 120 Bz/Acnit 1+1 5b
7.0 1 2 4 — 150 Dichlm 8

10.0 1 2 4 — 150 Tol/EtAc/Ac 18
2+1+1
14.0 1 2 4 — 300 Bz/EtAc 3+1 21
20.0 1 — 8 4 attaclay 100 Ac, 59

10 florisil 100 Dichlm
10 sodium sulphate
TABLE 10. Examples for the separation of residues by GPC with Bio Beads S—X3 in an
automatic device
Eluting Column Pesticides Fract ion Ref.

mixture length (cm) (ml)
EtAc/Tol 27 Organohlorines 100 — 150 60

3+1 Organophosphates 90 — 130
Phenoxy esters 90 — 130
35 Organochlorines 120 — 220 61
Cyclh/Dichlm 30 Organophosphates 80 — 270 62

85+15
35 Methyl carbamates 110 — 205 58
35 Organochlorines 120 — 220 63
Cyclh/EtAc 32 Organochlorines 100 — 170 19j

Other pesticides 100 — 160
Hex/Dichlm 20 Organochlorines 70 — 120 64

1052 COMMISSION ON PESTtCIDE CHEMISTRY
of more than 300 pesticides (19 j). Dextran gels have also been used for cleanup of
organophosphorus compounds but they require much more time and solvent and exhibit
additional interactions between gel and pesticides.
Under the conditions used for plant extracts, GPC with Bio Beads can be applied in the
analysis of fats and oils effectively removing lipids before analysis of organochlorines
and less polar organophosphates. Another valuable feature is that GPC can be carried out
in an automatically controlled device. This versatile technique can be used as a general
cleanup step for almost any type of pesticide and substrate and may be supplemented if
necessary by an specific purification.
6.3 Other cleanup procedures

There are other cleanup steps available which can be applied only to certain groups of
pesticides and substrates. For example steam distillation, treatment with sulfuric acid
or calcium silicate (Calflo E) is suitable for most organochlorine compounds; for
organophosphates or methyl carbamates treatment with a coagulating solution. These may
offer ways for solving special cleanup problems but their applicability is rather limited.
They are not normally components of multiresidue procedures but could be incorporated if
required.
Sweep co—distillation has been frequently recommended in the frame of multiresidue

procedures. In principle, it is suitable for a broad range of pesticides and substrates
(fat, plant extracts). It is not very time—consuming and does not need special adsorbents
nor large volumes of solvent; instead, it needs a high gas flow. As this technique can
give rise to problems in recovery and affect the stability of some sensitive pesticides, it
has been adopted in only a few laboratories that are experienced in the field.
6.4 No cleanup
Due to the high selectivity and/or sensitivity of some GLC detectors, crude extracts can be
analysed in principle without any cleanup. This is, however, only possible for organo—
phosphorus or organonitrogen pesticides with the FPD or the Hall electrolytic conductivity
detector and for some fruits with the thermionic detectors operated in phosphorus node.
Co—extractives may, however, rapidly shorten the life—time of the GLC column. In practice,
this mode of of operation can only be recommended if the load capacity of the detector and
the column has been carefully determined and the working parameters (capacity and inertness
of the column, selectivity and sensitivity of the detector) are regularly observed and
controlled.
7 DETERMINATION OF RESIDUES
7.1 GLC analysis
At present gas—liquid chromatography employing specific detectors (ECD, TID, FPD, Hall
electrolytic conductivity detector) is the most widely used technique for the identification
and quantitation of the compounds in the sample extract.
7.1.1 Application of packed columns

Although many packings have been recommended in the literature, most separations can be
achieved by using not more than 5 stationary phases of differing polarities. These 5
could be selected from non—polar silicones (e.g. SE—30, OV—1O1): moderately polar silicones
(e.g. OV—17, OV—210); polar silicones (e.g. OV—225); polyethers (e.g. Carbowax 20M);
polyesters (e.g. NPGS, DEGS); the examples being approximately in the order of increasing
polarity.
Table 11 shows chromatographic conditions applied in some IIRPs. The most important
parameter in the selection of supports, packing and chromatographic equipment is inertness.
Because of the high sensitivity of many residues to the surface activity only the most
inert supports (e.g. Gaschrom Q, Chromosorb W HP) are recommended for use with a minimum
coating of 3% liquid phase. It is essential to use pyrex glass injectors and columns washed
with hydrochloric acid and treated with dimethyl dichlorosilane. Acid washed pyrex wool
should be used for closing the packings but quartz wool gives better results. The inertness
of the column varies depending on the contaminating substances injected and on the quality
of the solvents and carrier gas used. Therefore the regular control and the maintenance
of the column inertness are advisable. The injection of a carbaryl/prophan mixture was
found to be valuable for testing the inertness of the column. If the response ratio of
carbaryl/propham is equal to or higher than 0.5 at a 5 ng level with a nitrogen specific
detector the Inertness of the system is suitable for the analysis of labile pesticides
(33). If the first few cm of the packing and the quartz wool are changed regularly the
life of columns can be reasonably extended. The inertness of the column can be improved
by the injection of few ul Silyl 8 column conditioner or a similar agent. It was found
necessary to change the quartz wool used after silylation (33).
TABLE 11. Gas chromatographic conditions applied in some MRPs
First Column size Packinga Column temp. Carrier gas Compounds

author length x i.d. °C flow rate
[cm] ml/min
AOAC [5a] 183 x 0.4 10% DC—200 180 80 general

