Section A7.1.1.1.1 Hydrolysis as a function of pH and...
Transcript of Section A7.1.1.1.1 Hydrolysis as a function of pH and...
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 10
Section A7.1.1.1.1 Annex Point IIA7.6.2.1
Hydrolysis as a function of pH and identification of
breakdown products
1 REFERENCE
Official use only
1.1 Reference Lewis, C.J. (2000): (14
C)-TI-435: Hydrolytic stability.
Covance, Harrogate, England; unpublished report no. 586/140-D2142
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
92/69/EEC, C.7 and US EPA, Subdivision N, Section 161-1
2.2 GLP Yes
2.3 Deviations None (to EC directive)
3 MATERIALS AND METHODS
3.1 Test material [thiazolyl-14
C]TI-435
3.1.1 Lot/Batch number A-980501
3.1.2 Specific activity 3.88 MBq/mg
968.76 MBq/mmol
3.1.3 Purity Radiochemical purity: >98%
X
3.1.4 Further relevant
properties
Water solubility (20°C): 327 mg/L
(see Morrissey & Kramer, 2000a)
3.2 Reference substance Yes (for identification of parent compound and degradation products):
TI-435 (unlabelled parent compound)
Degradation products:
CTNU: N-(2-chlorothiazol-5-ylmethyl)-N’-nitrourea
TZMU: N-(2-chlorothiazol-5-ylmethyl)-N’-methylurea
ACT.HCl: 2-chlorothiazol-5-ylmethylamine hydrochloride
3.3 Test solution See Tables A7_1_1_1_1-1 and A7_1_1_1_1-2 X
3.4 Testing procedure
3.4.1 Test system See Table A7_1_1_1_1-3
3.4.2 Temperature Preliminary study: 50°C (pH 4, 7 and 9)
Definitive study: 25°C (pH 5, 7 and 9)
Additional definitive study: 62°C and 74°C (pH 9)
3.4.3 pH All vials tested were within +/- 0.2 pH units of the intended pH both
after sterilization and at the end of the experiment.
3.4.4 Duration of the test Preliminary study: 5 days (pH 4 and 7), 25 days (pH 9)
Definitive study: 33 days (pH 5, 7 and 9)
Additional definitive study (pH 9): 7 days (62°C) and 1.9 days (74°C)
3.4.5 Number of replicates As given in Table A7_1_1_1_1-2
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 10
Section A7.1.1.1.1 Annex Point IIA7.6.2.1
Hydrolysis as a function of pH and identification of
breakdown products
3.4.6 Sampling Sampling intervals:
Preliminary study: 0, 0.1, 1 and 5 days (pH 4 and 7) and 0, 0.1, 1, 5, 11,
15, 19 and 25 days (pH 9)
Definitive study: 0, 5, 9, 15, 20, 27 and 33 days (pH 5, 7 and 9)
Additional definitive study (pH 9): 0, 1, 3 and 7 days (62°C) and 0,
0.25, 1 and 1.9 days (74°C)
3.4.7 Analytical methods Identification of the parent compound and transformation products:
HPLC (ODS-H column, UV detection at 265 nm) or TLC (silica gel
K6F plates).
Measurement of radioactivity: LSC
No sample preparation was necessary.
3.5 Preliminary test Yes,
4 RESULTS
4.1 Concentration and
hydrolysis values
See Table A7_1_1_1_1-4 to Table A7_1_1_1_1-11
4.2 Hydrolysis rate
constant
See Table A7_1_1_1_1-12
4.3 Dissipation time See Table A7_1_1_1_1-12
The half-life at 20°C and pH 9 was calculated from the Arrhenius plot.
The calculated rate constant was 0.000494 day-1
and from this a half-life
of 1401 days (ca. 3.8 years) was calculated.
4.4 Concentration time
data
See Figure A7_1_1_1_1-1 to A7_1_1_1_1-3
Since TI-435 was stable at pH 4, 5 and 7 (25°C and 50°C) and at pH 9
(25°C) no concentration-time plot is provided.
4.5 Specification of the
transformation
products
See Table A7_1_1_1_1-13
No transformation products were found at pH 4, 5 and 7 (25°C and
50°C) and only trace amounts were found at pH 9 (25°C).
Figure A7_1_1_1_1-4 shows the Proposed hydrolysis pathways of
TI-435.
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
Degradation – abiotic degradation hydrolysis as a function of pH:
92/69/EEC, C.7 and US EPA, Subdivision N, Section 161-1; Deviations
(to EC directive): none
5.2 Results and
discussion
The radiochemical purity of the application solution was determined at
each time of dosing (preliminary, definitive and additional definitive
study) and was at any time >98%. The results of the study are
summarised in Tables A7_1_1_1_1-4 to A7_1_1_1_1-11. The half-lives
were calculated using first-order kinetics. The total recovery of the
applied radioactivity was in the range of 96% to 103%.
A half-life of 1401 days for a temperature of 20°C and a pH-value of 9
was calculated according to the Arrhenius equation using the data from
the tests performed at 50°C, 62°C and 74°C.
5.2.1 kH pH 9: 0.048 (50°C), 0.188 (62°C), 1.013 (74°C)
5.2.2 DT50 pH 9: 14.4 days (50°C), 3.7 days (62°C), 0.68 days (74°C)
5.2.3 r2
pH 9: 0.997 (50°C, 62°C and 74°C)
5.3 Conclusion TI-435 is stable in sterile buffer solutions at pH 4, 5 and 7, but degrades
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 10
Section A7.1.1.1.1 Annex Point IIA7.6.2.1
Hydrolysis as a function of pH and identification of
breakdown products
at pH 9. However, at relevant temperatures of 20°C the degradation is
very slow (calculated half-life: 1401 days). Relevant amounts of
metabolites were formed only at elevated temperatures.
5.3.1 Reliability 1
5.3.2 Deficiencies None
Evaluation by Competent Authorities
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2004/11/20
Materials and Methods Despite minor deficiencies applicant’s version is acceptable.
Comments:
The mentioned radiochemical purity of > 98% of test substance [thiazolyl-14
C]TI-
435 corresponds to the radiochemical purity that was determined in control
measurements within the study time. The stated radiochemical purity according to
the certificate of analysis amounts to 99.2 % (TLC radiochromatography) and
99.4 % (HPLC radiochromatography), respectively.
The correct caption of Table A_7_1_1_1_1-2 is “Description of test solution”
instead of the current caption “Type and composition of buffer solution”.
The description for the preparation of the test medium (see Table A_7_1_1_1_1-
2) should be more comprehensible as follows: “Aliquots of 3 mL were taken from
the buffer solutions and were dispensed into borosilicate glass vials which were
then sealed and sterilised by autoclaving. (…)”
Results and discussion Despite minor deficiencies applicant’s version is acceptable.
Comments:
The sampling times of the hydrolysis of a.s. in pH 9 at 74 °C in Table
A_7_1_1_1_1-11 are 0, 0.25, 1, and 1.9 days and not 0, 1, 3, and 7 days.
The hydrolysis rate constant kh in Table A_7_1_1_1_1-12 is listed in the unit
[days-1
]. The given justification that no hydrolysis rate constants at pH 4, 5, and 7
can be calculated (see *) is not appropriate. A rate constant can not be calculated
as there is no significant hydrolysis. The first-order reaction model can not fit the
data as the model is inadequate to describe the data (see low correlation
coefficients r2).
The duration of the additional definitive test in pH 9 at 74 °C in Table
A_7_1_1_1_1-12 is 1.8 days which is more precise
In the original study at Doc. IV-A, Section No. 7.1.1.1.1 the Arrhenius equation
and the calculation procedure of rate constant in pH 9 at 20 °C is lacking. Only
the Arrhenius plot with intercept and slope is pictured. Generally, the whole
calculation procedure should be demonstrated in the study reporting to be
transparent.
Conclusion Applicant’s version is acceptable.
Comments:
The hydrolysis rate constant kh under item 5.2.1 is listed in the unit [days-1
].
The degradation products in pH 9 are CTNU (N-(2-chlorothiazol-5-ylmethyl)-N’-
nitrourea), TZMU (N-(2-chlorothiazol-5-ylmethyl)-N’-methylurea), and ACT.HCl
(2-chlorothiazol-5-ylmethylamine hydrochloride). The latter seems to be the final
transformation product.
Reliability 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 10
Section A7.1.1.1.1 Annex Point IIA7.6.2.1
Hydrolysis as a function of pH and identification of
breakdown products
Acceptability Original study and study summary are acceptable
Remarks
COMMENTS FROM
Date Give date of the comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Table A7_1_1_1_1-1: Type and composition of buffer solutions
pH Type of buffer (final
molarity)
Composition
4 0.01 M potassium hydrogen
phthalate
0.01 M sodium hydroxide solution were added to 0.01 M
potassium hydrogen phthalate solution until the pH was
4.0 at 50°C.
5 0.01 M sodium citrate 0.01 M trisodium citrate solution were added to 0.01 M
citric acid solution until the pH was 5.0 at 25°C.
7 0.01 M TRIS maleic acid 0.01 M sodium hydroxide solution were added to 0.01 M
TRIS-maleic acide solution until the pH was 7.0 (at 25°C
or 50°C).
9 0.01 M borate-boric acid The pH of 0.0025 M sodium tetraborate solution was
adjusted to 9.0 with either 0.01 sodium hydroxide solution
or 0.01 boric acid solution (at 25°C, 50°C, 62°C or 74°C).
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 10
Table A7_1_1_1_1-2: Type and composition of buffer solutions
Criteria Details
Purity of water BDH ‘HiPerSolv’ water for HPLC (Merck)
Preparation of test medium Aliquots of 3 mL were dispensed into borosilicate glass
vials which were then sealed and sterilised by
autoclaving. About 0.9 µg [thiazolyl-14
C]TI-435
diluted in approximately 20 µl acetonitrile (equivalent
to 45 mg/L) was aseptically injected onto the surface of
the buffer solutions and then mixed.
Test concentrations (mg a.i./L) 0.3 mg a.i./L
Temperature (°C) pH 4: 50°C
pH 5: 25°C
pH 7: 25°C/50°C
pH 9: 25°C/50°C/62°C/74°C
Controls Two control vials per pH-value
Identity and concentration of co-solvent Acetonitrile, concentration: ca. 0.7%
Replicates Duplicates
Table A7_1_1_1_1-3: Description of test system
Criteria Details
Glass ware Borosilicate glass vials (capacity: 4 mL, type 4-CV
from Chromacol, Welwyn Garden City, Hertfordshire)
Other equipment Water bath, pH meter
Method of sterilization Autoclaving
Table A7_1_1_1_1-4: Hydrolysis of [14
C]TI-435 and transformation products in pH 5 at 25°C (expressed
as percentage of applied radioactivity)
TI-435
Sampling times (days)
0 5 9 15 20 27 33
Parent compound 98.3 98.1 98.4 97.1 97.0 96.5 99.1
ACT.HCl ND ND ND ND ND ND ND
CTNU ND ND ND ND ND ND ND
TZMU ND ND ND ND ND ND ND
Unresolved ND 0.2 0.3 0.2 0.3 0.5 0.7
Total % recovery 98.3 98.3 98.7 97.3 97.3 96.9 99.8
ND = Not detected
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 10
Table A7_1_1_1_1-5: Hydrolysis of [14
C]TI-435 and transformation products in pH 7 at 25°C (expressed
as percentage of applied radioactivity)
TI-435
Sampling times (days)
0 5 9 15 20 27 33
Parent compound 98.1 99.3 97.5 97.7 97.1 102.9 98.1
ACT.HCl ND ND ND ND ND ND ND
CTNU ND ND ND ND ND ND ND
TZMU ND ND ND ND ND ND ND
Unresolved 0.3 0.2 0.9 0.8 0.7 0.4 0.3
Total % recovery 98.5 99.6 98.4 98.5 97.8 103.4 98.4
ND = Not detected
Table A7_1_1_1_1-6: Hydrolysis of [14
C]TI-435 and transformation products in pH 9 at 25°C (expressed
as percentage of applied radioactivity)
TI-435
Sampling times (days)
0 5 9 15 20 27 33
Parent compound 97.7 98.2 99.8 97.8 99.2 96.4 93.8
ACT.HCl ND ND ND ND ND ND ND
CTNU ND ND ND ND 0.9 1.4 1.8
TZMU ND ND ND ND 0.3 0.4 0.6
Unresolved 0.3 0.3 0.8 0.1 0.4 0.5 0.6
Total % recovery 98.0 98.6 100.6 97.9 100.9 98.8 96.8
ND = Not detected
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 7 of 10
Table A7_1_1_1_1-7: Hydrolysis of [14
C]TI-435 and transformation products in pH 4 at 50°C (expressed
as percentage of applied radioactivity)
TI-435
Sampling times (days)
0 0.1 1 5
Parent compound 100.7 96.3 99.1 97.5
ACT.HCl ND ND ND ND
CTNU ND ND ND ND
TZMU ND ND ND ND
Unresolved 0.5 0.6 0.7 0.3
Total % recovery 101.2 96.9 99.8 97.8
ND = Not detected
Table A7_1_1_1_1-8: Hydrolysis of [14
C]TI-435 and transformation products in pH 7 at 50°C (expressed
as percentage of applied radioactivity)
TI-435
Sampling times (days)
0 0.1 1 5
Parent compound 100.6 96.2 100.4 95.5
ACT.HCl ND ND ND ND
CTNU ND ND ND ND
TZMU ND ND ND ND
Unresolved 0.8 0.6 0.6 06
Total % recovery 101.4 96.8 101.1 96.1
ND = Not detected
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 8 of 10
Table A7_1_1_1_1-9: Hydrolysis of [14
C]TI-435 and transformation products in pH 9 at 50°C (expressed
as percentage of applied radioactivity)
TI-435
Sampling times (days)
0 0.1 1 5 11 15 19 25
Parent compound 98.9 100.1 95.6 77.9 57.6 50.0 40.9 29.1
ACT.HCl ND ND 0.4 10.4 27.5 36.3 44.3 52.8
CTNU ND ND 3.3 8.2 7.7 6.0 4.9 3.9
TZMU ND ND 1.3 3.2 6.0 7.7 9.4 10.8
Unresolved 0.5 0.4 0.8 0.3 0.6 0.2 0.4 0.7
Total % recovery 99.5 100.5 101.5 100.1 99.3 100.2 99.9 97.3
ND = Not detected
Table A7_1_1_1_1-10: Hydrolysis of [14
C]TI-435 and transformation products in pH 9 at 62°C (expressed
as percentage of applied radioactivity)
TI-435
Sampling times (days)
0 1 3 7
Parent compound 99.6 83.0 55.8 27.1
ACT.HCl ND 7.7 28.0 53.5
CTNU ND 5.1 3.1 1.7
TZMU ND 3.2 8.2 14.7
Unresolved 0.4 0.6 0.4 0.7
Total % recovery 100.0 99.6 95.6 97.7
ND = Not detected
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 9 of 10
Table A7_1_1_1_1-11: Hydrolysis of [14
C]TI-435 and transformation products in pH 9 at 74°C (expressed
as percentage of applied radioactivity)
TI-435
Sampling times (days)
0 1 3 7
Parent compound 99.5 74.6 36.6 14.4
ACT.HCl ND 10.8 41.2 59.2
CTNU ND 4.7 2.1 0.7
TZMU ND 6.5 16.8 22.6
Unresolved 0.5 0.4 0.6 0.5
Total % recovery 100.0 97.0 97.3 97.3
ND = Not detected
Table A7_1_1_1_1-12: Hydrolysis rate constant as a function of pH and temperature
Study pH Temperature
[°C]
Duration
[days]
kh Half-life
(days)
Correlation
coefficient
Preliminary
test
4 50 5 0.003* * 0.075*
7 50 5 0.007* * 0.290*
9 50 25 0.048 14.4 0.997
Definitive
test
5 25 33 0.000* * 0.008*
7 25 33 -0.001* * 0.071*
9 25 33 0.001 * 0.210*
Additional
definitive
test
9 62 7 0.188 3.7 0.997
9 74 <2 1.013 0.68 0.997
* Rate of degradation too slow to compute a half-life
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 10 of 10
Table A7_1_1_1_1-13: Specification and amount of transformation products
Code
name
CAS name Maximum amount (percentage of applied radioactivity) in
pH 9 aqueous solution at
50°C 62°C 74°C
ACT.HCl 2-chlorothiazol-5-ylmethylamine
hydrochloride
52.8 53.5 59.2
CTNU N-(2-chlorothiazol-5-ylmethyl)-
N’-nitrourea
8.2 5.1 4.7
TZMU N-(2-chlorothiazol-5-ylmethyl)-
N’-methylurea
10.8 14.7 22.6
Figure A7_1_1_1_1-1: Hydrolysis of [14C]TI-435 and transformation products in pH 9 at 50°C
Figure A7_1_1_1_1-2: Hydrolysis of [14C]TI-435 and transformation products in pH 9 at 62°C
Figure A7_1_1_1_1-3: Hydrolysis of [14C]TI-435 and transformation products in pH 9 at 74°C
Figure A7_1_1_1_1-4: Proposed hydrolysis pathways of TI-435
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project 852224 Page 1 of 7
Section A7.1.1.1.2 Annex Point IIA7.6.2.2
Phototransformation in water including identity of the
products of transformation
1 REFERENCE Official
use only
1.1 Reference Babczinski, P. and Bornatsch, W. (2000): Photolysis of [nitroimino-14
C]TI-435 and [thiazolyl-2-14
C]TI-435 in sterile aqueous buffer
solution.
Bayer AG, 51368 Leverkusen, Germany; unpublished report no. MR
248/00
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
SETAC and US EPA 161-2
2.2 GLP Yes
2.3 Deviations Yes
Deviations (to SETAC): temperature 25±1°C instead of 20±3°C
3 MATERIALS AND METHODS
3.1 Test material [14
C]TI-435
3.1.1 Radiolabelling [nitroimino-14
C]TI-435 and [thiazolyl-2-14
C]TI-435
3.1.2 Lot/Batch number [nitroimino-14
C]TI-435: 11553/1
[thiazolyl-2-14
C]TI-435: 11649/2
3.1.3 Specific
radioactivity
[nitroimino-14
C]TI-435: 3.78 MBq/mg
[thiazolyl-2-14
C]TI-435: 3.84 MBq/mg
3.1.4 Purity [nitroimino-14
C]TI-435:
Radiochemical purity: > 99% according to radio HPLC
Chemical purity: > 99% according to HPLC, UV at 210 nm
[thiazolyl-2-14
C]TI-435:
Radiochemical purity: > 99% according to radio TLC
Chemical purity: > 99% according to HPLC, UV at 210 nm
3.1.5 UV/VIS absorption
spectra and
absorbance value
See Figure A7_1_1_1_2-1
3.1.6 Further relevant
properties
Water solubility (20°C): 327 mg/L
(see Morrissey & Kramer, 2000a)
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project 852224 Page 2 of 7
Section A7.1.1.1.2 Annex Point IIA7.6.2.2
Phototransformation in water including identity of the
products of transformation
3.2 Reference
substances
Yes (for identification of parent compound and degradation products):
TI-435 (unlabelled parent compound)
Degradation products:
HMIO: 4-Hydroxy-2-methylamino-2-imidazolin-5-one
MAI: 3-Methylamino-1H-imidazo[1,5-c]imidazole
MG: Methylguanidine
MIO: 2-Methylamino-2-imidazolin-5-one
MU: Methylurea
TMG: N-(2-chlorothiazol-5-ylmethyl)-N’-methylguanidine
TZMU: N-(2-chlorothiazol-5-ylmethyl)-N’-methylurea
FA: Formamide
3.3 Test solution See Table A7_1_1_1_2-1
3.4 Testing procedure
3.4.1 Test system See Table A7_1_1_1_2-2
3.4.2 Properties of light
source
See Table A7_1_1_1_2-2
3.4.3 Determination of
irradiance
The measurement of the intensity of artificial irradiance was performed
with a radiometer (see Table A7_1_1_1_2-2) and by actinometry (see
Table A7_1_1_1_2-1).
3.4.4 Temperature 25±1°C
3.4.5 pH The initial and the final pH was 7.0 for both the nitroimino-14
C]TI-435
solution and the [thiazolyl-2-14
C]TI-435 solution (test solutions and dark
controls).
3.4.6 Duration of the test 18 days
3.4.7 Number of
replicates
One test vessel per radiolabel. Initial test volume: 200 mL.
3.4.8 Sampling Directly after transferring the test solution into the test vessel, an aliquot
of 20 mL was withdrawn for set-up of the dark controls (3 x 5 mL) and
as zero-time samples (3 x 1 mL). Thereafter, volumes of 4 mL were
sampled at 1.5, 4, 24, 120, 264 and 432 hours.
One mL of the 4 mL samples was frozen immediately after sampling as a
reserve material.
3.4.9 Analytical methods Radioactivity: liquid scintillation counting (LSC)
Concentration of test substance and photolysis products: TLC on RP-18
plates and silica gel plates.
LOQ for a single zone: 0.5 Bq (corresponding to ca. 0.43% of the
applied radioactivity for a single spot on a two-dimensional TLC plate).
Photodegradates were purified by HPLC using an HP 1050 Liquid
Chromatograph with UV detector and radioactivity monitor, Ramona-90
with a solid glass scintillator cell.
The test solutions were analysed directly without sample preparation.
The PU foam plug of each trap was extracted twice with 20 mL ethyl
acetate. Aliquots of the extract were used for radioactivity assessment
and were further investigated if the radioactivity content was > 1% of the
applied amount.
The soda lime of the CO2 trap was dissolved in 18% HCl. The liberated
CO2 was absorbed with Carbosorb/Permafluor E + and the radioactivity
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project 852224 Page 3 of 7
Section A7.1.1.1.2 Annex Point IIA7.6.2.2
Phototransformation in water including identity of the
products of transformation
was determined by LSC.
3.5 Transformation
products
Transformation products tested: Yes
3.5.1 Method of analysis
for transformation
products
As described in Section 3.4.9.
4 RESULTS
4.1 Screening test Not performed
4.2 Actinometer data Actinometry was only used to measure the intensity of the artificial
irradiance (photon flow: 1.89 x 1017
photons/s, photon flow density:
125.86 x 1014
photons/s x cm2).
4.3 Controls [nitroimino-14
C]TI-435: C0 = 100.1% AR, Cend = 93.8% AR
[thiazolyl-2-14
C]TI-435: C0 = 95.0% AR, Cend = 104.1% AR
4.4 Photolysis data
4.4.1 Concentration
values
See Table A7_1_1_1_2-3
4.4.2 Mass balance See Table A7_1_1_1_2-3
4.4.3 kcp No actinometer study
4.4.4 Kinetic order pseudo first order
4.4.5 kcp / k
ap No actinometer study
4.4.6 Reaction quantum
yield (cE)
No actinometer study
4.4.7 kpE No actinometer study
4.4.8 Half-life (t1/2E) Experimental half-life: 3.3 hours (mean of two radiolabel studies).
Corresponding half-life under summer (June) solar light conditions at
Phoenix/USA: 0.6 days.
Corresponding half-life under winter (December) solar light conditions
at Phoenix/USA: 1.6 days.
x
4.5 Specification of
the transformation
products
See Table A7_1_1_1_2-3
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
Test guidelines: SETAC and US EPA 161-2
Deviations (to SETAC): temperature 25±1°C instead of 20±3°C
The photolytic degradation of [nitroimino-14
C]TI-435 and [thiazolyl-2-14
C]TI-435 was investigated in sterile aqueous buffer solution at pH 7.
The test solutions were exposed to simulated sunlight in 350 mL quartz
glass vessels in the Heraeus ®Suntest apparatus equipped with a xenon
lamp and a cooling platform. Dark controls were kept in a second
Suntest apparatus. The samples were maintained at 25±1°C and exposed
to light for 18 days.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project 852224 Page 4 of 7
Section A7.1.1.1.2 Annex Point IIA7.6.2.2
Phototransformation in water including identity of the
products of transformation
5.2 Results and
discussion
TI-435 degraded rapidly in the irradiated samples with a mean DT50-
value (two radiolabels) of 3.3 hours.
Major photolytic degradation products of [nitroimino-14
C]TI-435 were
MG, TZMU, HMIO and MU with maximum levels of 34.7%, 29.3%,
26.6% and 11.0% of the applied radioactivity, respectively. MAI, MIT,
TMG and MIO were also identified, but their amounts did not exceed
10% of the applied radioactivity.
[Thiazolyl-14
C]TI-435 degraded to three major breakdown products, i.e.
TZMU, formamide (FA) and MIT. Maximum values of 39.7% (TZMU),
16.1% (FA) and 11.8% (MIT) were analysed. MAI and TMG were
identified as minor degradation products (maxima <10% of the applied
radioactivity).At the end of the study after 18 days, 0.8% of the applied
radioactivity was photo-mineralised to CO2 from [nitroimino-14
C]TI-435,
whereas 34.1% was mineralised from [thiazolyl-14
C]TI-435. Organic
volatile compounds were detected only in trace amounts (<0.1% of the
applied radioactivity).
5.3 Conclusion The degradation in the dark controls was negligible. Sterile conditions
and a pH-value of 7 were maintained throughout the test. Validity
criteria of the test can be considered as fulfilled.
Considering the rapid photolytic breakdown determined at a pH value
and a temperature typical for a natural environment, solar radiation will
significantly contribute to the degradation of the test substance in aquatic
test systems. It can also contribute to the elimination of residues of TI-
435 by means of mineralization of the thiazole ring.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Evaluation by Competent Authorities
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2006/09/08
Materials and Methods The applicant’s version is acceptable and indicates no relevant discrepancies.
Results and discussion The applicant’s version is acceptable with minor restrictions.
Remark to Item 4.4.8:
Under this item the applicant provides the experimental half-life and the
corresponding environmental half-life under midsummer solar light conditions at
Phoenix/USA. The result of the calculation of the equivalent exposure time for
midday midsummer at 40°, is here not presented.
In the study the ratio of the photon flow density of the xenon-lamp to that of
sunlight of the midsummer scenario (40° latitude) was calculated to be 1.25.
Therefore, exposure to xenon light in the test apparatus for one hour was
equivalent to an exposure to midday midsummer sunlight conditions (40° latitude)
of 1.25 hours.
Conclusion The applicant's version is adopted.
Reliability 1
Acceptability acceptable
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project 852224 Page 5 of 7
Section A7.1.1.1.2 Annex Point IIA7.6.2.2
Phototransformation in water including identity of the
products of transformation
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project 852224 Page 6 of 7
Table A7_1_1_1_2-1: Description of test solution and controls
Criteria Details
Purity of water Milli-Q-water (conductivity: 21 mΩ, total organic
carbon: 21 ppb)
Preparation of test chemical solution The test substances were dissolved in acetonitrile and
a purity of ≥ 98.1% (nitroimino-label) and 100%
(thiazolyl-label) was determined. Aliquots of 0.8 mL
(nitroimino-label) and 0.19 mL (thiazolyl-label) were
diluted in 200 mL buffer solution, sonicated, shaken
and transferred into the test vessels.
Buffer solution: 0.01 mol/L phosphate buffer, pH 7,
autoclaved before use.
Test concentrations (mg a.s./L) Initial concentration TI-435 (C0): 0.3 mg/L
Temperature ( C) 25°C ± 1°C
Preparation of actinometer solution A solution of 0.01 M uranyl nitrate and 0.05 M oxalic
acid per litre was prepared and sub-samples of 5.0 mL
were irradiated for 10 minutes. The remaining oxalic
acid was determined by titration with a 0.01 M
KMnO4 solution.
Controls Triplicate dark controls per radiolabel
Identity and concentration of co-solvent Acetonitrile
Content: 0.4% v/v ([nitroimino-14
C]TI-435),
0.1% v/v ([thiazolyl-2-14
C]TI-435)
Table A7_1_1_1_2-2: Description of test system
Criteria Details
Laboratory equipment Test vessels: 350 mL quartz glass vessels with trap
attachment for volatile organic products and CO2, or
with glass stopper
Radiometer: Radialux Light Measuring Instrument
(Atlas/Xenotest Co.) equipped with a global sensor
(λ = 300 to 800 nm), sensor: about 2.2 cm above the
sample platform
Test apparatus Heraeus ®Suntest cabinet equipped with a xenon
lamp (λ > 290 nm)
Properties of artificial light source:
Nature of light source Xenon lamp
Emission wavelenght spectrum 280 to 830 nm
Light intensity Prior to test: 1035 W/m²
End of test: 1018 W/m²
Filters UV glass filter cutting off wavelengths < 290 nm
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project 852224 Page 7 of 7
Table A7_1_1_1_2-3: Recovery and distribution of the radioactivity after photolysis of [nitroimino-14
C]TI-435 and [thiazolyl-14
C]TI-435 in buffer solution (values given in % of
applied radioactivity)
Condi-
tion
Expos.
[hours]
CO2 TI-435 TZMU MAI MIT TMG MU MG MIO HMIO FA Not
identif.*
Total
[nitroimino-14
C]TI-435
irradiat. 0 n.s. 100.1 n.d. n.d. n.d. <0.5 n.d. n.d. n.d. n.d. - 1.7 102.1
1.5 n.s. 74.3 10.4 1.3 1.3 0.7 n.d. <0.5 n.d. 3.0 - 5.6 97.0
4 n.s. 27.2 24.3 3.9 4.2 1.7 0.9 3.0 4.2 13.6 - 10.4 93.4
24 n.s. 0.7 29.3 4.2 5.7 1.5 4.0 11.0 4.4 26.6 - 9.6 97.0
120 n.s. 0.6 24.4 0.9 6.2 1.4 7.7 20.4 4.2 18.8 - 10.8 95.4
264 0.4 <0.5 24.0 n.d. 7.1 1.6 9.2 29.5 2.1 9.4 - 12.0 95.6
432 0.8 <0.5 18.7 n.d. 4.4 1.0 11.0 34.7 2.4 7.1 - 10.5 91.0
dark 432 <0.1 93.8 1.2 <0.5 <0.5 <0.5 0.9 <0.5 n.d. n.d. - 1.0 98.4
[thiazolyl-14
C]TI-435
irradiat. 0 n.d. 95.0 n.d. n.d. n.d. 2.4 - - - - n.d. 4.6 102.0
1.5 1.0 75.8 10.2 3.1 3.3 0.9 - - - - n.d. 4.8 99.0
4 3.9 25.3 31.4 6.5 8.3 2.0 - - - - 5.3 15.5 98.0
24 10.8 0.5 39.7 8.7 11.8 3.0 - - - - 9.9 13.9 98.2
120 20.9 n.d. 31.5 2.4 7.1 2.9 - - - - 16.1 16.0 96.9
264 27.6 n.d. 31.7 n.d. 3.7 2.2 - - - - 16.0 14.0 95.4
432 34.1 n.d. 27.5 n.d. 1.6 1.6 - - - - 14.1 15.4 94.4
dark 432 0.3 104.1 n.d. n.d. n.d. n.d. - - - - n.d. 1.9 106.3
* no single compound exceeded 10% of the applied radioactivity
n.s. not sampled
n.d. not detected
TZMU: N-(2-chlorothiazol-5-ylmethyl)-N’-methylurea
MAI: 3-Methylamino-1H-imidazo[1,5-c]imidazole
MIT: 7-Methylamino-4H-imidazo[5,1-b][1,2,5]thiadiazin-4-one
TMG: N-(2-chlorothiazol-5-ylmethyl)-N’-methylguanidine
MU: Methylurea
MG: Methylguanidine
MIO: 2-Methylamino-2-imidazolin-5-one
HMIO: 4-Hydroxy-2-methylamino-2-imidazolin-5-one
FA: Formamide
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 1 of 5
Section A7.1.1.2.1 Annex Point IIA7.6.1.1
Ready biodegradability
1 REFERENCE
Officialuse only
1.1 Reference Bealing, D.J., Watson, S. (1999): TI-435: Assessment of ready biodegradability by measurement of carbon dioxide evolution. Covance, Harrogate, England; unpublished report no. 586/162-D2145
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with letter of access
None
1.2.3 Criteria for data protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes Directive 92/69/EEC, C.4-C
2.2 GLP Yes
2.3 Deviations Yes On day 20, the minimum temperature recorded was 18.5°C (guideline requirement: 22 ± 2°C), but this was not considered to have influenced the outcome of the study.
