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
PROPINEB
Explanation
Propineb was evaluated by the 1977 JMPR (FAO/WHO, 1979). 1/ A
temporary ADI and temporary MRLs were estimated by that meeting. MRLs
were identical to those of the ethylene-bisdithiocarbamates.
New information was received by the 1984 JMPR on current GAP and
on residues from supervised trials in accordance with such practices.
RESIDUES IN FOOD AND THEIR EVALUATION
USE PATTERN
Propineb, a propylene-bisdithiocarbamate fungicide, is used, with
very few exceptions, similarly to the ethylene-bisdithiocarbamates. It
is used as a protection treatment on several crops for the control of
various fungi, especially Oomycetes such as Phytophthora spp,
Pythium spp and other pathogens belonging to the Ascomycetes,
Basidiomycetes and Fungi imperfecti.
The current use pattern is summarized in Table 1. The main uses
are preventive control of fungal diseases on grapes, potatoes (against
Phytophthora), apples, tomatoes and tobacco.
RESIDUES RESULTING FROM SUPERVISED TRIALS
Information on residues resulting from supervised trials, mainly
from the Federal Republic of Germany, included data from trials on
apples, pears, sour cherries, peaches, plums, grapes, celeriac,
potatoes and tomatoes. Information was also received on residues in
processed commodities derived from some of the crops mentioned, such
as juice from apples, cherries and tomatoes, must and wine from
grapes, apple sauce, jam from cherries, mash from pears and plums and
tomato ketchup. The data are summarized in Table 2.
Apples
Propineb residues expressed as CS2, ranged from 0.7-6.0 mg/kg on
the day of treatment and from about 0.36-1.5 mg/kg after 14 days. The
propylenethiourea (PTU) levels at the same sampling dates were
0.2-0.5 mg/kg and 0.03-0.11 mg/kg respectively. The PTU residues in
cold-pressed apple juice were slightly lower than in juice pasteurized
at 60-70°C. In the latter, the maximum PTU residue was 0.06 mg/kg. The
PTU residues in apple sauce cooked for a short period at ca. 125°C
ranged from <0.01 to 0.05 mg/kg.
1/ See Annex 2 for FAO and WHO documentation
TABLE 1. Use Pattern of Propineb
Dosage rate Applications Preharvest interval
(kg a.i./ha) (no.) (days)
Africa
Grapes 0.35-21 4-10 14
Potatoes 0.7-2.1 4-8 3
Tomatoes 0.7-4.2 4-8 3
Peanuts 1.4-2.1 2-4 21
Asia
Potatoes 1.05-1.4 8-20 1
Tomatoes 1.05-1.75 8-20 1 7
Beans 1.05-2.1 12 7
Cucurbits 1.2 2
Australia and New Zealand
Potatoes 1.05-2.8 4-8 7
Tomatoes 0.84-1.75 4-8 7-10
Europe (except Mediterranean area)
Pome fruit 1.4-2.8 8-12 7-28
Stone fruit 1.4-2.8 2-3 7-28