FDA [6h] Chrom W—HP purpose
80—100 mesh 200 120
FDA [6h] 183 x 0.4 10% DC—200 200 120 general

15% QF—1 1:1 purpose
Chrom W-HP,
80—100 mesh
183 x 0.4 15% OV—210 190 80 HCB, BHC

Chrom W—HP isomers
confirmation
183 x 0.4 2% DEGS 165—210 60 confirmation

Gas Chrom Q,
80—100 mesh
Ambrus [31] 90 x 0.2 3% OV—22 140 [1 mm] 14_35b general

45 x 0.3 Gas Chrom Q purpose
100—120 mesh 10°/mm, 240 [2 mm]
3% OV—101 148 [1 mm] general

Gas Crhom Q 10°/mm, 240 [2 mm] purpose
100—120 mesh 180 or 200
1.95% SP—2401 + 180 or 200 chlorinated

1.5% SP—2250 hydrocarbons
Supelcoport
100—120 mesh
3% NPGS 140—220 confirmation

Gas Chrom Q
100—120 mesh
Ambrus [31] 3% SE—30 160—240 pyrethroids

Gas Chrom Q confirmation
100—120 mesh
Becker [19a] 183 x 0.2 3% SE—30 210 30 chlorine

Chrom WAWDMCS containing
80—100 mesh pesticides
triazines
183 x 0.2 2% FS—1265 210 45 OP

Chrom W—AW—DMCS
60—80 mesh
Ebing [19f] 210 x 0.17 4% OV—l 140 118 mm], 20 OP

Chrom W—HP—DMCS 8°/mm, 285 [2 mm]
0.12—0.15 mm
210 x 0.17 4% oV—17 170 [18 mm], 20 OP

Chrom W—HP—DMCS 8°/mm, 315 [6 mm]
0.12—0.15 mm
Ebing [19b] 206 x 0.19 4% OV—17 200, 4°/mm, 70 OP

Chrom W—HP—DMCS 230
0.12—0.15 mm
Eichner [19e] 380 x 0.2 5% QF—1 200 30 chlorine

Chrom WAWDMCS containing
80—100 mesh pesticides
Luke [13] 120 x 0.2 2% DEGS 180 60 ) carbamates

Chrom W—AW ) triazines
80—100 mesh ) organochlorine
) organosulfur OP
120 x 0.2 2% DEGS + 0.5% 180 25—30 ) miscellaneous
}13PO4 ) organonitrogen
30.5 x 0.2 ) pesticides
2% DEGS + 0.5% 120 25—30
H3PO4
Chrom W-AW
80—100 mesh
First Column size Packing Column temp. Carrie r gas Compounds

author length x i.d. °C flow rate
[cm] ml/min
Luke [13] 120 x 0.2 2% 0V101 200 60 ) carbamates

Chrom WHP ) triazines
100—120 mesh ) organochlorine
) organosulfur OP
76.2 x 0.2 4% SE3O + 6.5% OV—21O 200 60 ) miscellaneous
Chrom W—HP ) organonitrogen
80—100 mesh ) pesticides
Specht [19h] 180 x 0.4 5% OV1O1 180 [5 mm], 90 organochlorine

Gas Chrom Q 2°/mm, and OP
70—100 mesh 200°C [5 minI
180 x 0.4 1.5% oV—17 + 1.95% QF—1 200 [5 mm], 90 organochlorine

Chrom W—HP 2°/mm, and OP
100—120 mesh 220 [5 mm]
120 x 0.4 2.5% XE—60 190 90 organochlorine

Chrom G—AW—DNCS and OP
80—100 mesh
180 x 0.4 2% DEGS + 0.5% H3P04 180 90 organochlorine

Chrom W—HP and OP
100—120 mesh
Specht [19h] 200 x 0.2 15% QF—1 + 10% DC—200 1:1 200 60 organochlorine
Gas Chrom Q and OP
70—100 mesh
Stijve [19i] 160 x 0.3 1.5% OV—17 + 1.95% QF—1 210 40 organochlorine
Chrom W—DMCS and OP
100—120 mesh
160 x 0.3 2% DEGS + 0.5% H3PO4 185 40 organochlormne