3 MATERIALS AND METHODS
3.1 Test material TI-435 PAI
3.1.1 Lot/Batch number 30036608
3.1.2 Specification PAI
3.1.3 Purity
3.1.4 Further relevant properties
Solubility in water (20°C) : 327 mg/L (see Morrissey & Kramer, 2000a)
3.1.5 Composition of Product
Not applicable
3.1.6 TS inhibitory to micro-organisms
No
3.1.7 Specific chemical analysis
None
3.2 Reference substance
Yes Sodium benzoate
3.2.1 Initial concentration of reference substance
According to guideline
3.3 Testing procedure
3.3.1 Inoculum / test species
See Table A7_1_1_2_1-1
3.3.2 Test system See Table A7_1_1_2_1-2
3.3.3 Test conditions See Table A7_1_1_2_1-3
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 2 of 5
Section A7.1.1.2.1 Annex Point IIA7.6.1.1
Ready biodegradability
3.3.4 Method of preparation of test solution
The test substance was insufficiently soluble in water to permit dosing from a concentrated aqueous stock solution. The test substance was weighed onto PTFE discs and added, together with the weighing supports, to the test vessels and the toxicity control.
3.3.5 Initial TS concentration
51.9 - 52.0 mg TS/L corresponding to a nominal concentration of 15 mg DOC/L
3.3.6 Duration of test 28 days
3.3.7 Analytical parameter
CO2 evolution
3.3.8 Sampling 2, 4, 6, 8, 10, 15, 16, 19, 23, 28 days
3.3.9 Intermediates/ degradation products
Not identified
3.3.10 Nitrate/nitrite measurement
No
3.3.11 Controls Reference substance control without test substance; reference substance control with test substance (toxicity control).
3.3.12 Statistics None
4 RESULTS
4.1 Degradation of test substance
4.1.1 Graph See Figure A7_1_1_2_1-1
4.1.2 Degradation Percentage degradation at the end of incubation: Sodium benzoate: 82.5% theoretical CO2 yield (mean of duplicates) TI-435: 1.5% theoretical CO2 yield (mean of duplicates) Toxicity control: 77% theoretical CO2 yield (65% theoretical CO2 yield after 15 days)
4.1.3 Other observations None
4.1.4 Degradation of TS in abiotic control
No abiotic control
4.1.5 Degradation of reference substance
See Figure A7_1_1_2_1-1
4.1.6 Intermediates/ degradation products
Not determined
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
Directive 92/69/EEC, C.4-C, CO2 Evolution Test (Modified Sturm Test) The pH was measured in the blank and reference vessels, but due to technical reasons not in the vessels containing TI-435.
5.2 Results and discussion
The blank-corrected CO2 yield of TI-435 after 28 days of incubation was only 1.5% (mean of two trials) of the theoretical maximum yield (165 mg CO2). Therefore, TI-435 cannot be classified as readily biodegradable.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 3 of 5
Section A7.1.1.2.1 Annex Point IIA7.6.1.1
Ready biodegradability
The biodegradation of the reference substance sodium benzoate was clearly above 60% of the theoretical yield within 14 days and the 10-day period (10% in the first 4 days). TI-435 present in the toxicity control did not inhibit the microbial degradation of the reference substance.
5.3 Conclusion The biodegradation of the reference substance sodium benzoate was above 60% of the theoretical yield within 14 days and the differences in degradation between the replicates was by less than 20%. This demonstrates the validity of the test. Under the test conditions, TI-435 was not readily biodegradable. In the toxicity control, TI-435 did not inhibit the microbial degradation of the reference substance.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2005-08-17
Materials and Methods applicant’s version is acceptable.
Results and discussion applicant's version is adopted
Conclusion applicant's version is adopted
Reliability 1
Acceptability acceptable
Remarks none
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 4 of 5
Table A7_1_1_2_1-1: Inoculum / Test organism
Criteria Details
Nature Activated sludge
Species Not applicable
Strain Not applicable
Source Sewage treatment plant treating predominantly domestic sewage
Sampling site Burley Menston sewage treatment works (Yorkshire Water), England
Laboratory culture Not applicable
Method of cultivation Not applicable
Preparation of inoculum for exposure None
Pre-treatment None
Initial cell concentration Not applicable
Table A7_1_1_2_1-2: Test system
Criteria Details
Culturing apparatus Test vessels
Number of culture flasks/concentration 2
Aeration device CO2-free air
Measuring equipment Barium hydroxide titration
Table A7_1_1_2_1-3: Test conditions
Criteria Details
Composition of medium Synthetic mineral salts medium containing potassium dihydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate dihydrate, ammonium chloride, calcium chloride dihydrate, magnesium sulphate heptahydrate, ferric chloride hexahydrate, hydrochloric acid.
Additional substrate No
Test temperature 20.8 to 22.6°C On day 20, the minimum concentration recorded was 18.5°C. This minor fluctuation to the required temperature of 22 ± 2°C is not considered to have influenced the outcome of the study.
pH Start: 7.5 (Blank), not determined for TI-435 due to the risk of the pH electrode becoming coated with the undissolved test substance. End: 7.4 (Blank), 7.4 (TI-435)
Aeration of dilution water Yes Air-flow: 50 to 100 mL/min
Suspended solids concentration 30 mg/L
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 5 of 5
Figure A7_1_1_2_1-1: Percentage biodegradation in the CO2 Evolution Test
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
Section A7.1.1.2.2 Annex Point IIA7.6.1.2
Inherent biodegradability
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ ] Limited exposure [ ] Other justification [ X ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.1.1.2.3 Annex Point IIIA XII.2.1
Biodegradation in seawater
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ ] Limited exposure [ X ] Other justification [ ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.1.2.1.1 Annex Point IIIA XII.2.1
Aerobic biodegradation
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ ] Limited exposure [ ] Other justification [ X ]
Detailed justification:
X
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. Document IIIA, Section A7
Biocidal active substance: Clothianidin
Page 1-12
PT 18 January 2014
Section IIIA 7.1.2.1.2
Annex point IIIA, XII.2.1
Anaerobic biodegradation
1 Reference Official use only
1.1 Reference (2013),
1.2 Data protection Yes
1.2.1 Data owner
1.2.3 Criteria for data protection
2 Guidelines and Quality Assurance
2.1 Guideline study
2.2 GLP Yes
2.3 Deviations
X
Sumitomo Chemical Takeda Agro Co., Ltd. Document IIIA, Section A7
Biocidal active substance: Clothianidin
Page 2-12
PT 18 January 2014
3 Materials and Methods
3.1 Test material (Test substance and reference standards)
Common Name: Clothianidin (TI-435) Chemical name: (E)-1-(2-chloro-1,3-thiazol-5-ylmethyl)-3-
methyl-2-nitroguanidine
Molecular formula: C6H8ClN5O2S Molecular weight: 249.68
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
X
3.1.4 Composition of Product
X
3.1.5 Further relevant properties
3.1.6 Method of analysis Reverse Phase HPLC method Radiochemical purity by HPLC and TLC.
Detection: UV
1 TI-435 is another name for clothianidin.
Sumitomo Chemical Takeda Agro Co., Ltd. Document IIIA, Section A7
Biocidal active substance: Clothianidin
Page 3-12
PT 18 January 2014
3.2 Reference substance TMG
3.3 Test system Characterisation at 0 DAT: Veal calf manure:
Pig manure:
Chicken manure:
X
3.4 Testing procedure
3.4.1 Test system Application of [14C]-clothianidin to 3 manures; veal calf, pig and chicken. X
3.4.2 Temperature 20 ± 2°C under anaerobic conditions for veal calf and pig and aerobic conditions for chicken.
3.4.3 pH NA
3.4.4 Duration of the test 181 days
3.4.5 Number of replicates
3.4.6 Sampling Veal calf, pig and chicken manure was sampled at 0, 7, 14, 30, 59, 120 and 181 days after treatment (DAT)
3.4.7 Analytical methods Reverse Phase HPLC method
Detection: UV
TLC method
X
3.5 Preliminary test
Sumitomo Chemical Takeda Agro Co., Ltd. Document IIIA, Section A7
Biocidal active substance: Clothianidin
Page 4-12
PT 18 January 2014
4 Results and Discussion
4.1
5 Applicant's Summary and Conclusion
5.1 Materials and methods The rate of transformation and nature of transformation products of [14C]-clothianidin was studied at 20 ± 2°C under anaerobic conditions for veal calf and pig manure and aerobic conditions for chicken manure. Samples were taken at 0, 7, 14, 30, 59, 120 and 181 DAT. Control samples (treated with non-radiolabelled clothianidin) were incubated in parallel.
Veal calf and pig manures were conditioned for 21 days at 20 ± 2°C under anaerobic conditions. Dispensed and conditioned manure samples,
, were further conditioned in individual glass vessels for 4 days
(anaerobic incubations) or 19 days (aerobic incubations) prior to clothianidin application. Vessels were maintained at 20 ± 2°C in the dark and had a flow of moistened nitrogen (veal calf and pig manure) or air (chicken manure) through them. The veal calf and pig manure was checked to ensure it was anaerobic prior to clothianidin application.
Samples were removed for analysis
immediately after application of [14C]-clothianidin and at times up to 181 DAT.
Degradation rates of clothianidin and its main metabolite were
X
Sumitomo Chemical Takeda Agro Co., Ltd. Document IIIA, Section A7
Biocidal active substance: Clothianidin
Page 5-12
PT 18 January 2014
determined.
5.2 Results and discussion
X
X
Sumitomo Chemical Takeda Agro Co., Ltd. Document IIIA, Section A7
Biocidal active substance: Clothianidin
Page 6-12
PT 18 January 2014
There were no individual metabolites, other than TMG, detected at > 6% AR in any manure sample analysed,
Clothianidin and TMG were identified by co-chromatography with reference standards by HPLC and TLC.
Degradation rates for clothianidin determined using SFO kinetics are summarised below:
Manure type DT-50 (days) Veal calf 31.5 Pig 13.4 Chicken 16.2
SFO was considered the best fit
X
X
X
5.2.1 DT50 Degradation rates for clothianidin determined using SFO kinetics: X
Sumitomo Chemical Takeda Agro Co., Ltd. Document IIIA, Section A7
Biocidal active substance: Clothianidin
Page 7-12
PT 18 January 2014
Manure type DT50 (days) Veal calf 31.5 Pig 13.4 Chicken 16.2
X
5.3 Conclusion Clothianidin degraded in veal calf and pig manures incubated under anaerobic conditions and in chicken manure incubated under aerobic conditions with DT-50 values of 32, 13 and 16 days, respectively.
The main degradation product was identified as TMG.
There were no other degradation products present at > 6% AR.
X
5.3.1 Reliability 1
5.3.2 Deficiencies None reported
Evaluation by Competent Authorities
Evaluation by Rapporteur Member State
Date 2014/05/14
Sumitomo Chemical Takeda Agro Co., Ltd. Document IIIA, Section A7
Biocidal active substance: Clothianidin
Page 8-12
PT 18 January 2014
Materials and Methods
Sumitomo Chemical Takeda Agro Co., Ltd. Document IIIA, Section A7
Biocidal active substance: Clothianidin
Page 9-12
PT 18 January 2014
Results and discussion
Sumitomo Chemical Takeda Agro Co., Ltd. Document IIIA, Section A7
Biocidal active substance: Clothianidin
Page 10-12
PT 18 January 2014
Conclusion
Reliability
Acceptability
Remarks
Comments from ...
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. Document IIIA, Section A7
Biocidal active substance: Clothianidin
Page 11-12
PT 18 January 2014
Sumitomo Chemical Takeda Agro Co., Ltd. Document IIIA, Section A7
Biocidal active substance: Clothianidin
Page 12-12
PT 18 January 2014
Sumitomo Chemical Takeda Agro Co., Ltd. Clothianidin August 2006
Section A7.1.2.1.2 Annex Point IIIA XII.2.1
Anaerobic biodegradation
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ ] Limited exposure [ ] Other justification [ X ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
RCC project no. 852224 Page 1 of 2
Sumitomo Chemical Takeda Agro Co., Ltd. Clothianidin August 2006
RCC project no. 852224 Page 2 of 2
Section A7.1.2.1.2 Annex Point IIIA XII.2.1
Anaerobic biodegradation
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
Section A7.1.2.2.1 Annex Point IIIA XII.2.1
Aerobic aquatic degradation study
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ ] Limited exposure [ ] Other justification [ X ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project 852224 Page 1 of 9
Section A7.1.2/02 and
A7.1.2.2.2/02
Annex Point IIIA XII 2.1
Rate and route of degradation in aquatic systems
including identification of metabolites and degradation
products
Water/sediment degradation study
1 REFERENCE
Official
use only
1.1 Reference Reddemann, J. (2000): Anaerobic aquatic metabolism of the active
ingredient TI-435.
Bayer AG, 51368 Leverkusen, Germany; unpublished report no. MR-
497/00
x
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
US EPA Pesticide Assessment Guidelines, Subdivision N, Chemistry:
Environmental Fate §162-3 Anaerobic Aquatic Metabolism, 1982
2.2 GLP Yes
2.3 Deviations No x
3 METHOD
3.1 Test material itroimino-14
C] TI-435
3.1.1 Lot/Batch number 11553/1
3.1.2 Specification Specific radioactivity: 3.78 MBq/mg
Radiochemical purity: > 99% according to radio HPLC
Chemical purity: > 99% according to HPLC, UV at 210 nm
3.1.3 Purity
3.1.4 Further relevant
properties
Solubility in water (20°C): 327 mg/L
(see Morrissey & Kramer, 2000a)
3.2 Reference
substance
Yes (for identification of parent compound and degradation products):
TI-435 (unlabelled parent compound)
Degradation products:
TZU: N-(2-chloro-5-thiazolylmethyl)-urea
TZMU: N-(2-chloro-5-thiazolylmethyl)-N’-methylurea
TMG: N-(2-chloro-5-thiazolylmethyl)-N’-methylguanidine
TZNG: N-(2-chloro-5-thiazolylmethyl)-N’-nitroguanidine
MNG: N-methyl-N’-nitroguanidine
3.3 Test system
3.3.1 Water/sediment
systems
Water and sediment were taken from a pond located on the Bayer
research farm in Howe, Indiana, USA. The pond has no history of
chemical treatment or known run-off contamination from chemical
treatments.
For water/sediment characteristics see Table A7_1_2_2_2/02-1.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project 852224 Page 2 of 9
Section A7.1.2/02 and
A7.1.2.2.2/02
Annex Point IIIA XII 2.1
Rate and route of degradation in aquatic systems
including identification of metabolites and degradation
products
Water/sediment degradation study
3.3.2 Test system
sampling
The test system was sampled on June 4, 1997 and the samples were
shipped to the test facility on June 9, 1997.
3.3.3 Test system
equilibration
Prior to the start of the test, water and sediment were separated by
decanting, and stones and plant debris were removed from the moist
sediment. Dry weight of the sediment was determined to be 29.5%. On
July 7, 1997, 42 mL of pond water were added to 224 g moist sediment
(= 66 g dry weight) resulting in a water:sediment ratio of 3:1. Sucrose
(2.5 g) was added to each test system to enhance microbial growth to
speed up the process of getting anaerobic conditions. Then the
incubation devices were purged with argon to replace oxygen, closed
and pre-incubated at 20 1°C in the dark for about 7 weeks. One week
before treatment, the redox potential had dropped to –235 to –255mV
and –58 to -115mV in water and sediment, respectively, and the oxygen
content in the water was 0-1% of saturation.
3.3.4 Test conditions Test vessels: 250 mL Erlenmeyer flasks to which an inert, gas-tight bag
was connected for sampling of volatiles.
Agitation: none;
Oxygen conditions: anaerobic;
Light conditions: dark;
Temperature: 20 ±1°C.
3.3.5 Rate of application Based on a total annual use rate of 300 g a.s./ha and assuming overspray
of a water of 2m depth, the concentration in the water phase is 15 µg
a.s./L. Accordingly, a nominal amount of 3.0 µg a.s. was applied to each
test system taking into account the total water volume of 200mL.
3.3.6 Preparation of
application solution [Nitroimino-
14C]TI-435 was dissolved in acetonitrile (32.12 g
a.s./mL).
3.3.7 Application 93.4 µL of the application solution was applied to the water surface of
each test system using an Eppendorf Comforpette. Argon was passed
through the headspace of the test system for 10 minutes and
subsequently the test system was slightly shaken without disturbing the
sediment phase to achieve homogeneous distribution of the test
substance in the water phase. The test systems then were placed in a box
with a continuous nitrogen flow (50 mL/min).
x
3.3.8 Duration of test 360 days
3.3.9 Sampling and
extractions
Duplicate vessels were dismantled and processed at 0, 1, 3, 7, 14, 30,
59, 90, 135, 182, 240 and 360 days after treatment.
Before dismantling the test systems, N2 was sucked through the test
system and the gas tight bag at a rate of 200 mL/min. for 30 minutes to
eluate potential volatile compounds from the system. The gaseous
stream was directed through a trapping system for CO2 and organic
volatiles.
Immediately after opening of the test vessels, redox potential, pH and
oxygen content were measured in the supernatant water and the redox
potential was measured in the sediment.
At each sampling date, the supernatant water was carefully separated
from the sediment. An aliquot was used for determination of radioactive
CO2 and/or carbonates. The remaining water was centrifuged, the
precipitate added to the sediment phase, and an aliquot of the
supernatant was concentrated under reduced pressure and subjected to
x
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project 852224 Page 3 of 9
Section A7.1.2/02 and
A7.1.2.2.2/02
Annex Point IIIA XII 2.1
Rate and route of degradation in aquatic systems
including identification of metabolites and degradation
products
Water/sediment degradation study
TLC analysis.
The sediment first of all was extracted using organic solvents, i.e. three
times with acetonitrile, then once with acetonitrile/H2O (50:50, v/v),
followed by one extraction with dichloromethane. The extracts were
combined, concentrated and subjected to TLC. In addition, aliquots of
sediment were extracted with methanol : water (1 : 1, v/v) under reflux
for 2 h (all samples), with 0.05M 1-pentane-sulfinic acid in methanol :
water (7 : 3, v/v) under reflux for 2h (from day 1 onwards) or with
acetonitrile : 1M HCl (7 : 3, v/v) under reflux for 4 h (from day 3
onwards). In regards of the extracted radioactivity, only the extracts
from the acetonitrile-HCl extraction procedure were analysed by TLC.
The amount of radioactivity remaining in the extracted sediment (“non
extractable”) was determined by combustion.
3.3.10 Controls Two test systems without and two systems with test substance treatment
were set up in addition for determination of the biological activity in the
sediment in the course of the test period
3.3.11 Analytical methods Radioactivity: liquid scintillation counting (LSC)
Concentration of test substance and degradation products: TLC on Silica
gel 60 plates.
Solvent system:
i) dichloromethane/acetonitrile/acetic acid 70/30/1 (v/v/v)
ii) butanol/water/acetone/acetic acid 65/10/5/15 (v/v/v/v)
Solvent system i) was used for water phase and all extracts, whilst
solvent system ii) was used additionally for a second development of the
TLC plates with the acetonitrile/1M HCl extracts for separation of polar
components.
LOQ for a single component in the water and organic phase extracts was
1% of the applied radioactivity, and 2% for the acetonitrile/1M HCl
extracts.
3.3.12 Intermediates/
degradation
products
No degradate was formed at amounts >4.5% of the applied radioactivity,
Parent TO-435 was confirmed by TLC, HPLC-MS.
3.3.13 Calculation of
dissipation rates
Dissipation of TI-435 from the water phase, the sediment and the whole
test system was calculated using the computer software ModelManager
Vers. 1.1.
4 RESULTS
4.1 Test conditions
during incubation
Anaerobic conditions were demonstrated by the measurements of redox
potential and dissolved oxygen. During the test period, redox potential
varied between –113 and –212mV and between –123 and –210mV in
the water and sediment phase, respectively, and the oxygen content in
the water phase did not exceed 2% of maximum saturation at any
sampling date.
pH values ranged from 4.7 to 5.0 between days 0 and 135, and increased
thereafter to pH 6.7 to 7.1.
The mean temperature was 20.29°C (min/max: 19.90/20.90°C).
4.2 Recovery Three aliquots of the application solution were measured by LSC during
the application procedure and the mean (3.09 g a.s./test system) was
taken as the initial 100% value.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project 852224 Page 4 of 9
Section A7.1.2/02 and
A7.1.2.2.2/02
Annex Point IIIA XII 2.1
Rate and route of degradation in aquatic systems
including identification of metabolites and degradation
products
Water/sediment degradation study
Within the course of the study, the total recoveries varied between
95.1% and 101.7% of the applied radioactivity (for details see Table
A7_1_2_2_2/02-2).
4.3 Distribution of
radioactivity
During the course of the experiment, the amount of radioactivity in the
water phase decreased from 89.8% of applied on day 0 to 1.4% on day
360, whereas the radioactivity in the sediment increased from 9.9% to
95.2% in the same period. The amount of extractable residues was 9.4%
on day 0, increased to a maximum of 46.4% on day 14 and declined to
14.3% by the final sampling. Bound residues increased from 0.5% on
day 0 to a maximum of 82.6% on day 182, and decreased thereafter to
80.9% on day 360.
For details see Table A7_1_2_2_2/02-2.
x
4.4 Identification of
radioactivity
4.4.1 Degradation of the
test substance
In the water phase, the amount of TI-435 steadily decreased from 87.4%
of applied radioactivity on day 0 to below the limit of detection, i.e.
<1% of applied, on day 135.
In the sediment, the amount of TI-435 increased from 9.0% on day 0 to
a maximum amount of 41.2% of the applied radioactivity on day 3 and
decreased thereafter to below the limit of detection on day 240.
For details see Table A7_1_2_2_2/02-2.
x
4.4.2 Formation of
degradation
products
In the water phase, only the parent compound was found in quantifiable
amounts. No additional fraction was detected by TLC at an amount
above the LOD of 1% of applied radioactivity.
In the sediment, five polar fractions were detected none of them ever
exceeding an amount of 4.3% of the applied radioactivity. The retention
time of any of those fractions did not match with any of the available
reference substances, and additional identification efforts were not
feasible in regards of the low amounts of the individual fractions.
For details see Table A7_1_2_2_2/02-2.
4.4.3 Mineralisation &
volatile organic
compounds
Neither CO2 nor any organic volatile compound was detected in the test
systems at significant amounts at any sampling date. Recovery was
always < 0.1% of the applied radioactivity
For details see Table A7_1_2_2_2/02-2.
4.5 Half-life of the test
substance
The half-life of TI-435 in the water phase, sediment and the whole
system is presented in Table A7_1_2_2_2/02-3.
x
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
US EPA Pesticide Assessment Guidelines, Subdivision N, Chemistry:
Environmental Fate §162-3 Anaerobic Aquatic Metabolism, 1982.
The degradation of [nitroimino-14
C]TI-435 was investigated in one US
water/sediment system (Howe farm pond). The test substance was
applied at a concentration of 15 µg a.s./L water (based on the use rate of
300 g a.s./ha and overspray of a water of 2 m depth) to the aquatic
system consisting of 66 g sediment (dry weight) and 200 g water. The
test systems were incubated in the dark at 20°C for 360 days and 0, 1, 3,
7, 14, 30, 59, 135, 182, 240 and 360 days after treatment, duplicate
vessels were processed.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project 852224 Page 5 of 9
Section A7.1.2/02 and
A7.1.2.2.2/02
Annex Point IIIA XII 2.1
Rate and route of degradation in aquatic systems
including identification of metabolites and degradation
products
Water/sediment degradation study
5.2 Results and
discussion
The amount of radioactivity detected in the water phase rapidly
decreased within the course of the study to levels of 1.4% of the
applied radioactivity on day 360. Bound residues in the sediment
reached on average 81% at the end of incubation.
No degradates were found in the water phase and five not identified
polar fractions occurred in the sediment, none of them exceeding a
maximum amount of 4.3% of the applied radioactivity. Volatiles
including CO2 accounted for less than 0.1% of the applied radioactivity
at any sampling.
DT50 of TI-435 was calculated to be 4, 11 and 21 days for the water
phase, sediment phase and the whole system, respectively.
Total recoveries of the applied radioactivity ranged from 95.1% to
101,7%. Validity criteria of the test can be regarded as fulfilled.
5.3 Conclusion Under anaerobic conditions, TI-435 disappears rapidly from the water
phase to the sediment, with non-extractable residues forming the major
sink in time.
5.3.1 Reliability 1
5.3.2 Deficiencies None
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project 852224 Page 6 of 9
Evaluation by Competent Authorities
Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2007-01-10
Materials and Methods Apart from smaller discrepancies (see below), applicants version is acceptable.
Comments:
2.3. Deviations: Yes; deviating to the study protocol, the results of the sterile
samples were not reported since no degradation of the parent compound was
observed and no further information relevant for the study was indicated.
More specifically:
1.1.Reference includes data from Amendment no.: 1 to “Anaerobic aquatic
metabolism of the active ingredient TI-435” by Reddemann, J. (2001).
Bayer AG, 51368 Leverkusen, Germany; unpublished report no. MR-497/00
3.3.7. Application: after each application the aqueous phase was gently mixed by
rotating the incubation vessels…
3.3.9. Sampling and extractions: the extracted sediment was stored up to one year
at about –20°C until an aggravated extraction was performed. Stability studies
showed that TI-435 was stable under the aggravated extraction conditions applied.
Because of the low extracted amount of radioactivity in case of exhaustive and
hot extraction, only the acid hot extracts were analyzed by means of TLC within a
few days after preparation. (amendment to last two paragraphs)
Results and discussion Despite minor reporting deficiencies (see below) the applicant´s version is
adopted.
More specifically:
4.3: Distribution of radioactivity: Bound residues……slightly decreased
thereafter….(amendment to last sentence)
4.4.1 Degradation of the test substance: In the entire system the amount of TI-435
gradually declined from 96.4% of applied radioactivity at day 0 to < 1% at 240
days post treatment.
4.5 Half-life of the test substance: The DT-values presented in the Table are
according to non-linear first order kinetics.
Conclusion The applicant´s version is accepted.
The partitioning and degradation behaviour (fate) of clothianidin was studied in
an anaerobic aquatic system using pond water and corresponding sediment.
During a period of 360 days, decrease of clothianidin in the water phase is rapid
with a calc. non-linear first-order dissipation half-life of 4 days; the corresponding
half-life for the entire system being 21 days. Concurrently, in the sediment the
amount of non-extractable residues steadily increased to reach 81% after 360
days. Metabolism of clothianidin in the entire system is insignificant (no
metabolite > 5% was found). Ultimate biodegradation is negligible (< 0.1% CO2
at any sampling date).
The results of the anaerobic water/sediment study show a rapid translocation of
clothianidin from the water phase to the sediment with resultant formation of a
very high plateau of bound residues, both negligible metabolism and
mineralization.
Reliability 1
Acceptability acceptable
Remarks none
COMMENTS FROM ... (specify)
Date Give date of comments submitted
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project 852224 Page 7 of 9
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project 852224 Page 8 of 9
System Pond on Howe Farm, IN, USA
Supernatant water
Total organic carbon [mg/L]
Dissolved organic carbon [mg/L]
Total water hardness [°dH]
9.7
9.7
2.5
Sediment
Particle size:
sand [%]
silt [%]
clay [%]
29.1
50.2
20.7
Sediment type (according to USDA) silt loam
Organic carbon [mg C/100 g dry mass] 6.21
Nitrogen [mg N/100 g dry mass] 540
Phosphorus [mg P/100 g dry mass] 981
pH (aq. dest.)
(CaCl2)
5.8
5.0
Cation Exchange Cap. [meq/100 g dry mass] 28
Respiratory activity of microflora
Day 0 [mg CO2/h/kg dry sediment]
Day 360 [mg CO2/h/kg dry sediment]
10
8
Table A7_1_2_2_2/02-2: Degradation of TI-435 and formation of metabolites in water/sediment systems
(values are given as % of applied radioactivity)
Days after Pond on Howe Farm, IN, USA
application 0 1 3 7 14 30 59 90 135 182 240 360
WATER PHASE 89.8 81.7 53.4 41.2 22.6 11.9 4.0 2.5 1.1 0.6 0.3 1.4
Origin 1.0 1.3 2.0 n.d. n.d. 1.1 1.5 1.6 1.1 n.d. n.d. 1.3
TI-435 87.4 80.0 50.7 40.1 21.4 10.9 2.7 1.0 n.d. n.d. n.d. n.d.
diffuse radioact. 1.4 n.d. 1.1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
SEDIMENT* 9.9 20.0 47.0 57.3 75.8 84.2 91.2 92.6 96.6 95.9 95.3 95.2
extractable 9.4 18.0 42.1 44.6 46.4 37.6 24.8 11.7 16.4 13.3 18.2 14.3
Origin n.d. n.d. n.d. n.d. 3.7 4.1 6.5 2.4 7.8 6.5 6.5 13.2
TI-435 9.0 17.8 41.2 40.6 38.0 22.5 6.7 2.4 2.3 1.3 n.d. n.d.