Berries and 2.1-2.8 2-3 14
other small fruit
Grapes 1.75-2.8 4-10 21-56
Cucumbers 0.84-1.4 2-4 3-7
Celery 0.84-1.0 2-3 7-28
Potatoes 1.05-2.8 4-8 7-10
Tomatoes 0.84-1.7 4 3-7
Hops 1.5-4.2 10-14 14-35
Tobacco 2.1-2.8 10-16 7
Europe (Mediterranean area)
Pome fruit 1.4-2.8 8-12 7-10
Stone fruit 2.0 2-3 28
Citrus fruit 2.1-4.2 3-6 14
Grapes 1.75-2.8 3-10 21-28
Cucurbits 0.84-1.4 2-4 4-15
Potatoes 1.05-2.8 4-8 7-28
Tomatoes 0.84-1.75 4-8 4-15
Tobacco 2.1-2.8 10-16 7
TABLE 1. (continued)
Dosage rate Applications Preharvest interval
(kg a.i./ha) (no.) (days)
Near East
Potatoes 1.4-2.5 3
Tomatoes 1.4-2.9 3
Citrus fruit 2.4
Cucumbers 1.4 3
Grapes 0.7-2.1
South America
Tobacco 1.75-2.1 8-10 7
1 In areas with heavy rainfall
TABLE 2. Propineb Residues in Various Crops from Supervised Trials, Federal Republic of Germany
Crop Year Application1 Residues
Pre-
No. Rate harvest Propineb as CS2 PTU
(kg a.i. interval
/ha) (days) average range average range
APPLE 2 1978 12 2.8 0 4.1 3.1-6.0 0.23 0.2-0.26
4 3.4 2.8-3.9 0.17 0.16-0.17
7 3.3 1.9-4.1 0.22 0.21-0.23
10 2.5 1.1-4.2 0.13 0.11-0.15
13 0.84 0.79-0.89 0.085 0.08-0.09
11 2.8 0 5.1 4.2-5.9 0.45 0.40-0.49
4 3.6 3.3-3.8 0.30 0.30
7 2.2 1.6-2.6 0.28 0.27-0.29
10 1.2 1.1-1.2 0.15 0.11-0.2
13 1.2 0.95-1.5 0.10 0.09-0.11
fruit 12 2.8 0 1.8 1.2-2.4 0.07
5 1.5 0.79-2.7 0.09
7 1.8 1.7-1.9 0.05
10 0.84 0.84 0.05
14 0.81 0.79-0.84 0.05
juice 10 <0.1 <0.01
sauce 10 <0.1 0.03
fruit 1980 12 2.8 10 0.89 0.73-1.05 0.079
juice, cold 10 0.34 0.33-0.44 0.015
juice, 65°C 10 <0.05 0.046
sauce 10 <0.05 0.017
fruit 1978 12 2.8 0 0.89 0.63-1.15 0.08
4 0.89 0.07
7 0.84 0.11
10 0.47 0.05
14 0.36 0.04
TABLE 2. (continued)
Crop Year Application1 Residues
Pre-
No. Rate harvest Propineb as CS2 PTU
(kg a.i. interval
/ha) (days) average range average range
juice, cold 10 0.19 0.17-0.21 <0.01
juice, 65°C 10 0.28 0.26-0.29 <0.01
sauce, 125°C 10 <0.1 <0.1 0.05
fruit 1980 12 1.57 10 0.16 0.14-0.18 0.01 0.009-0.011
juice, cold 10 <0.1 <0.01
juice, 65° 10 <0.1 <0.01
sauce 10 <0.1 <0.01
fruit 12 1.57 10 2.4 0.058 0.056-0.060
juice, cold 10 1.25 1.2-1.3 0.017 0.015-0.019
juice, 65° 10 <0.05 0.052 0.048-0.056
sauce 10 0.09 0.09-0.095 0.052 0.050-0.054
fruit 1982 10 2.1 21 0.96 0.92-0.99 0.027 0.026-0.027
28 0.80 0.72-0.88 0.026 0.021-0.03
juice, 65° 21 <0.05 0.025 0.023-0.027
sauce 21 <0.05 0.021 0.021-0.021
PEAR
fruit 1982 10 2.1 21 0.52 0.52-0.52 0.057 0.050-0.063
28 0.55 0.52-0.58 0.053 0.050-0.055
sauce, 125° 21 <0.05 <0.01
fruit 10 2.1 17 <0.05 <0.01
sauce, 120° 17 <0.05 <0.01
TABLE 2. (continued)
Crop Year Application1 Residues
Pre-
No. Rate harvest Propineb as CS2 PTU