Chrom W—HP and OP
100—120 mesh
Notes: a particle sizes 60—80, 80—100, 100—120 mesh are equivalent to 0.25—0.177, 0.177—0.15,
0.15—0.125 = respectively
b flow rate is selected to achieve optimum performance of the specific detectors
Most of the methods recommend chromatographic columns of unnecessary large capacity which
results in long analysis time (50 to 98 mm for certain compounds) (16) and loss of
sensitivity of the detection. These disadvantages may be partly compensated by increasing
carrier gas flow rate and temperature. However, the former may adversely affect the
detector performance while the latter increases the decomposition of labile compounds.
Narrow (i.d. 2 mm) and short (50—120 cm) columns eliminate the disadvantages mentioned above
(13,31). With appropriate selection of particle size of packing and inner diameter of the
column the greatest number of effective plates per unit time can be achieved at an optimal
flow rate for the specific detector used (33).
Because of the great number of pesticides which can be analysed by GLC, even if 180—200 cm
long columns of large capacity are used and the interferences from plant materials and
reagents are eliminated, any single peak on the chromatogram may represent more than one
pesticide. The detected compounds must be investigated further, at least on another column
of different polarity. On the other hand, it is rare to find in an extract more than one
compound having similar biological effects except for chlorinated hydrocarbons. Thus the
use of slow large capacity columns has no advantage over the quick short columns.
7.1.2 Application of capillary columns

The efficiency of capillary columns and the relative speed of analysis (number of effective
plates generated within unit time) are much better than those of short packed columns which
explains the rapid widespread acceptance of their use. The main advantage of GLC on
capillary columns is that it yields particularly narrow and high peaks. For this reason,
pesticide residues can be identified with greater reliability and may be quantitated with
better sensitivity. At the same time, an excellent separation of pesticides from each
other and from co—extractives can be obtained. In residue analysis, wall coated open
tubular (WCOT) columns are used almost exclusively. The liquid phase is deposited on the
inner walls of the capillary (10—50 n long, 0.2—0.5 mm i.d.) as an 0.05—1 um thin,
continuous and uniform film throughout the column.
As column materials, borosilicate glass or fused silica are suitable. In earlier years most
glass columns commercially available were very expensive and not sufficiently deactivated
for residue analysis. Workers in this field often made the capillaries in their own
laboratory by using a glass drawinging machine and carried out the pretreatment and coating
operations themselves. Unlike glass columns, fused silica capillaries cannot be drawn in
the laboratory. The columns commercially available are very thin but are covered by a
protective polyimide coating which makes them very flexible. When rolled up, their ends
remain straight and are always ready for installation; a section broken off can be reused
immediately. A further advantage is that the inner surface can be easily and thoroughly
deactivated.
Workers with limited experience with the capillary technique are recommended to use coated
fused silica columns commercially available. In recent years their performance has been
improved considerably and there are now several types which meet the high demands of residue
analysis. The most important aspect is deactiation which plays such an important role in
trace analysis.
Particularly promising are commercial capillaries with immobilised stationary phases, where
the coating is cross—linked and bound to the surface by covalent chemical bonds, e.g.
Durabond (J & W), CB phases (Chrompack), Ultra (Hp), Mega (Erba) etc. Phases of this kind
exhibit very low bleeding and can even be rinsed with some solvents to removing extraneous
deposits which may lead to tailing peaks after some routine use.
Commercially coated columns, however, are rather expensive and may sometimes not offer the
optimal solution for a specific separation problem (e.g. in PCB analysis). In such cases
it is advisable to start with blank glass or fused silica columns and to coat them with the
selected phase in one's own laboratory.
When injecting 1—2 ul of the solution to be analysed, the resulting volume of solvent vapour
is so large that with the usual carrier gas flow of only 2—3 ml/min, pesticides would arrive
at the column not as a small band but only as a diffuse zone. For analysis of the
TABLE 12. Examples for GLC conditions for separating some pesticide groups with glass or
fused silica capillary columns
Pesticide Length i.d. Station. Column temp. Detector Ref.

group m mm phase °C 'C/mm
Organochlorine 60 0.33 SE—30 180—260 2 ECD 34

pesticides, PCB 50 0.3 SE—30/SE—52 150—230 2 ECD 35
40 0.3 SE—30 150—200 1 ECD 36
30 0.3 OV—61 140—230 5 ECD 37
20 0.25 oV—17 80—220 7 ECD 38
Organophosphorus 50 0.35 SE—30 200—290 4 FPD 39

pesticides 25 0.3 DEGA 100—250 8 TID 40
20 0.3 SE—54 120—200 4 MS 41
Methylcarbamate 18 0.31 SE—52 170—190 4 TID 42

insecticides 12 0.3 SE—54 130—145 3 TID 43
Triazine 12 0.3 Carbowax 20M 120—220 15 TID 44

herbicides 22 0.25 SE—52 110—220 2 TID 45
Phenylurea 15 0.3 SE_52a 90—210 8 TID/ECD 45

herbicides 15 0.3 SE—52, OV—73 4 FID/TID 47
Pyrethroids 25 0.23 OV—101 50—210 25 ECD 48

