PESTICIDE RESIDUES IN FOOD - 1984
Sponsored jointly by FAO and WHO
EVALUATIONS 1984
The monographs
Data and recommendations of the joint meeting
of the FAO Panel of Experts on Pesticide Residues
in Food and the Environment and the
WHO Expert Group on Pesticide Residues
Rome, 24 September - 3 October 1984
Food and Agriculture Organization of the United Nations
Rome 1985
CHLORFENVINPHOS
Explanation
Chlorfenvinphos was reviewed by the 1971 JMPR and MRLs were
recommended for 24 commodities. At that time the compound was not
widely applied to citrus and no residue data were submitted for
evaluation by the JMPR. At present chlorfenvinphos is registered for
use on citrus in several countries to control scale insects such as
Coccoidea and Diaspididae.
Information on use patterns on citrus and on residues resulting
from supervised trials was made available and is reviewed in this
addendum.
RESIDUES IN FOOD AND THEIR EVALUATION
USE PATTERN
On citrus fruit
The use of chlorfenvinphos on citrus has developed since the 1971
JMPR in several countries. The manufacturer provided a list of
registrations for chlorfenvinphos on citrus and national pre-harvest
intervals where these had been established. This and other information
provided by the Spanish government is summarized in Table 1.
Chlorfenvinphos is applied as a foliar spray at concentrations
generally between 0.04% and 0.06% active ingredient. Application
volumes up to 6.000 1/ha are used. The number of applications is
typically one and occasionally two.
RESIDUES RESULTING FROM SUPERVISED TRIALS
The manufacturer provided extensive information on residues
resulting from supervised trials on oranges and lemons in several
countries. Applications were made with chlorfenvinphos E.C. at dose
rates between 1.1 and 2.4 kg/ha. (Table 2).
In addition the Spanish government provided data on official
supervised trials carried out on mandarins, oranges and lemons in four
Spanish provinces in order to study chlorfenvinphos degradation over a
28-day post-application period (Table 3) and data on the final residue
levels at harvest time in precocious fruits (Table 4). These last
studies were carried out according to common Spanish agricultural
practice. Infestation by scale-insects (Diaspididae) generally occurs
at the end of the spring and by the end of the summer. Consequently
one or two treatments are usually applied, in the first fortnight of
June and/or the first fortnight of September. The most precocious
fruit-varieties are harvested in Spain from the beginning of October.
Table 1. Chlorfenvinphos registrations on citrus fruit
Pre-harvest
Country Formulation Interval (days)
Chile 24% W/V EC 30
Cyprus 24% W/V EC 20
Greece 24% W/V EC -
" 25% WP -
Iran 24% W/V EC -
Japan 24% W/V EC 14
" 50% W/V EC 14
Jordan 24% W/V EC 21
Morocco 20% + 2.5% Cypermethrin EC -
" 24% W/V EC -
Portugal 24% W/V EC -
Spain 15% + 2.5% Cypermethrin EC 30
" 24% W/V EC 30
Uruguay 24% W/V EC 28
Zambia 24% W/V EC -
Table 2. Residues resulting from supervised trials on citrus