(kg a.i. interval
/ha) (days) average range average range
CHERRY, SOUR 3
fruit 1982 3 1.58 0 5.22 4.88-5.55 0.11 0.10-0.11
14 0.77 0.71-0.83 0.051 0.05-0.052
21 0.26 0.23-0.29 0.034 0.032-0.035
28 0.15 0.13-0.17 0.017 0.010-0.024
35 0.05 0.053-0.053 <0.01
juice 28 0.09 0.076-0.11 0.013 0.012-0.013
jam 28 0.05 0.049-0.056 0.017 0.017-0.017
fruit 1979 3 2.1 0 3.4 2.3-4.7 0.35 0.31-0.39
7 0.87 0.83-0.91 0.14 0.13-0.14
14 0.56 0.55-0.56 0.13 0.10-0.15
21 0.50 0.46-0.53 0.04 0.03-0.05
28 0.23 0.21-0.25 0.02 0.02
juice 21 0.06 <0.05-0.08 0.05 0.05-0.05
jam 21 0.09 0.089-0.094 0.02 0.02-0.02
fruit 3 1.58 0 3.2 3.1-3.2 0.35 0.34-0.35
7 2.1 1.9-2.2 0.31 0.26-0.35
14 0.23 0.21-0.24 0.03 0.03-0.033
21 0.21 0.18-0.23 0.02 0.018-0.022
28 <0.05 0.02 0.018-0.022
juice 21 <0.05 0.12 0.11-0.12
jam 21 0.12 0.10-0.14 0.067 0.056-0.078
TABLE 2. (continued)
Crop Year Application1 Residues
Pre-
No. Rate harvest Propineb as CS2 PTU
(kg a.i. interval
/ha) (days) average range average range
fruit 3 1.58 0 5.8 2.5-9.3 0.43 0.39-0.46
7 1.9 1.7-2.3 0.33 0.31-0.34
14 0.56 0.54-0.57 0.065 0.062-0.067
21 0.41 0.33-0.49 0.093 0.092-0.094
28 <0.1 0.023 0.022-0.024
juice 21 <0.1 0.021 0.019-0.022
jam 21 <0.1 0.020 0.02-0.02
PEACH
fruit 1980 3 1.58 0 5.46 5.43-5.48
7 4.15 4.07-4.22
14 2.38 2.30-2.41
21 2.35 2.30-2.40 0.025 0.021-0.029
28 0.95 0.9-1.0
PLUMS 4
fruit 1979 3 2.1 0 1.5 1.4-1.5 0.08 0.07-0.09
7 0.72 0.68-0.76 0.05 0.05-0.05
14 0.40 0.38-0.42 0.04 0.03-0.04
21 0.31 0.30-0.32 0.02 0.02-0.03
28 0.25 0.24-0.25 0.04 0.04
pulp 21 <0.1 0.18 0.17-0.18
fruit 3 1.58 0 1.0 0.89-1.11 0.03 0.03-0.04
7 0.39 0.38-0.40 0.03 0.03-0.03
14 0.44 0.42-0.46 0.04 0.03-0.04
21 0.12 0.1-0.14 0.01 0.12
28 <0.05 0.01 0.009-0.01
TABLE 2. (continued)
Crop Year Application1 Residues
Pre-
No. Rate harvest Propineb as CS2 PTU
(kg a.i. interval
/ha) (days) average range average range
pulp 21 <0.1 0.21 0.17-0.24
fruit 1982 3 1.58 0 1.5 1.5-1.5 0.03 0.02-0.03
14 0.8 0.7-0.8 0.04 0.03-0.04
21 0.6 0.5-0.6 0.04 0.03-0.04
28 0.2 0.2-0.2 <0.01 <0.01-<0.01
35 0.2 0.2-0.2 0.02 0.01-0.02
pulp 28 <0.05 0.07 0.05-0.08
fruit 3 1.58 0 1.2 1.1-1.2 0.02 0.02-0.02
14 0.2 0.2-0.2 0.02 0.02-0.02
21 0.4 0.3-0.4 0.02 0.02-0.02
28 <0.05 <0.05-<0.05 0.01 <0.01-0.01
35 0.3 0.3-0.3 0.02 0.02-0.02
pulp 28 <0.05 <0.05 0.05 0.04-0.06
fruit 3 1.58 0 1.2 1.1-1.2 0.04 0.03-0.05
14 0.1 0.1-0.1 <0.01 <0.01-<0.01
21 0.4 0.3-0.4 0.02 0.02-0.02
28 0.06 0.05-0.06 <0.01 <0.01
35 <0.05 <0.01 <0.01
pulp 28 <0.05 0.05 0.04-0.05
fruit 1980 3 1.58 21 0.36 0.35-0.37 <0.01
pulp 21 <0.05 0.04 0.04-0.04
fruit 3 1.58 21 0.34 0.33-0.35 <0.01