15 0.32 OV—1 180—245 3 ECD 19g
Fungicides 35 0.22 SE—30 100—250 5 ECD 50
30 0.3 FFAP 180 — TID 51

Ethylenthiourea
8 0.25 Carbowax 20M 60—220 30 FPD 52
Phenoxy herbicidesb 60 0.27 SE—30 130—230 4 ECD 53
TriphenyltinsC 12 0.22 OV—101 40—250 10 FPD 54
Benomyld 50 0.25 OV—101 150 TID 55
Notes: a: as isocyanates C: as methyl derivatives
as pentafluorobenzylic esters d: as carbendazim acetate and 2—AB acetate

organochiorine compounds with the ECD, sensitivity is usually high enough for a split system
to be used which results in a proportion (e.g. one tenth) of the injected solution as a
sharp band on to the column. In other cases, however, e.g. for total diet studies or when
working with other selective detectors, the highest sensitivity nay be required.
Recommended techniques include injection at low temperature followed by a rapid temperature
rise to start separation; the on—column injection with a very thin needle using a special
valve inlet; or the moving—needle injector evaporating the solvent on a needle tip before
introducing it into the carrier gas stream.
Table 12 shows some examples for separation conditions described in the literature for the
analysis of pesticide residues in food matrices. As can be seen, methyl silicone gums such
as SE—30 and similar phases (SE—52, SE—54, OV—1701) when used with the ECD provide
particularly good separations for the organochlorine compounds and PCBs. Less viscous
phases are not as satisfactory for some risk remains that some volatile components may
enter the ECD contaminating it seriously. Non—polar as well as more polar columns are
suitable for organophosphates, triazines etc. They can be combined with all types of
selective detectors including mass spectrometry. In most cases a temperature programme
will provide the best separation conditions for the numerous representatives of a certain
pesticide group. Extracts injected on to capillary columns should be reasonably clean
although there are no special cleanup requirements. The same multiresidue cleanup
procedures used for GLC with packed columns are satisfactory.
The loadability of capillary columns with pesticides plus co—extractives depends on the
thickness of the film of stationary phase. Optimum film thickness for residues is about
0.1 Urn. Heavier coating will result in peak broadening and is not recommended for best
separation and sensitivity. Even for 0.1 Um films, loadability is still sufficiently high
in most cases if extracts have been properly cleaned up. Overloading will be easily
perceptible for it results in a typical peak distortion (usually called "leading", slowly
ascending and sharply descending peaks). If overloading occurs, a smaller injection volume
or a diluted solution should be used.
7.1.3 Detection of the residues

Of the GLC detectors presently available the electron capture (ECD), thermionic (TID, AFID),
flame photometric (FPD), and Hall electrolytic conductivity (HECD) detectors are used
exclusively in the MRPs. The mass spectrometer, the most specific detector for GLC, is
applicable for screening of few compounds or for confirmation.
The AFID, FPD and HECD are element selective while ECD detects all compounds having electron
absorbing properties such as nitro, 1,2—diketo, and halogen derivatives. All detectors
have undergone continuous development, resulting in improved selectivity, sensitivity and
stability but their limitations have to be borne in mind when they are used in NRPs. The
performance of the detectors depend considerably on the construction and on the operating
conditions and it may vary even when detectors of sane make are compared. Some changes in
the detector parameters also occur as a function of operation time.
Application of ECD requires properly cleaned sample extracts which can only be achieved
with solvents and adsorbents of high purity. In addition to the cleanup, special attention
should be given to the interpretation of the results due to the variation of recovery and
detector response from compound to compound.
The AFID is specific to phosphorus and nitrogen. In case of heated bead detector the ratio
of P/N sensitivity can vary between 10 and 50 depending on the construction and operating
conditions. As the plant extracts usually contain naturally occurring nitrogen compounds,
the cleanup needs to be almost as rigorous as in case of ECD, in contrast to the earlier
detectors which contained an alkali salt tip over the flame. Therefore the direct injection
of concentrated plant extracts is rarely possible in case of heated bead AFID in spite of
its excellent selectivity expressed in terms of response ratio of phosphorus and hydrocarbon
compounds.
The FPD is one of the most reliable GLC detectors. Its performance is mainly influenced by
the design, oxygen/hydrogen ratio and by the total oxygen and carrier gas flow. Carbon
compounds produce peaks in the microgramne range only, therefore the interference from
carbon compounds is not usually a problem. It was found that interference from S in the P
node is more likely to occur than from P in the S node, unless working at S levels near the
detection limit (84). For example, broccoli, Brussels sprouts, cauliflower, onions, peas
and radish give significant peaks with the FPD in the P mode at a sensitivity range of
about 0.1—5 ng residues (13). Hence, the positive response in the P mode should always be
confirmed.
The Hall extrolytic conductivity detector detects Cl, N, or S with good selectivity, but
its sensitivity is lower than in case of other detectors. Its performance largely depends
on the operating conditions and it is rather difficult to achieve and especially to maintain
the optimal operating conditions. It is used routinely in relatively few laboratories.
7.2 Thin-layer chromatographic analysis