Trial Country/ Citrus/ Dose rate (a.i.) Applications Interval between
year variety last application Residues
% kg/ha No. Interval and harvest mg/kg
1 Italy 1977 Femminello/ 0.05 (a) 1 10 Weeks Whole 0.52
lemon 10 Weeks Peel 1.59
10 Weeks Juice <0.01
2 Italy 1978 Moro/orange 0.05 (a) 1 17 Weeks Pulp <0.01
17 Weeks Peel 2.20
17 Weeks Juice <0.01
17 Weeks Whole 0.51
3 Italy 1974 Tarocco/orange 0.06 (a) 1 15 Days Whole 0.72
15 Days Pulp <0.01
30 Days Whole 0.69
30 Days Pulp <0.01
45 Days Whole 0.56
45 Days Pulp <0.01
60 Days Whole 0.55
60 Days Pulp <0.01
4 Italy 1982 Nostrano/orange 0.05 (b) 1 4 Weeks Pulp <0.01
4 Weeks Juice <0.01
4 Weeks Peel 1.90
4 Weeks Whole 0.48
8 Weeks Pulp <0.01
8 Weeks Juice <0.01
8 Weeks Peel 1.40
8 Weeks Whole 0.35
13 Weeks Pulp 0.01
13 Weeks Juice 0.01
13 Weeks Peel 1.15
13 Weeks Whole 0.29
Table 2. (continued)
Trial Country/ Citrus/ Dose rate (a.i.) Applications Interval between
year variety last application Residues
% kg/ha No. Interval and harvest mg/kg
5 Japan 1968 Japanese orange 1.68 1 95 Days Pulp <0.01
95 Days Peel 0.58
6 Japan 1968 Japanese orange 2.24 1 95 Days Pulp <0.01
95 Days Peel 0.72
7 Morocco 1982 Maroclate/ 1.6 1 23 Weeks Pulp <0.01
orange 23 Weeks Juice <0.01
23 Weeks Peel 0.13
23 Weeks Whole 0.03
8 Portugal 1977 Navel/orange 0.04 0.8 1 5 Weeks Pulp <0.01
5 Weeks Peel 0.70
5 Weeks Juice <0.01
5 Weeks Whole 0.21
13 Weeks Pulp <0.01
13 Weeks Peel 0.52
13 Weeks Juice <0.01
13 Weeks Whole 0.17
9 Portugal 1977 Navel/orange 0.06 1.2 1 5 Weeks Pulp <0.01
- 5 Weeks Peel 0.80
5 Weeks Juice <0.01
5 Weeks Whole 0.26
13 Weeks Pulp <0.01
13 Weeks Peel 0.70
13 Weeks Juice <0.01
13 Weeks Whole 0.23
Table 2. (continued)
Trial Country/ Citrus/ Dose rate (a.i.) Applications Interval between
year variety last application Residues
% kg/ha No. Interval and harvest mg/kg
10 Portugal 1977 Navel/orange 0.12 2.4 1 5 Weeks Pulp <0.01
5 Weeks Peel 1.00
5 Weeks Juice <0.01
5 Weeks Whole 0.33
11 Portugal 1977 Navel/orange 0.04 0.8 2 2 months 5 Weeks Pulp <0.01
5 Weeks Peel 1.20
5 Weeks Juice <0.01
5 Weeks Whole 0.40
12 Portugal 1977 Navel/orange 0.06 1.2 2 2 months 5 Weeks Pulp <0.01
5 Weeks Peel 1.60
5 Weeks Juice <0.01
5 Weeks Whole 0.53
13 Portugal 1977 Navel/orange 0.12 2.4 2 2 months 5 Weeks Pulp <0.01
5 Weeks Peel 3.35
5 Weeks Juice <0.01
5 Weeks Whole 1.11
14 S. Africa 1975 Valencias/ 0.02 (c) 2 50 days 15 Weeks Whole 0.24
orange 15 Weeks Pulp <0.01
15 Weeks Juice <0.01
22 Weeks Whole 0.20
22 Weeks Pulp <0.01
22 Weeks Juice <0.01
Table 2. (continued)
Trial Country/ Citrus/ Dose rate (a.i.) Applications Interval between
year variety last application Residues
% kg/ha No. Interval and harvest mg/kg
15 S. Africa 1975 Valencias/ 0.04 (c) 1 24 Weeks Whole 0.02
orange 24 Weeks Pulp <0.01
24 Weeks Juice <0.01
32 Weeks Whole 0.02
32 Weeks Pulp <0.01
32 Weeks Juice <0.01
16 S.Africa 1975 Valencias/
orange 0.04 (c) 2 50 days 15 Weeks Whole 0.61
15 Weeks Pulp <0.01
15 Weeks Juice <0.01
22 Weeks Whole 0.36
22 Weeks Pulp <0.01
22 Weeks Juice <0.01