PZ1-5** n.d. n.d. n.d. 2.0 3.0 8.6 6.9 2.3 6.5 5.3 8.6 n.d.
diffuse radioact. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
not extractable 0.5 2.0 4.9 12.9 29.3 46.6 66.4 80.9 80.1 82.6 77.0 80.9
14CO2 - <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
TOTAL 99.7 101.7 100.4 98.6 98.3 96.1 95.2 95.1 97.7 96.5 95.6 96.6
n.d. : not detected (< 1% of the applied radioactivity; < 2% of the applied radioactivity for hot acid extraction)
* comprises findings of extractions with organic solvents and hot acid (acetonitrile : 1M HCl, 7 : 3)
** sum of 5 not identified polar metabolites (amount of individual metabolites varied between 2.0 and 4.3%
of the applied radioactivity)
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project 852224 Page 9 of 9
Table A7_1_2_2_2/02-3: Dissipation times of TI-435 in an aquatic system
Compartment DT50 DT90
Water 4.0 days 37.8 days
Sediment 11.2 days 37.2 days
Entire system 21.0 days 63.0 days
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 6
Section A7.1.3 Annex Point IIA7.7
Adsorption/desorption screening test
1 REFERENCE
Official use only
1.1 Reference Lewis, C.J. (2000): [14
C]TI-435: Adsorption/desorption in soil.
Covance, Harrogate, England; unpublished report no. 586/139-D2142
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
OECD 106 (May 1981), US EPA Subdivision N, Section 163-1 and
Environmental Chemistry and Fate Guideline for Registration of
Pesticides in Canada Section B (1987)
2.2 GLP Yes
2.3 Deviations No
3 MATERIALS AND METHODS
3.1 Test material [thiazolyl-14
C]TI-435
3.1.1 Lot/Batch number A-980501
3.1.2 Specific activity 3.88 MBq/mg
968.76 MBq/mmol
3.1.3 Purity Radiochemical purity: >99%
Chemical purity: 98.3%
3.1.4 Further relevant
properties
Solubility in water (20°C) : 327 mg/L
(see Morrissey & Kramer, 2000a)
3.1.5 Method of analysis Identification of TI-435 and reference substances:
HPLC or TLC.
Measurement of radioactivity: LSC
3.2 Degradation
products
Degradation products tested: Yes
At any time of the test all degradation products accounted for < 1% of
the a.s. added.
3.2.1 Method of analysis
for degradation
products
See 3.1.5
3.3 Reference
substances
Yes (for identification of parent compound and
possible degradation products):
TI-435 (unlabelled parent compound)
Degradation products:
CTNU: N-(2-chlorothiazol-5-ylmethyl)-N’-
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 6
Section A7.1.3 Annex Point IIA7.7
Adsorption/desorption screening test
nitrourea
TZMU: N-(2-chlorothiazol-5-ylmethyl)-N’-
methylurea
ACT.HCl: 2-chlorothiazol-5-ylmethylamine hydrochloride
3.3.1 Method of analysis
for reference
substance
See 3.1.5
3.4 Soil types Available data are given in Table A7_1_3-1
3.5 Testing procedure
3.5.1 Test system Adsorption and desorption of TI-435 was
measured using a batch equilibrium procedure to
determine Koc values of [thiazolyl-14
C]TI-435 in
three US and two European soils.
3.5.2 Test solution and
Test conditions
The test substance TI-435 was tested in a concentration range of 0.04 to
5.0 µg a.s./mL.
3.6 Test performance
3.6.1 Preliminary test According to OECD 106
Degree of saturation: 5 µg a.s./mL
Equilibration: 49 hours for the adsorption and
24 hours for the desorption
Soil/solution ratio: 5:1 w/w, 2:1 w/w and 1:1 w/w
3.6.2 Screening test:
Adsorption
According to OECD 106
3.6.3 Screening test:
Desorption
According to OECD 106
3.6.5 Other test None
4 RESULTS
4.1 Preliminary test The obtained solution and equilibration time is
acceptable; the applicability of the test substance
TI-435 is given.
4.2 Screening test:
Adsorption
Solid weight: 10 g
Supernatant volume: 10 mL
Degree of adsorption: 24-42%, 74-90%, 47-70%,
53-76% and 28-43% for Quincy, Elder, Crosby,
Laacher Hof and BBA 2.1 soil, respectively.
4.3 Screening test:
Desporption
Solid weight: 10 g
Supernatant volume: 10 mL
Degree of desorption: 24-41%, 6-15%, 17-27%, 14-26% and 31-37% of
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 6
Section A7.1.3 Annex Point IIA7.7
Adsorption/desorption screening test
adsorbed TI-435 for Quincy, Elder, Crosby, Laacher Hof and BBA 2.1
soil, respectively.
4.4 Calculations
4.3.1 Ka, Kd Calculations of adsorption and desorption constants are given in Table
A7_1_3-2
4.3.2 Kaoc, Kdoc Calculations of adsorption and desorption constants are given in Table
A7_1_3-2
4.5 Degradation
products
TI-435 was found to be stable (< 1% degradation) during both
processes, i.e. adsorption and desorption.
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
The test system is described in 3.5.1 (batch equilibrium procedure). The
OECD guideline is fulfilled, no relevant deviations from the guideline
occurred.
5.2 Results and
discussion
The Kaoc –values varied between 84 and 345 and
were in a tighter range than the Freundlich
isotherm (0.52 to 4.14). This indicates that the
organic carbon content of the soil is of great
importance for the adsorption of TI-435. The
Kdoc–values (95 to 382) were higher than the
adsorption constants for all soils indicating a
partial irreversible adsorption.
There was a good correlation between the concentrations adsorbed and
in solution for the concentration range tested.
5.2.1 Adsorbed a.s. [%] The percentage adsorption of test substance varied between 24 and 90%
of the applied a.s. depending on soil type and concentration.
5.2.2 Ka 0.52 - 4.14 mg/g
5.2.3 Kd 0.62 - 4.58 mg/g
5.2.4 Kaoc 84 - 345 mg/g (mean: 160 mg/g) x
5.2.5 Ka/Kd 0.69 - 0.90 (mean: 0.84)
5.3 Conclusion Based on the classification of MCCALL ET AL. (1980), TI-435 is
classified as being medium to highly mobile in the soils tested.
5.3.1 Reliability 1
5.3.2 Deficiencies None
Evaluation by Competent Authorities
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2006-05-19
Materials and Methods The applicant’s version is adopted.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 6
Evaluation by Competent Authorities
Results and discussion The applicant’s version is adopted.
Comment to Items 5.2.2; 5.2.3.; 5.2.4:
For the adsorption/desorption coefficients Ka and Kd as well as for the Kaoc value
the wrong units are used. The units have to be changed from mg/g to ml/g.
Conclusion Chlothianidin is classified as being medium to highly mobile in the soils tested.
The geometric mean value of the KaOC (applied in the environmental exposure
assessment) amounts to 140 ml g-1
.
Reliability 1
Acceptability acceptable
Remarks
COMMENTS FROM
Date Give date of the comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 6
Table A7_1_3-1: Classification and physico-chemical properties of soils used as adsorbents
Quincy Elder Crosby Laacher Hof BBA 2.1
Origin Grant County,
WA, USA
Watsonville,
CA, USA
New Holland,
OH, USA
Monheim,
Germany
Jockgrim,
Germany
Sand (2000 - 53 µm) 76 59 27 70 93
Silt (53 – 2 µm) 20 25 43 16 3
Clay (< 2 µm) 4 16 30 14 4
Classification (acc. to USDA) loamy sand sandy loam clay loam sandy loam sand
organic carbon [%] 0.4 1.2 1.2 2.1 0.5
organic matter [%] 0
.
7
2
.
1
2
.
1
3
.
6
0
.
9
pH
(water)
8
.
4
7
.
6
6
.
6
6
.
8
4
.
1
pH (1
M KCl)
7
.
2
6
.
2
5
.
2
6
.
2
3
.
7
CEC
[mEq/1
00 g]
3
.
0
1
2
.
7
6
.
8
7
.
4
3
.
3
WHC
(at pF
0)
3
3
.
7
4
2
.
9
5
0
.
1
5
4
.
8
3
2
.
4
CEC = cation exchange capacity WHC = water holding capacity
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 6
Table A7_1_3-2: Adsorption and desorption constants of [14
C]TI-435 in five different soils
Soil Adsorption Desorption Mobility*
Ka Kaoc 1/n Kd Kdoc 1/n Kddes (serial)**
Quincy 0.52 129 0.8351 0.62 154 0.8068 0.69 high
Elder 4.14 345 0.8088 4.58 382 0.8115 3.88 medium
Crosby 1.48 123 0.8216 1.67 139 0.8240 1.66 high
Laacher Hof 1.77 84 0.8146 1.99 95 0.8136 1.98 high
BBA 2.1 0.59 119 0.8648 0.85 170 0.8843 0.90 high
MEAN n.a. 160 0.8290 n.a. 188 0.8280 n.a.
* classification according to MCCALL ET AL. (1980)
** serial desorption at 5 µg/mL according to the Canadian guideline
n.a. not applicable
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
Section A7.1.4.1 Annex Point IIIA XII.2.1
Field study on accumulation in the sediment
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ X ] Limited exposure [ ] Other justification [ ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.1.4 Annex Point IIIA XII.2.2
Further studies on adsorption and desorption in water/sediment systems
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ ] Limited exposure [ ] Other justification [ X ]
Detailed justification:
X
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2005
RCC project no. 852224 Page 1 of 9
Section A7.2.1/02 and
A7.2.2.1/02 Annex Point IIIA XII 1.1
Aerobic degradation in soil, initial study
The rate and route of degradation including the
identification of the processes involved and identification
of any metabolites and degradation products in at least
three soil types under appropriate conditions
1 REFERENCE
Official
use only
1.1 Reference Schad, T. (2000c): Aerobic degradation and metabolism of TI-435 in six
soils.
Bayer AG, 51368 Leverkusen, Germany; unpublished report no. MR-
419/99
x
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
SETAC (1995) and US EPA Subdivision N, 162-1
2.2 GLP Yes
2.3 Deviations No
3 MATERIALS AND METHODS
3.1 Test material [14
C]TI-435
3.1.1 Radiolabelling [thiazolyl-2-14
C]TI-435
3.1.2 Lot/Batch number 11649/2
3.1.3 Specific
radioactivity
3.84 MBq/mg
3.1.4 Purity Radiochemical purity: > 99% according to both radio HPLC and TLC
Chemical purity: > 99% according to HPLC, UV at 210 nm
3.1.5 TS inhibitory to
microorganisms
No
3.2 Reference
substance
Yes (for identification of parent compound and degradation products):
TI-435 (unlabelled parent compound)
Degradation products:
TZNG: N-(2-chloro-5-thiazolylmethyl)-N’-nitroguanidine
TZU: N-(2-chloro-5-thiazolylmethyl)-urea
TZMU: N-(2-chloro-5-thiazolylmethyl)-N’-methylurea
3.3 Test system
3.3.1 Soils The route and rate of degradation was investigated in 6 US soils
For soil characteristics see Table A7_2_1_02-1.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2005
RCC project no. 852224 Page 2 of 9
Section A7.2.1/02 and
A7.2.2.1/02 Annex Point IIIA XII 1.1
Aerobic degradation in soil, initial study
The rate and route of degradation including the
identification of the processes involved and identification
of any metabolites and degradation products in at least
three soil types under appropriate conditions
3.3.2 Test system
sampling
All soils were taken freshly from US fields and shipped immediately to
the test facility. Prior to the start of the test, they were stored for a few
days in a refrigerator to maintain their biological activity.
3.3.3 Test system
preparation
A few days before starting the test, the soils were carefully air dried and
sieved to a particle size of 2 mm. Subsequently, the soil moisture
capacity was determined. The microbial biomass was determined
immediately before the start and within the course of the study
according to ANDERSON AND DOMSCH (1978).
3.3.4 Test conditions Incubation system: 300 mL Erlenmeyer flasks closed with a trapping
attachment (containing soda lime and quartz wool) that permitted some
gas exchange but which adsorbed potential 14
C-volatiles including CO2;
Oxygen conditions: aerobic;
Light conditions: dark;
Temperature: 20 ± 1°C;
Soil moisture: 75% of the 1/3 bar moisture content for all soils.
3.3.5 Rate of application 13.3 µg a.s./100 g dry soil, equivalent to an annual rate of
approximately 300 g a.s./ha (assuming 15 cm soil depth and 1.5 g/cm3
soil density).
3.3.6 Preparation of test
solution and
application
An adequate amount of the test substance (dissolved in acetonitrile) was
applied to an aliquot of about 40 g soil, which was then homogeneously
mixed into the remaining total amount of soil using a tumble mixer.
Aliquots corresponding to 100 g of dry soil were weighed into the test
vessels (for all soils except Crosby only 50g treated soil were incubated
in the test vessel for the sampling day 181).
3.3.7 Control of moisture
content
The test vessels were weighed monthly. A loss of soil moisture was
balanced by the addition of appropriate amounts of distilled water. Prior
to opening the incubation vessel, volatile compounds possibly still
present in the headspace of the vessel were transferred into the trapping
attachment by purging with water-saturated air.
3.3.8 Duration of test 181 days for all soils except Crosby for which an additional sampling
was done after 379 days.
x
3.3.9 Sampling and
extractions
Duplicate or single vessels were processed on 0 (>1 hour), 1, 7, 62, 120
and 181 days after treatment. In case of soil Crosby duplicate test
systems were additionally sampled on day 379 after treatment.
At each sampling date, the soil was extracted four times with
acetonitrile followed by one extraction step with water. Then residual
radioactivity in soil was determined via LSC following combustion of
soil aliquots. To obtain some information on the nature of residues
remaining in soil, the soils were additionally subjected to hot extraction
with acetonitrile : water (50:50, v/v) by refluxing for 2 hours.
x
3.3.10 Biomass
determination
For the purpose of biomass determination at the beginning and in the
course of the study period (days 0 and 181 for all soils, and in addition
on day 379 for soil Crosby), samples with and without active ingredient
were incubated under identical conditions as in the main experiment.
3.3.11 Analytical methods Radioactivity: liquid scintillation counting (LSC); directly (for liquid
samples e.g. extracts) or after combustion (for soil samples only)
Concentration of test substance and degradation products: TLC on
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2005
RCC project no. 852224 Page 3 of 9
Section A7.2.1/02 and
A7.2.2.1/02 Annex Point IIIA XII 1.1
Aerobic degradation in soil, initial study
The rate and route of degradation including the
identification of the processes involved and identification
of any metabolites and degradation products in at least
three soil types under appropriate conditions
a) Silica gel RP-18 F-254 plates; mobile phase: methanol/acetone/water
(10:10:80, v/v/v); vertical development;
b) Silica gel NH2 F-254 plates; mobile phase: i) methanol for 3 minutes
followed by ii) acetonitrile/Merck Titrisol buffer pH2 (8.8:0.2, v/v) for
15 minutes; horizontal development.
3.3.12 Intermediates/
degradation
products
Identified
Degradation products were identified by TLC co-chromatography and
detection in the UV chamber at 254 nm. Radioactive regions were
quantified by the software package Tina (version 2.08, Raytest).
4 RESULTS
4.1 Recovery The actually applied radioactivity was determined by combustion of
small aliquots of each soil immediately after homogenisation. These
values were taken as 100% for all further data evaluations.
The radioactivity determined on day 0 ranged between 96.4% and
103.6% of the applied radioactivity. During the course of the study, the
total recoveries varied between 87.1 and 96.4% of the applied
radioactivity in soil Crosby, 99.0 and 101.6% in soil Elder, 96.8 and
105.0% in soil Fuguay, 101.9 and 105.0% in soil Quincy, 99.1 and
103.1% in soil Sparta and between 96.5 and 99.8% in soil Susan.
4.2 Extracted and
non-extracted
radioactivity
With the exception of soil Fuguay, the amount of extractable residues
decreased with time primarily due to the increase in bound residues and
mineralisation.
The most significant decrease in extractable radioactivity occurred in
soil Crosby, i.e. from 94.0% on day 0 to 68.8% on day 181 and 65.1%
on day 379. In the other soils, extractable radioactivity decreased from
95.8 to 101.9% on day 0 to 81.4 to 91.2% on day 181. The non-
extractable radioactivity in all soils varied between 3.7 and 11.7% of
applied radioactivity on day 181 of incubation, and was 9.5% in soil
Crosby after 379 days.
For details see Table A7_2_1_02-2.
4.3 Degradation of the
test substance
After 181 days, between 63.6 and 95.3% of the applied radioactivity
represented TI-435. In soil Crosby, which was incubated for 379 days,
the amount of TI-435 decreased to 60.3% at the end of the test period.
For details see Table A7_2_1_02-2.
4.4 Mineralisation After 120 days of incubation, 1.5 to 8.1 of the applied radioactivity was
mineralised to 14
CO2 in the six soils, and the release of 14
CO2 increased
further to values between 2.1 and 10.7% after 181 days. After 379 days
incubation of the Crosby soil, 16.9% of the applied radioactivity was
detected as 14
CO2. This soil showed the highest mineralisation rate up
from sampling day 62.
No additional volatile products were detected (<0.1% of applied
radioactivity).
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2005
RCC project no. 852224 Page 4 of 9
Section A7.2.1/02 and
A7.2.2.1/02 Annex Point IIIA XII 1.1
Aerobic degradation in soil, initial study
The rate and route of degradation including the
identification of the processes involved and identification
of any metabolites and degradation products in at least
three soil types under appropriate conditions
4.5 Metabolites and
degradation
products
TZNG and TZMU were the only metabolites identified in all soils.
Maximum amounts in the different soils varied between 0.2 and 0.7% of
applied radioactivity for TZNG and between 0.3 and 1.8% of applied
radioactivity for TZMU. Unidentified radioactivity can be differentiated
in radioactivity remaining at the origin of TLC and diffuse radioactivity
spread over the TLC lane, with maximum amounts varying between 1.3
and 3.9% and 1.5 and 2.0% of applied radioactivity, respectively.
For details see Table A7_2_1_02-2.
4.6 Degradation rate
x
4.7 Degradation route The proposed degradation pathway of TI-435 in soil is presented in
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
Aerobic degradation and metabolism of TI-435 was investigated in six
US soils according to SETAC (1995) and US EPA Subdivision N, 162-1.
No deviations occurred. The test substance was applied at a
concentration of 13.3 µg a.s./100 g dry soil, equivalent to an annual
application rate of approximately 300 g a.s./ha assuming 15cm soil depth
and bulk density of 1.5. The soils were incubated in the dark at 20°C for
181 days, with the exception of soil Crosby that was incubated for 379
days.
5.2 Results and
discussion
DT50 values for the degradation of TI-435 in soil ranged between 533
and 1328 days. However, these values have to be treated very carefully
since they were extrapolated far beyond the experimental period.
5.3 Conclusion Validity criteria can be considered as fulfilled.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2005
RCC project no. 852224 Page 5 of 9
Section A7.2.1/02 and
A7.2.2.1/02 Annex Point IIIA XII 1.1
Aerobic degradation in soil, initial study
The rate and route of degradation including the
identification of the processes involved and identification
of any metabolites and degradation products in at least
three soil types under appropriate conditions
Evaluation by Competent Authorities
Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2007-01-10
Materials and Methods Apart from some amendments (see below) the applicants version is acceptable.
More specifically:
1.1 reference: included are data from amendment No.: 1 by Schad, T. (2001):
Aerobic degradation and metabolism of TI-435 in six soils.
Bayer AG, 51368 Leverkusen, Germany; unpublished report no. MR-419/99
3.3.8: Duration of test: the metabolism part of the study was performed with soil
Crosby and therefore the test duration was 379 days in contrast to the examination
of the degradation kinetics, which was performed in the other five soils with a test
duration of 181 days.
3.3.9 Sampling and extractions: the amount of bound residues was calculated as
remaining radioactivity in soil (after first extraction at room temperature)
substracted by the radioactivity measured in the second extracts. The radioactivity
measured in the filters (< 3,7%) were added to bound residues. Hence, the
radioactivity which was not extracted by the first and second extraction procedure
was regarded as bound residue.
Results and discussion Apart from some reporting deficiencies (see below) the applicants version is
acceptable.
In the six aerobic laboratory soil degradation tests, the amount of extracted
radioactivity only slightly decreased with time with up to 95,2 % of unchanged
clothianidin still identified after 120 days. First order DegT 50 values determined
for clothianidin in the individual soils amounted to more than one year . Two
metabolites, TZNG and TZMU, were detected in the soil extracts, none of which
exceeding 1,8% of applied radioactivity. Unidentified radioactivity amounted to a
maximum amount of 3,9%. Mineralization was negligible accounting for a max. of
8,1 % after 120 days resp. max. 16,9 % in one soil after 379 days. The amount of
bound residues slightly increased towards the end of the study with a max. of 9.9%
after 120 days resp. 11.7% in one of the six soils after181 days.
More specifically:
4.6 Degradation rate: calculations were performed using the computer software
Microsoft Excel 97, the results rounded to one or two digits. The mathematical
assessment of the metabolism data was performed using the ASCL Optimise
Software package (MGA Software, 1996). All reaction steps were assumed to be
of first order. The corresponding correlation coefficients (R2) for the DT 50 values
calculated varied between 0,7176 (Susan) and 0,9987 (Quincy) with 0,9595 for
Elder. In soil Fuguay > 95% total radioactivity were still identified after 181 days.
Conclusion The applicant's summary and conclusion is acceptable. In light of DT 50 values up
to more than one year due to both negligible metabolism and ultimate
biodegradation, clothianidin is in an overall assessment highly persistent in soil
Reliability 1
Acceptability acceptable
Remarks none
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2005
RCC project no. 852224 Page 6 of 9
Section A7.2.1/02 and
A7.2.2.1/02 Annex Point IIIA XII 1.1
Aerobic degradation in soil, initial study
The rate and route of degradation including the
identification of the processes involved and identification
of any metabolites and degradation products in at least
three soil types under appropriate conditions
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2005
RCC project no. 852224 Page 7 of 9
Soil Crosby Elder Fuguay Quincy Sparta Susan
Soil type (according to USDA) silt loam loam loamy sand loamy sand sand silt loam
Particle size (according to USDA)
sand 2000-50 µm [%]
silt 50-2 µm [%]
clay < 2 µm [%]
17.7
58.8
23.5
50.2
38.1
11.7
77.2
19.8
3.0
79.6
13.6
6.8
92.1
7.0
0.9
18.7
53.9
27.4
Particle size (according to DIN)
sand 2000-63 µm [%]
silt 63-2 µm [%]
clay < 2 µm [%]
15.6
60.9
23.5
47.0
41.3
11.7
74.4
22.6
3.0
-
-
-
92.0
7.1
0.9
14.3
58.3
27.4
pH (water)
(CaCl2)
6.74
6.01
6.67
5.84
6.67
5.84
6.8
-
6.22
5.31
6.66
5.91
organic carbon [%]
organic matter [%]
1.37
2.36
1.41
2.43
0.35
0.6
0.4
0.8
0.73
1.26
3.27
5.62
CEC [meq/100 g soil] 15 18 5 6.08 6 30
Microbial biomass*
Day 0 [mg microbial C/kg soil]
Day 181 [mg microbial C/kg soil]
Day 379 [mg microbial C/kg soil]
476
244
177
195
135
n.d.
16
25
n.d.
176
54
n.d.
116
25
n.d.
498
409
n.d.
75% of 333 mbar moisture
[g water to 100 g dry soil]
19.85 16.91 9.6 12.65 5.36 30.58
* On day 0 determined in soil without active substance. On day 181 and 379 determined in soil containing the active substance.
n.d.: not determined
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2005
RCC project no. 852224 Page 8 of 9
Soil Days
after
appli-
cation
14CO2
Not
extracted
radio-
activity
Extracted
radio-
activity
Origin
TI-435
TZNG
TZMU
Diffuse
radio-
activity
Total
Crosby 0 n.m. 2.5 94.0 0.2 93.7 n.d. n.d. 0.1 96.4
silt loam 7 0.1 2.5 89.9 0.2 89.6 <0.1 <0.1 <0.1 92.4
62 5.3 4.7 83.2 1.1 80.2 0.2 0.8 0.9 93.2
120 8.1 3.5 80.7 1.2 76.2 0.7 1.6 0.9 92.4
181 10.7 7.7 68.8 1.6 63.6 0.7 1.4 1.5 87.1
379 16.9 9.5 65.1 1.7 60.3 0.5 1.4 1.3 91.4
Elder 0 n.m. 2.1 97.7 0.2 97.5 n.d. n.d. 0.1 99.8
loam 7 0.2 2.8 97.2 0.1 97.1 n.d. n.d. n.d. 100.1
62 1.2 1.5 99.0 n.d. 98.6 n.d. n.d. 0.4 101.6
120 2.0 1.9 97.3 1.1 95.2 0.1 0.3 0.6 101.2
181 2.5 5.3 91.2 1.5 87.5 0.2 0.3 1.8 99.0
Fuguay 0 n.m. 1.7 95.4 0.1 95.3 n.d. n.d. <0.1 97.1
loamy 7 0.2 3.2 98.8 0.7 98.0 n.d. n.d. n.d. 102.2
sand 62 0.8 2.0 98.8 0.3 97.9 n.d. 0.2 0.4 101.7
120 1.5 2.6 92.7 2.0 89.3 n.d. 0.6 0.8 96.8
181 2.1 3.7 99.2 1.4 95.3 0.1 0.8 1.8 105.0
Quincy 0 n.m. 1.7 101.9 <0.1 101.9 n.d. n.d. <0.1 103.6
loamy 7 0.8 2.4 100.2 0.8 99.3 <0.1 n.d. n.d. 103.3
sand 62 4.0 4.3 96.7 1.2 93.1 0.2 1.1 1.1 105.0
120 5.6 6.4 90.0 1.8 85.8 0.4 1.5 0.6 101.9
181 7.0 8.3 86.9 1.9 80.8 0.5 1.8 2.0 102.2
Sparta 0 n.m. 2.5 100.6 0.1 98.9 n.d. n.d. 1.6 103.0
sand 7 0.6 2.9 98.7 0.1 98.6 n.d. n.d. n.d. 102.2
62 3.3 4.4 95.3 1.1 93.5 n.d. 0.2 0.5 103.0
120 4.8 9.9 88.3 3.5 82.5 0.3 0.6 1.4 103.1
181 5.2 7.9 85.9 3.9 79.6 0.3 0.8 1.3 99.1
Susan 0 n.m. 2.7 95.8 0.1 95.6 n.d. n.d. <0.1 98.5
silt 7 0.2 2.5 94.6 0.9 93.7 n.d. n.d. n.d. 97.3
loam 62 1.7 2.9 94.7 0.4 94.1 n.d. n.d. 0.1 99.3
120 2.7 2.8 94.3 1.2 92.1 0.1 0.4 0.6 99.8
181 3.4 11.7 81.4 1.3 78.3 0.2 0.2 1.5 96.5
n.m. = not measured n.d. = not detected
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2005
RCC project no. 852224 Page 9 of 9
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 1 of 9
Section A7.2.1 and
A7.2.2.1 Annex Point IIIA XII 1.1
Aerobic degradation in soil, initial study
The rate and route of degradation including the
identification of the processes involved and identification
of any metabolites and degradation products in at least
three soil types under appropriate conditions
1 REFERENCE
Official
use only
1.1 Reference Gilges, M. (2000): Aerobic degradation and metabolism of TI-435 in
four soils.
Bayer AG, 51368 Leverkusen, Germany; unpublished report no. MR-
497/99; amended report of 9 April 2001
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
SETAC (1995) and US EPA Subdivision N, 162-1
2.2 GLP Yes
2.3 Deviations No
3 MATERIALS AND METHODS
3.1 Test material [14
C]TI-435
3.1.1 Radiolabelling [nitroimino-14
C]TI-435 and [thiazolyl-2-14
C]TI-435
3.1.2 Lot/Batch number [nitroimino-14
C]TI-435: 11553/1
[thiazolyl-2-14
C]TI-435: 11649/4
3.1.3 Specific
radioactivity
[nitroimino-14
C]TI-435: 3.78 MBq/mg
[thiazolyl-2-14
C]TI-435: 3.84 MBq/mg
3.1.4 Purity [nitroimino-14
C]TI-435:
Radiochemical purity: > 99% according to radio HPLC
Chemical purity: > 99% according to HPLC, UV at 210 nm
[thiazolyl-2-14
C]TI-435:
Radiochemical purity: > 98% according to radio TLC
Chemical purity: > 99% according to HPLC, UV at 210 nm
3.1.5 TS inhibitory to
microorganisms
No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 2 of 9
Section A7.2.1 and
A7.2.2.1 Annex Point IIIA XII 1.1
Aerobic degradation in soil, initial study
The rate and route of degradation including the
identification of the processes involved and identification
of any metabolites and degradation products in at least
three soil types under appropriate conditions
3.2 Reference
substance
Yes (for identification of parent compound and degradation products):
TI-435 (unlabelled parent compound)
Degradation products:
TZNG: N-(2-chloro-5-thiazolylmethyl)-N’-nitroguanidine
TZU: N-(2-chloro-5-thiazolylmethyl)-urea
TZMU: N-(2-chloro-5-thiazolylmethyl)-N’-methylurea
MNG: N-methyl-N’-nitroguanidine
NTG: Nitroguanidine
TMG: N-(2-chloro-5-thiazolylmethyl)-N’-methylguanidine
3.3 Test system
3.3.1 Soils The route and rate of degradation was investigated in 3 European soils
and 1 US soil.
3.3.2 Test system
sampling
The soils Laacher Hof and Höfchen were sampled freshly from the field
and the soils BBA 2.2 and Howe were freshly taken from wooden boxes
in which the soils were stored (in open area under grass cover to
maintain their biological activity).
3.3.3 Test system
preparation
A few days before starting the test, the soils were air dried to such an
extend that they could be sieved to a particle size of 2 mm.
Subsequently, the soil moisture was determined. The microbial biomass
was determined immediately before the start and within the course of
the study according to ANDERSON AND DOMSCH (1978).
3.3.4 Test conditions Incubation system: 300 mL Erlenmeyer flasks to which traps for the
adsorption of volatile compounds (CO2 and organic volatiles) were
attached.
Oxygen conditions: aerobic
Light conditions: dark
Temperature: 20 ± 1°C
Soil moisture: 40% of the maximum water holding capacity (Laacher
Hof and Höfchen) or 75% of 333 mbar moisture (BBA 2.2 and Howe)
3.3.5 Preparation of test
solution and
application
The test substance (dissolved in acetonitrile) was applied to an aliquot
of about 40 g soil which was then homogeneously mixed into the
remaining total amount of soil. Aliquots corresponding to 100 g of dry
soil were weight into the test vessels.
Soils Laacher Hof, Höfchen and BBA 2.2 were applied with
[nitroimino-14
C]TI-435 and soil Howe with [thiazolyl-2-14
C]TI-435.
3.3.6 Rate of application 13.3 µg a.s./100 g dry soil, equivalent to an annual rate of
approximately 300 g a.s./ha (assuming 15 cm soil depth and 1.5 g/cm3
soil density).
3.3.7 Duration of test 120 days or 365 days
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 3 of 9
Section A7.2.1 and
A7.2.2.1 Annex Point IIIA XII 1.1
Aerobic degradation in soil, initial study
The rate and route of degradation including the
identification of the processes involved and identification
of any metabolites and degradation products in at least
three soil types under appropriate conditions
3.3.8 Sampling and
extractions
Duplicate or single vessels were processed at 0, 1, 7, 14, 33, 61, 90 and
120 days after treatment. In case of soils BBA 2.2 and soil Howe,
additional sampling intervals were on day 180, 271 and 365 after
treatment.