Because of the rapid development in the instrumentation of gas chromatography and more
recently the high—pressure liquid chromatography providing higher sensitivity and separation
power, thin-layer chromatography is used only occasionally in many laboratories. However,
its advantages, namely the versatility, speed and low cost could be utilized more in many
laboratories where the required facilities of GLC and HPLC are not available. In addition,
TLC is an excellent means for confirmation of results obtained by GLC and HPLC methods.
Table 13 gives some examples for the applicability of TLC methods.
TABLE 13. Application of TLC in MRPs
First author Layer Development system Visualization Compounds
AOAC (5a) Alumina C Heptane/Ac 98+2 AgNO3/2—phenoxyethanol organochlorines

FDA (6e)
Alumina C 15—20% DMF in
Eth, tetrabromophenolphthalein ethyl thiophosphates
Methylcyclohexane ester, AgNO3, citric acid
FDA (6g) Silic AR 2,2,4—Trimethylpen p—nitrobenzylpyridine, tetra— OP

tane/Ac/Chlfm 70+25+5 ethylenpentamine
Anibrus (56) Silica gel H EtAc or Dichlm chlorine vapor, o—tolidine + carbamates,
potassium iodide ureas, triazines,
misc.
Silica gel H EtAc or Dichlm NaOH + p—nitrobenzenediazonium carbamates

fluoroborate
Silica gel H EtAc or Dichlm bioassay with fungi spores fungicides

(Aepergillue niger L.)
Silica gel H EtAc or Dichlm horse blood serum, acetyl thio— OF,
choline iodide + 2,6—dichloro— carbamates
phenol indophenol
Silica gel H EtAc or Dichlm human blood plasma a—naphthyl OP,

acetate, fast blue salt B carbamates
Alumina, EtAc or Dichlm UV radiation halogen

AgNO3—impreg. containing
compounds
Alumina C EtAc or Dichlm p—dimethylaminobenzaldehyde ureas, some

carbamates
Stijve (19i) Alumina N PE or FE/Ac 99+1 AngNO3 + UV organochlorines

or Alumina
60—F254
Silica gel H Hex/Dichlm/Eth 8+1+2 human blood plasma, 8—naphthyl OP
acetate, fast blue salt B
Canadian Man. (7) Silica gel Hex/Ac 99+1 or AgNO3 + UV organochlorines

Hex/Bz 9+1 to 1+1
DDR—Manual (66) Silica gel G Bz/Ac 95+5 or 66+34 bovine liver extract, OP,
8—naphthyl carbamates
Thier (67,68) Silica gel G Hex/Ac/Eth 8+2+1 2,6—dichloro/dibromo/quinone OP

chloroimine, formic acid
Silica gel G PE/Eth 95+5 AgNO3/2—phenoxyethanol phenoxy

herbicides
(methyl esters)
Onley (69) Alumina GF Bz/Chlfm/Meth 25+9+1 HC1, dimethylaminobenzaldehyde ureas
El—Dib (70) Silica gel Hex/Ac 7+3 dimethylaminobenzaldehyde methyl

carbamates
Delley (71) Silica gel Tol/Ac 85+15 chlorine vapor, potassium triazines
iodide + starch
Abbott (72) Silica gel Chlfm/Ac 9+1 brilliant green, bromine capor triazines
Sundararajan (49) Alumina, Bz/Hex 55+45 UV radiation pyrethroids