17 S.Africa 1975 Valencias/
orange 0.04 (c) 2 50 Days 15 Weeks Whole 0.24
15 Weeks Pulp <0.01
15 Weeks Juice <0.01
22 Weeks Whole 0.30
22 Weeks Pulp <0.01
22 Weeks Juice <0.01
18 Spain 1980 Verna/lemon 0.048 1.104 1 15 Days Peel 0.87
15 Days Peel <0.01
15 Days Whole 0.37
30 Days Pulp <0.01
30 Days Whole 0.24
Table 2. (continued)
Trial Country/ Citrus/ Dose rate (a.i.) Applications Interval between
year variety last application Residues
% kg/ha No. Interval and harvest mg/kg
19 Spain 1980 Verna/lemon 0.06 1.38 1 15 Days Peel 1.05
15 Days Pulp <0.01
15 Days Whole 0.46
30 Days Peel 0.94
30 Days Pulp <0.01
30 Days Whole <0.01
30 Days Whole 0.45
20 Spain 1980 Verna/lemon 0.072 1.656 1 15 Days Peel 1.99
15 Days Pulp <0.01
15 Days Whole 0.91
30 Days Peel 1.06
30 Days Pulp <0.01
30 Days Whole 0.48
21 Spain 1981 Verna/lemon 0.048 1.104 1 1 Day Whole 0.34
14 Days Whole 0.17
21 Days Whole 0.14
29 Days Whole 0.04
22 Spain 1981 Verna/lemon 0.06 1.38 1 1 Day Whole 1.63
14 Days Whole 0.37
21 Days Whole 0.25
29 Days Whole 0.13
23 Spain 1981 Verna/lemon 0.072 1.656 1 1 Day Whole 1.69
14 Days Whole 0.80
21 Days Whole 0.29
29 Days Whole 0.30
Table 2. (continued)
Trial Country/ Citrus/ Dose rate (a.i.) Applications Interval between
year variety last application Residues
% kg/ha No. Interval and harvest mg/kg
24 Spain 1982 Verna/lemon 0.0225 1.595 1 1 Day Whole 0.32
1 Day Juice <0.01
7 Days Whole 0.32
7 Days Juice <0.01
14 Days Whole 0.33
14 Days Juice <0.01
21 Days Whole 0.29
21 Days Juice <0.01
28 Days Whole 0.16
28 Days Juice <0.01
35 Days Whole 0.12
35 Days Juice <0.01
49 Days Whole 0.09
49 Days Juice <0.01
60 Days Whole 0.06
60 Days Juice <0.01
25 Spain 1982 Verna/lemon 0.03 2.1 1 1 Day Whole 0.81
1 Day Juice <0.01
7 Days Whole 0.61
7 Days Juice <0.01
14 Days Whole 0.31
14 Days Juice <0.01
21 Days Whole 0.31
21 Days Juice <0.01
28 Days Whole 0.31
28 Days Juice <0.01
35 Days Whole 0.25
35 Days Juice <0.01
49 Days Whole 0.16
49 Days Juice <0.01
60 Days Whole 0.12
60 Days Juice <0.01
Table 2. (continued)
a) Application volume/ha is not indicated
b) Application volume 6 1/tree
c) Application volume 25 1/tree
Table 3. Residues of chlorfenvinphos in Spanish citrus fruits
Application (1)
Trial Number Citrus/Variety Location Residues, mg/kg (2), at intervals (days)
No. Dose Rate (a.i.) after last application (whole fruit (3))
% kg/ha 0 7 14 21 28
26 Satsuma mandarin Alicante 1 0.036 2.16 0.6 0.4 0.5 0.5 0.5
Castellon 1.2 0.9 0.9 0.8 0.8
Valencia 1.7 1.5 1.2 1.1 1.0
Average 1.16 0.93 0.86 0.8 0.76
27 (4) Navelina orange Alicante 1 0.03 1.8 0.45 0.36 0.31 0.21 0.17
Castellon 0.40 0.29 0.21 0.17 0.15
Valencia 0.41 0.23 0.23 0.20 0.19
Average 0.42 0.30 0.25 0.19 0.17
28 (4) Fino lemon Alicante 1 0.03 1.8 0.87 0.67 0.67 0.58 0.50
Murcia 0.59 0.48 0.33 0.39 0.34
Average 0.72 0.57 0.50 0.48 0.42
29 (5) Verna Lemon Murcia - 1 1 0.072 4.3 4.74 3.95 2.92 2.49 1.99
Murcia - 2 1.53 1.15 0.87 0.71 0.62
Average 3.13 2.55 1.89 1.60 1.30
(1) Spray volume 6.000 1/ha of chlorfenvinphos E.C.