pulp 21 <0.05 <0.05 0.049-0.051
TABLE 2. (continued)
Crop Year Application1 Residues
Pre-
No. Rate harvest Propineb as CS2 PTU
(kg a.i. interval
/ha) (days) average range average range
GRAPES, WHITE 5
fruit 1979 8 2.8 79 1.4 1.24-1.93 0.085 0.076-0.093
must 79 0.77 0.69-0.84 0.022 0.017-0.026
wine (fust) 0.07 0.04-0.09 0.12 0.11-0.12
fruit 8 2.8 63 0.79 0.66-0.95 0.055 0.044-0.066
must 63 0.26 0.16-0.29 0.052 0.049-0.055
wine (bottled) <0.05 <0.05 0.019 0.017-0.021
fruit 1980 8 1.4-2.8 42 2.6 2.5-2.6 0.17 0.16-0.17
must 42 0.20 0.17-0.22 0.04 0.042-0.043
wine <0.05 0.05 0.052-0.056
fruit 1981 8 1.4-2.8 69 0.75 0.71-0.79 0.048 0.044-0.052
must 69 0.41 0.40-0.42 0.071 0.067-0.074
wine 179 0.05 0.05-0.05 0.10 0.09-0.11
fruit 1982 8 2.8 73 1.7 1.6-2.0 0.1
must 73 1.15 0.76-1.45 0.07 0.066-0.073
wine (bottled) <0.05 0.007 0.086-0.087
GRAPES, RED 6
fruit 1982 6 1.4 35 0.5 0.4-0.6 0.03 0.03-0.03
must 35 0.1 0.1-0.1 0.2 0.2-0.2
wine 162 0.1 0.1-0.1 0.1 0.1-0.1
TABLE 2. (continued)
Crop Year Application1 Residues
Pre-
No. Rate harvest Propineb as CS2 PTU
(kg a.i. interval
/ha) (days) average range average range
fruit 5 1.4-2.8 49 0.2 0.2-0.2 0.08 0.08-0.08
must 49 0.05 <0.05-0.08 0.02 0.02-0.02
wine 176 0.05 0.04-0.06 0.07 0.06-0.1
fruit 6 1.4-2.8 42 0.07 0.06-0.07 0.02 0.02-0.02
must 42 0.08 0.06-0.1 0.04 0.04-0.05
wine 162 <0.05 0.05 0.04-0.06
CELERIAC
roots 1978 3 1.05 0 <0.05 <0.05
14 <0.05 <0.05
21 <0.05 <0.05
28 <0.05 <0.05
leaves 0 8.9 7.4-11 <0.05
14 0.47 0.42-0.53 <0.05
21 0.14 <0.05
28 <0.05 <0.05
roots 3 1.05 0 <0.1 <0.05
14 <0.1 <0.05
21 <0.1 <0.05
28 <0.1 <0.05
leaves 0 13 12-14 <0.05
14 1.4 <0.05
21 0.63 0.58-0.68 <0.05
28 0.41 0.32-0.49 <0.05
35 0.28 0.27-0.30 <0.05
TABLE 2. (continued)
Crop Year Application1 Residues
Pre-
No. Rate harvest Propineb as CS2 PTU
(kg a.i. interval
/ha) (days) average range average range
POTATOES
1979 8 1.3 0 0.12 <0.01
1 <0.04 <0.01
4 <0.04 <0.01
7 <0.04 <0.01
8 1.3 0 <0.04 <0.01
1 <0.04 <0.01
4 <0.04 <0.01
7 <0.04 <0.01
TOMATOES
fruit 1978 6 1.26-1.68 0 1.8 1.4-2.2 0.1 0.05-0.14
1 1.0 0.57-1.55 0.08
4 0.13 0.07-0.19
7 0.34 0.25-0.55 <0.01
10 0.36 0.34-0.37 0.03
juice 4 0.21 0.20-0.21 0.03
ketchup 4 <0.1 0.05 0.04-0.05
6 1.26-1.68 0 1.2 1.0-1.4 0.07 0.06-0.08
1 0.63 0.4-0.85 0.09 0.08-0.09
4 0.14 0.11-0.16
7 0.39 0.37-0.40 0.08 0.07-0.09
10 0.39 0.31-0.46 0.02 0.02-0.02
juice 4 0.28 0.26-0.29 0.03 0.02-0.03
ketchup 4 0.14 0.11-0.16 0.03 0.03-0.03
TABLE 2. (continued)
Crop Year Application1 Residues
Pre-
No. Rate harvest Propineb as CS2 PTU
(kg a.i. interval
/ha) (days) average range average range
1979 6 0.8-1.6 0 0.86 0.84-0.87 0.043 0.039-0.047