AgNO3—impreg.
It has been demonstrated that by the proper application of TLC methods reproducible results
can be obtained even at the 0.05—0.1 mg/kg residue level for many pesticides. It is
recommended to spot reference compounds on each plate at the limit of detection in order to
indicate whether the optimum condition for the detection and elution has been achieved or
not. In the latter case the reference spot may not be properly visible or its Rf value
differs from the usual one (56). The reference compound should be selected from those
which are seen on the plates only when the detection has been carried out properly.
It was found that the elution order of 120 pesticides tested did not change regardless the
relative humidity of the air in the developing chamber or the mode of saturation of the
chamber (12) though the latter especially, greatly affects the Rf values. Consequently
spotting two or three compounds of different Rf values on the plates and comparing their Rf
values to those found in the sample significantly increases the probability of correct
identification of the residues which is very important at the screening stage. Particularly
suitable are commercially available factory—coated plates which are easier to handle,
yield more defined spots and permit better quantification.
Sample material carried over into the concentrated extract influences both the separation
and the detectability. Overloaded plates cannot be used for either qualitative or
quantitative determination. The loadability of the layer depends on the mode of detection
and to some extent on the developing solvent.
Table 14 gives some examples from the results of a systematic study carried out with
different plant materials under various chromatographic conditions applying the extract
obtained with the column chromatographic extraction method (17) described in Section 5.
In addition to the described procedure the samples were extracted in a column which
contained 7 g of mixed adsorbent (see Table 9, Ref.8) under the Florisil and sodium sulfate
layer. The preparation of detecting reagents and the developing methods were similar to
those described in Ref. 56. The samples selected were considered to represent the most
difficult cases in various sample groups, so the results obtained can be used as a guide
for the other samples as well. However, it has to be emphasized that the co—extractives
from different samples may have different Rf ranges and intensity and therefore, the
applicability of the given method has to be checked for each sample.
TABLE 14. Loadability of TLC plates: Grams of sample aliquots which can be spotted from extracts obtained
with column chromatographic extraction on Florisil (CE) (17) or with additional mixed adsorbents (CE+MA)
Crop Develop, p—DAB AgNO3/UV Enzyme Fungi C12/o—Tol. Fluorobor.

solvent CE CE+HA CE CE-I-MA CE CE+HA CE CE+MA CE CE-I-MA CE CE+MA
Onion Dichlm 0.2 1 0.5 1 0.1 0.2 <0.2 <0.2 0.5 1 0.2 0.5
PE/Eth 1+2 — — 0.5 1 0.05 0.1 <0.2 <0.2 0.5 1 0.2 0.5
EtAc 0.2 0.5 0.05 0.05 0.05 0.1 <0.2 <0.2 0.1 0.5 0.1 0.2
Carrot PE/Eth 1+2 — — 1 2 0.1 0.5 <0.2 <0.5 0.2 0.5 0.25 2
EtAc 0.1 0.5 1 2 0.1 0.5 0.5 0.5 0.1 0.25 0.1 0.5
Lemon Dichlm 0.1 0.5 1 2 0.2 0.2 <0.2 0.5 0.1 0.25 0.1 0.5
PE/Eth 1+2 — — 1 2 0.5 0.5 <0.2 0.2 0.2 0.5 0.1 0.5
EtAc 0.1 0.5 1 2 0.2 0.5 <0.2 <0.2 0.2 0.5 0.2 0.5
Spinach Dichlm 0.25 0.5 0.25 1 0.05 0.25 0.5 1 0.25 1 0.2 1
PE/Eth 1+2 — — 0.5 1 0.1 0.5 0.25 2 0.1 2 0.05 1

EtAc 0.1 0.5 <0.1 1 0.1 0.5 0.25 2 0.1 1 0.1 1
Cabbage Dichlm 0.5 2 0.2 1 0.1 0.2 0.2 <0.5 0.5 1 1 2

PE/Eth 1+2 — — 0.5 1 0.1 0.2 0.2 <0.5 0.2 2 0.2 2
EtAc 0.1 1 0.2 1 0.05 0.2 <0.2 <0.5 0.2 0.5 0.2 1
Raisin Dichlm 0.2 0.5 2 2 0.05 0.1 0.2 1 0.2 0.4 0.2 0.5
PE/Eth 1+2 — — 1 2 0.05 0.1 0.5 0.5 0.2 0.5 0.2 0.5
EtAc 0.2 0.5 2 2 0.05 0.1 0.5 0.5 0.2 0.5 0.1 0.4
Pesticides used with solvents:

Layer Dichlm PE/Eth 1+2 EtAc
p—DAB: p—dimethylaminobenzaldehyde + HC1 Alumina Diuron Diuron
AgNO3/UV: AgNO3 impreganted in the layer + UV Alumina Atrazine AldrinDieldrin Captafol

Enzyme: human blood plasma, a—naphthyl acetate, Silicagel H Triazophos Mevinphos,Carbaryl Dioxicarb
Fast Blue Salt B
Fungi: spore suspension of A. niger Silicagel H Folpet Carbedazim Folpet
C12/o—Tol.: o—tolidine and potassium iodide Silicagel H Chlorpropham SecbumetonAtrazine Atrazine
Fluorobor.: NaOH + p—nitrobenzene diazonium Silicagel H Carbaryl Dioxacarb,Carbaryl Carbaryl