At each sampling date, the soil was four times extracted with
acetonitrile and the fifth time with water. To obtain some information on
the nature of residues remaining in soil, the soils were additionally
subjected to hot extraction with acetonitrile : water (50:50, v/v) by
refluxing for two hours. The amount of bound residues was calculated
as remaining radioactivity in soil (obtained by combustion after first
extraction) substracted by the radioactivity measure in the second (hot)
extracts. The radioactivity measured in the filters (≤ 2.7% of applied
radioactivity) was added to bound residues.
3.3.9 Biomass
determination
For the purpose of biomass determination at the beginning and at the
end of the study (day 120 for soils Laacher Hof and Höfchen, day 180
and 365 for soil Howe and day 120, 180 and 365 for soil BBA 2.2),
samples with and without active ingredient were incubated under
identical conditions as in the main experiment.
3.3.10 Analytical methods Radioactivity: liquid scintillation counting (LSC)
Concentration of test substance and degradation products: TLC on RP-
18 plates and silica gel plates.
LOQ for a single component in the extracts: 0.1% of the applied
radioactivity, corresponding to ca. 0.2 µg/kg soil.
3.3.11 Intermediates/
degradation
products
Identified
Degradation products were identified by TLC co-chromatography and
detection in the UV chamber at 254 nm. The identity of all
degradation products was confirmed by HPLC-MS/MS.
4 RESULTS
4.1 Recovery The total recovery of radioactivity on day 0 was taken as 100%. Within
the course of the study, the total recoveries varied between 91.5 and
109. 2% of the applied radioactivity in the silt loam (Laacher Hof),
100.2 and 107.0% in the silt (Höfchen), 97.2 and 101.7% in the
loamy sand (BBA 2.2) and between 96.8 and 101.4% in the sandy
loam (Howe).
4.2 Extracted and
non-extracted
radioactivity
The amount of extracted residues decreased with time in all soils while
bound residues were increasing. The most significant decrease
occurred in soil Höfchen, i.e. from 97.7% on day 0 to 82.5% on
day 120. After 120 days of incubation, the non-extracted radioactivity
reached 5.9 - 9.4% of the applied radioactivity in the German soils
and 5.1% in the US soil.
For details see Table A7_2_1-2.
4.3 Degradation of the
test substance
After 120 days, between 54.3 and 85.8% of the applied radioactivity
represented TI-435. In the loamy sand and sandy loam (BBA 2.2 and
Howe), which were incubated for 365 days, the amount decreased to
57.8% and 75.8%, respectively.
For details see Table A7_2_1-2.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 4 of 9
Section A7.2.1 and
A7.2.2.1 Annex Point IIIA XII 1.1
Aerobic degradation in soil, initial study
The rate and route of degradation including the
identification of the processes involved and identification
of any metabolites and degradation products in at least
three soil types under appropriate conditions
4.4 Degradation rate
4.5 Mineralisation
4.6 Metabolites and
degradation
products
Four metabolites were identified of which only MNG (N-methyl-N’-
nitroguanidine) exceeded 10% of the applied radioactivity in one of the
tested soils (Laacher Hof). TZNG (N-(2-chloro-5-thiazolylmethyl)-N’-
nitroguanidine) amounted to 9.1% in the silt soil (Höfchen) on day 120
with increasing tendency. Maximum amounts of 6.7% and 2.4% were
identified as NTG (Nitroguanidine) and TZMU (N-(2-chloro-5-
thiazolylmethyl)-N’-methylurea), respectively. The amount of
unidentified radioactivity (origin and diffuse radioactivity) did not
exceed 5% of the applied radioactivity.
The degradation rate of MNG (N-methyl-N’-nitroguanidine) could not be
calculated since the highest concentration (10.7% of the applied
radioactivity) occurred at the end of incubation (day 120).
4.7 Degradation route
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
Aerobic degradation and metabolism of TI-435 was investigated in three
German (silt loam, silt and loamy sand) and one US (sandy loam) soil
according to SETAC (1995) and US EPA Subdivision N, 162-1. No
deviations occurred. The test substance was applied at a
concentration of 13.3 µg a.s./100 g dry soil, equivalent to an annual rate
of approximately 300 g a.s./ha. The soils were incubated in the dark at
20°C for either 120 (silt loam and silt) or 365 (loamy sand and sandy
loam) days.
5.2 Results and
discussion
Total recoveries of applied radioactivity ranged between 91.5 and
109.2%. The amount of extracted radioactivity showed a tendency to
decrease with time due to a slow increase in the amount of bound
residues and due to mineralisation. After 120 days, TI-435 represented
68.6 and 54.3% of the applied radioactivity in Laacher Hof and Höfchen,
respectively, and after 365 days TI-435 represented 57.8 and 75.8% of
the applied radioactivity in BBA 2.2 and Howe, respectively. MNG (N-
methyl-N’-nitroguanidine) was identified as a major metabolite with a
maximum level of 10.7% of the applied radioactivity.
DT50 values for the degradation of TI-435 in soil ranged between 143
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 5 of 9
Section A7.2.1 and
A7.2.2.1 Annex Point IIIA XII 1.1
Aerobic degradation in soil, initial study
The rate and route of degradation including the
identification of the processes involved and identification
of any metabolites and degradation products in at least
three soil types under appropriate conditions
and 1001 days (first order).
5.3 Conclusion Validity criteria can be considered as fulfilled.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Evaluation by Competent Authorities
Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2007-01-10
Materials and Methods The applicants version is acceptable.
The aerobic degradation and metabolism of TI-435 were investigated in three
German soils and one US soil with an application rate of 300 g a.i./ha. Two
different radiolabels were used. The studies were performed in compliance with
the resp. SETAC Procedures and the US EPA-Guideline §162-1. The soil samples
were incubated in the dark at 20°C with a moisture content of 75% of 1/3 bar (two
soils) resp. 40% MWHC (two soils).
Results and discussion The applicants version is adopted.
In the four aerobic laboratory soil degradation tests, the amount of extracted
radioactivity only slightly decreased with time with up to 86% of unchanged
clothianidin still identified after 120 days.
First order DT 50 values determined for clothianidin in the individual soils range
from 143 days to > 1 year.
A total number of four metabolites were detected in the soil extracts, with MNG
appearing at a max. level of 10.7% after 120 days in one soil. Furthermore, two
metabolites were found at lower levels between 5 and 10% whereas TZMU only
occurred at levels < 5%.
Mineralization was low to negligible accounting for a max. of 11,2% after 120
days resp. max. 14.8% in one soil after 365 days.
The amount of bound residues slightly increased towards the end of the study with
a max. of 9,4% after 120 days resp. 12.8% in one of the four soils after one year.
Conclusion The applicant's summary is acceptable. In light of DT 50 values up to more than
one year due to only minor metabolism and negligible ultimate degradation,
clothianidin shows in an overall assessment high persistence in soil.
Reliability 1
Acceptability acceptable
Remarks none
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 6 of 9
Section A7.2.1 and
A7.2.2.1 Annex Point IIIA XII 1.1
Aerobic degradation in soil, initial study
The rate and route of degradation including the
identification of the processes involved and identification
of any metabolites and degradation products in at least
three soil types under appropriate conditions
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 7 of 9
Soil
Origin
Laacher Hof
Germany
Höfchen
Germany
BBA 2.2
Germany
Howe
USA
Soil type (according to USDA) silt loam silt loamy sand sandy loam
Particle size (according to USDA)
sand 2000-50 µm [%]
silt 50-2 µm [%]
clay < 2 µm [%]
36.9
51.1
12.0
8.5
81.3
10.2
80.5
12.3
7.2
65.7
26.4
7.9
Particle size (according to DIN)
sand 2000-63 µm [%]
silt 63-2 µm [%]
clay < 2 µm [%]
35.9
53.0
11.2
8.2
81.5
10.3
79.7
13.1
7.2
63.5
28.6
7.9
pH (water)
(CaCl2)
8.1
7.3
7.8
7.2
6.0
6.3
6.7
6.7
organic carbon [%]
organic matter [%]
0.9
1.5
2.7
4.6
2.5
4.3
1.1
1.9
CEC [meq/100 g soil] 8 15 10 10
Microbial biomass*
Day 0 [mg microbial C/kg soil]
Day 120 [mg microbial C/kg soil]
Day 365 [mg microbial C/kg soil]
216
222
n.d.
552
476
n.d.
285
259
182
166
n.d.
81
40% WHCmax [g water to 100g dry soil]
75% of 333 mbar moisture
[g water to 100 g dry soil]
14.6
20.7
25.3
n.d.
18.0
16.1
13.7
14.8
Pesticide use history no prior use of
TI-435**
no prior use of
TI-435 or other
chloronicotinyl
compounds
no prior use of
TI-435 or other
chloronicotinyl
compounds
no prior use of
TI-435 or other
chloronicotinyl
compounds
* On day 0 determined in soil without active substance. On day 120 and 365 determined in soil containing the active substance.
** Imidacloprid was used as a seed dressing on sugar beets in April 1996 (<120 g/ha).
n.d.: not determined
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 8 of 9
Table A7_2_1-2: Recovery of radioactivity and distribution of the active substance and metabolites after
application of [14C]TI-435 to 4 different soils and aerobic incubation at 20°C (values given
in % of applied radioactivity)
Soil/
label
position
Days
after
appli-
cation
14CO2 Non-
extracted
radio-
activity
Extracted
radio-
activity
Origin
TI-435 TZNG
TZMU
MNG
NTG
Diffuse
radio-
activity
Total
Laacher 0 n.m. 2.1 98.0 0.4 92.6 n.d. n.d. n.d. n.d. 5.0* 100
Hof 1 <0.1 2.0 101.9 0.3 100.7 n.d. n.d. n.d. n.d. 0.9 103.9
silt loam/ 7 0.2 2.8 106.2 2.7 98.5 0.7 0.9 1.0 n.d. 2.3 109.2
14 0.4 2.9 99.6 2.3 90.2 1.0 1.1 2.1 0.1 2.9 102.8
nitroimino 33 1.1 5.0 95.1 0.3 84.0 2.6 2.2 5.2 0.2 0.6 101.3
61 2.2 3.8 85.5 0.4 71.3 3.3 2.3 6.3 1.2 0.6 91.5
90 3.8 4.4 95.4 0.4 74.6 4.5 2.2 8.9 3.2 1.6 103.6
120 5.1 8.5 92.5 0.3 68.6 5.1 2.4 10.7 3.7 1.8 106.1
Höfchen 0 n.m. 2.4 97.7 0.3 92.0 n.d. n.d. n.d. n.d. 5.5* 100
silt/ 1 0.1 2.1 103.9 0.4 102.7 n.d. n.d. n.d. n.d. 0.8 106.1
7 0.4 3.9 102.6 0.6 97.0 2.0 0.9 1.7 n.d. 0.5 107.0
nitroimino 14 1.0 3.3 98.6 2.2 88.4 3.0 1.2 3.1 0.2 0.5 102.8
33 3.1 5.1 95.5 0.4 79.4 5.8 1.9 6.1 0.7 1.1 103.8
61 6.0 6.0 88.2 0.5 68.7 7.2 1.5 6.6 2.7 1.0 100.2
90 8.8 7.5 88.1 0.5 64.2 8.2 1.0 8.2 5.3 0.7 104.4
120 11.2 9.4 82.5 0.3 54.3 9.1 1.1 9.5 6.7 1.7 103.1
BBA 2.2 0 n.m. 2.0 98.1 0.4 93.6 n.d. n.d. n.d. n.d. 4.1* 100
loamy 1 <0.1 2.2 95.4 0.5 94.2 n.d. n.d. n.d. n.d. 0.6 97.7
sand/ 7 0.2 2.9 95.9 0.5 92.8 0.4 0.3 1.3 n.d. 0.6 99.0
14 <0.1 2.7 98.9 2.8 92.3 0.5 0.8 1.6 0.3 0.6 101.7
nitroimino 33 1.2 4.4 91.7 0.1 84.3 2.1 1.1 3.3 0.1 0.5 97.2
61 2.4 5.2 91.4 0.6 82.3 2.4 0.9 3.6 1.0 0.7 98.9
90 3.5 5.0 91.7 0.4 77.2 3.3 1.2 5.2 2.7 1.6 100.2
120 4.7 5.9 90.0 0.3 73.3 4.4 1.2 5.9 3.4 1.5 100.5
180 6.7 7.9 85.5 0.5 69.1 4.8 0.8 5.1 3.9 1.5 100.0
271 9.2 11.2 78.5 0.4 60.3 5.2 0.8 5.2 5.2 1.4 98.8
365 11.3 12.8 77.1 0.3 57.8 6.0 0.7 5.4 6.5 0.5 101.2
Howe 0 n.m. 1.8 98.2 0.4 93.6 n.d. n.d. - - 4.3* 100
sandy 1 0.1 1.7 95.2 0.4 93.5 <0.1 n.d. - - 1.3 97.0
loam/ 7 0.7 2.6 97.6 0.4 96.3 0.4 0.2 - - 0.3 100.7
14 1.3 2.5 97.7 1.2 95.6 0.2 0.2 - - 0.6 101.4
thiazolyl 33 2.5 3.2 93.8 0.4 91.9 0.9 0.1 - - 0.6 99.5
61 3.8 2.7 91.0 0.5 88.2 1.3 0.3 - - 0.7 97.5
90 5.5 4.1 90.3 0.9 86.7 1.5 0.3 - - 1.0 99.9
120 6.9 5.1 89.1 0.2 85.8 1.7 0.3 - - 1.3 101.2
180 9.0 5.0 86.0 0.4 81.9 1.9 0.3 - - 1.5 99.9
271 12.1 5.5 79.3 0.7 75.4 2.3 0.2 - - 0.7 96.8
365 14.8 6.6 79.0 0.5 75.8 2.5 0.2 - - 0.2 100.4
n.m. = not measured n.d. = not detected
* The radioactivity in the hot extracts was added to Diffuse Radioactivity since no identification by TLC was made.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 9 of 9
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 1 of 6
Section A7.2.2.2 Annex Point IIIA XII.1.1
Field soil dissipation and accumulation
1 REFERENCE
Official
use only
1.1 Reference Schramel, O. (2000b): Dissipation of TI-435 (600 FS) in soil under field
conditions (France, Germany, Great Britain).
Bayer AG, 51368 Leverkusen, Germany; unpublished report no. RA-
2065/98
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd. / Bayer CropScience
1.2.2 Companies with
letter of access
No
1.2.3 Criteria for data
protection
Data on existing active substance for first entry to Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
SETAC (1995) and ECPA Guidance Document on Field Soil Dissipation
Studies, D/97/NM/2047 (1997)
2.2 GLP Yes
2.3 Deviations Deviations (to SETAC): No crops were grown.
3 MATERIALS AND METHODS
3.1 Test material TI-435 (600 FS)
3.1.1 Lot/Batch number 06568/0015
3.1.2 Type of
formulation
FS (flowable concentrate for seed treatment)
3.1.3 Content of a.s. (TI-
435)
620.0 g/L
3.1.4 Further relevant
properties
a.s. not inhibitory to microorganisms
a.s. not volatile (vapour pressure: 1.3 · 10-10
Pa)
3.1.5 Stability of the test
substance
The guidelines of formulation development ensure that on a chemical
and physical basis the test substances and their dilutions (as spray liquid)
correspond to the international requirements and have sufficient stability.
3.1.6 Method of analysis Analysis according to method 00540 (as described in section A4.2)
based on liquid chromatography with electrospray MS/MS detection.
The limit of quantification (LOQ) and the limit of detection (LOD) for
TI-435 are 5 µg/kg soil and 2 µg/kg soil, respectively.
3.2 Degradation
products
Apart from the parent compound, soil samples were analysed for the
degradation products:
MNG: N-methyl-N’-nitroguanidine
TZNG: N-(2-chloro-5-thiazolylmethyl)-N’-nitroguanidine
3.2.1 Method of analysis
for degradation
products
As described in 3.1.6. The limit of quantification (LOQ) for MNG and
TZNG is 5 µg/kg soil both. The limit of detection (LOD) for MNG and
TZNG is 2 µg/kg soil both.
3.3 Reference
substance
The parent compound and the degradation products TZNG and MNG
were used as reference substances for co-chromatography.
Isotopically labelled internal standards (d3-TI-435, 13
C, 15
N-TZNG and
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 2 of 6
Section A7.2.2.2 Annex Point IIIA XII.1.1
Field soil dissipation and accumulation
3.3.1 Method of analysis
for reference
substance
3.4 Test system To determine the extent of dissipation of TI-435
in Northern European soils, four trials were settled in typical agricultural
regions with different climates and soil types in Germany
, the UK and France . They
were conducted without vegetation.
3.5 Soil types
3.6 Testing procedure
3.6.1 Test substance
application
A single spray application was made on bare soil in spring 1998 at a rate
of equivalent 150 g a.s./ha with 300 L/ha water (plot sizes: 225 to
360 m2).
3.7 Sampling and
work-up
3.7.1 Soil sampling Samples were taken immediately after drying of the spray and at
11 intervals thereafter. The last samples were taken after about two years
(725 to 750 days after application). From all trials, 20 treated and at least
10 control samples were taken (cores of 5 cm in diameter). The sampling
spots were distributed statistically over the plots to get representative
samples. Samples were deep frozen (≤ -18°C) until analysis.
3.7.2 Sample work-up Soil samples were extracted with a mixture of acetonitrile/water/acetic
acid (200:800:0.8, v/v/v). Thereafter, internal standard was added and
the extract analysed as described in 3.1.6.
4 RESULTS
4.1 Controls All concentrations in the control samples were below the limit of
detection except for one sample with MNG residues being between the
LOD and the LOQ (UK trial, day 0).
4.2 Total residues The total residues in the 0-10 cm soil layer ranged from 98.7-130 µg/kg
soil on day 0 and decreased to 7.3-38.4 µg/kg until the end of the study
after two years. In the 10-20 cm soil layer, the total residues remained
between the LOQ and LOD and in the 20-30 cm layer below 2 µg/kg
(LOD) during the test period.
4.3 Residues of TI-435 On day 0, the concentration of TI-435 ranged from 98.7 to 128 µg/kg
soil in the 0-10 cm layer. At the end of the study after 2 years, 7.3 to
35.8 µg TI-435/kg soil were detected. No translocation of the active
substance into deeper soil layer could be observed in any trial. In the 10-
20 cm soil layer, concentrations remained below the LOQ and in the
20-30 cm layer below the LOD.
4.4 Residues of MNG The metabolite MNG could be detected in the 0-10 cm soil layer in
concentrations between the LOQ and LOD at 3 trial locations (total of 15
samples). No residues could be detected in deeper soil layers.
4.5 Residues of TZNG The metabolite TZNG was detected above the LOQ in one single sample
(UK, day 479) at a concentration of 6.1 µg/kg in the 0-10 cm soil layer.
In the other three trials, TZNG was not detected in any soil layer during
the whole test period.
4.6 Degradation of DT50- and DT90-values are presented in Table A7_2_2_2-2.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 3 of 6
Section A7.2.2.2 Annex Point IIIA XII.1.1
Field soil dissipation and accumulation
total residues in
soil
4.7 Degradation of
TI-435 in soil
DT50- and DT90-values are presented in Table A7_2_2_2-3.
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
The field soil dissipation and accumulation of TI-435 was studied
according to SETAC (1995) and ECPA Guidance Document on Field
Soil Dissipation Studies, D/97/NM/2047 (1997). Deviating from
SETAC, no crops were grown.
5.2 Results and
discussion
After 24 months of test duration, a mean of 19% of the applied amount
based on total residues was recovered from the soil. Total residues were
recovered with half-life periods of 19 to 362 days, with a mean value of
135 days.
After 24 months of tests duration, a mean of 19% of the applied amount
based on the active substance was recovered from the soil. The active
substance TI-435 was degraded with half-life periods of 16 to 258 days,
with a mean value of 103 days.
Translocation of TI-435 into deeper soil layers than 10-20 cm can be
excluded down to a concentration of 2 µg/kg corresponding to less than
2% of the initial concentration of the active substance.
The only exception was the UK trial , where residues
could be found in the 0-10 cm layer. No
translocation into soil layers below 20 cm was observed.
5.3 Conclusion TI-435 is persistent in soil.
5.3.1 Reliability 1
5.3.2 Deficiencies None
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 4 of 6
Section A7.2.2.2 Annex Point IIIA XII.1.1
Field soil dissipation and accumulation
Evaluation by Competent Authorities
Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE (*)
Date 2007-01-10
Materials and Methods The applicant´s version is acceptable. In this study conducted in compliance with the
requirements of the guidelines stated, the dissipation behaviour and the translocation
of TI-435 into deeper soil layers was determined in soil without vegetation under field
conditions. Four trials were located in typical agricultural regions in Germany, Great
Britain and France. A single spray application of TI-435 (600FS) to bare soil was
conducted between March and May 1998. The application rate was 150 g a.i./ha for all
trials.
Results and discussion The applicant´s version is acceptable with the exception of the DT50 calculation. In all
eight trials the concentrations of the total residues of clothianidin in soil declined with
time. All trials have been evaluated with both SFO and FOMC-kinetics. The
respective DT50 and DT90-values are given in table 1. Since the fit for SFO-kinetics is
very poor (r2 ranging from 0.69 to 0.88) an additional FOMC evaluation has been
performed. Although the optical check is acceptable, no chi2 values have been
documented due to FOCUS-kinetics report.
Therefore a pragmatic approach has been chosen in the risk assessment (DOC IIA) to
derive DT50-values for PEC-calculations.
. Table 1: Degradation of clothianidin under field conditions. DT50 values based on 2
models and normalised to 12 and 20ºC, respectively
clothianidin
field data
Mean soil
temp *, ºC
fitted SFO model fitted FOMC model
DT50
(d) DT50(12º) DT50(20º) DT50 (d)
DT50
(12º)
DT50
(20º)
D, bare soils 8.9 32 25 13 16 12 7
D 10.6 165 148 79 76 68 36
UK 10.5 506 449 239 258 229 121
F 11.7 240 234 125 62 61 32
UK. crop.
soils 10.5 394 349 186 189 168 88
F 10.6 263 235 125 29 26 14
F 17.6 369 578 305 126 197 104
ES 18.5 219 368 195 82 138 73
Arithmetric
mean 12.4 273 298 157 105 112 59
Geometric
mean 12.0 219 226 120 76 78 41
*: Temperature is not cited in Docs, extracted from Pflanzenschutz-Nachrichten Bayer
56/2003, 1, p.68.
Conclusion The half-lives confirm that TI-435 is persistent in soil also under field conditions. The
validity criteria are fulfilled.
Reliability 1
Acceptability acceptable
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 5 of 6
Section A7.2.2.2 Annex Point IIIA XII.1.1
Field soil dissipation and accumulation
Remarks In a separate report (MR-414/00, dated 2000/9/20) the author recalculated the DT50
values (fitted FOMC Model) for clothianidin on the experimental basis of the study
evaluated above to fit a simple first order model (fitted SFO Model) using the
modelling software package ModelManager. The resulting DT50 values varied
between 32 – 506 days. In a second step, based on the average soil temperatures these
recalculated SFO DT50 values were transformed to the reference temperature of 20°C
(Q10 = 2.2). This conversion results in DT 50 values for clothianidin in the four bare
soil trials tested in a range from 13 – 239 days.
Hence, depending on the calculation method large variations can be observed between
the calculated half-lives!
The applicant has announced that considering the DT 90 (f) > 1 year and the DT 50 (f)
> 3 months, a soil accumulation study in two soil types with test sites in F, UK and D
is ongoing, with a final report to be expected in 2005.
COMMENTS FROM ...
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 6 of 6
Table A7_2_2_2-1: Soil characteristics (0-30 cm layer)
Soil
Origin
Burscheid
Germany
Monheim
Germany
Bury St.
Edmunds, UK
Guiseniers
France
Soil type (according to USDA) silty loam sandy loam sandy loam silt loam
Particle size (according to USDA)
sand 2000-50 µm [%]
silt 50- 2 µm [%]
clay < 2 µm [%]
15.9
67.3
16.8
68.1
21.5
10.4
63.6
19.9
16.5
12.9
76.0
11.1
Particle size (according to DIN)
sand 2000-63 µm [%]
silt 63- 2 µm [%]
clay < 2 µm [%]
13.2
70.0
16.8
65.2
24.4
10.4
61.6
21.9
16.5
8.1
80.8
11.1
pH (CaCl2)
(KCl)
6.25
6.45
6.32
6.80
7.45
7.96
5.90
5.94
organic carbon [%]
organic matter [%]
0.97
1.67
0.89
1.53
0.86
1.48
1.16
2.0
CEC [meq Ba/100 g dry soil] 15 10 13 13
moisture capacity [g/100 g dry soil] 37.5 29.6 34.3 48.1
Table A7_2_2_2-2: Degradation of total residues of TI-435 in soil
Location Soil layer [cm] DT50 [days] DT90 [days] Order of function
Germany
(Burscheid)
0-10 19 345 1st order multi
compartment model
Germany
(Monheim)
0-10 96 1090 1st order multi
compartment model
Great Britain (Bury
St. Edmunds)
0-10 362 * 1st order multi
compartment model
France
(Guiseniers)
0-10 62 * 1st order multi
compartment model
Mean value 135 -
* Calculated DT90-values of >>1000 days were neglected (Model Manager, Version 1.1, Cherwell Scientific
Ltd., Oxford, UK).
Table A7_2_2_2-3: Degradation of TI-435 in soil
Location Soil layer [cm] DT50 [days] DT90 [days] Order of function
Germany
(Burscheid)
0-10 16 364 1st order multi
compartment model
Germany
(Monheim)
0-10 76 1290 1st order multi
compartment model
Great Britain (Bury
St. Edmunds)
0-10 258 * 1st order multi
compartment model
France
(Guiseniers)
0-10 62 * 1st order multi
compartment model
Mean value 103 -
* Calculated DT90-values of >>1000 days were neglected (Model Manager, Version 1.1, Cherwell Scientific
Ltd., Oxford, UK).
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.2.2.3 Annex Point AIII XII.1.4
Extend and nature of bound residues
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ X ] Limited exposure [ ] Other justification [ ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project no. 852224 Page 1 of 7
tion A7.2.2.4
Annex Point AIII XII.1.4
Other soil degradation studies
The rate and route of degradation of a metabolite
1 REFERENCE
Official
use only
1.1 Reference Dorn, R. (2000): Degradation of 14
C-MNG, a degradate of TI-435, in
three different soils.
SLFA 67435 Neustadt/Weinstrasse, Germany; unpublished report no.
TAK06
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
SETAC (1995)
2.2 GLP Yes
2.3 Deviations None (to SETAC)
3 MATERIALS AND METHODS
3.1 Test material [14
C]MNG
3.1.1 Radiolabelling [nitroimino-14
C]MNG
3.1.2 Lot/Batch number radiolabelled MNG: 14627623
3.1.3 Specific
radioactivity
1.730 MBq/mg
3.1.4 Radiochemical
purity
96.2% according to radio TLC
97.1% according to radio HPLC
3.1.5 TS inhibitory to
microorganisms
No
3.2 Reference
substance
None
3.3 Test system
3.3.1 Soils The rate of degradation was investigated in 3 German soils (Laacher
Hof AXXa, Laacher Hof AIII and Höfchen am Hohenseh).
For soil characteristics see Table A7_2_2_4/01-1.
3.3.2 Test system
sampling
The soils were sampled freshly from the field less than 3 months before
start of the test.
3.3.3 Test system
preparation
After arrival at the test facility, the soils were carefully air-dried and
sieved to a particle size of 2 mm. 100 g dry soil were weighed into
each test vessel and soil moisture was adjusted to approximately 48% of
MWHC. Then the vessels were closed with a cotton wool stopper and
pre-incubated at 20 2°C in the dark for five days. The microbial
biomass was determined immediately before the start and at the end of
the test period according to ANDERSON AND DOMSCH (1978).
3.3.4 Test conditions
attachment (containing soda lime and oil wetted quartz wool) that
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project no. 852224 Page 2 of 7
tion A7.2.2.4
Annex Point AIII XII.1.4
Other soil degradation studies
The rate and route of degradation of a metabolite
permitted some gas exchange but which adsorbed potential 14
C-volatiles
including CO2;
Oxygen conditions: aerobic;
Light conditions: dark;
Temperature: 20 ± 1°C;
Soil moisture: 48% of the maximum water holding capacity.
3.3.5 Rate of application 9.5 µg/100 g dry soil
3.3.6 Preparation of test
solution and
application
A stock solution was prepared by dissolving the test substance in
acetonitrile:water (1:1, v/v) to a final concentration of 1.787 mg/mL.
The test substance was to be applied to the soil in distilled water. An
appropriate volume of the stock solution was transferred into a
volumetric vessel, the organic solvent was evaporated under a gentle
stream of N2 and the vessel was made up to volume with distilled water.
Appropriate amounts of the aqueous application solution were pipetted
in small drops to the surface of the pre-incubated soil samples. The test
systems were closed with the trapping system for volatiles and
incubated under appropriate conditions.
3.3.7 Control of moisture
content
The test vessels were weighed monthly. A loss of soil moisture was
balanced by the addition of appropriate amounts of distilled water.
3.3.8 Duration of test 126 days x
3.3.9 Sampling and
extractions
Duplicate or single vessels were processed on 0, 1, 7, 14, 33, 61, 90 and
120 days after treatment.
At each sampling date, the soil was extracted three times with
acetonitrile, followed by one extraction with 0.01M CaCl2. Then
residual radioactivity in soil was determined via LSC following
combustion of soil aliquots. To obtain information on the nature of
residues remaining in soil, the soils were additionally subjected a
Soxhlet extraction with acetonitrile/water (1:1, v/v).
3.3.10 Biomass
determination
For the purpose of biomass determination at the beginning and at the
end of the study period, samples without (day 0) and with active
substance (day 120) were prepared and incubated under identical
conditions as in the main experiment.
3.3.11 Analytical methods Radioactivity: liquid scintillation counting (LSC)
Concentration and characterization of the application solution:
HPLC; pre- and main column filled with Superspher 60 RP Select B;
gradient of 2 solvents: (A) acetic acid (1%, v/v) + 1 g/L ammonium
acetate in water, and (B) acetonitrile; flow rate: 1.0 mL/min.
Identification of test substance and degradation products in extracts:
a) organic extract: TLC on Silica gel RP18 F254 plates; mobile phase:
methanol:acetone:water (10/10/80, v/v/v);
b) CaCl2 extract: TLC on Silica gel 60 F254 plates; mobile phase: 1-
butanol/H2O/acetone/glacial acetic acid (65/10/5/15, v/v/v/v);
c) soxhlet extract: TLC on Silica gel 60 WF254; mobile phase: 1-
butanol/H2O/acetone/glacial acetic acid (65/10/5/15, v/v/v/v).