1 0.79 0.61-0.97 0.028 0.027-0.029
4 0.67 0.45-0.89 0.019 0.016-0.022
7 0.50 0.39-0.61 0.052 0.044-0.06
10 0.23 0.21-0.24 0.055 0.051-0.058
juice 4 0.41 0.35-0.51 0.12 0.12-0.13
ketchup 4 <0.05 0.046 0.025-0.087
fruit 1980 6 1.26-1.68 4 0.39 0.38-0.39 0.012 0.012-0.013
juice 4 0.24 0.22-0.26 0.017 0.016-0.018
ketchup 4 <0.05 0.044 0.039-0.048
fruit 1980 6 1.26-1.68 4 0.075 0.07-0.08 0.011 0.01-0.011
juice 4 0.23 0.20-0.26 0.018 0.016-0.02
ketchup 4 <0.05 0.038 0.036-0.039
fruit 1980 6 0.84-1.68 5 0.75 0.024 0.022-0.025
ketchup 5 0.07 0.06-0.07 0.079 0.076-0.081
fruit 1978 6 0.84-1.68 0 0.54 0.46-0.61 0.03
1 0.43 0.38-0.48 0.05
4 0.38 0.36-0.39 0.04
7 0.32 0.30-0.34 0.02
fruit 1978 6 0.84-1.68 0 0.66 0.47-0.84 0.04
1 0.22 0.16-0.28 0.05
4 0.30 0.28-0.32
7 0.08 0.07-0.1 0.02
TABLE 2. (continued)
1 A 70% W.P. formulation was used in all trials.
2 Two additional trials on aDDles gave similar results.
3 Four additional trials on sour cherries, three in 1980 and one in 1982, gave similar results.
4 Three additional trials on plums gave similar results.
5 Sixteen additional trials on white grades, three in 1979, six in 1980, three in 1981 and four in 1982, gave similar results.
6 Four additional trials on red grapes in 1982 gave similar or lower residues.
Source: Bayer, 1978-1983
Pears
Propineb residues expressed as CS2 ranged from about 2.3 to
9.3 mg/kg on the day of treatment and from 0.2 to 6.8 mg/kg after 14
days. Maximum levels of PTU at the latter sampling date were about
0.1 mg/kg. PTU residues in pear mash were <0.01 mg/kg.
Cherries
Initial residues of propineb as CS2 were 2.3-5.6 mg/kg, and
after 14 days the highest CS2 level found was 0.9 mg/kg. PTU levels
14 days after the last application ranged from 0.03 to 0.15 mg/kg.
Residues in the juice from cherries harvested 21-28 days after the
last application were of the order of 0.01-0.12 mg/kg and jam made
from cherries picked at the same dates contained 0.02-0.08 mg/kg.
Peaches
Propineb levels, expressed as CS2 decreased from about 5.4 mg/kg
initially to 2.5 mg/kg 14 days later and to about 1 mg/kg after 28
days (the recommended preharvest interval in several countries).
Plums
Propineb levels, as CS2, of about 0.9-1.5 mg/kg on the day of
treatment decreased to 0.4-0.8 mg/kg after 14 days and to about
0.1-0.25 mg/kg 28 days after the last application. The levels of PTU
were in the range <0.01-0.04 mg/kg both 14 and 28 days after the last
application. PTU levels in the processed pulp were somewhat higher
than in the fresh fruit sampled at the same time (21-28 days after
harvest).