(2) Sum of E and Z isomers.
(3) Residue levels in pulp were all below the analytical limit of determination (0.02 mg/kg)
(4) Each value is the average of 3 individual samples analysed by 3 different laboratories
(5) Each value is the average of 2 individual samples analysed by 2 different laboratories.
Table 4. Chlorfenvinphos residues in Spanish precosious citrus fruits at harvest time
Application (1) Interval (days) between Residue, mg/kg
Trial number Citrus/variety Location last application and (2) at harvest
No. Dose Rate (a.i.) harvest time
% kg/ha (Whole fruit (3))
30 (4) Satsuma mandarin Valencia 1(June) 0.03 1.8 95 0.19
Valencia 1 (Sept.) 17 0.50
Valencia 2(June &
Sept.) 17 0.66
Alicante 1(June 117 0.12
Alicante 1(Sept.) 26 0.31
Alicante 2(June &
Sept.) 26 0.51
Castellon 1(June 116 0.10
Castellon 1(Sept.) 26 0.47
Castellon 2(June &
Sept.) 26 0.48
AVERAGE 1(June) 110 0.13
1(Sept) 23 0.42
2(June &
Sept.) 23 0.55
31(4) Navelina orange Alicante 1(June) 0.03 1.8 131 0.11
Alicante 1(Sept.) 40 0.32
Alicante 2(June &
Sept.) 40 0.49
Table 4. (continued)
Application (1) Interval (days) between Residue, mg/kg
Trial number Citrus/variety Location last application and (2) at harvest
No. Dose Rate (a.i.) harvest time
% kg/ha (Whole fruit (3))
31 (4) Navelina orange Valencia 1 (June) 125 0.15
Valencia 1 (Sept.) 40 0.41
Valencia 2 (June &
Sept.) 40 0.46
Average 1 (June) 128 0.13
1 (Sept.) 40 0.36
2 (June &
Sept.) 40 0.47
32 Clementina
mandarin Castellon 1 (June) 0.03 1.8 126 0.02
Castellon 1 (Sept.) 36 0.44
Castellon 2 (June &
Sept.) 36 0.78
(1) Application volume 6.000 1/ha
(2) Sum of E and Z isomers
(3) Residues in pulp were all below the analytical limit of determination (0.02 mg/kg)
(4) Each value is the average of 2 individual samples analysed by 2 laboratories.
Data on residue levels in mandarins and oranges after one or two
applications of chlorfenvinphos (1.8 kg/ha a.i.) in June and/or
September are reported in Table 4. Samples of each citrus variety were
collected on the first legal harvest-day of October.
In most of the 32 trials reported, residues of E and Z
isomers were separately determined. The figures in the tables
represent the sum of the two isomers. Since the limit of determination
of each isomer was 0.01 mg/kg, where separate determinations were
made, and no residues of either were found the sum is shown as less
than 0.02 mg/kg. In all cases peel and pulp were analysed separately.
Residue levels in the pulp were all below the analytical limit of
determination. Analysis of peeled fruit and juice, in addition to
whole fruit, indicates that chlorfenvinphos does not migrate from peel
to the edible portion of the fruit even after extended periods.