LOD: 125 dpm per lane equivalent to 7222 counts/mm2.
3.3.12 Degradation
products
Not identified.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project no. 852224 Page 3 of 7
tion A7.2.2.4
Annex Point AIII XII.1.4
Other soil degradation studies
The rate and route of degradation of a metabolite
4 RESULTS
4.1 Recovery Nine aliquots of the application solution were measured by LSC during
the application procedure and the mean (9.52 g/test system) was taken
as the applied amount (100%) for all further data evaluations.
Within the course of the study, the total recoveries varied between 95.05
and 97.22% of the applied radioactivity in the sandy loam (Laacher Hof
AXXa), 90.18 and 97.66% in the silt loam (Laacher Hof AIII) and
between 94.19 and 97.67% in the silt (Höfchen).
4.2 Extracted and
non-extracted
radioactivity
The amount of extractable residues decreased with time in all soils due
to the increase in bound residues and mineralisation. The most
significant decrease occurred in soil Höfchen, i.e. from 96.74% on day 0
to 63.13% on day 120, followed by soil Laacher Hof AIII (97.12 to
66.24%) and soil Laacher Hof AXXa (96.74 to 80.14%). After 120 days
of incubation, the non-extractable radioactivity amounted to 14.94,
16.27 and 11.01% of applied radioactivity in the three soils,
respectively.
For details see Table A7_2_2_4/01-2.
4.3 Degradation of the
test substance
After 120 days, 40.60, 43.53 and 34.60% of the applied radioactivity
represented MNG in soil Laacher Hof AXXa, soil Laacher Hof AIII and
soil Höfchen, respectively.
For details see Table A7_2_2_4/01-2.
4.4 Mineralisation After 120 days of incubation, 5.39, 11.75 and 16.60% of the applied
radioactivity were mineralised to 14
CO2 in Laacher Hof AXXa, Laacher
Hof AIII and Höfchen soil, respectively. At one sampling date, a
negligible amount of other volatile products was found in Höfchen soil.
4.5 Metabolites and
degradation
products
Identification of degradation products was not done. However, the
portion of non-identified radioactivity increased continuously in soil
Laacher Hof AXXa to a maximum of 39.55% of applied radioactivity on
day 120. In soil Laacher Hof AIII and Höfchen not identified
radioactivity amounted to 18.41% and 24.76% of applied radioactivity at
the end of the test period, whilst the maximum amount of 22.35 and
28.56% of applied radioactivity in these soils was reached on day 33 and
day 61, respectively.
For details see Table A7_2_2_4/01-2.
4.6 Degradation rate For the degradation of MNG in soil the following DT50 values were
calculated based on simple first order kinetics:
86.4 days
108.0 days
82.4 days
4.7 Route of
degradation
Not applicable since identification of degradation products was not done.
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
Aerobic degradation of MNG was investigated in three German soils
(sandy loam, silt loam and silt) according to SETAC (1995). No
deviations to SETAC occurred. The test substance was applied on top of
the soil at a concentration of 9.52 µg/100 g dry soil. The soils were
incubated in the dark at 20°C for 120 days.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project no. 852224 Page 4 of 7
tion A7.2.2.4
Annex Point AIII XII.1.4
Other soil degradation studies
The rate and route of degradation of a metabolite
5.2 Results and
discussion
DT50 values for the degradation of MNG in soil were calculated
according to simple first-order model and were 86.4, 108.0 and 82.4 days
for the sandy loam, the silt loam and the silt soil, respectively.
5.3 Conclusion Validity criteria can be considered as fulfilled.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Evaluation by Competent Authorities
Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2007-01-10
Materials and Methods applicants version is acceptable
Comment:
3.3.8 Duration of test: 120 days
Results and discussion applicant's version can be adopted.
In the aerobic laboratory soil degradation test with MNG in 3 soils, total
extractable radioactivity only slightly decreased with time down to levels
between 63.1 – 80.1% after 120 days. At study end, unchanged MNG still
represented 34.0 - 43.5% of the applied radioactivity, the formation of in this
study not further identified radioactivity varied between 18.4 – 39.6%. The
amount of non-extractable residues increased during the course of the study to
levels between 11 – 16.3%after 120 days. Mineralization observed after 120
days accounted for 5.4 – 16.6%. First order DT 50 values determined for MNG
in the individual soils range from 82.4 – 108 days.
Conclusion The applicant's summary and conclusion is acceptable.
The metabolite MNG indicates DT50 values up to 108 days and a low level of
ultimate biodegradation together with the formation of a moderate plateau of
bound residues.
Reliability 1
Acceptability acceptable
Remarks none
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project no. 852224 Page 5 of 7
tion A7.2.2.4
Annex Point AIII XII.1.4
Other soil degradation studies
The rate and route of degradation of a metabolite
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project no. 852224 Page 6 of 7
Table A7_2_2_4/01-1: Characteristic of the soils
Soil
Origin
Laacher Hof
AXXa
Laacher Hof
AIII
Höfchen am
Hohenseh
Soil type (according to USDA) sandy loam silt loam silt
Particle size (according to USDA)
sand 2000-50 µm [%]
silt 50-2 µm [%]
clay < 2 µm [%]
72.4
22.6
5.0
36.9
51.1
12.0
8.5
81.3
10.2
Particle size (according to DIN)
sand 2000-63 µm [%]
silt 63-2 µm [%]
clay < 2 µm [%]
n.d.
n.d.
n.d.
35.9
53.0
11.2
8.2
81.5
10.3
pH (water)
(CaCl2)
7.17
6.32
7.88
6.72
7.30
6.52
organic carbon [%]
organic matter [%] = OC * 1.72
1.02
1.75
0.98
1.69
1.55
2.67
CEC [meq/100 g soil] 8 8 15
Microbial biomass*
Day 0 [mg microbial C/kg soil]
Day 126 [mg microbial C/kg soil]
365
239
276
190
389
292
WHCmax [g water to 100g dry soil] 34.42 36.40 63.10
* On day 0 determined in soil without active substance, on day 126 determined in soil containing the active
substance.
n.d.: not determined
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 May 2005
RCC project no. 852224 Page 7 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 5
Section A7.2.3.1/01 Annex Point IIIA XII.1.2
Adsorption and desorption of metabolites and degradation products
1 REFERENCE
Officialuse only
1.1 Reference (2000):
1.2 Data protection Yes
1.2.1 Data owner
1.2.2 Companies with letter of access
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes OECD 106 (1981), US EPA Subdivision N, § 163-1 (1982) and Environmental chemistry and fate guidelines for registration of pesticides in Canada: Trade Memorandum T-1-255, Section 6.2B
2.2 GLP Yes
2.3 Deviations No
3 MATERIALS AND METHODS
3.1 Radiolabelled test material
3.1.1 Molecular formula
3.1.2 Molecular weight
3.1.3 Lot/Batch number
3.1.4 Specific activity
3.1.5 Purity
3.1.6 Further relevant properties
None
3.1.7 Method of analysis HPLC with Radio-HPLC-Detector and UV-Detector
3.2 Degradation products
3.3 Reference substance
3.3.1 Method of analysis for reference substance
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 5
Section A7.2.3.1/01 Annex Point IIIA XII.1.2
Adsorption and desorption of metabolites and degradation products
3.4 Soil types
3.5 Testing procedure
3.5.1 Test system
3.5.2 Test solution and Test conditions
3.6 Test performance
3.6.1 Preliminary test
3.6.2 Screening test: Adsorption
3.6.3 Screening test: Desorption
3.6.4 HPLC-method According to ”OECD-HPLC-method”: No
3.6.5 Other test None
4 RESULTS
4.1 Preliminary test
4.2 Screening test: Adsorption
4.3 Screening test: Desorption
4.4 Material balance
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 5
Section A7.2.3.1/01 Annex Point IIIA XII.1.2
Adsorption and desorption of metabolites and degradation products
4.5 Calculations
4.5.1 Ka , Kd
4.5.2 Kaoc , Kdoc
4.6 Degradation product(s)
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
Adsorption and desorption of [14C]MNG were measured using a batch equilibrium procedure according to OECD 106. The guideline is fulfilled, no relevant deviations from the guideline occurred.
5.2 Results and discussion
The Kaoc–values varied between 5.2 and 34.3 and the Kdoc–values between 13.0 and 44.0.
5.2.1 Adsorbed amount [%]
5.2.2 Ka 0.02 -0.37 mg/g
5.2.3 Kd 0.15 -0.48 mg/g
5.2.4 Kaoc 5.2 -34.3 mg/g (mean: 20.5 mg/g) x
5.2.5 Ka/Kd 0.77 , 1.27 , 0.72
5.3 Conclusion Based on the classification of MCCALL ET AL. (1980), MNG is classified as being very highly mobile in soil.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 5
Section A7.2.3.1/01 Annex Point IIIA XII.1.2
Adsorption and desorption of metabolites and degradation products
Evaluation by Competent Authorities
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2005-02-02
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 5
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 5
Section A7.2.3.1/02 Annex Point IIIA XII.1.2
Adsorption and desorption of metabolites and
degradation products
1 REFERENCE
Official
use only
1.1 Reference Möndel, M. and Hein, W. (2000): Adsorption/desorption of 14
C-TZNG, a
degradate of TI-435, on five different soils.
SLFA, 67435 Neustadt/Weinstrasse, unpublished report of study TAK01
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
OECD 106 (1981), US EPA Subdivision N, § 163-1 (1982) and
Environmental chemistry and fate guidelines for registration of
pesticides in Canada: Trade Memorandum T-1-255, Section 6.2B
2.2 GLP Yes
2.3 Deviations No
3 MATERIALS AND METHODS
3.1 Radiolabelled test
material
[14
C]TZNG
(= [14
C] N-(2-chloro-5-thiazolylmethyl)-N’-nitroguanidine)
TZNG is a degradate of TI-435 in soil.
3.1.1 Molecular formula C5H6ClN5O2S
3.1.2 Molecular weight 235.7 g/mol
3.1.3 Lot/Batch number 14627721
3.1.4 Specific activity 0.85 MBq/mg
3.1.5 Purity Radiochemical purity: 97.9% (TLC Radiochromatography)
97.4% (HPLC Radiochromatography)
Chemical purity: 98.7% (HPLC-UV Chromatography)
3.1.6 Further relevant
properties
None
3.1.7 Method of analysis HPLC with Radio-HPLC-Detector and UV-Detector
3.2 Degradation
products
Degradation products tested: No
3.3 Reference
substance Non-labelled TZNG was used as reference substance for co-
chromatography.
Lot no.: 89066524
Chemical purity: 98.6%
3.3.1 Method of analysis
for reference
substance
See 3.1.5
3.4 Soil types
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 5
Section A7.2.3.1/02 Annex Point IIIA XII.1.2
Adsorption and desorption of metabolites and
degradation products
3.5 Testing procedure
3.5.1 Test system Adsorption and desorption of TZNG was measured using a batch
equilibrium procedure to determine Koc values of [14
C]TZNG in three
US and two European soils.
The soils were air-dried, 2 mm sieved and stored at room temperature
until use. Before defined amounts of soil were weighted into the test
vessels (Borosilicate glass centrifuge tubes of 42 mL), the residual
moisture contents of the stored soils were determined and taken into
account.
[14
C]TZNG was dissolved in a 0.01 M CaCl2 solution and applied to the
soils.
3.5.2 Test solution and
Test conditions
The test substance TZNG was tested in a concentration range of 0.04 to
5.0 mg/L. The tests were performed in the dark at 20±1°C.
3.6 Test performance
3.6.1 Preliminary test According to ”OECD 106”: Yes
3.6.2 Screening test:
Adsorption
According to ”OECD 106”: Yes
A volume of 20 mL CaCl2 solution containing nominal concentrations of
0.04, 0.2, 1.0 and 5.0 mg TZNG/L was added to the soils (equivalent
to 7g dry weight for the Elder soil and 12g for the other soils). Soil
and supernatant were separated by centrifugation after the respective
shaking periods on a rotary shaker. Each soil and concentration was
tested in duplicate.
3.6.3 Screening test:
Desorption
According to ”OECD 106”: Performed
One desorption step was carried out at concentrations of 0.04, 0.2 and
1.0 mg/L, while 3 serial desorption steps were performed at 5.0 mg/L.
For this, the application solution was replaced by a fresh 0.01 M CaCl2
solution and shaken vigorously for 24 hours. Soil and supernatant
were separated by centrifugation on a rotary shaker. Each soil and
concentration was tested in duplicate.
3.6.4 HPLC-method According to ”OECD-HPLC-method”: No
3.6.5 Other test None
4 RESULTS
4.1 Preliminary test In preliminary tests, a soil/solution ratio of 1:1.67 (w/v) and an
equilibration time of 24 hours were determined to be used in the
definitive test. However, for the Elder soil, a soil/solution ratio of
1:2.86 (w/v) was determined to be used in the definite test.
[14
C]TZNG was analysed in the supernatant after 24, 48, and 72 hours
shaking period and found to be stable (95% unchanged test
compound).
4.2 Screening test:
Adsorption
The amount adsorbed to the soils ranged from 22.7 to 34.8% for soil
Quincy, 57.8 to 82.3% for soil Elder, 59.6 to 81.2% for soil Crosby,
55.3 to 78.8% for soil Laacher Hof and 26.6 to 48.7% for soil
BBA 2.1.
4.3 Screening test:
Desorption
The proportion of adsorbed [14
C]TZNG desorbed from the soils ranged
from 14.4 to 30.9% for soil Laacher Hof, from 31.9 to 49.3% for soil
BBA 2.1, from 14.5 to 29.7% for soil Crosby, from 13.7 to 30.4% for
soil Elder and from 45.2 to 55.2% for soil Quincy.
4.4 Material balance The recovery rate of applied radioactivity varied between 92.1% and
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 5
Section A7.2.3.1/02 Annex Point IIIA XII.1.2
Adsorption and desorption of metabolites and
degradation products
162.0% for the five soils and four concentrations.
4.5 Calculations
4.5.1 Ka , Kd Calculations of adsorption and desorption constants are given in Table
A7_2_3_1_02-2
4.5.2 Kaoc , Kdoc Calculations of adsorption and desorption constants are given in Table
A7_2_3_1_02-2
4.6 Degradation
product(s)
The test substance was found to be stable for the duration of the test.
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
Adsorption and desorption of [14
C]TZNG were measured using a batch
equilibrium procedure according to OECD 106. The guideline is
fulfilled, no relevant deviations from the guideline occurred.
5.2 Results and
discussion
The Kaoc–values varied between 204.5 and 432.5 and the Kdoc–values
between 270.8 and 527.2.
There was good correlation between the concentrations adsorbed and in
solution for the concentration range tested (r > 0.99) in all soils.
5.2.1 Adsorbed amount
[%]
The percentage adsorption of test substance varied between 22.7 and
82.3% of the applied amount depending on soil type and concentration.
5.2.2 Ka 0.63 - 4.71 mg/g
5.2.3 Kd 0.83 - 5.75 mg/g
5.2.4 Kaoc 204.5 - 432.5 mg/g (mean: 275.4 mg/g) x
5.2.5 Ka/Kd 0.76 - 0.88 (mean: 0.81)
5.3 Conclusion Based on the classification of MCCALL ET AL. (1980), TZNG is classified
as being moderately mobile in soil.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 5
Section A7.2.3.1/02 Annex Point IIIA XII.1.2
Adsorption and desorption of metabolites and
degradation products
Evaluation by Competent Authorities
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2005/02/02
Materials and Methods The applicant’s version is acceptable d.
Results and discussion Despite minor deficiencies the applicant’s version is acceptable.
Comments:
Items 4.5 and 5.2:
The applicant does not provide the unit of the adsorption/desorption coefficients
Ka and Kd as well as of the organic-carbon normalized adsorption/desorption
coefficients Kaoc and Kdoc. The correct unit is cm3 g
-1.
Items 5.2.2, 5.2.3, and 5.2.4:
The applicant does provide an incorrect unit of mg g-1
for Ka and Kd as well as for
Kaoc. The correct unit is cm3 g
-1.
Conclusion The applicant’s version is acceptable.
Reliability 1
Acceptability Despite minor deficiencies the original study and the study summary are
acceptable.
Remarks
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 5
Table A7_2_3_1_02-1: Classification and physico-chemical properties of soils used as adsorbents
Quincy Elder Crosby Laacher Hof BBA 2.1
Origin Ephrata,
WA, USA
Watsonville,
CA, USA
New Holland,
OH, USA
Monheim,
Germany
Jockgrim,
Germany
Sand (2000 - 50 µm) 92 75 19 72 90
Silt (50 – 2 µm) 6 16 57 23 8
Clay (< 2 µm) 2 9 24 5 2
Classification (acc. to USDA) sand sandy loam silt loam sandy loam sand
organic carbon [%] 0.2 1.1 1.2 1.0 0.4
organic matter [%] 0.4 1.9 2.0 1.8 0.7
pH (water) 6.7 6.9 7.0 7.2 5.9
pH (CaCl2) 6.2 6.5 7.0 6.3 5.6
CEC [meq/100 g] 8 13 20 8 5
CEC = cation exchange capacity
Table A7_2_3_1_02-2: Adsorption and desorption constants of [14
C]TZNG in five different soils
Soil Adsorption Desorption Mobility*
Ka Kaoc 1/n Kd Kdoc 1/n Kddes (serial)**
Quincy 0.63 261.4 0.9010 0.83 346.2 0.8975 0.75 moderate
Elder 4.71 432.5 0.7832 5.75 527.2 0.7924 5.49 moderate
Crosby 2.84 242.6 0.8070 3.23 276.2 0.8059 3.21 moderate
Laacherhof 2.41 236.0 0.8003 2.86 280.6 0.7924 2.94 moderate
BBA 2.1 0.78 204.5 0.8059 1.03 270.8 0.7923 1.09 moderate
MEAN - 275.4 - - 340.2 - -
* classification according to MCCALL ET AL. (1980)
** serial desorption at 5 mg/L according to the Canadian guideline
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 8
Section A7.2.3.2/01 Annex Point IIIA XII.1.3
Mobility in at least three soil types and where relevant
mobility of metabolites and degradation products
1 REFERENCE
Official
use only
1.1 Reference Stupp, H.P. (2001b): Degradation and translocation behavior of the
insecticide active ingredient TI-435 under field conditions in a lysimeter
(autumn application).
Bayer AG, 51368 Leverkusen, Germany; unpublished report no.
MR051/01
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd. and Bayer CropScience
1.2.2 Companies with
letter of access
No
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
Germany BBA Part IV, 4-3
2.2 GLP Yes
2.3 Deviations No major deviations
3 MATERIALS AND METHODS
3.1 Test material [14
C]TI-435
3.1.1 Radiolabelling Thiazolyl-[methylene-14
C]TI-435
3.1.2 Lot/Batch number 10831
3.1.3 Specific radioactivity 4.51 MBq/mg
3.1.4 Purity Radiochemical purity: > 98% according to radio TLC
Chemical purity: > 99% according to HPLC
3.1.5 Further relevant
properties
TS not inhibitory to microorganisms
TS not volatile (vapour pressure: 1.3 · 10-10
Pa)
Water solubility (20°C): 327 mg/L (see Morrissey & Kramer, 2000a)
3.1.6 Method of analysis Analysis by TLC methods using silica gel plates (60 F254).
3.2 Degradation
products
Degradation products were analysed for in leachates and soil.
3.2.1 Method of analysis
for degradation
products
Comparison of radioactive areas with unlabelled standards of parent and
known degradation products.
3.3 Reference substance Parent and known metabolites:
TI-435 (unlabelled parent)
Guanidine hydrochloride
Methylguanidine hydrochloride
NTG: Nitroguanidine
MNG: N-methyl-N’-nitroguanidine
Urea
N-Methylurea
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 8
Section A7.2.3.2/01 Annex Point IIIA XII.1.3
Mobility in at least three soil types and where relevant
mobility of metabolites and degradation products
Cyanamide
Cyanamide acid
TZNG: N-(2-chloro-5-thiazolylmethyl)-N’-nitroguanidine
TMG: N-(2-chloro-5-thiazolylmethyl)-N’-methylguanidine
TZG: N-(2-chloro-5-thiazolylmethyl)-N’-guanidine
TZMU: N-(2-chloro-5-thiazolylmethyl)-N’-methylurea
TZU: N-(2-chloro-5-thiazolylmethyl)-urea
3.3.1 Method of analysis
for reference
substance
Analysis by standard TLC methods as described in section 3.1.6.
3.4 Soil types Depending on the soil layer, the sand content ranged from 68-82% and
the clay content from 8-19%. In the 0-10 cm layer, the organic C content
was 1.8% and the pH was 6.6 (0.01 M CaCl2). For further information
see Table A7_2_3_2_01-1
3.5 Testing procedure
3.5.1 Test system Undisturbed soil core: 1 m2 surface area, 1.3 m depth
sandy loam (Laacherhof AXXa)
Removed from the field in April 1994 and installed in an open lysimeter
facility (assignment: lysimeter no. 24).
3.5.2 Test substance
application
Thiazolyl[methylene-14
C]TI-435 formulated as WS 70
Applied as seed treatment in two consecutive years: equivalent to 100 g
a.s./ha on winter barley in September 1996 and 137.5 g a.s./ha on winter
wheat in October 1997; total actual amount of 23.75 mg a.s. per
lysimeter.
In October 1998 (3rd
year), untreated winter wheat was sown. During the
entire study, the surrounding (6.7 x 3.3 m) was sown uniformly with the
lysimeter.
3.5.3 Test conditions Relevant meteorological data like temperature (air and soil), rainfall, air
humidity, sunshine and wind velocity were recorded in the vicinity of the
lysimeter station (about 1 or 0.5 km apart). The lysimeter was
additionally irrigated in the first (109 mm water) and second year
(216 mm water).
The total precipitation + irrigation of each year were:
year 1 : September 1996 - August 1997 : 877.7 mm
year 2 : September 1997 - August 1998 : 860.1 mm
year 3 : September 1998 - August 1999 : 911.9 mm
3.6 Sampling and
work-up
3.6.1 Leachates In general, leachates were sampled every month (if they occurred, or
even twice per month in case of high quantities). The volume of each
leachate was measured and the radioactivity determined (Liquid
Scintillation Counting). The samples were deep-frozen at -20°C until
processing. The storage stability of the residues was confirmed over a
period of 24 month. Individual leachate samples were concentrated with
a vacuum evaporator and separated directly on TLC plates. Pooled
leachates of the 3rd
year were worked up by means of Craig partition.
Butanol as mobile phase and water as stationary phase were used to
separate the residues. The partition was repeated 150 times within about
8 hours. After separation in the Craig apparatus, the phases were
homogenised with propanol. Three fractions were finally obtained and
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 8
Section A7.2.3.2/01 Annex Point IIIA XII.1.3
Mobility in at least three soil types and where relevant
mobility of metabolites and degradation products
evaluated on TLC silica gel plates using two solvent systems (selectivity
for either polar or non-polar compounds). The radioactive zones on the
TLC plates were measured by means of a Bio-Imaging Analyzer. Total
radioactive residues were expressed as TI-435 equivalents (parent
equiv.).
3.6.2 Soil At the end of the study, the upper three soil layers (10-cm layers, 0-
30 cm) were completely removed from the lysimeter and separately
homogenised in a cement mixing machine. The deeper layers (30-
130 cm) were samples with a corer (three drill cores of about 50 cm2).
Up to the 50 cm layer, aliquots of the soil were extracted (at room
temperature and thereafter hot). Non-extractable residues were
determined by combustion of the extracted soils.
3.6.3 Plants The cereals were harvested in July 1997 (treated barley), August 1998
(treated wheat) and July 1999 (untreated wheat). The stems were cut off
directly above the ground and the ears (grains plus hulls) separated form
the straw. For analysis, the hulls were added to the straw. The samples
were homogenised under liquid nitrogen. Aliquots were combusted to
determine the Total Radioactive Residues (TRR). Grains were extracted
under reflux. The residues in the extracts were separated and identified
on TLC. The top soil layer (0-20 cm) was turned over with a spade after
the first and second harvest.
4 RESULTS
4.1 Material balance At the end of the study, a material balance was determined. The
distribution of the Total Radioactive Residues (TRR) is summarised in
Table A7_2_3_2_01-2. The losses of radioactivity (calculated value)
were attributed to mineralisation.
4.2 Leachates The total of precipitation and irrigation was 2650 mm at the end of the
study. About 36% of this amount could be recovered as leachate (Table
A7_2_3_2_01-3).
The concentration in the leachates was below 0.030 µg parent equiv./L
until March 1997 and increased to 0.052 µg parent equiv./L in May 1997
(first year). About 0.096 µg parent equiv./L were found in the leachate of
January 1998, and thereafter the concentrations varied between 0.069 µg
and 0.033 µg parent equiv./L (second year). The maximum concentration
was determined in the leachate sample of November 1998 and was
0.133 µg parent equiv./L. In the next leachate of December 1998,
0.112 µg parent equiv./L were detected. Thereafter, the concentrations
decreased again until the end of the study (last leachate May 1999:
0.073 µg parent equiv./L).
Additionally, annual leachate samples of the 2nd
and 3rd
year were
prepared by combining individual leachates. The maximum
concentration based on these annual samples was observed in the 3rd
year
and was 0.104 µg parent equiv./L (see Table A7_2_3_2_01-3). In
addition, the three leachates with the highest concentrations (i.e. of
January, November and December 1998) were analysed separately to
identify the residues. The distribution of the radioactivity is provided in
Table A7_2_3_2_01-4.
TI-435 was not detected in any of the leachates analysed. Known
metabolites could not be detected, whereas four unknowns were seen. In
the annual samples, the maximum concentration of a single unknown
compound was 0.065 µg parent equiv./L (U3, 3rd
year).
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 8
Section A7.2.3.2/01 Annex Point IIIA XII.1.3
Mobility in at least three soil types and where relevant
mobility of metabolites and degradation products
4.3 Soil The distribution of the applied radioactivity in the soil profile was
determined at the end of the study. The majority of the radioactivity was
determined in the top soil (0-20 cm) and amounted to 51.6% of the
applied amount. In the following two layers, 5.2% (20-30 cm) and 1.2%
(30-40 cm) of the applied radioactivity were determined. Only negligible
amounts were measured in deeper layers (Table A7_2_3_2_01-5).
The characterisation of the radioactivity in the three top layers is
provided in Table A7_2_3_2_01-6.
4.4 Plants The total radioactive residue in the grains of the first crop winter barley
was 20.5 µg parent equivalent/kg. In the second crop, after the second
application of TI-435, the concentration in wheat grains increased to
35.7 µg/kg parent equivalents. A low amount was determined in the
grains of the 3rd
crop wheat (3.9 µg parent equivalent/kg). For details see
Table A7_2_3_2_01-7.
From the total radioactive residues, 18.3% could be extracted from the
barley grains and 34.6% from the wheat grains (2nd
crop). With respect
to the low concentration in the 3rd
crop (wheat), no extraction was
performed. The parent compound and the metabolite TZNG could be
identified in the extracts. The concentration of TI-435 was found to be
0.7 µg/kg in barley grains and 1.1 µg/kg in wheat grains (Table
A7_2_3_2_01-8).
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
The German BBA guideline for lysimeter studies is an internationally
accepted guideline. No relevant deviations from the guideline occurred.
5.2 Results and
discussion
Distribution of radioactivity
The majority of the applied radioactivity was recovered from the soil
(about 60% of applied) and about 37% of applied was attributed to losses
by mineralisation.
Degradation and residues in soil, leachate and plants
The parent compound and the metabolite TZNG were identified in the
soil samples.
In the total leachates, less than 0.3% of applied radioactivity was
detected. The highest annual concentration was found for the 3rd
year and
was 0.104 µg parent equiv./L. Neither TI-435 nor any known metabolites
were identified in the leachates analysed. Unknown metabolite U3
represented the highest individual concentration (0.065 µg parent
equiv./L) in the annual leachate of the 3rd
year.
In the crops, 3.2% of the applied radioactivity was measured. The total
radioactive residue in the grains was highest in the 2nd
crop
(35.7 µg parent equiv./kg in winter wheat). TI-435 (maximum:
1.1 µg/kg) and the metabolite TZNG (maximum: 4.2 µg parent
equiv./kg) were identified.
5.3 Conclusion On the basis of these findings, TI-435 and its degradation products are
not expected to occur in relevant amounts in groundwater. Degradation
in soil continuous. No accumulation in plants is to be expected.
5.3.1 Reliability 1
5.3.2 Deficiencies None
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 8
Section A7.2.3.2/01 Annex Point IIIA XII.1.3
Mobility in at least three soil types and where relevant
mobility of metabolites and degradation products
Evaluation by Competent Authorities
EVALUATION BY RAPPORTEUR MEMBER STATE (*)
Date 2004/11/19
Materials and Methods The applicant’s version is adopted.
Results and discussion The applicant’s version is adopted.
Conclusion TI-435 and its degradation products are not expected to occur in relevant amounts
in groundwater. No accumulation in plants is to be expected.
Reliability 1
Acceptability acceptable
Remarks
COMMENTS FROM ...