Grapes
White grapes treated 8-11 times during the growing season showed
propineb residues, after the generally recommended preharvest
intervals of 42-60 days, ranging from 0.6 to 2.6 mg/kg. Residues in
red grapes, all from trials carried out in the same year, were lower.
After observing preharvest intervals of 35-49 days, the highest
residue found was 0.1 mg/kg. The residue in must was about 25-50
percent of the residue in the grapes from which the must was made.
This indicates that the propineb residues mainly occur on the skin,
with a substantial loss of the residue during the preparation of must.
Another loss of the parent compound occurs during further processing
from must to wine. The PTU residue showed a tendency to increase
slightly. The maximum levels of propineb as CS2 and of PTU found in
wine in a series of trials carried out according to GAP were 0.1 mg/kg
and 0.12 mg/kg respectively.
Celeriac
The roots of celeriac showed no measurable residue of propineb,
as CS2, or of PTU. After a preharvest interval of 14 days, the
propineb levels in leaves were 0.5-1.4 mg/kg and after 28 days, the
maximum residue found was 0.5 mg/kg. PTU could not be detected in the
leaves at any of the sampling dates.
Potatoes
In the potato tubers, propineb as CS2 and PTU were undetectable.
The limits of detection were 0.04 mg/kg and 0.01 mg/kg respectively.
Tomatoes
Residues of propineb expressed as CS2 in tomatoes sampled 4-7
days after the last application (the generally recommended preharvest
interval was about 0.25-0.9 mg/kg. The maximum levels of PTU at the
same sampling dates were about 0.1-0.2 mg/kg.
FATE OF RESIDUES
In Plants
Vogeler (1980) summarized the data on metabolism in plants and
processed commodities, such as wine, which were available to the 1977
JMPR together with more recent information.
The new studies identified the main metabolite, previously
unknown, as 4-methylimidazoline (Figure 1, VI) by comparing its mass
spectrum with that of the authentic compound. The structure was also
confirmed by its proton resonance spectrum in CD3COOD.
In the light of the new studies, the proposed structures of some
of the metabolites had to be corrected. The corrected structures and
the most probable metabolic pathway of propineb on and in plants; are
shown in Figure 1.
In Processing
Dreze & Vogeler (1979) evaluated the fate of 14C-propineb on
apples and in the preparation of apple sauce. The compound was
labelled in the C-1 position of the propylenediamine group; it was
sprayed first one time and in another experiment three times, and
residues on apples were analysed on the day of treatment and 14 days
after the (last) application. Apples were washed with methanol and
EDTA solution, then extracted with methanol. The following metabolites
were identified by TLC in the surface wash and in the methanol extract
and determined semi-quantitatively.
Compound Total
radioactivity
(%)
methyl-5,6-dihydro-3-H-imidazo }
[2,1-C] 1,2,4-dithiazole-3-thione }
(methyl-DIDT) } 8
(The position of the methyl group is unknown) }
Unknown }
PTU 8
Propyleneurea (PU) 5
4-methylimidazoline 10
2-methoxy-4-methylimidazoline 5
Less PTU was found in the methanol extracts when apples were
extracted without a prior surface stripping. This may be due to
partial degradation of PTU during extraction.
Apple sauce was made from 14C-propineb-treated apples by three
different methods: (1) not washed before slicing and cooking; (2)
washed in water for 5 minutes and (3) dipped in water for 5 minutes,
then in 10 percent NaOH solution for 5 minutes. The propineb
metabolites in the residue decreased to different extents according to
the procedure. The metabolites detected were 4-methyl-imidazoline,
propylenethiourea and small amounts of PTU (about 0.01 mg/kg).
Methyl-DIDT and 2-methoxy-4-methylimidazoline were not detected in the
apple sauce.
The metabolites found on grapes, after surface washing only, and
in wine are listed in Table 3. The stripping solution contained 27
percent of the total radioactivity in the grapes.