Residue levels in whole fruit were in all cases below 1 mg/kg
except those from trials Nos. 13 and 29. In trial No. 13 (orange
trees located in Portugal) a residue of 1.11 mg/kg was found after 5
weeks with two applications of 2.4 kg/ha. This is however the highest
treatment reported in all the portuguese trials. In trial No. 29 in
Murcia (Spain) residues in lemons from sub-trial 1 were higher than
1.0 mg/kg at the exceptional dose rate of 4.3 kg/ha, but those from
sub-trial 2, under the same conditions, were below 1 mg/kg at
pre-harvest intervals of 14-28 days.
METHODS OF RESIDUE ANALYSIS
Several residue methods, all based on gas chromatography, have
been developed for the analysis of citrus fruits. In an adaptation of
the manufacturer's method (Beynon et al, 1966 reported in the 1971
evaluation), representative sub-samples of the peel and pulp are
homogenized with 30% v/v acetone in redistilled petroleum spirit
(BP 60-70°C) or with a mixture of acetone and hexane. If the
determination is made by GLC with a flame photometric detector no
clean-up is necessary, but a Florisil column clean-up is used prior to
analysis with the electron capture detector. The E- and Z- isomers
are determined separately. The limit of determination of each isomer
is 0.01 mg/kg. Recoveries from all citrus varieties in pulp, peel and
whole fruit at several fortification levels are generally higher than
85% for both isomers.
NATIONAL MAXIMUM RESIDUE LIMITS
The following national maximum residue limits for citrus were
reported.
Country MRL (mg/kg)
Netherlands 1.0
Federal Rep. Germany 1.0
0.05 (peeled citrus fruit)
APPRAISAL
The meeting examined information provided by the manufacturer and
by the Spanish government on GAP of chlorfenvinphos on citrus fruit
and residues resulting from supervised trials.
Chlorfenvinphos is registered for use on citrus fruit in several
countries to control scale insects. It is applied as a foliar spray at
concentrations generally between 0.04% and 0.06% a.i. Application
volumes up to 6000 l/ha. are used and the number of applications is
typically one and occasionally two.
Residues data from 32 trials on orange, mandarin and lemon trees
indicate in all cases that chlorfenvinphos does not migrate from the
peel to the edible part of the fruit even after extended periods.
Residue levels in the pulp were all below the limit of determination.
Residues in whole fruit were in all cases below 1 mg/kg except one
residue of 1.11 mg/kg in oranges after 5 weeks (with two applications
of 2.4 kg/ha a.i.) and residues in lemons treated with 4.3 kg/ha.
The Meeting did not take into consideration the residues above
1.0 mg/kg because they occurred only in two trials of the 32
experiments reported, and when an extraordinarily high dose was
sprayed. Moreover in a second residue sub-trial in lemons under the
same conditions, residues were all below 1 mg/kg. In addition the
Spanish studies of residue levels at harvest time in fruits harvested
early after one or two applications of chlorfenvinphos showed residues
below 1.0 mg/kg in all cases.
The Meeting concluded that according to the good agricultural
practices reported, a maximum residue level for citrus of 1 mg/kg
would be suitable for use as an MRL. It was noted, however, that when
one formulation is used as its highest registered rate residues might
exceptionally exceed 1 mg/kg.
Analytical methods for the analysis of citrus fruit considered by
the Meeting are basically the same as those previously reviewed by the
1971 JMPR. The chlorfenvinphos residue is determined by GLC with flame
photometric detection, the E- and Z- isomers being determined
separately. The limit of each isomer is 0.01 mg/kg.
RECOMMENDATIONS
The meeting concluded that the residue levels shown below is
suitable for establishing a maximum residue limit for citrus fruit.
The limit refers to sum of E- and Z- isomers.
Commodity MRL (mg/kg) Pre-harvest interval
on which MRL is based
days)
Citrus 1 28
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1983 by the Servicio de Defensa contra Plagas e Inspección
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See Also:
Toxicological Abbreviations
Chlorfenvinphos (ICSC)
Chlorfenvinphos (WHO Pesticide Residues Series 1)
Chlorfenvinphos (Pesticide residues in food: 1994 evaluations Part II Toxicology)