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 8
Table A7_2_3_2_01-1: Soil characteristics
Classification Sandy loam
Depth [cm)] 0-10 10-20 20-30 30-40 40-50 50-60 60-70 70-80 80-90 90-100 100-110 110-120 120-130
sand [%]
silt [%]
clay [%]
70.8
20.7
8.6
69.4
22.2
8.5
68.3
21.1
10.6
67.5
20.7
11.8
70.3
18.0
11.8
71.7
15.2
12.6
75.5
15.1
9.4
73.2
13.0
13.8
68.7
12.8
18.5
70.2
12.2
17.6
78.0
10.4
11.6
77.3
8.8
13.8
815
10.2
8.3
organic C [%] 1.8 1.1 0.7 0.5 0.3 0.2 0.2 0.2 0.2 0.2 0.1 0.1 0.1
pH (water) 7.2 7.2 7.2 7.3 7.5 7.5 7.6 7.7 7.7 7.7 7.7 7.7 7.7
pH (CaCl2) 6.6 6.4 6.3 6.5 6.5 6.5 6.5 6.5 6.6 6.6 6.6 6.6 6.7
Table A7_2_3_2_01-2: Balance of Total Radioactive Residues (100% = 107.14 MBq resulting from two
applications)
Leachates Crops Soil Losses TOTAL
grains straw + hulls (mineralisation)
0.28% 0.25% 2.92% 59.29% 37.26%* 100%
* calculated value
Table A7_2_3_2_01-3: Annual amounts of leachates and total radioactive residues
Amount Total radioactive residues
[L] [µg parent equivalent/L]
1st year (Sept. 1996 to Aug. 1997) 273 0.013*
2nd
year (Sept. 1997 to Aug. 1998) 190 0.062
3rd
year (Sept. 1998 to Aug. 1999) 494 0.104
Sum : 956 Average: 0.060
Mean per year : 319
* calculated based on monthly samples
Table A7_2_3_2_01-4: Distribution of radioactivity in leachates
Sample Total charact. Origin TI-435 U3 U4 U5 U7 Diffuse
date [µg parent equivalent/ L]
3rd
year* 0.093 N.D. N.D. 0.065 0.012 0.001 0.003 0.012
Jan. 1998 0.096 n.d. n.d. 0.059 0.020 n.d. n.d. 0.017
Nov. 1998 0.133 n.d. n.d. 0.072 0.014 n.d. n.d. 0.047
Dec. 1998 0.112 n.d. n.d. 0.069 0.027 n.d. n.d. 0.015
* Quantification was performed by means of Craig partition. Limit of detection was about 0.001 µg/L (N.D.).
n.d. not detected (<0.02 µg/L)
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 7 of 8
Table A7_2_3_2_01-5: Distribution of radioactivity in the soil profile (sampling at the end of the study)
Soil layer Total radioactive residue Radioactivity
[cm] [µg parent equivalent/kg soil] [% of applied]
0-10 55.5 28.0
10-20 47.0 23.6
20-30 9.6 5.2
30-40 2.0 1.2
40-50 0.76 0.5
50-60 0.31 0.2
60-70 0.23 0.2
70-80 0.15 0.1
80-90 0.14 0.1
90-100 0.07 0.0
100-110 0.06 0.0
110-120 0.07 0.1
120-130 0.06 0.0
TOTAL - 59.3
Table A7_2_3_2_01-6: Distribution of radioactivity in soil extracts (sum of cold and hot extract)
Soil layer Origin TI-435 TZNG TMG U5 Diffuse
[cm] [µg/kg]*
0 - 10 33.4 1.23 25.4 5.21 n.d. n.d. 1.19
10 - 20 31.0 1.05 24.7 3.76 n.d. n.d. 1.25
20 - 30 6.69 0.32 5.48 0.55 n.d. n.d. 0.31
Total 70.84 2.59 55.5 9.49 n.d. n.d. 2.75
n.d. not detected (<0.01 µg/kg)
* Not identified zones (origin, U5 and diffuse radioactivity) were calculated as TI-435 equivalents. TZNG
and TMG were calculated based on their molecular weight.
Table A7_2_3_2_01-7: Yields and total radioactive residues (TRR) in crops
Plant 1st year 2
nd year 3
rd year
part winter barley* winter wheat* winter wheat
yield
[g/m2]
TRR
[µg par. equiv./kg]
yield
[g/m2]
TRR
[µg par.equiv./kg]
yield
[g/m2]
TRR
[µg par.equiv./kg]
Grain 1250 20.5 849 35.7 980 3.9
Straw & hulls 1969 126 840 353 829 60
* Crops grown from treated seeds
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 8 of 8
Table A7_2_3_2_01-8 Distribution of radioactivity in grains of 1st and 2
nd crop
Extracted Not extracted Origin TI-435 TZNG Diffuse
Plant part [µg parent equiv./kg]
barley grains/ 1st year 3.75 16.7 1.8 0.7 1.0 0.1
wheat grains/ 2nd
year 12.35 23.3 5.5 1.1 4.2 1.4
* TZNG was calculated based on molecular weight
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 7
Section A7.2.3.2/02 Annex Point IIIA XII.1.3
Mobility in at least three soil types and where relevant
mobility of metabolites and degradation products
1 REFERENCE Official
use only
1.1 Reference Stupp, H.P. (2001c): Degradation and translocation behavior of the
insecticide TI-435 in a lysimeter under field conditions.
Bayer AG, 51368 Leverkusen, Germany; unpublished report no.
MR599/00
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd. and Bayer CropScience
1.2.2 Companies with
letter of access
No
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
Germany BBA Part IV, 4-3
2.2 GLP Yes
2.3 Deviations No major deviations
3 MATERIALS AND METHODS
3.1 Test material [14
C]TI-435
3.1.1 Radiolabelling [Nitroimino-14
C]TI-435
3.1.2 Lot/Batch number 11553/1
3.1.3 Specific radioactivity 3.78 MBq/mg
3.1.4 Purity Radiochemical purity: > 99% according to radio TLC
Chemical purity: > 99% according to HPLC
3.1.5 Further relevant
properties
TS not inhibitory to microorganisms
TS not volatile (vapour pressure: 1.3 · 10-10
Pa)
Water solubility (20°C): 327 mg/L (see Morrissey & Kramer, 2000a)
3.1.6 Method of analysis Analysis by TLC methods using silica gel plates (60 F254).
3.2 Degradation
products
Degradation products were analysed for in leachates and soil.
3.2.1 Method of analysis
for degradation
products
Comparison of radioactive areas with unlabelled standards of parent and
known degradation products.
3.3 Reference substance Parent and known metabolites:
TI-435 (unlabelled parent)
Guanidine hydrochloride
Methylguanidine hydrochloride
NTG: Nitroguanidine
MNG: N-methyl-N’-nitroguanidine
Urea
N-Methylurea
Cyanamide
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 7
Section A7.2.3.2/02 Annex Point IIIA XII.1.3
Mobility in at least three soil types and where relevant
mobility of metabolites and degradation products
Cyanamide acid
TZNG: N-(2-chloro-5-thiazolylmethyl)-N’-nitroguanidine
TMG: N-(2-chloro-5-thiazolylmethyl)-N’-methylguanidine
TZG: N-(2-chloro-5-thiazolylmethyl)-N’-guanidine
TZMU: N-(2-chloro-5-thiazolylmethyl)-N’-methylurea
TZU: N-(2-chloro-5-thiazolylmethyl)-urea
3.3.1 Method of analysis
for reference
substance
Analysis by standard TLC methods as described in section 3.1.6.
3.4 Soil types Depending on the soil layer, the sand content ranged from 68-82% and
the clay content from 8-19%. In the 0-10 cm layer, the organic C content
was 1.8% and the pH was 6.6 (0.01 M CaCl2). For further information
see Table A7_2_3_2_02-1
3.5 Testing procedure
3.5.1 Test system Undisturbed soil core: 1 m2 surface area, 1.3 m depth
sandy loam (Laacherhof AXXa)
Removed from the field in April 1996 and installed in an open lysimeter
facility (assignment: lysimeter no. 17 and 18).
3.5.2 Test substance
application
[Nitroimino-14
C]TI-435 was formulated as SC 200
Applied as spray in two consecutive years: equivalent to 160 g a.s./ha on
grass in July 1997 and May 1998; total actual amount of 31.91 mg a.s.
on lysimeter no. 17 and 32.49 mg a.s. on lysimeter no. 18
The grass on the lysimeters and surrounding (about 3x3 m around each
lysimeter) was sown in June 1997.
3.5.3 Test conditions Relevant meteorological data like temperature (air and soil), rainfall, air
humidity, sunshine and wind velocity were recorded in the vicinity of the
lysimeter station (about 1 or 0.5 km apart). The lysimeters were
additionally irrigated in the first (168 mm water), second (45 mm water)
and third year (150 mm water).
The total precipitation + irrigation of each year were:
year 1 : July 1997 - July 1998 : 846.8 mm
year 2 : July 1998 - July 1999 : 929.6 mm
year 3 : July 1999 - July 2000 : 851.9 mm
3.6 Sampling and
work-up
3.6.1 Leachates In general, leachates were sampled every month (if they occurred). The
volume of each leachate was measured and the radioactivity determined
(Liquid Scintillation Counting). The samples were deep-frozen at -20°C
until processing. The storage stability of the residues was confirmed over
a period of 18 month.
Individual leachate samples, which were taken at the maximum Total
Radioactive Residue (TRR) and at intervals of about half a year, were
analysed for the parent and degradation products. The samples were
concentrated with a vacuum evaporator and separated directly on TLC
plates. Additionally, annual leachate samples were combined from
individual samples with respect to the amount of leachate. They were
worked up by means of Craig partition (for description of method see
Stupp, 2001b). The radioactive zones on the TLC plates were measured
by means of a Bio-Imaging Analyzer. Total radioactive residues were
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 7
Section A7.2.3.2/02 Annex Point IIIA XII.1.3
Mobility in at least three soil types and where relevant
mobility of metabolites and degradation products
expressed as TI-435 equivalents (parent equiv.).
3.6.2 Soil At the end of the study (August 2000), the upper three soil layers (10-cm
layers, 0-30 cm) were completely removed from the lysimeter and
separately homogenised in a cement mixing machine. The deeper layers
(30-130 cm) were sampled with a corer (three drill cores per lysimeter
with about 50 cm2). Up to the 50 cm layer, aliquots of the soil were
extracted with acetonitrile and water (at room temperature and thereafter
hot). Non-extractable residues were determined by combustion of the
extracted soils.
3.6.3 Plants Grass was regularly cut and the cut remained on the lysimeters as mulch
and rotted. The grass plants were mixed into the upper soil layer
(0-10 cm) before further analysis. Therefore, grass cut and remaining
grass plants were not analysed separately.
4 RESULTS
4.1 Material balance At the end of the study, a material balance was determined. The
distribution of the Total Radioactive Residues (TRR) is summarised in
Table A7_2_3_2_02-2. The losses of radioactivity (calculated values)
were attributed to mineralisation.
4.2 Leachates The total of precipitation and irrigation was 2628 mm at the end of the
study. About 49% of this amount could be recovered as leachate. The
two lysimeters behaved very similarly (Table A7_2_3_2_02-3).
The concentrations in the leachates were below 0.030 µg parent equiv./L
until January/February 1998 and increased to 0.196 µg parent equiv./L
(Lysimeter 17) respective 0.275 µg parent equiv./L (Lysimeter 18) in
June/July 1998 (first year). During autumn, the concentrations
approximately remained on this level before reaching in
November/December the peak concentrations of 0.402 µg (Lysimeter
17) and 0.514 µg parent equiv./L (Lysimeter 18). Thereafter, the
concentrations decreased (until December 1999) before increasing again
to 0.354 µg (Lysimeter 17) and 0.434 µg parent equiv./L (Lysimeter 18)
in March 2000.
Additionally, annual leachate samples were prepared by combining
individual leachates. The maximum concentration based on these annual
samples was observed in the 2nd
year and was 0.349 µg and 0.417 µg
parent equiv./L (see Table A7_2_3_2_02-3). The mean of the three years
and two lysimeters was calculated to be 0.281 µg parent equiv./L.
TI-435 was not detected in any individual leachates. MNG and NTG
amounted to maximum 0.116 µg/L (Lysimeter 18) and 0.074 µg/L
(Lysimeter 18), respectively. The distribution of the radioactivity in the
annual leachates is provided in Table A7_2_3_2_02-4.
Beside MNG and NTG, six unknown degradation products were seen.
The maximum concentrations of MNG and NTG occurred in the 3rd
year
and were, calculated as mean of the two lysimeters, 0.066 µg/L (MNG)
and 0.031 µg/L (NTG).
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 7
Section A7.2.3.2/02 Annex Point IIIA XII.1.3
Mobility in at least three soil types and where relevant
mobility of metabolites and degradation products
4.3 Soil The distribution of the applied radioactivity in the soil profile was
determined at the end of the study. The major part of the radioactivity
was determined in the top 10 cm and amounted to 30.4% of the applied
amount. In the next layer (10-20 cm), 7.3% of the applied radioactivity
were determined. Only negligible amounts were measured in deeper
layers (Table A7_2_3_2_02-5).
The characterisation of the radioactivity in the three top layers is
provided in Table A7_2_3_2_02-6.
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
The German BBA guideline for lysimeter studies is an internationally
accepted guideline. No relevant deviations from the guideline occurred.
5.2 Results and
discussion
5.3 Conclusion On the basis of these findings, TI-435 and its degradation products are
not expected to occur in relevant amounts in groundwater. Degradation
in soil continuous. No accumulation in plants is to be expected.
5.3.1 Reliability 1
5.3.2 Deficiencies None
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 7
Section A7.2.3.2/02 Annex Point IIIA XII.1.3
Mobility in at least three soil types and where relevant
mobility of metabolites and degradation products
Evaluation by Competent Authorities
EVALUATION BY RAPPORTEUR MEMBER STATE (*)
Date 2004/11/19
Materials and Methods The applicant’s version is adopted.
Results and discussion The applicant’s version is adopted.
Conclusion TI-435 and its degradation products are not expected to occur in relevant amounts
in groundwater. No accumulation in plants is to be expected.
Reliability 1
Acceptability acceptable
Remarks
COMMENTS FROM ...
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 4
Section A7.3.1 Annex Point IIIA VII.5
Phototransformation in air (estimation method)
1 REFERENCE
Official
use only
1.1 Reference Hellpointner, E. (1998): Calculation of the chemical lifetime of TI-435
in the troposphere.
Bayer AG, 51368 Leverkusen, Germany; unpublished report no. MR-
705/98
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study No
No guideline specified; an estimation was made according to:
Atkinson, R. (1985): Kinetics and mechanisms of the gas-phase:
Reactions of the hydroxyl radical with organic compounds under
atmospheric conditions. Chem. Rev., 86, 69-201.
Atkinson, R. (1988): Estimation of gas-phase hydroxyl radical rate
constants for organic chemicals. Environ. Toxicol. Chem., 7, 435-442.
X
2.2 GLP No (not relevant)
2.3 Deviations Not relevant
3 MATERIALS AND METHODS
3.1 Substance TI-435
3.2 Model calculation The computer program AOPWIN version 1.87 (8/98) was used. X
4 RESULTS
4.1 Photochemical
reactions
Based on the molecular structure of TI-435, mainly reactions with
photochemically produced hydroxyl radicals are expected to determine
the degradation rate and chemical lifetime of TI-435 in the air.
According to ATKINSON, the total reactivity is divided in 4 single
contributions of which reaction with nitrogen, hydrogen abstractions and
addition of hydrogen to the aromatic ring are relevant for TI-435.
4.2 Half-life in air Based on this overall OH rate constant of 136.97 x 10-12
cm3/molecule
sec., a half-life of 1 hour for TI-435 in air is assumed. This corresponds
to a chemical lifetime of 1.4 hours using a 12-hour day which is regarded
as the global 12-hour day time concentration (excluding the night).
This estimation does not consider any contribution of an attack by other
radicals (i.e. by nitrate radicals). Furthermore, it should be taken into
account that the OH radical concentration in the night decreases to zero.
A more conservative assessment of the overall OH radical rate constant
(e.g. not considering the addition of OH radicals to the aromatic ring)
would result in a maximum chemical lifetime of 1.5 hours in air.
X
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 4
Section A7.3.1 Annex Point IIIA VII.5
Phototransformation in air (estimation method)
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
The chemical lifetime of TI-435 in the troposphere was calculated using
the computer program AOPWIN version 1.87 (8/98).
5.2 Results and
discussion
A half-life of 1 hour for TI-435 in air is assumed corresponding to a
chemical lifetime of 1.4 hours using a 12-hour day which is regarded as
the global 12-hour day time concentration (excluding the night).
X
5.3 Conclusion Based on the relatively short chemical lifetime of TI-435, accumulation
in the air is not to be expected.
X
5.3.1 Reliability 1
5.3.2 Deficiencies No
Evaluation by Competent Authorities
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2006-05-19
Guideline and Quality
Assurance
Applicant’s version is acceptable.
Comment:
The reference Atkinson, R. (1985) is published in Chem. Rev. volume 85 and not
in volume 86.
Materials and Methods In general, applicant’s version is acceptable.
Comments:
At first, applicant used the following model input parameter for the estimation of
the phototransformation of the a.s. in the air (see Hellpointer, 1998):
12-hours-day with a OH radical concentration of 1.5x106 radicals cm
-3 (= global
12-hours-day-time concentration excluding the night).
However, these input parameters are not in agreement with the input parameters
fixed in the EU TGD on Risk Assessment (2003), Part II, Chapter 2.3.6.3:
24-hours-day with a OH radical concentration of 0.5x106 radicals cm
-3 (=global
24-hours mean concentration).
The applicant was requested by the C.A. to submit a further estimation of the
phototransformation in air using the EU standard input parameters. This second
estimation is available under Doc. IV-A, Section No. 7.3.1. In this estimation
the revised version 1.91 of the software programme AOPWIN was applied.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 4
Section A7.3.1 Annex Point IIIA VII.5
Phototransformation in air (estimation method)
Results and discussion In general, applicant’s version is acceptable.
The chemical lifetime was introduced by the applicant. The definition of the
chemical lifetime is as follows:
2ln
life_halflifetime_chemical
Comments:
The applicant’s conservative assessment of the chemical lifetime of the a.s.
resulting in a chemical lifetime of 1.5 hours is not transparently documented.
The overall OH rate constant consists of the contributions “hydrogen
abstraction”, “reaction rates with nitrogen, sulfur and –OH” and “OH addition
to aromatic rings”. In the original study, p.3, “results” as well as in the study
summary, item 4.2, “half-life in air” the applicant stated that for the
conservative assessment the contribution of the assumed “OH addition to
aromatic rings” was not taken into account (marked with ** in appendix 4 of
the original study). In contrast, in the original study, p. 3, “summary” the
applicant stated that the conservative assessment is solely based on the
contribution of OH radical reaction (= “reaction rates with nitrogen, sulfur
and –OH”).
Calculations of C.A. show
- a chemical lifetime of 1.5 hours using the contribution of the OH radical
reaction (= not taken into account the assumed “OH addition to aromatic
rings”and the “hydrogen abstraction”) and
- a chemical lifetime of 1.4 hours using the contribution of the “hydrogen
abstraction” and the “reaction rates with nitrogen, sulfur and –OH” (= not
taken into account the assumed “OH addition to aromatic rings”).
The evaluated study summary comprises only the results of the primarily
submitted original study. Results of the second original study submitted later
in the dossier evaluation process are only considered by the C.A. in the
conclusion (see below) and in Doc. II-A, Environmental Effect Assessment.
As the results of both original studies do not affect the overall conclusion for
the behaviour of the a.s. in air a revised version of the study summary
(including the results of the later handed out original study) was not requested
by C.A.
Conclusion The halflife of the a.s. in the troposphere was calculated using the software
programme AOPWIN. A halflife of 0.94 hours for the a.s. in air is estimated
corresponding to a chemical lifetime of 1.4 hours using a 12-hours-day with a OH
radical concentration of 1.5x106 radicals cm
-3 which is regarded as the global 12-
hours-day-time concentration (excluding the night). A halflife of 2.81 hours for
the a.s. in air is estimated corresponding to a chemical lifetime of 4.1 hours using a
24-hours-day with a OH radical concentration of 0.5x106 radicals cm
-3 which is
regarded as the global 24-hours-mean concentration.
Based on these results, an accumulation of the a.s. in the air is not to be expected.
Reliability 1
Acceptability The two original studies (Doc. IV-A, Section No. 7.3.1) as well as the study
summary (Doc. III-A, Section No. 7.3.1) are acceptable, although there are some
minor deficiencies in the study summary.
Remarks
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 4
Section A7.3.1 Annex Point IIIA VII.5
Phototransformation in air (estimation method)
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 5
Section A7.4.1.1 Annex Point IIA7.1
Acute toxicity to fish
1 REFERENCE
Officialuse only
1.1 Reference (1998):
1.2 Data protection Yes
1.2.1 Data owner
1.2.2 Companies with letter of access
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes OECD No. 203 (1992) in compliance with the Directive 92/69/EEC C.1
2.2 GLP Yes
2.3 Deviations No
3 MATERIALS AND METHODS
3.1 Test material
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
3.1.4 Composition of Product
Not applicable
3.1.5 Further relevant properties
3.1.6 Method of analysis
3.2 Preparation of TS solution for poorly soluble or volatile test substances
3.3 Reference substance
No
3.4 Testing procedure
3.4.1 Dilution water
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 5
Section A7.4.1.1 Annex Point IIA7.1
Acute toxicity to fish
3.4.2 Test organisms
3.4.3 Test system
3.4.4 Test conditions
3.4.5 Duration of the test 96 h
3.4.6 Test parameter Mortality
3.4.7 Sampling
3.4.8 Monitoring of TS concentration
3.4.9 Statistics
4 RESULTS
4.1 Limit Test
4.1.1 Concentration
4.1.2 Number/ percentage of animals showing adverse effects
4.1.3 Nature of adverse effects
4.2 Results test substance
4.2.1 Initial concentrations of test substance
X
4.2.2 Actual concentrations of test substance
4.2.3 Effect data (Mortality)
4.2.4 Concentration / response curve
4.2.5 Other effects
4.3 Results of controls
4.3.1 Number/ percentage of animals showing adverse effects
4.3.2 Nature of adverse effects
4.4 Test with reference substance
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 5
Section A7.4.1.1 Annex Point IIA7.1
Acute toxicity to fish
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
The acute toxicity of TI-435 Technical to fish (rainbow trout) was determined in a static limit test according to OECD No. 203 (1992) in compliance with the Directive 92/69/EEC C.1. The nominal test concentration was 100 mg a.s./L.
5.2 Results and discussion
None of the seven test animals died during exposure for 96 h and none of the control animals died within this time.
5.2.1 LC0 100 mg/L
5.2.2 LC50 > 100 mg/L
5.2.3 LC100 > 100 mg/L
5.3 Conclusion The validity criteria can be considered as fulfilled.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2004-10-04
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 5
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 5
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 5
Section A7.4.1.2/01 Annex Point IIA7.2
Acute toxicity to invertebrates Daphnia magna
1 REFERENCE
Officialuse only
1.1 Reference (2000b):
1.2 Data protection Yes
1.2.1 Data owner
1.2.2 Companies with letter of access
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes OECD No. 202 (1984) and Directive 92/69/EEC C.2
2.2 GLP Yes
2.3 Deviations No (to EC Directive)
3 MATERIALS AND METHODS
3.1 Test material
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
3.1.4 Composition of Product
3.1.5 Further relevant properties
3.1.6 Method of analysis
3.2 Preparation of TS solution for poorly soluble or volatile test substances
3.3 Reference substance
3.4 Testing procedure
3.4.1 Dilution water
3.4.2 Test organisms
3.4.3 Test system
3.4.4 Test conditions
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 5
Section A7.4.1.2/01 Annex Point IIA7.2
Acute toxicity to invertebrates Daphnia magna
3.4.5 Duration of the test 48 h
3.4.6 Test parameter Mortality and immobility
3.4.7 Sampling Sampling intervals: 0 and 48 h
3.4.8 Monitoring of TS concentration
3.4.9 Statistics
4 RESULTS
4.1 Limit Test Not performed
4.2 Results test substance
4.2.1 Initial concentrations of test substance
Nominal test concentrations: 0, 7.5, 15, 30, 60 and 120 mg a.s./L
4.2.2 Actual concentrations of test substance
4.2.3 Effect data (Immobilisation)
4.2.4 Concentration / response curve
4.2.5 Other effects
4.3 Results of controls
4.4 Test with reference substance
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
The acute toxicity of TI-435 Technical to invertebrates (Daphnia magna) was determined in a static test according to OECD No. 202 (1984) in compliance with the Directive 92/69/EEC C.2. Duplicate test solutions with the following nominal test concentrations were used: 0, 7.5, 15, 30, 60 and 120 mg a.s./L.
5.2 Results and discussion
None of the daphnids in the test and control solutions showed any adverse effects.
5.2.1 EC0 120 mg a.s./L X
5.2.2 EC50 > 120 mg a.s./L X
5.2.3 EC100 > 120 mg a.s./L X
5.3 Conclusion The validity criteria can be considered as fulfilled.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 5
Section A7.4.1.2/01 Annex Point IIA7.2
Acute toxicity to invertebrates Daphnia magna
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 5
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 5
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 5
Section A7.4.1.2/02 Annex Point IIA7.2
Acute toxicity to invertebrates Daphnia magna
1 REFERENCE
Officialuse only
1.1 Reference (1997):
1.2 Data protection Yes
1.2.1 Data owner
1.2.2 Companies with letter of access
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes OECD No. 202 (1984) and Directive 92/69/EEC C.2
2.2 GLP Yes
2.3 Deviations No
3 MATERIALS AND METHODS
3.1 Test material
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
3.1.4 Composition of Product
Not applicable
3.1.5 Further relevant properties
3.1.6 Method of analysis
3.2 Preparation of TS solution for poorly soluble or volatile test substances
3.3 Reference substance
3.4 Testing procedure
3.4.1 Dilution water
3.4.2 Test organisms
3.4.3 Test system
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 5
Section A7.4.1.2/02 Annex Point IIA7.2
Acute toxicity to invertebrates Daphnia magna
3.4.4 Test conditions
3.4.5 Duration of the test 48 hours
3.4.6 Test parameter Immobility (determined after 24 and 48 hours)
3.4.7 Sampling
3.4.8 Monitoring of TS concentration
3.4.9 Statistics
4 RESULTS
4.1 Limit Test
4.2 Results test substance
4.2.1 Initial concentrations of test substance
Nominal test concentrations: 0, 1.0, 3.2, 10, 32, 100 and 270 mg/L
4.2.2 Actual concentrations of test substance
4.2.3 Effect data (Immobilisation)
4.2.4 Concentration / response curve
4.2.5 Other effects
4.3 Results of controls
4.4 Test with reference substance
4.4.1 Concentrations
4.4.2 Results
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
The acute immobilisation toxicity of TI-435 Technical to invertebrates (Daphnia magna STRAUS) was determined in a static test according to OECD No. 202 (1984) and Directive 92/69/EEC C.2. The following nominal test concentrations were used: 0, 1.0, 3.2, 10, 32, 100 and 270 mg/L. No deviations to the test guidelines occurred.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 5
Section A7.4.1.2/02 Annex Point IIA7.2
Acute toxicity to invertebrates Daphnia magna
5.2 Results and discussion
After 24 hours of exposure to TI-435 Technical, no immobility of daphnids was observed up to the highest test concentration. However, at the end of the test (48 hours), immobile daphnids were observed at test concentrations ≥ 10 mg/L.
5.2.1 EC0 (48 hours) 3.2 mg/L
5.2.2 EC50 (48 hours) 40 mg/L (confidence interval: 31 – 51 mg/L) X
5.2.3 EC100 (48 hours) > 270 mg/L
5.3 Conclusion The validity criteria can be considered as fulfilled.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 5
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 5
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 6
Section A7.4.1.3 Annex Point IIA7.3
Growth inhibition test on algae
1 REFERENCE
Officialuse only
1.1 Reference (2000):
1.2 Data protection Yes
1.2.1 Data owner
1.2.2 Companies with letter of access
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
2.2 GLP Yes
2.3 Deviations
X
3 MATERIALS AND METHODS
3.1 Test material
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
3.1.4 Composition of Product
3.1.5 Further relevant properties
3.1.6 Method of analysis
3.2 Preparation of TS solution for poorly soluble or volatile test substances
3.3 Reference substance
3.4 Testing procedure
3.4.1 Culture medium
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 6
Section A7.4.1.3 Annex Point IIA7.3
Growth inhibition test on algae
3.4.2 Test organisms
3.4.3 Test system
3.4.4 Test conditions
3.4.5 Duration of the test 120 h
3.4.6 Test parameter Cell density, biomass (area under the growth curve) and growth rate
3.4.7 Sampling
3.4.8 Monitoring of TS concentration
3.4.9 Statistics
4 RESULTS
4.1 Limit Test
4.2 Results test substance
4.2.1 Initial concentrations of test substance
Nominal concentrations: 0, 3.8, 7.5, 15, 30, 60 and 120 mg a.s./L
4.2.2 Actual concentrations of test substance
4.2.3 Growth curves
4.2.4 Concentration / response curve
4.2.5 Cell concentration data
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 6
X
4.3 Results of controls
4.4 Test with reference substance
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
The toxicity of TI-435 towards the freshwater alga Selenastrum capricornutum was tested according to FIFRA Subdivision J Series 123-2 which is in compliance with EC Directive 92/69/EEC, C.3. A static test over 120 hours with nominal concentrations of 0, 3.8, 7.5, 15, 30, 60 and 120 mg a.s./L was performed.
5.2 Results and discussion
The EC50-value for cell density was calculated to be 75 mg a.s./L after 72 h. The values for biomass and growth are given below.
X
5.2.1 NOErC 15 mg a.s./L (72 h) X
5.2.2 ErC50 > 120 mg a.s./L (72 h) X
5.2.3 EbC50 70 mg a.s./L (72 h) X
5.3 Conclusion Validity criteria can be considered as fulfilled.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 6
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
X
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 6
6 APPLICANT'S SUMMARY AND CONCLUSION
6.1 Materials and methods
The toxicity of TI-435 towards the freshwater alga Selenastrum capricornutum was tested according to FIFRA Subdivision J Series 123-2 which is in compliance with EC Directive 92/69/EEC, C.3. A static test over 120 hours with nominal concentrations of 0, 3.8, 7.5, 15, 30, 60 and 120 mg a.s./L was performed.
6.2 Results and discussion
The EC50-value for cell density was calculated to be 75 mg a.s./L after 72 h, 52 mg/L after 96 h and 57 mg/L after 120 h. The values for biomass and growth are given below.
X
6.2.1 NOErC 15 mg a.s./L (72 h, 96 h), 30 mg/L (120 h) X
6.2.2 ErC50 > 120 mg a.s./L (72 h, 96 h, 120 h) X
6.2.3 EbC50 70 mg a.s./L (72 h), 55 mg/L (96 h), 56 mg/L (120 h) X
6.3 Conclusion Validity criteria can be considered as fulfilled.
6.3.1 Reliability 1
6.3.2 Deficiencies No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 6
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 1 of 5
Section A7.4.1.4 Annex Point IIA7.4
Inhibition to microbial activity (aquatic)
1 REFERENCE Official
use only
1.1 Reference Bealing, D.J. and Watson, S. (2000): TI-435 technical: Determination of
inhibition of respiration of activated sludge.
Covance Laboratories Ltd, Harrogate, North Yorkshire HG3 1PY,
England; unpublished report 586/210-D2145
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
Directive 88/302/EEC, Part C, identical to OECD 209
2.2 GLP Yes
2.3 Deviations No
3 MATERIALS AND METHODS
3.1 Test material As given in section 2
3.1.1 Lot/Batch number 50071820 (see Certificate of Analysis in Appendix 1 in the report)
3.1.2 Specification As given in section 2
3.1.3 Purity
3.1.4 Composition of
Product
Not applicable
3.1.5 Further relevant
properties
Water solubility (20°C): 327 mg/L
(see Morrissey & Kramer, 2000a)
3.1.6 Method of analysis No analysis of test substance performed
3.2 Preparation of TS
solution for poorly
soluble or volatile
test substances
See Table A7_4_1_4-1
3.3 Reference
substance
Yes
3,5-dichlorophenol
3.3.1 Method of analysis
for reference
substance
No analysis of reference substance performed
3.4 Testing procedure
3.4.1 Culture medium Synthetic sewage concentrate (according to OECD 209, 100-fold)
3.4.2 Inoculum /
test organism
See Table A7_4_1_4-2
3.4.3 Test system See table A7_4_1_4-3
3.4.4 Test conditions See table A7_4_1_4-4
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 2 of 5
Section A7.4.1.4 Annex Point IIA7.4
Inhibition to microbial activity (aquatic)
3.4.5 Duration of the test 3 hours
3.4.6 Test parameter Respiration inhibition
3.4.7 Analytical
parameter
Oxygen measurement
3.4.8 Sampling at the end of the study after 3 hours
3.4.9 Monitoring of TS
concentration
no
3.4.10 Controls 4 controls without test substance
3.4.11 Statistics
4 RESULTS
4.1 Preliminary test
4.2 Results test
substance
4.2.1 Concentrations of
test substance
1.0, 10, 100, and 1000 mg/L
4.2.2 Concentration/
response curve
4.2.3 Effect data The treatment with TI-435 Technical did not result in significant
inhibition at any of the concentrations (no reduction of the respiration
rate compared to the controls). Accordingly, the EC50 for TI-435
Technical is > 1000 mg/L.