METHODS OF RESIDUE ANALYSIS
The GLC method of analysis for ETU without derivatization,
developed by Otto et al (1977), was adapted for PTU and improved,
especially in the extraction procedure, in order to avoid PTU
degradation during the analysis. PTU is measured directly by GLC,
using a flame photometric detector operating in the sulpha mode
(394 nm). The limit of determination is 0.01 mg/kg.
NATIONAL MAXIMUM RESIDUE LIMITS
Some national MRLs (Table 4) not included in the 1977 Evaluations
or amended since then were reported to the meeting. Unless otherwise
stated, the limits are expressed as CS2. The current preharvest
intervals for the commodities concerned are also listed.
TABLE 3. Propineb Metabolites in Grapes and Wine
Metabolite 1 I II VI VII VIII IX X not not
identified extractable
Commodity
grapes % 41 9 7 1.2 5 4 9 18 6
mg/kg 13 1.1 0.6 0.15 0.5 0.5 1.9 5.6 2 1.9
wine % 2 25 13 12 48
mg/kg 0.03 0.3 0.15 0.2
1 - propineb; II - PTU; VI - methylimidazoline; VII - N-formylpropylene-diamine; VIII - 2-methoxy-4-methylimidazoline;
IX - propyleneurea (PU); X - methyl-DIDT
2 In propineb equivalents
TABLE 4. National MRLs Reported to the Meeting
Country Commodity MRL Preharvest interval
(mg/kg CS2) (days)
Australia Citrus fruit 0.2 7
Austria Fruits 2 (grapes) 14
Vegetables 2 14
Other food crops 0.05
Belgium Fruits (except citrus} 2 28
Currants (red, white) 28
Other small fruit 14
Vegetables 2
Fruiting vegetables 3
Other vegetables 28
Cereals 0.1
Brazil Apples, pears 3.0 7
Peaches 3.0 7
Plums 1.0 7
Grapes 5.0 7
Strawberries 3.0 7
Bananas (whole fruit) 1.0 7
Bananas (pulp) 0.1 7
Cucumbers 0.5 7
Melons 1.0 7
Beans, carrots 0.5 7
Potatoes 0.1 7
Wheat 0.2 7
France Cucumbers, melons 0.1 7
Tomatoes 2.0 7
Lettuce 3.0 15
Celery 0.5 15
Beans 0.5 7
German Pome fruit, stone fruit 3.0
Democratic Small fruit and berries 3.0
Citrus fruit 0.1
Brassicas, fruiting
vegetables, leafy vegetables
legumes, root vegetables,
stem vegetables 3.0
Root vegetables (except
potatoes) 3.0
Potatoes 0.1 10
TABLE 4. (continued)
Country Commodity MRL Preharvest interval
(mg/kg CS2) (days)
Nuts 3.0
Cereals, milled cereal
products 0.1
Eggs, meat, milk 0.1
Fish 0.1
Animal and vegetable fats 0.1
Food crops for infant diets 0.1
Federal Fruits 2.0
Republic Vegetables (except cucumbers
of Germany and tomatoes) 2.0
Cucumbers, tomatoes 1.0 7
Potatoes 0.2 7
Other food crops 0.2
Hungary Apples, pears 2.0 30
Grapes 2.0 30
Cucumbers 2.0 5
Peppers, tomatoes 3.0 7
Peppers, tomatoes for
industrial processing 5.0 5
Hops (dry) 80 14
Mushrooms 2.0 2
Japan Fruits 0.71 calculated 45-60
Vegetables 0.11 as propineb 7
Luxembourg Fruits 2
Vegetables (except cucumbers,
tomatoes) 2
Cucumbers, tomatoes 1
Netherlands Currants (red, black, white),
other small fruits 3
Other fruit 2 1
Lettuce 4 2
Cucumber, melon 1
Bulb vegetables 0.5
Legume vegetables 0.2
Other vegetables 2 1
Cereal grains 0.5
Potatoes 0.2
Other food crops 0 (0.2)
All food commodities PTU 0.02 mg/kg
Heat/treated food PYU 0.1 mg/kg
TABLE 4. (continued)
Country Commodity MRL Preharvest interval
(mg/kg CS2) (days)
South Africa Grapes 3
Grapes (table) 3 14(28-42)
Loganberries, youngberries 3 14
Tomatoes 3 3
Potatoes 0.5 3
Peanut hay 3 21
Sweden Fruits, including berries 1
Vegetables (except carrots) 1
Carrots 0.3
Switzerland Fruits 2 21
Vegetables 2 7-21
Potatoes 0.05
Cereal grains 0.1
Tobacco 50
1 of which no more than 0.5 mg/kg from a PTU precursor
2 of which no more than 2 mg/kg from a PTU precursor
APPRAISAL
The meeting reviewed information on residue levels of propineb
from supervised trials on various crops, mainly from the Federal
Republic of Germany. The residue level of propylenethiourea (PTU) was
evaluated in these trials. The latter compound can occur as a
metabolite of propineb on plants or as an impurity in technical
propineb.