fluoroborate
Note: Detecting reagents, layers and pesticides used

7.3 HPLC analysis

In residue analysis, the use of IIPLC is particularly useful for pesticides which are not
directly amenable to GLC determination, such as those that lack thermal stability, e.g.
methylcarbamate insecticides (73,74,75) or phenylurea herbicides (76,77); cannot be
analysed directly (phenoxyacetic acids, 78) or are not sufficiently volatile (e.g. some
benzimidazole fungicides, 79,80) without further derivatisation. There are a number of
examples that demonstrate that HPLC is equally as suitable as GLC for some additional
compound classes such as sythetic pyrethroids, organophosphates and triazines mainly because
of simpler cleanup procedures and faster analyses. In many cases HPLC offers better
separation and faster and more accurate analysis than it is possible with TLC. However it
is much more expensive, requires regular maintenance and is not as universally applicable
as TLC. The main drawback of HPLC is that detectors currently available are much less
sensitive and selective than in GLC.
The UV detector with variable wavelength is mostly used in multiresidue analysis. Its
selectivity is best for pesticides with absorption maxima at high wavelengths. The
sensitivity depends largely on the extinction coefficients of pesticides and co—extractives
present but usually the detection limit will not be better than 0.1—0.5 mg/kg even if up to
100 ul are injected for analysis.
The more efficient fluorescence detection was originally suitable only for individual
pesticides exhibiting proper fluorescence of the molecule, but is now of increasing
application for post—column derivatisation in multiresidue analysis of methylcarbamates
using dansyl chloride (81) or o—phthalaldehyde/2—mercaptoethanol (82).
Separation is performed on 5—10 im silica gel and usually reversed—phase or other surface
modified material is used. As a rule, reversed—phase conditions are particularly versatile
for residue analysis of low polarity pesticides because of broad applicability and low
risk of irreversible contamination of the column by co—extractives. Separation qualities
of column packings commercially available may, however, differ widely according to the
brand. Very promising is the combination of columns with different separation properties
by column—switching techniques (83).
When a broad spectrum cleanup procedure is used (e.g. gel permeation chromatography) the
cleaned extract may well be used for both GLC and HPLC determinations, each of them covering
different groups of pesticides. It should be kept in mind, however, that most current
cleanup methods have been elaborated and proved for GLC analysis with selective detectors
and will not necessarily offer the best performance when used with HPLC. As in GLC all
identifications based on HPLC will need a confirmation by another suitable procedure.
CONCLUSIONS
Most of the multiresidue procedures considered in this paper were developed some years ago
and are capable of identifying and determining a large number of pesticide residues. In
the meantime, many of them have undergone some standardization by national or international
bodies. The advantage of the use of standardized processes is evident. The comparison and
assessment of various processes indicate, however, that the procedures used in analytical
practice are not necessarily restricted to the pesticides specified by the authors but may
cover many more compounds. This is particularly true for pesticides introduced in recent
years. There is therefore a great demand for information on which of the pesticides of
current importance will be included in a certain method. Thus it would be for the benefit
of the analysts if the demonstrated extension of standardized procedures was published,
regularly providing information on both positive as well as negative results.
A study of the results of monitoring programmes indicates that most of the compounds
detected can easily be determined by MRPs. This approach may mislead those who are not
familiar with the preconditions of the analytical programme and are interested only in the
results and the actual residue situation. Exclusive use of MRPs will therefore draw
attention to a specific number of compounds and will not provide information on the
existence or significance of other pesticide residues. For this reason the MRPs should
never be applied uncritically in routine analysis and the pesticides specified in market
control, selective field survey and environmental monitoring programmes should not be
selected according to the analytical possibilities of HRPs but rather by considering actual
use patterns and practice, the probability of the appearance of a residue and its toxicity.
The detailed list of compounds which were looked for should be specified in every report.
Most standardized IIRPs were developed on the basis of partitioning and adsorption column
chromatography clean—up steps. In the meantime, gel permeation chromatography has proven
its efficiency as an excellent basic cleanup step removing the surplus of co—extractives or
lipids in the crude sample extract. The aliquots of an extract precleaned by GPC can be
used directly for certain GLC or TLC analyses or can be further purified with specific
processes to meet the requirements of the various pesticides and sample matrices.
Since speed and low cost of analysis (46) are priorities in most laboratories the most
promising way of achieving this is the use of miniaturized methods for cleanup involving a
basic GPC precleaning step.
The mode of detection of residues may vary from one laboratory to another depending on the
facilities available. The degree of sample concentration and cleanup requirement depend
strongly on the mode and condition of detection. The operating conditions have to be
optimized individually in each laboratory. The actual detecting parameters govern the kind
and sequence of cleanup steps, and every laboratory has to establish its own internal
procedure, including confirmation which is preferably based on standardized processes of
widely used, internationally accepted methods.
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APPENDIX
Compounds frequently reported to be present in food commodities
Organohalogen compounds Organophosphorus compounds
aldrin acephate
DDT, DDD, DDE and isomers azinphos—methyl
dieldrin azinphos—ethyl
endosulfan bromophos
HCH isomers bromophos—ethyl
hexachlorobenzene carbopheno thion
lindane chlorfenvinphos
quintozene chlorpyrifos
captafol dialifos
captan diazinon
chlorothalonil dichlorvos
dichlof luanid dimethoate/omethoate
dicloran ditalimfos
dithianon ethion
folpet fenitrothion
fenthion
Dithiocarbamates malathion
methamidophos
Triazines methidation
mevimphos
atrazine parathion
parathion methyl
Carbamates phosalone
phosphamidon
carbaryl pirimiphos—methyl
chlorpropham sulfotep
ethiofencarb tetrachlorvinphos
pirimicarb triazophos
propham trichloronate
propoxur
Other pesticides Synthetic pyrethroids
benomyl cypermethrin
carbendazim deltamethrin
chinomethionate fenvalerate
chlormequat permethrin
daminozide
dichloran
dinobuton Other residues from pesticides
dinocap
dinoseb—acetate bromide ion
diquat
dodine
ethephon
etrimphos
fenarimo 1
imazalil
iprodione
metalaxyl
nitrothal—isopropyl
paraquat
pendimethalin
phosphine
procymidone
propargite
propiconazol
thiabendazol
tolylfluanid
trichlorphenidin
vinclozolin