4.3 Results of controls
4.4 Test with
reference
substance
4.4.1 Concentrations
4.4.2 Results
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
TI-435 Technical was tested for its inhibition to microbial activity
according to Directive 88/302/EEC, Part C (identical to OECD 209).
Activated sludge was exposed to 1.0, 10, 100, and 1000 mg a.s./L and
the respiration rate measured in comparison to control solutions and to
the reference substance 3,5-dichlorophenol.
5.2 Results and
discussion
In a 3-hour range-finding test, TI-435 Technical did not inhibit the
respiration of activate sludge at concentrations up to and including
1000 mg/L.
5.2.1 EC50 > 1000 mg/L (nominal)
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 3 of 5
Section A7.4.1.4 Annex Point IIA7.4
Inhibition to microbial activity (aquatic)
5.3 Conclusion The control respiration rates used to obtain the mean lay within 15% of
each other. The EC50 of the reference inhibitor, 3,5-dichlorophenol, lay
between 5 and 30 mg/L, indicating that the sludge used in this study was
neither unusually sensitive nor abnormally robust. Thus, the validity
criteria can be considered as fulfilled.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Evaluation by Competent Authorities
Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2005-08-17
Materials and Methods applicants version is acceptable
Results and discussion applicant's version is adopted
Conclusion applicant's version is adopted
Reliability 1
Acceptability acceptable
Remarks none
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 4 of 5
Table A7_4_1_4-1: Preparation of TS solution for poorly soluble or volatile test substances
Criteria Details
Dispersion Yes
Vehicle No
Procedure Due to insufficient solubility, the required exposure
concentrations were achieved by making direct
additions of the test substance to the test vessels
which contained reverse-osmosis water and synthetic
sewage. The test substance was homogeneously
dispersed by ultrasonication before adding the
inoculum.
Table A7_4_1_4-2: Inoculum / Test organism
Criteria Details
Nature Activated sludge
Source Sewage treatment plant treating predominantly
domestic sewage
Sampling site Burley Menston sewage treatment works (Yorkshire
Water)
Laboratory culture No
Preparation of inoculum for exposure Dilution to a nominal solids content of 4 g/L, pH
adaptation from 5.91 to 6.51 (with 1 M NaOH)
Pretreatment Aeration and feeding overnight with synthetic sewage
on two occasions
Initial cell concentration 4 g suspended solids/L
Table A7_4_1_4-3: Test system
Criteria Details
Culturing apparatus Culture flasks
Number of culture flasks/concentration 2
Aeration device Compressed air was delivered to each test vessel by a
Pasteur pipette.
Measuring equipment Dissolved oxygen (DO) was measured with a DO
probe.
Test performed in closed vessels due to significant
volatility of TS
No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 5 of 5
Table A7_4_1_4-4: Test conditions
Criteria Details
Test temperature 20.9 to 21.6°C
pH of diluted inoculum 6.51 after adjustment
Aeration of dilution water No
Suspended solids concentration 4 g/L
Sumitomo Chemical Takeda Agro Co., Ltd. Clothianidin August 2006
Section A7.4.2 Annex Point IIA7.5
Bioconcentration
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ X ] Limited exposure [ ] Other justification [ ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.4.3.1 Annex Point AIII XIII.2.1
Prolonged toxicity to an appropriate species of fish
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ X ] Limited exposure [ ] Other justification [ ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 6
Section A7.4.3.2 Annex Point IIIA XIII 2.2
Effects on reproduction and growth rate on an appropriate species of fish
1 REFERENCE
Officialuse only
1.1 Reference (2000):
1.2 Data protection Yes
1.2.1 Data owner
1.2.2 Companies with letter of access
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes US EPA OPPTS draft guideline No. 850.1400 (1996), US EPA-FIFRA Subdivision E, Series 72-4 (1982) and ASTM Standard E1241-88 (1988)
2.2 GLP Yes
2.3 Deviations No
3 MATERIALS AND METHODS
3.1 Test material
3.1.1 Lot/Batch number
3.1.2 Specification 2
3.1.3 Purity
3.1.4 Further relevant properties
3.1.5 Method of analysis
3.2 Preparation of TS solution for poorly soluble or volatile test substances
3.3 Reference substance
3.4 Testing procedure
3.4.1 Dilution water
3.4.2 Test organisms
3.4.3 Handling of embryos and larvae (OECD 210/212)
3.4.4 Test system
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 6
Section A7.4.3.2 Annex Point IIIA XIII 2.2
Effects on reproduction and growth rate on an appropriate species of fish
3.4.5 Test conditions
3.4.6 Duration of the test 33 days, including a 5-day embryo hatching period and a 28-day post hatch juvenile growth period.
3.4.7 Test substance concentrations
Nominal test concentrations: 1.3, 2.5, 5.0, 10 and 20 mg a.s./L
3.4.8 Preparation of test solutions
3.4.9 Controls X
3.4.10 Test parameters
3.4.11 Examination/ Sampling
3.4.12 Monitoring of TS concentration
3.4.13 Monitoring of other parameters
3.4.14 Statistics
4 RESULTS
4.1 Range finding test
4.2 Results test substance
4.3 Hatching
4.3.1 Hatching time
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 6
Section A7.4.3.2 Annex Point IIIA XIII 2.2
Effects on reproduction and growth rate on an appropriate species of fish
4.3.2 Hatching success
4.4 Mortality
4.5 Growth
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
The early life-stage toxicity of TI-435 Technical to fish (fathead minnow) was tested according to US EPA OPPTS draft guideline No. 850.1400 (1996), US EPA-FIFRA Subdivision E, Series 72-4 (1982) and ASTM Standard E1241-88 (1988). The guidelines are in compliance with OECD 210. Fathead minnows were exposed 28 days post-hatch to nominal concentrations of 0, 1.3, 2.5, 5.0, 10 and 20 mg a.s./L. Hatching, mortality and growth of the fish was observed.
5.2 Results and discussion
Exposure to TI-435 at the concentrations tested showed no statistically significant effects on hatching success, larval survival, total length, wet weight or dry weight as compared to the controls.
5.2.1 NOEC 20 mg a.s./L (nominal)
5.2.2 LOEC > 20 mg a.s./L (nominal)
5.2.3 MATC > 20 mg a.s./L (nominal)
5.3 Conclusion
5.3.1 Reliability 1
5.3.2 Deficiencies No
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Materials and Methods
Results and discussion
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 6
Section A7.4.3.2 Annex Point IIIA XIII 2.2
Effects on reproduction and growth rate on an appropriate species of fish
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 6
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 6
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
Section A7.4.3.3.1 Annex Point IIIA XIII.2.3
Bioaccumulation in an appropriate species of fish
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ X ] Limited exposure [ ] Other justification [ ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.4.3.3.2 Annex Point IIIA XIII.2.3
Bioaccumulation in an appropriate invertebrate species
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ ]
Limited exposure [ X ] Other justification [ ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 5
Section A7.4.3.4 Annex Point IIIA XIII 2.4
Effects on reproduction and growth rate with an appropriate invertebrate species
1 REFERENCE
Officialuse only
1.1 Reference (1998):
1.2 Data protection Yes
1.2.1 Data owner
1.2.2 Companies with letter of access
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes OECD No. 211
2.2 GLP Yes
2.3 Deviations None
3 MATERIALS AND METHODS
3.1 Test material
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
3.1.4 Further relevant properties
3.1.5 Method of analysis
3.2 Preparation of TS solution for poorly soluble or volatile test substances
3.3 Reference substance
3.3.1 Reference substance concentrations
3.4 Testing procedure
3.4.1 Dilution water
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 5
Section A7.4.3.4 Annex Point IIIA XIII 2.4
Effects on reproduction and growth rate with an appropriate invertebrate species
3.4.2 Test organisms
3.4.3 Handling of offspring
3.4.4 Test system
3.4.5 Test conditions
3.4.6 Duration of the test 21 d
3.4.7 Test substance concentrations
Nominal test concentrations: 0.041, 0.12, 0.37, 1.1, 3.3, 9.9 and 29.7 mg/L
3.4.8 Preparation of test solutions
3.4.9 Controls
3.4.10 Test parameter
3.4.11 Examination/ sampling
3.4.12 Monitoring of TS concentration
3.4.13 Statistics
4 RESULTS
4.1 Range finding test
4.2 TS concentrations during the test
4.3 Mortality
4.4 Number of young Daphnia
4.5 First appearance of juveniles
4.6 Test of the reference substance
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 5
Section A7.4.3.4 Annex Point IIIA XIII 2.4
Effects on reproduction and growth rate with an appropriate invertebrate species
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
The toxicity of TI-435 Technical to Daphnia magna reproduction was tested according to OECD No. 211 . No deviations to the guideline occurred. Daphnia magna
were exposed in a semi-static test to nominal concentrations of 0.041, 0.12, 0.37, 1.1, 3.3, 9.9 and 29.7 mg/L for 21 days.
5.2 Results and discussion
5.2.1 NOEC (reproduction)
0.12 mg/L (nominal)
5.2.2 LOEC (reproduction)
0.37 mg/L (nominal)
5.2.3 EC50 (reproduction)
5.7 mg/L
5.2.4 NOEC (mortality of parental)
0.37 mg/L (nominal)
5.2.5 LOEC (mortality of parental)
1.1 mg/L (nominal)
5.2.6 EC50 (mortality of parental)
29.7 mg/L (nominal)
5.3 Conclusion Mortality of female Daphnia did not exceed 20% at the end of the test. The mean number of living offspring produced per parent animal surviving at the end of the test was > 60 in the control groups. The validity criteria can be considered as fulfilled
5.3.1 Reliability 1
5.3.2 Deficiencies No
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 5
Section A7.4.3.4 Annex Point IIIA XIII 2.4
Effects on reproduction and growth rate with an appropriate invertebrate species
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 5
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 6
Section A7.4.3.5.1/01 Annex Point IIIA XIII 3.4
Effects on sediment dwelling organisms
1 REFERENCE
Official use only
1.1 Reference (1999):
1.2 Data protection Yes
1.2.1 Data owner
1.2.2 Companies with letter of access
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
Proposal for a BBA guideline "Effects of plant protection products on the development of sediment-dwelling larvae of Chironomus riparius in a water-sediment system." (1995)
2.2 GLP Yes
2.3 Deviations No
3 MATERIALS AND METHODS
3.1 Test material
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
3.1.4 Further relevant properties
3.1.5 Method of analysis
3.2 Reference substance
3.3 Testing procedure
3.3.1 Test water
3.3.2 Test sediment
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 6
Section A7.4.3.5.1/01 Annex Point IIIA XIII 3.4
Effects on sediment dwelling organisms
3.3.3 Test organisms
3.3.4 Test system
3.3.5 Test conditions
3.3.6 Duration of the test 28 days
3.3.7 Test substance concentrations
Nominal concentrations: 0.1, 0.32, 0.56, 1.0, 1.8, 3.2 and 10 µg/L
3.3.8 Preparation of test solutions and application
3.3.9 Controls
3.3.10 Test parameter
3.3.11 Monitoring of TS concentration
3.3.12 Monitoring of other parameters
3.3.13 Statistics The EC-values were calculated by Probit analysis. The χ2-test was performed to establish different sensitivities of sexes (p=0.05).
4 RESULTS
4.1 TS concentrations during the test
4.2 Physical and chemical parameters
4.3 Emergence rate
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 6
Section A7.4.3.5.1/01 Annex Point IIIA XIII 3.4
Effects on sediment dwelling organisms
4.4 Development rate
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
.
5.2 Results and discussion
5.2.1 EC15/NOEC (emergence rate)
0.00072 mg a.s./L
5.2.2 EC5 (emergence rate)
0.00057 mg a.s./L
5.2.3 EC10 (emergence rate)
0.00065 mg a.s./L
5.2.4 EC50 (emergence rate)
0.00106 mg a.s./L
5.3 Conclusion Guideline requirements were fulfilled since 90% of the inserted larvae matured to adults in the controls.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 6
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 6
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 6
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 6
Section A7.4.3.5.1/02 Annex Point IIIA XIII 3.4
Effects on sediment dwelling organisms
1 REFERENCE
Officialuse only
1.1 Reference (1998):
1.2 Data protection Yes
1.2.1 Data owner
1.2.2 Companies with letter of access
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
2.2 GLP Yes
2.3 Deviations No
3 MATERIALS AND METHODS
3.1 Test material
3.1.1 Lot/Batch number
3.1.2 Specification Not applicable
3.1.3 Purity
3.1.4 Appearance
3.1.5 Method of analysis
3.2 Reference substance
3.3 Testing procedure
3.3.1 Test water
3.3.2 Test sediment
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 6
Section A7.4.3.5.1/02 Annex Point IIIA XIII 3.4
Effects on sediment dwelling organisms
3.3.3 Test organisms
3.3.4 Test system
3.3.5 Test conditions
3.3.6 Duration of the test 28 days
3.3.7 Test substance concentrations
A single nominal concentration of 0.1 mg /L was tested (limit test).
3.3.8 Preparation of test solutions and application
3.3.9 Controls
3.3.10 Test parameter
3.3.11 Monitoring of TS concentration
3.3.12 Monitoring of other parameters
3.3.13 Statistics
4 RESULTS
4.1 TS concentrations during the test
4.2 Physical and chemical parameters
The physical and chemical parameters were similar between the treatment and the control throughout the study.
4.3 Emergence rate
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 6
Section A7.4.3.5.1/02 Annex Point IIIA XIII 3.4
Effects on sediment dwelling organisms
4.4 Development rate
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
In a static test, first instars larvae were exposed to a single nominal concentration of 0.1 mg /L for 28 days and emergence and development of midges was observed.
5.2 Results and discussion
5.2.1 EC15/NOEC (emergence rate and development rate)
≥ 0.1 mg /L
5.3 Conclusion Guideline requirements were fulfilled since 100% of the inserted larvae matured to adults in the controls.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 6
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2004-10-11
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 6
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 6
Sumitomo Chemical TI-435 April 2010
Harlan Laboratories project no. 852224 Page 1 of 8
Section A7.4.3.5.1/03 Annex Point IIIA XIII 3.4
Effects on sediment dwelling organisms
1 REFERENCE
Official use only
1.1 Reference (2001):
1.2 Data protection Yes
1.2.1 Data owner
1.2.2 Companies with letter of access
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study
2.2 GLP Yes
2.3 Deviations
3 MATERIALS AND METHODS
3.1 Test material TI-435
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
3.1.4 Further relevant properties
3.1.5 Method of analysis
Sumitomo Chemical TI-435 April 2010
Harlan Laboratories project no. 852224 Page 2 of 8
Section A7.4.3.5.1/03 Annex Point IIIA XIII 3.4
Effects on sediment dwelling organisms
3.2 Reference substance
3.3 Testing procedure
3.3.1 Test water
3.3.2 Test sediment
3.3.3 Test organisms
3.3.4 Test system
3.3.5 Test conditions
3.3.6 Duration of the test 48 hours
3.3.7 Test substance concentrations
TI-435 technical: 0.007, 0.013, 0.025, 0.050 and 0.10 mg/L
3.3.8 Preparation of test solutions and application
3.3.9 Controls
3.3.10 Test parameter
3.3.11 Monitoring of TS concentration
3.3.12 Monitoring of other parameters
3.3.13 Statistics
Sumitomo Chemical TI-435 April 2010
Harlan Laboratories project no. 852224 Page 3 of 8
Section A7.4.3.5.1/03 Annex Point IIIA XIII 3.4
Effects on sediment dwelling organisms
4 RESULTS
4.1 TS concentrations during the test
4.2 Physical and chemical parameters
4.3 Immobilisation
Sumitomo Chemical TI-435 April 2010
Harlan Laboratories project no. 852224 Page 4 of 8
Section A7.4.3.5.1/03 Annex Point IIIA XIII 3.4
Effects on sediment dwelling organisms
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
The acute toxicity of TI-435 to larvae of Chironomus riparius was
determined in 48-hour static toxicity tests at 20 ± 2°C.
After 24
and 48 hours, the numbers of immobilised Chironomus riparius were recorded.
5.2 Results and discussion
5.2.1 48-hour EC50 (immobilisation)
TI-435 : 0.029 mg/L
5.3 Conclusion
5.3.1 Reliability 1
5.3.2 Deficiencies No
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ...
Date Give date of comments submitted
Sumitomo Chemical TI-435 April 2010
Harlan Laboratories project no. 852224 Page 5 of 8
Section A7.4.3.5.1/03 Annex Point IIIA XIII 3.4
Effects on sediment dwelling organisms
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical TI-435 April 2010
Harlan Laboratories project no. 852224 Page 7 of 8
Sumitomo Chemical TI-435 April 2010
Harlan Laboratories project no. 852224 Page 8 of 8
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 12
Section A7.4.3.6 Annex Point IIIA XIII.2
Mesocosm study
1 REFERENCE
Officialuse only
1.1 Reference (2001):
1.2 Data protection Yes
1.2.1 Data owner
1.2.2 Companies with letter of access
None
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes SETAC guidance document on testing procedures for pesticides in freshwater mesocosms (1991) OECD draft guidance document: Freshwater lentic field tests (1996)
2.2 GLP Yes
2.3 Deviations No
3 MATERIALS AND METHODS
3.1 Test material TI-435
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
3.1.4 Appearance
3.1.5 Method of analysis
3.2 Reference substance
No
3.3 Testing procedure
3.3.1 Test sediment
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 12
Section A7.4.3.6 Annex Point IIIA XIII.2
Mesocosm study
3.3.2 Test water
3.3.3 Test organisms
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 12
Section A7.4.3.6 Annex Point IIIA XIII.2
Mesocosm study
3.3.4 Test system
3.3.5 Establishment of the test conditions
3.3.6 Application date
3.3.7 Test substance concentrations
0.10, 0.32, 1.0, 3.2, and 10 µg/L TI-435
3.3.8 Preparation of test solutions and application
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 12
Section A7.4.3.6 Annex Point IIIA XIII.2
Mesocosm study
3.3.9 Controls
3.3.10 Duration of the test 14 weeks
3.3.11 Test parameter
3.3.12 Sampling
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 12
Section A7.4.3.6 Annex Point IIIA XIII.2
Mesocosm study
3.3.13 Monitoring of TS concentration
3.3.14 Statistics
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 12
Section A7.4.3.6 Annex Point IIIA XIII.2
Mesocosm study
4 RESULTS
4.1 TS concentrations during the test
4.2 Physical and chemical parameters
4.3 Effects on aquatic organisms
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 7 of 12
Section A7.4.3.6 Annex Point IIIA XIII.2
Mesocosm study
4.4 Effects on freshwater insects
X
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 8 of 12
Section A7.4.3.6 Annex Point IIIA XIII.2
Mesocosm study
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
Toxic effects of TI-435 on a freshwater ecosystem was tested in accordance with the relevant guidelines at the time the study was performed,
No deviations from the guidelines occurred.
5.2 Results and discussion
5.2.1 EAC (Ecologically Acceptable Concentration)
10 µg/L TI-435
5.3 Conclusion The quality and validity criteria were fulfilled. The used
mesocosm ponds modelled a realistic freshwater ecosystem with sufficient representation from all different trophic levels. The study focussed on the toxicity to aquatic insects, because earlier studies indicated that this might be of concern. Clear concentration-effect relationships were obtained in case of toxic effects. Based on these relationships and univariate statistics NOEC’s as well as an EAC based on recovery data were obtained. The study period was sufficient to demonstrate complete recovery of the affected populations.
5.3.1 Reliability 1 X
5.3.2 Deficiencies No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 9 of 12
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ...
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 10 of 12
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 11 of 12
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 12 of 12
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 1 of 6
Section A7.5.1.1 Annex Point IIA7.4
Inhibition to microbial activity (terrestrial)
1 REFERENCE
Official
use only
1.1 Reference Keirs, D.C. and Caley, C.Y. (1999): The effects of TI-435 50% WDG
on soil microflora.
Inveresk Research, Tranent EH33 2NE, Scotland; unpublished report
no. 17938
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
OECD no. 216 and 217 (drafts of January 1999)
2.2 GLP Yes
2.3 Deviations No
3 MATERIALS AND METHODS
3.1 Test material TI-435 formulated as 50% WDG
3.1.1 Lot/Batch number IW016-046
3.1.2 Specification Not applicable, WDG formulation of TI-435
3.1.3 Purity Not applicable, WDG formulation of TI-435
3.1.4 Composition of
Product
49.3% TI-435 (active substance), 50.7% inerts
3.1.5 Further relevant
properties
None
3.2 Reference
substance
Yes
Dinoseb acetate, purity: 98.1%
3.3 Testing procedure
3.3.1 Soil sample A sandy loam soil (64% sand, 26% silt, 10% clay, pH 6.8, 1.1% Corg)
was used as test soil. It was collected from a grassland field in June
1999, sieved (2 mm) and stored at 4°C until the start of the study (July
1999). Before use, the moisture content and the maximum water holding
capacity (MWHC = 47.6 g water/100 dw soil) was determined and the
soil was adjusted to ca. 40% MWHC. The carbon content of the
metabolically active microbial biomass was determined at the start of
the experiment according to ANDERSON AND DOMSCH (1978)1.
3.3.2 Test system
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 2 of 6
Section A7.5.1.1 Annex Point IIA7.4
Inhibition to microbial activity (terrestrial)
3.3.3 Application of TS The soil was treated at a rate equivalent to 150 g a.s./ha and 5 times this
rate, i.e. 750 g a.s./ha. Assuming a soil depth of 5 cm and a soil density
of 1.5 g/cm3, these rates corresponded to 0.2 mg and 1.0 mg a.s./kg soil.
For further details on application of TS see Table A7_5_1_1-2
3.3.4 Test conditions See Table A7_5_1_1-3
3.3.5 Test parameters and
analytical methods
Soil respiration: After addition of glucose (equivalent to 3.0 g/kg dry
soil), the quantities of carbon dioxide released were measured for at
least 12 hours by means of an infra-red gas analyser.
Nitrogen transformation: After treatment, soil samples in the nitrogen
transformation test were amended with 0.5% (w/w) lucerne meal
(3.5% N, C:N ratio of 11.5:1) to stimulate nitrogen transformation. At
the sampling days, samples of lucerne-amended soil were extracted with
KCl (2 M; 200 mL). Samples of unamended and untreated soil were
either extracted directly or after addition of nitrate to assess nitrification
of unamended soil and the efficiency of nitrate extraction. Extracts and
residues were separated by centrifugation. After filtration, the extracts
were analysed for the total oxidisable nitrogen and nitrite in solution on
an Aquatec 5400 Flow Injection Analyser and Autosampler. Nitrite was
determined by reaction with acidified sulphanilamide to form a diazo
compound and reacted with N-(1-naphthyl)-ethylene-diamine
dihydrochloride to form a purple azo dye compound. Nitrate was
reduced to nitrite (using a cadmium reductor coil) and analysed as
described above. Final nitrate levels were calculated by subtraction of
free nitrite levels formed by reduction of nitrate.
3.3.6 Duration of the test 28 days
3.3.7 Sampling At intervals of 0-3 h, 7, 14 and 28 days post-application, sub-samples
(ca. 50 g dry weight) of the incubated soils were taken for analysis.
3.3.8 Monitoring of TS
concentration
No
3.3.9 Controls Each test (soil respiration and transformation) included a positive
control (3 soil samples treated with Dinoseb acetate) and a solvent
control (3 soil samples treated with distilled-grade water only).
A further soil sample (nitrate control) was neither treated nor amended
with lucerne meal to determine the nitrogen transformation in
unamended soil and the efficiency of extraction of nitrate.
3.3.10 Statistics Results at each sample point were analysed separately using analysis of
variance (ANOVA). Pairwise comparison between each treated group
and the corresponding control group were compared using Dunnett’s
test (Dunnett, 1955 and 19642). The significance level was p<0.05.
4 RESULTS
4.1 Range finding test Not performed
4.2 Microbial biomass At the start of the experiment the microbial biomass was determined to
be 466.2 mg C/kg dw soil
4.3 Results test
substance
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 3 of 6
Section A7.5.1.1 Annex Point IIA7.4
Inhibition to microbial activity (terrestrial)
4.3.1 Soil respiration Mean CO2 evolution decreased between day 0 and day 7 and between
day 14 and day 28 in all samples. Mean respiration rates were
comparable between the solvent controls and the two treatments on
day 0 and day 7 and differed only by about 3% at the low dose and 1.5%
at the high dose. On day 14, a significant effect was determined at the
low dose (6% deviation to the control). However, no significant effects
were seen at the higher dose on this sampling date. Moreover, no effects
were seen in both low and high dose at the end of the study after
28 days.
Mean respiration rate
[mL CO2/kg dry soil equiv. and hour]
Sampling Control 150 g a.s./ha 750 g a.s./ha
0-3 hours 10.91 11.27 11.11
7 days 7.79 8.00 7.91
14 days 7.78 8.27* 8.09
28 days 6.24 6.70 6.68
* significantly different from control (p < 0.05)
In summary, short-term respiration of soil treated with TI-435 50%
WDG at up to 750 g a.s./ha deviated from the solvent controls by less
than 25% at each sampling.
4.3.2 Nitrogen
transformation
Mean nitrate levels were comparable at the beginning (about 6.7 mg
N/kg dry soil) and increased over time in all samples up to
approximately 55 mg N/kg dry soil on day 28. Deviations from the
solvent controls were about 3 - 4% at the low dose and between 4 and
14% at the high dose. No significant effects were determined.
Concentration of nitrate
[mg N/kg dry soil equiv.]
Sampling Control 150 g a.s./ha 750 g a.s./ha
0-3 hours 6.6 6.8 7.5
7 days 22.6 23.5 23.5
14 days 35.1 36.5 37.6
28 days 53.5 55.0 55.4
In summary, nitrogen transformation in soil treated with TI-435 50%
WDG at up to 750 g a.s./ha deviated from the solvent controls by less
than 25% at each sampling.
4.4 Results of controls
4.4.1 Test with reference
substance (positive
control)
Soil respiration: In the soils treated with Dinoseb acetate, the rates of
short-term respiration were between 42.8% and 65.7% lower than the
rates found in the solvent controls, during the 28-day experiment. All
values were statistically significant (p<0.05).
Nitrogen transformation: In the soils treated with Dinoseb acetate, the
nitrate concentrations were significant lower (p<0.05) compared to the
controls (42.5% after 14 days and 32.5% after 28 days).
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 4 of 6
Section A7.5.1.1 Annex Point IIA7.4
Inhibition to microbial activity (terrestrial)
4.4.2 Nitrate control Levels of nitrate in soil which had not been amended with lucerne or
treated with the test substance, increased from 5.2 mg to 23.3 mg N/kg
over the incubation period, demonstrating significant nitrification
activity.
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
The effects of TI-435 50% WDG on respiration and nitrogen
transformation of soil microflora under aerobic conditions was
determined according to OECD 216 and 217. TI-435 50% WDG was
incorporated into a sandy loam soil at treatment rates of 0.2 mg a.s./kg
dw soil (equivalent to the maximum field application rate, i.e. 150 g
a.s./ha) and 1.0 mg a.s./kg dw soil
.
5.2 Results and
discussion
5.3 Conclusion Validity criteria can be considered as fulfilled
Based on these results, TI-435 is no expected to adversely affect the soil
microflora when applied up to 750 g a.s./ha (equivalent to 1.0 mg a.s./kg
dry soil).
5.3.1 Reliability 1
5.3.2 Deficiencies No
Evaluation by Competent Authorities
Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2007-01-05
Materials and Methods applicant’s version is acceptable although testing was performed with a product
other than the biocidal product SPU-01850-I. However, despite the differing
composition of both products, the results obtained here are considered acceptable
to assess the potential adverse effects of the active substance chlothianidin on soil
micro-organisms.
The soil was treated at a rate equivalent to 150 g a.s./ha and 5 times this rate, i.e.
750 g a.s./ha. Assuming a soil depth of 10 cm and a soil density of 1500 kg/m3
dry weight, (as decided on TM III/06) these rates corresponded to 0.1 mg and
0.5 mg a.s./kg dry soil.
Results and discussion applicant's version is adopted.
Conclusion applicant's version is adopted
Reliability 1
Acceptability acceptable
Remarks none
COMMENTS FROM ...
Date Give date of comments submitted
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 5 of 6
Section A7.5.1.1 Annex Point IIA7.4
Inhibition to microbial activity (terrestrial)
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 July 2005
RCC project no. 852224 Page 6 of 6
Table A7_5_1_1-1: Test system
Criteria Details
Culturing apparatus 2.5 L plastic containers
Number of vessels / concentration 3
Amount of soil/culturing apparatus 1.2 kg
Aeration device No
Measuring equipment Infra-red gas analyser (respirometer) to determine the
soil respiration activity
Photometer to determine nitrate and nitrite extracted
from soil
Test performed in closed vessels No, plastic containers were sealed with a snap-top lid
containing holes to maintain aeration
Table A7_5_1_1-2: Application of test substance
Criteria Details
Application procedure Applied in aqueous solution
Carrier Distilled-grade water
Concentration of a.s. in treatment solutions 100 mg a.s./L (5 x maximum field application rate)
20 mg a.s./L (maximum field application rate)
Liquid carrier control Yes
Distilled-grade water
Procedure Soil replicates were treated by evenly dispensing
12.0 mL aliquots of the treatment solutions onto the
soil surface in the test containers. The soil was mixed
thoroughly during and after treatment. Control
samples were treated in the same manner but with
12.0 mL of distilled-grade water only.
Table A7_5_1_1-3: Test conditions
Criteria Details
Organic substrate After treatment, soil samples for the nitrogen
transformation test were amended with ca. 0.5%
(w/w) lucerne meal and thoroughly mixed.
Incubation temperature 20 ± 2°C
Soil moisture Ca. 40% maximum water holding capacity (MWHC),
i.e. 19.0 g water/100 dw soil; The soil moisture
content was controlled at weekly intervals and re-
adjusted to 40% MWHC using distilled-grade water.