Additional information was obtained on the metabolic pathway of
propineb in plants, especially apples and grapes. Several metabolites
and intermediate products were identified and the most probable
pathway of residue degradation was elucidated in more detail. Some new
information was also obtained on improved methods of residue analysis
for PTU in commodities of plant origin.
The meeting examined residue data from supervised trials
reflecting good agricultural practice on apples, pears, sour cherries,
peaches, plums, grapes, celeriac (root and leaves), potatoes and
tomatoes.
RECOMMENDATIONS
From the available data, the meeting concluded that the maximum
residue levels of propineb expressed as CS2 were similar to the TMRLs
established for the ethylene bisdithiocarbamates.
In addition, the meeting recommended the following estimated
maximum residue level as a TMRL:
Commodity TMRL (mg/kg) Preharvest interval on which
recommendations are based
Celeriac (roots) 0.1 14
This proposal is not included in the current temporary MRLs for
the ethylenebisdithiocarbamates.
The meeting estimated the following maximum residue levels of PTU
from supervised trials in which propineb was applied according to good
agricultural practice. In the absence of an ADI for PTU, or propineb
including PTU, these are recorded as guideline levels. They refer only
to PTU.
Commodity Guideline level Preharvest interval on
(mg/kg as PTU) which GL is based
Apples 0.1 10
Pears 0.1 17-21
Cherries, sour 0.1 14-21
Peaches 0.05 14
Plums 0.1 7-14
Grapes 0.1 28-35
Celeriac 0.05 14
Potatoes 0.02 7-10
Tomatoes 0.1 3-7
FURTHER WORK OR INFORMATION
Desirable
1. Further development and validation of the methods of analysis for
the separate determination of ethylenebisdithiocarbamates and
propylenebisdithiocarbamates, which are ETU and PTU precursors.
The meeting was informed that work was in progress in some
countries to meet the 1980 JMPR requirement for such methods to
be provided by 1983 and recognized the problems met in the
development of them.
2. Residue data, on a few crops, obtained by use of a specific
method for ETU and PTU precursors to be compared with data
obtained by the validated head space CS2 GLC procedure.
3. Residue data from crops on which the ETU or PTU precursors are
used simultaneously or alternately with other fungicides, e.g.
thiram, which are not ETU precursors. Emphasis should be given to
crops that are in general household-cooked or heat-processed,
e.g. some leafy vegetables, apples and tomatoes.
REFERENCES
Bayer Reports on residues from supervised trials. Submitted by Bayer
1978-1983 AG to FAO. (Unpublished)
Dreze, P. & Vogeler, K. Studies on the metabolism of propineb in and
1979 on apples and in the apple sauce preparation process.
Report RA-542 submitted by Bayer AG to FAO. (Unpublished)
Otto, S., Keller, W. & Drescher, N. A new gas chromatographic
1977 determination of ethylenethiourea residues without
derivatization. J. Environ. Sci. Health, B12 (3): 179-191.
Vogeler, K. Report on hitherto conducted studies on propineb
1980 metabolism on and in plants. Report RA-16 submitted by
Bayer AG to FAO. (Unpublished)
See Also:
Toxicological Abbreviations
Propineb (Pesticide residues in food: 1977 evaluations)
Propineb (Pesticide residues in food: 1985 evaluations Part II Toxicology)
Propineb (Pesticide residues in food: 1993 evaluations Part II Toxicology)