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Pure & App!. Chem., Vol. 58, No. 7, pp. 1035—1062, 1986.

Printed in Great Britain.

INTERNATIONAL UNION OF PURE

IUPAC Reports on Pesticides (21)

The proper application of MRPs requires knowledge of extractability of different compounds

PURIFICATION Gel Other

limited number of solvents, liquid—liquid partitioning, adsorbent column chromatography or

2 FIELDS OF APPLICATION OF MULTIRESIDUE PROCEDURES (MRPs)

The main areas of residues analysis are:

(i) Disappearance studies following the application of individual compounds

(ii) (determination of pesticide residue content of raw agricultural commodities moving

(iii) determination of pesticide residues in food prepared for human consumption

(iv) identification and quantitation of residues in environmental elements.

3 SELECTION OF COMPOUNDS AND COMMODITIES FOR REGULATORY ANALYSIS

— are sold in large quantities and used extensively;

— themselves or their residues are highly toxic;

4 PREPARATION OF SAMPLES FOR ANALYSIS

— 200 PE/Eth 94+6

— 30 Dichlm 120 Bz/Acnit 1+1

150 Ac — 150 Dichim

100 200 Ac 80 — 200 PE/Dichlm

100 200 Ac 200 — 100 Dichlm 32 cm Bio Beads

Ebing (19d,e,f) OC, OP 100 200 Ac 1/5 250 W, 2xSO Sweep—Co—

4.2 Preparation of portion of sample to be analysed

5 EXTRACTION AND LIQUID-LIQUID PARTITIONING

TABLE 2. Some clean—up procedures used for analysis of organochlorine

Telling (25,26) 0.5 (Soln in Hex) 22 g Alumina N 150 Hex

Steinwandter 0.5 (Soln in PE) 20 g Silica gel 250 PE

Specht (19j) 0.3 (Soln in GPC 32 cm BioBeads 100+65 Cyclh/EtAc

Stijve (28) 0.1 (Soln in PE) 3 g Florisil 30 PE/Dichlm 8+2

Greve (29) 0.05 (Soln in Hex) 2 g Alumina B 15 Hex

Notes: N — neutral, B — basic

TABLE 3. Applicability of multiresidue procedures

Explanation of columns 1—7 in Table

3 Becker: Ac/water/Dichim, Silica/carbon, 1 eluate

4 Anibrus: Ac/water/Dichlm, mixed adsorbent, 1 eluate

5 Ambrus: Ac/water/Dichlm, Alumina N, 2 eluates

Explanation of signs: Detectors used:

c from crude extract only (no column clean—up)

from GPC eluate only (applies only to procedure 7)

Organohalogen pesticides (continued)

Binapacryl -H-E2 e -H-E2

Benfluralin -H-El +-I-E2 -H-E -H-El -H-El

Acephate -H- ++F5

Organophosphorus pesticides (continued)

Pyrethrins +4-E +4-E34

Cypermethrin +4-El +4- -H-E2

*Pesticide can also be determined by E.

Carbamate insecticides and herbicides

Pesticides which cannot be recovered by the multiresidue procedures cited

Azocyclotin Bromoxynil Chiormequat Amitrole

In comparison, acetone can be obtained commercially in higher purity grades, is more

Table 4. Elution behaviour of some organochlorine compounds on Florisil

Author AOAC Specht Mestres Stijve

Solvents PE/Eth PE/Eth PE/Eth PE PE/Eth PE/Dichlm

Notes: + : quantitative recovery

TABLE 5. Elution behaviour of some organophosphorus compounds on 20 g activated

Author AOAC (Sa) Mills (5a) Backman (65)

Solvents PE/Eth Dichlm/Hec/Acnit Bz/Eth Ac