Method of soil incubation As bulk; 3 soil samples per concentration/solvent
control/positive control and per test (respiration and
nitrogen transformation), 1 untreated and unamended
soil sample (nitrate control)
Aeration No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.1.2/01 Annex Point IIIA XIII.3.2
Acute toxicity to earthworms or other soil non-target macro-organisms
1 REFERENCE
Officialuse only
1.1 Reference (1998b):
1.2 Data protection Yes 1.2.1 Data owner 1.2.2 Companies with
letter of access
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes OECD No. 207 (1984) and Directive 87/302/EEC, Part C
2.2 GLP Yes
2.3 Deviations
3 METHOD
3.1 Test material
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
3.1.4 Composition of Product
3.1.5 Further relevant properties
3.1.6 Method of analysis
3.2 Reference substance
3.2.1 Method of analysis for reference substance
3.3 Testing procedure
3.3.1 Preparation of the test substance
3.3.2 Application of the test substance
3.3.3 Test organisms
3.3.4 Test system
RCC project no. 852224 Page 1 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.1.2/01 Annex Point IIIA XIII.3.2
Acute toxicity to earthworms or other soil non-target macro-organisms
3.3.5 Test conditions
3.3.6 Test duration 14 days
3.3.7 Test parameter Mortality and body weight
3.3.8 Examination
3.3.9 Monitoring of test substance concentration
3.3.10 Statistics
4 RESULTS
4.1 Filter paper test
4.2 Rangefinder test
4.2.1 Concentration
4.2.2 Proposed LC50
4.3 Definite test
4.3.1 Initial concentrations of test substance
0, 10, 18, 32, 56 and 100 mg/kg dw artificial soil
4.3.2 Effect data (Mortality)
4.3.3 Concentration / effect curve
4.3.4 Other effects
4.4 Results of controls
4.4.1 Mortality
4.4.2 Number/ percentage of earthworms showing adverse effects
4.4.3 Nature of adverse effects
4.5 Test with reference substance
RCC project no. 852224 Page 2 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.1.2/01 Annex Point IIIA XIII.3.2
Acute toxicity to earthworms or other soil non-target macro-organisms
4.5.1 Concentrations
4.5.2 Results
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
The acute toxicity of TI-435 technical to earthworms was tested according to OECD No. 207 (1984) and Directive 87/302/EEC, Part C. Eisenia foetida were exposed to nominal concentrations of 0, 10, 18, 32, 56 and 100 mg a.s./kg dw artificial soil and effects on mortality and body weight were observed.
5.2 Results and discussion
After 7 days, there was 100% mortality in 56 and 100 mg/kg treatments, with some mortality in all TI-435 treatments. After 14 days, there was 100% mortality in 32, 56 and 100 mg/kg treatments, with some mortality in all lower TI-435 treatment replicates. There were no control mortalities. Surviving earthworms in the 10 and 18 mg/kg treatments showed a significant reduction in mean body weight at the end of the test.
5.2.1 NOEC < 10 mg/kg dw soil (based on reduction in body weight)
5.2.2 LC50 (7 days exposure)
18.58 mg/kg dw soil (calculated)
5.2.3 LC50 (14 days exposure)
13.21 mg/kg dw soil (calculated)
5.2.4 LC100 (14 days exposure)
32 mg/kg dw soil (nominal)
5.3 Conclusion Validity criteria can be considered as fulfilled
.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
RCC project no. 852224 Page 3 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.1.2/01 Annex Point IIIA XIII.3.2
Acute toxicity to earthworms or other soil non-target macro-organisms
COMMENTS FROM ... (specify)
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 4 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 7 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.1.2/02 and A7.5.2.1/02 Annex Point IIIA XIII.3.2
Acute toxicity to earthworms or other soil non-target macro-organisms Reproduction study with earthworms or other soil non-target macro-organisms
1 REFERENCE
Officialuse only
1.1 Reference (2000):
1.2 Data protection Yes 1.2.1 Data owner 1.2.2 Companies with
letter of access
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
2.2 GLP Yes
2.3 Deviations No
3 METHOD
3.1 Test material TI-435
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
3.1.4 Composition of Product
3.1.5 Further relevant properties
3.1.6 Method of analysis
3.2 Reference substance
3.2.1 Method of analysis for reference substance
3.3 Testing procedure
3.3.1 Preparation of the test substance
3.3.2 Application of the test substance
RCC project no. 852224 Page 1 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.1.2/02 and A7.5.2.1/02 Annex Point IIIA XIII.3.2
Acute toxicity to earthworms or other soil non-target macro-organisms Reproduction study with earthworms or other soil non-target macro-organisms
3.3.3 Test organisms
3.3.4 Test system
3.3.5 Test conditions
3.3.6 Test duration 28 days
3.3.7 Test parameter Mortality and reproduction
3.3.8 Examination
3.3.10 Statistics
4 RESULTS
4.1 Filter paper test
4.2 Soil test
4.2.1 Initial concentrations of test substance
0.01, 0.032, 0.1, 0.32 and 1.0 mg/kg dw artificial soil
4.2.2 Effect data (Mortality)
4.2.3 Concentration / effect curve
4.2.4 Other effects
4.3 Results of controls
4.3.1 Mortality
4.3.2 Reproduction
4.4 Test with reference substance
4.4.1 Concentrations
4.4.2 Results
RCC project no. 852224 Page 2 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.1.2/02 and A7.5.2.1/02 Annex Point IIIA XIII.3.2
Acute toxicity to earthworms or other soil non-target macro-organisms Reproduction study with earthworms or other soil non-target macro-organisms
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
The toxicity of TI-435 to collembola was tested according to ISO/FDIS 11267 (1998). Folsomia candida were exposed to nominal concentrations of 0.01, 0.032, 0.1, 0.32 and 1.0 mg/kg dw artificial soil and effects on mortality and reproduction were observed.
5.2 Results and discussion
5.2.1 LC50 (mortality) 1.02 mg/kg dw soil (calculated)
5.2.2 LOEC (mortality) 1.0 mg/kg dw soil (nominal)
5.2.3 NOEC (mortality) 0.32 mg/kg dw soil (nominal)
5.2.4 EC50 (reproduction) 0.76 mg/kg dw soil (calculated) X
5.2.5 LOEC (reproduction)
1.0 mg/kg dw soil (nominal)
5.2.6 NOEC (reproduction)
0.32 mg/kg dw soil (nominal)
5.3 Conclusion Validity criteria can be considered as fulfilled
5.3.1 Other Conclusions
5.3.2 Reliability 1
5.3.3 Deficiencies No
RCC project no. 852224 Page 3 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ... (specify)
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 4 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 7 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 6
Section 7.5.1.3/01 and
7.5.2.2/01 Annex Point IIIA XIII.3.4
Acute toxicity to plants
Long-term test with terrestrial plants
1 REFERENCE
Official
use only
1.1 Reference Brignole, A.J.; Porch, J.R. and Krueger, H.O. (2000a): TI-435 50%
WDG: A toxicity test to determine the effects of the test substance on
seedling emergence of ten species of plants.
Wildlife International, Ltd. Easton, Maryland 21601, USA; unpublished
report of project 197-126
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
US EPA OPPTS 850.4100 and 850.4225
2.2 GLP Yes
2.3 Deviations No
3 METHOD
3.1 Test material TI-435 50% WDG
3.1.1 Lot/Batch number IW016-046
3.1.2 Specification Not applicable, WDG formulation of TI-435
3.1.3 Purity Not applicable, WDG formulation of TI-435
3.1.4 Composition of
Product
49.3% TI-435 (active substance), 50.7% inerts
3.1.5 Further relevant
properties
None
3.1.6 Method of analysis The spray mixture of TI-435 50% WDG was diluted in
acetonitrile:NANOpure® water (10:90), as necessary, and analysed by
direct injection on the HPLC with UV detection.
LOQ: 1.0 mg a.s./L
3.2 Preparation of TS
solution for poorly
soluble or volatile
test substances
Not relevant. The active substance TI-435 is neither poorly soluble nor
volatile.
3.3 Reference
substance
No
3.4 Blank formulation Yes
Tan powder (TI-435 50WDG Blank Formulation)
3.5 Testing procedure
3.5.1 Preparation of
spray mixtures
The spray mixture for the test concentration (240 ppm a.s.) was
prepared by diluting 0.4875 g of the test substance to a volume of
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 6
Section 7.5.1.3/01 and
7.5.2.2/01 Annex Point IIIA XIII.3.4
Acute toxicity to plants
Long-term test with terrestrial plants
1000 mL with reverse osmosis water. Accordingly, the spray mixture
for the formulation blank was prepared by diluting 0.4878 g of the
formulation blank to a volume of 1000 mL with reverse osmosis water.
3.5.2 Test plants
3.5.3 Test system
3.5.4 Test conditions The soil surfaces were sprayed with TI-435 50% WDG at the nominal
concentration of equivalent 225 g a.s./ha (spray volume equivalent to
940 L/ha), a formulation blank and a water control. For further details
see Table A7_5_1_3_01-3.
3.5.5 Test duration 15 days
3.5.6 Test parameter Emergence, growth and changes in general condition of seedlings
Observations on day 10 were made to document seedlings emergence.
Observations on day 14 were made to document seedling emergence
and growth, and to determine changes in general condition of seedlings.
The growth of emerged seedling was evaluated by assessing the height
and dry weight. Seedling condition was described by noting possible
signs of phytotoxicity (i.e. necrosis, leaf wrinkle, chlorosis, plant
lodging or plant stunting).
3.5.7 Sampling Analytical samples were collected immediately after spray mixtures
were prepared. Triplicate samples were collected from the 225 g a.s./ha
treatment group spray mixture in order to verify the test concentration
and homogeneity in the dosing solution. Single samples were collected
from the formulation blank and the negative control spray mixtures.
3.5.8 Method of analysis
of the plant material
Not relevant. Only height and dry weight of living seedlings were
determined at test termination.
3.5.9 Statistics A t-test was used to determine if the mean emergence, height or weight
of the treatment group differed significantly from the mean of the
pooled controls (water control and formulation blank). Dunnett’s test
was used in establishing the NOEC by determining significant
differences between the treatments and the water control.
4 RESULTS
4.1 Results test
substance
4.1.1 Applied initial
concentration
Analysis of the spray mixture showed that the test concentration was in
the range of 218 - 234 ppm a.s., i.e. 90.9 – 97.4% of nominal (mean:
94.9%).
4.1.2 Phytotoxicity rating There were no apparent adverse treatment-related effects on any of the
10 plant species tested.
4.1.3 Plant height The heights of treated plants at test termination (day 14) were in the
range of 96 - 106% of the pooled controls.
4.1.4 Plant dry weights The dry weights of treated plants at test termination (day 14) were in the
range of 94 - 113% of the pooled controls.
4.1.5 Emergence The emergence of treated plants at test termination (day 14) was in the
range of 78 - 110% of the pooled controls.
4.1.6 Number of dead None for all species
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 6
Section 7.5.1.3/01 and
7.5.2.2/01 Annex Point IIIA XIII.3.4
Acute toxicity to plants
Long-term test with terrestrial plants
plants
4.1.7 Effect data For effect data see Table A7_5_1_3_01-4.
Differences in seedling emergence and growth between the 225 g a.s./ha
treatment group means and the pooled control means were minor and
not statistically significant (p>0.05). Therefore, the application of
TI-435 50% WDG at a rate equivalent to 225 g a.s./ha was
determined to be the NOEC for emergence and growth of all species
tested.
4.1.8 Concentration /
response curve
Not relevant (see 4.1.7)
4.1.9 Other effects None for all species and treatment groups
4.2 Results of controls
4.2.1 Applied initial
concentration
Analysis of the formulation blank and of the water control showed that
neither contained TI-435.
4.2.2 Number/
percentage of plants
showing adverse
effects
Neither seedlings of the formulation blank nor seedlings of the water
control showed adverse effects.
4.3 Test with
reference
substance
Not performed
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
Toxic effects of TI-435 50% WDG on seedling emergence and growth
of plants were tested according to US EPA OPPTS
850.4100 and 850.4225. No deviations from the guidelines occurred.
5.2 Results and
discussion
X
5.2.1 NOEC 225 g a.s./ha for emergence and growth of all species tested
5.3 Conclusion There were no observed treatment-related effects on any of the test
species.
X
5.3.1 Reliability 1
5.3.2 Deficiencies No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 6
Section 7.5.1.3/01 and
7.5.2.2/01 Annex Point IIIA XIII.3.4
Acute toxicity to plants
Long-term test with terrestrial plants
Evaluation by Competent Authorities
Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2005-08-16
Materials and Methods Applicant’s version is acceptable.
Results and discussion There were no apparent adverse treatment-related effects on 9 of the 10 plant
species tested. For Lycopersicon esculentum however a reduction in emergence of
22 % compared to the control was observed at the only tested concentration of
225 g a.s/ha.. However, the difference to the control was not statistically
significant. Therefore, the overall NOEC from this study is 225 g a.s./ha.
Conclusion For all tested species a NOEC of 225 g a.s./ha can be derived from this study for
emergence and growth, as no statistically significant effects compared to the
control were found.
Reliability 1
Acceptability acceptable
Remarks The performed test is an acute plant test and can not be submitted as acute and
long-term study.
COMMENTS FROM ... (specify)
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 6
Family Species Common name Source (seed)
Dicotyledonae Leguminosae Phaseolus
vulgaris
Pinto bean Meyer Seed Co.,
Baltimore, MD
Compositae Lactuca sativa Lettuce Territorial Seed Co.,
Cottage Grove, OR
Cruciferae Brassica olearaea Cabbage Meyer Seed Co.,
Baltimore, MD
Leguminosae Glycine max Soybean Johnny’s Selected
Seeds, Albion, ME
Solanaceae Lycopersicon
esculentum
Tomato Meyer Seed Co.,
Baltimore, MD
Cruciferae Raphanus sativus Radish Meyer Seed Co.,
Baltimore, MD
Monocotyledonae Liliaceae Allium cepa Onion Territorial Seed Co.,
Cottage Grove, OR
Gramineae Lolium perenne Ryegrass Meyer Seed Co.,
Baltimore, MD
Gramineae Zea mays Field corn Johnny’s Selected
Seeds, Albion, ME
Gramineae Triticum aestivum Wheat Arrowhead Mills
Inc., Hereford, TX
Table A7_5_1_3_01-2: Test system
Criteria Details
Test type Greenhouse
Container type Plastic pots (16 cm diameter, 11 cm-deep)
Seed germination potential Not stated
Identification of the plant species Seeds were impartially assigned to pre-labelled
growth pots on the day of test initiation.
Number of replicates 4
Numbers of plants per replicate per dose 10
Date of planting October 12, 1999
Plant density 10 seeds per pot put into 10 single holes in the soil
surface (surface: 201 cm²)
Date of test substance application October 12, 1999
High of plants at application Application was performed directly after planting the
seeds.
Date of phytotoxicity rating or harvest See 3.5.6
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 6
Table A7_5_1_3_01-3: Test conditions
Criteria Details
Test type Seedling emergence and growth
Method of application A pressurised spray applicator was used to spray the soil
surface in pots.
Number of applications: 1
Application levels 225 g a.s./ha (spray volume equivalent to 940 L/ha)
Dose rate 225 g a.s./ha
Substrate characteristics sand soil composed of industrial quartz sand, kaolinite clay
and peat (ratio 50:4:5)
soil analysis showed 91% sand, 2% silt, 7% clay, 2.4%
organic matter and a pH of 7.8
limestone (to buffer the pH) and a slow-release fertiliser
were added
Watering of the plants Water lost through transpiration and evaporation replaced by
subirrigation with well water
Temperature 23 to 28°C
Photoperiod 12 hours
Light regime 411 to 7518 kW/m2 light intensity
(natural sunlight not supplemented with artificial lighting)
Relative humidity 21 to 89%
Wind volatility Not relevant, test performed in greenhouse.
Observation periods and duration of test Observations were made on day 10 (seedlings emergence)
and day 14 (seedling emergence, growth and changes in
general condition of seedlings).
Test duration: 15 days
Pest control No
Any other treatments and procedures No
Table A7_5_1_3_01-4: Emergence and effective phytotoxicity of treated seeds (225 g a.s./ha) on day 14
Plant Absolute numbers Per cent relative to pooled controls
Plant
height [cm]
Plant dry
weight [mg]
Emergence Plant
height [%]
Plant dry
weights [%]
Emergence
[%]
Pinto bean 20.2 245 9.75 102 110 99
Cabbage 5.1 9.2 9.5 106 98 107
Field corn 40.0 176 9.75 97 101 103
Lettuce 4.3 3.6 9.25 103 113 97
Onion 7.2 2.9 8.75 105 98 101
Radish 6.0 22 8.25 97 111 94
Ryegrass 8.0 2.1 10.0 99 95 110
Soybean 26.1 313 10.0 97 94 100
Tomato 4.2 6.9 5.75 106 100 78
Wheat 25.5 26 9.75 96 104 100
Table A7_5_1_3_01-5: Validity criteria for terrestrial plant toxicity according to EPA OPPTS 850.4100
Fulfilled Not fulfilled
Adverse effect > 25% on one or more plant species (EPA) x
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 6
Section 7.5.1.3/02 Annex Point IIIA XIII.3.4
Acute toxicity to plants
1 REFERENCE
Official
use only
1.1 Reference Brignole, A.J.; Porch, J.R. Krueger, H.O. and Kendall, T.Z. (2000b): TI-
435 50% WDG: A toxicity test to determine the effects of the test
substance on vegetative vigor of ten species of plants.
Wildlife International, Ltd. Easton, Maryland 21601, USA; unpublished
report of project 197-127
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
US EPA OPPTS 850.4150
2.2 GLP Yes
2.3 Deviations No
3 METHOD
3.1 Test material TI-435 50% WDG
3.1.1 Lot/Batch number
3.1.2 Specification Not applicable, WDG formulation of TI-435
3.1.3 Purity Not applicable, WDG formulation of TI-435
3.1.4 Composition of
Product
49.3% TI-435 (active substance), 50.7% inerts
3.1.5 Further relevant
properties
None
3.1.6 Method of analysis The spray mixture of TI-435 50% WDG was diluted in
acetonitrile:NANOpure® water (10:90), as necessary, and analysed
by direct injection on the HPLC with UV detection.
LOQ: 1.0 mg a.s./L
3.2 Preparation of TS
solution for poorly
soluble or volatile
test substances
Not relevant. The active substance TI-435 is neither poorly soluble nor
volatile.
3.3 Reference
substance
No
3.4 Blank formulation Yes
Tan powder (TI-435 50WDG Blank Formulation)
3.5 Testing procedure
3.5.1 Preparation of
spray mixtures
The spray mixture for the test concentration (240 ppm a.s.) was
prepared by diluting 0.4868 g of the test substance to a volume of
1000 mL with reverse osmosis water. Accordingly, the spray mixture
for the formulation blank was prepared by diluting 0.4867 g of the
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 6
Section 7.5.1.3/02 Annex Point IIIA XIII.3.4
Acute toxicity to plants
formulation blank to a volume of 1000 mL with reverse osmosis water.
3.5.2 Test plants See Table A7_5_1_3_02-1
3.5.3 Test system See Table A7_5_1_3_02-2
3.5.4 Test conditions A spray application of TI-435 50% WDG at a nominal concentration of
equivalent to 225 g a.s./ha (spray volume equivalent to 940 L/ha), a
formulation blank and a water control was made to the plant foliage. For
further details see Table A7_5_1_3_02-3.
3.5.5 Test duration 15 days
3.5.6 Test parameter Plant growth and condition (phytotoxicity)
Plant growth was evaluated by assessing the height and dry weight.
Plant condition was described by noting possible signs of phytotoxicity
(i.e. necrosis, leaf wrinkle, chlorosis, plant lodging or plant stunting).
Plant heights and condition were observed on day 0 (prior to
application), days 7 and 14. Shoot dry weights were determined at test
termination.
3.5.7 Sampling Analytical samples were collected immediately after spray mixtures
were prepared. Triplicate samples were collected from the 225 g a.s./ha
treatment group spray mixture in order to verify the test concentration
and homogeneity in the dosing solution. Single samples were collected
from the formulation blank and the negative control spray mixtures.
3.5.8 Method of analysis
of the plant material
Not relevant. Only height and dry weight of plants were determined.
3.5.9 Statistics
4 RESULTS
4.1 Results test
substance
4.1.1 Applied initial
concentration
Analysis of the spray mixture showed that the test concentration was in
the range of 225 - 239 ppm a.s., i.e. 93.8 – 99.4% of nominal (mean:
96.8%).
4.1.2 Phytotoxicity rating There were no apparent adverse treatment-related effects on any of the
10 plant species tested.
4.1.3 Plant height The heights of treated plants at day 7 and at day 14 were in the range of
96 - 105% and 97 - 105% of the pooled controls, respectively.
4.1.4 Plant dry weights The dry weights of treated plants at day 14 were in the range of
91 - 109% of the pooled controls.
4.1.5 Number of dead
plants
None for all species
4.1.6 Effect data For effect data see Table A7_5_1_3_02-4.
Differences between treatment group means and the pooled control
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 6
Section 7.5.1.3/02 Annex Point IIIA XIII.3.4
Acute toxicity to plants
means were minor and not statistically significant (p>0.05).
Therefore, the application of TI-435 50% WDG at 225 g a.s./ha was
determined to be the NOEC for vegetative vigor in all species tested.
4.1.7 Concentration /
response curve
Not relevant (see 4.1.6)
4.1.8 Other effects None for all species and treatment groups
4.2 Results of controls
4.2.1 Applied initial
concentration
Analysis of the formulation blank and of the water control showed that
neither contained TI-435.
4.2.2 Number/
percentage of plants
showing adverse
effects
Neither plants of the formulation blank nor plants of the water control
showed adverse effects.
4.3 Test with
reference
substance
Not performed
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
Toxic effects of TI-435 50% WDG on vegetative vigor of
plants were tested according to US EPA OPPTS 850.4150. No
deviations from the guideline occurred.
5.2 Results and
discussion
5.2.1 NOEC 225 g a.s./ha for vegetative vigor of all species tested
5.3 Conclusion There were no observed treatment-related effects on any of the test
species.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Evaluation by Competent Authorities
Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 04.02.2005
Materials and Methods Applicant’s version is acceptable.
Results and discussion Applicant's version can be adopted.
Conclusion Applicant's version can be adopted.
Reliability 1
Acceptability acceptable
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 6
Section 7.5.1.3/02 Annex Point IIIA XIII.3.4
Acute toxicity to plants
Remarks
COMMENTS FROM ... (specify)
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 6
Table A7_5_1_3_02-1: Test plants
Family Species Common name Source (seed)
Dicotyledonae Leguminosae Phaseolus
vulgaris
Pinto bean Meyer Seed Co.,
Baltimore, MD
Compositae Lactuca sativa Lettuce Territorial Seed Co.,
Cottage Grove, OR
Cruciferae Brassica olearaea Cabbage Meyer Seed Co.,
Baltimore, MD
Leguminosae Glycine max Soybean Johnny’s Selected
Seeds, Albion, ME
Solanaceae Lycopersicon
esculentum
Tomato Meyer Seed Co.,
Baltimore, MD
Cruciferae Raphanus sativus Radish Meyer Seed Co.,
Baltimore, MD
Monocotyledonae Liliaceae Allium cepa Onion Territorial Seed Co.,
Cottage Grove, OR
Gramineae Lolium perenne Ryegrass Meyer Seed Co.,
Baltimore, MD
Gramineae Zea mays Field corn Johnny’s Selected
Seeds, Albion, ME
Gramineae Triticum aestivum Wheat Arrowhead Mills
Inc., Hereford, TX
Table A7_5_1_3_02-2: Test system
Criteria Details
Test type Greenhouse
Container type Plastic pots (11 cm diameter, 10 cm-deep)
Seed germination potential Not stated
Identification of the plant species Seedlings were randomly assigned to the treatment
and control groups and labelled with the species
name, project number, treatment group, replicate
designation and plant number.
Number of replicates 6
Numbers of plants per replicate per dose 5 plants, each in a separate pot
Date of planting September 27 to October 7, 1999
Plant density 1 plant per pot
Date of test substance application October 15, 1999
High of plants at application Pinto bean: 14.4 cm, cabbage: 8.3 cm, field corn:
18.6 cm, lettuce: 4.98 cm, onion: 8.4 cm, radish:
8.8 cm, ryegrass: 11.5 cm, soybean: 13.4 cm, tomato:
5.4 cm, wheat: 18.9 cm (mean values)
Date of phytotoxicity rating or harvest See 3.5.6
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 6
Table A7_5_1_3_02-3: Test conditions
Criteria Details
Test type Vegetative vigor
Method of application pressurised spray applicator
spray of plant foliage
Number of applications: 1
Application levels 225 g a.s./ha (spray volume equivalent to 940 L/ha)
Dose rate 225 g a.s./ha
Substrate characteristics sand soil composed of industrial quartz sand, kaolinite clay
and peat (ratio 50:4:5)
soil analysis showed 91% sand, 2% silt, 7% clay, 2.4%
organic matter and a pH of 7.8
limestone (to buffer the pH) and a slow-release fertiliser
were added
Watering of the plants Water lost through transpiration and evaporation replaced by
subirrigation with well water
Temperature 23 to 28°C
Photoperiod 12 hours
Light regime 411 to 7149 kW/m2 light intensity
(natural sunlight not supplemented with artificial lighting)
Relative humidity 21 to 89%
Wind volatility Not relevant, test performed in greenhouse.
Observation periods and duration of test Plant heights and condition were observed on day 0 (prior to
application), days 7 and 14. Shoot dry weights were
determined at test termination.
Test duration: 15 days
Pest control No
Any other treatments and procedures No
Table A7_5_1_3_02-4: Plant heights and dry weights of treated plants (225 g a.s./ha)
Plant Absolute numbers Per cent relative to pooled controls
Plant height
at day 7
[cm]
Plant height
at day 14
[cm]
Plant dry
weight at
day 14 [mg]
Plant height
at day 7
[%]
Plant height at
day 14
[%]
Plant dry
weight at
day 14 [%]
Pinto bean 19.2 26.1 1.43 96 98 101
Cabbage 12.7 16.8 0.85 105 104 101
Field corn 44.4 66.9 1.02 100 100 96
Lettuce 9.0 13.1 0.16 103 105 91
Onion 13.8 16.0 0.022 96 100 100
Radish 11.6 14.6 0.179 99 101 104
Ryegrass 15.9 21.4 0.068 100 100 96
Soybean 22.7 31.1 1.34 98 97 98
Tomato 10.2 18.1 0.709 100 98 95
Wheat 31.2 34.9 0.226 101 101 109
Table A7_5_1_3_02-5: Validity criteria for terrestrial plant toxicity according to
EPA OPPTS 850.4150 (vegetative vigor test)
Fulfilled Not fulfilled
Adverse effect > 25% on one or more plant species (EPA) x
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.2.1/01 Annex Point IIIA XIII.3.2
Reproduction study with earthworms or other soil non-target macro-organisms
1 REFERENCE
Officialuse only
1.1 Reference (1999):
1.2 Data protection Yes 1.2.1 Data owner 1.2.2 Companies with
letter of access None
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
2.2 GLP Yes
2.3 Deviations None
3 METHOD
3.1 Test material TI-435 50% WDG
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
3.1.4 Composition of Product
3.1.5 Further relevant properties
3.1.6 Method of analysis
3.2 Reference substance
3.2.1 Method of analysis for reference substance
3.3 Testing procedure
3.3.1 Preparation of the test substance
3.3.2 Application of the test substance
RCC project no. 852224 Page 1 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.2.1/01 Annex Point IIIA XIII.3.2
Reproduction study with earthworms or other soil non-target macro-organisms
3.3.3 Test organisms
3.3.4 Test system
3.3.5 Test conditions
3.3.6 Test duration 28 days (adult earthworms) + 28 days (development of offspring)
3.3.7 Test parameter Mortality, body weight and reproduction
3.3.8 Examination
3.3.9 Monitoring of test substance concentration
3.3.10 Statistics
4 RESULTS
4.1 Results of test substance
4.1.1 Application rate
4.1.2 Mortality
4.1.3 Body weights
4.1.4 Reproduction
4.1.5 Other effects
4.2 Results of controls
4.2.1 Mortality
4.2.2 Body weights
RCC project no. 852224 Page 2 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.2.1/01 Annex Point IIIA XIII.3.2
Reproduction study with earthworms or other soil non-target macro-organisms
4.2.3 Reproduction
4.3 Test with reference substance
4.3.1 Concentration
4.3.2 Mortality
4.3.3 Body weights
4.3.4 Reproduction
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
The reproduction toxicity of TI-435 50% WDG to earthworms was tested
Earthworms were exposed to 150 g a.s./ha and five times this rate (750 g a.s./ha) and effects on
mortality, body weight and reproduction were observed. No major deviations from the guidelines occurred.
5.2 Results and discussion
5.3 Conclusion At application rates up to the maximum field application rate, no negative effects on earthworm reproduction are to be expected. Validity criteria can be considered as fulfilled
5.3.1 Reliability 1
5.3.2 Deficiencies No
RCC project no. 852224 Page 3 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ... (specify)
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 4 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 7 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 7
Section A7.5.1.2/02 and A7.5.2.1/02 Annex Point IIIA XIII.3.2
Acute toxicity to earthworms or other soil non-target macro-organisms
Reproduction study with earthworms or other soil non-target macro-organisms
1 REFERENCE
Official use only
1.1 Reference (2000):
1.2 Data protection Yes
1.2.1 Data owner
1.2.2 Companies with letter of access
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
2.2 GLP Yes
2.3 Deviations No
3 METHOD
3.1 Test material TI-435
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
3.1.4 Composition of Product
3.1.5 Further relevant properties
3.1.6 Method of analysis
3.2 Reference substance
3.2.1 Method of analysis for reference substance
3.3 Testing procedure
3.3.1 Preparation of the test substance
3.3.2 Application of the test substance
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 7
Section A7.5.1.2/02 and A7.5.2.1/02 Annex Point IIIA XIII.3.2
Acute toxicity to earthworms or other soil non-target macro-organisms
Reproduction study with earthworms or other soil non-target macro-organisms
3.3.3 Test organisms
3.3.4 Test system
3.3.5 Test conditions
3.3.6 Test duration 28 days
3.3.7 Test parameter Mortality and reproduction
3.3.8 Examination
3.3.9 Monitoring of test substance concentration
3.3.10 Statistics
4 RESULTS
4.1 Filter paper test
4.2 Soil test
4.2.1 Initial concentrations of test substance
0.01, 0.032, 0.1, 0.32 and 1.0 mg/kg dw artificial soil
4.2.2 Effect data (Mortality)
4.2.3 Concentration / effect curve
4.2.4 Other effects
4.3 Results of controls
4.3.1 Mortality
4.3.2 Reproduction
4.4 Test with reference substance
4.4.1 Concentrations
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 7
Section A7.5.1.2/02 and A7.5.2.1/02 Annex Point IIIA XIII.3.2
Acute toxicity to earthworms or other soil non-target macro-organisms
Reproduction study with earthworms or other soil non-target macro-organisms
4.4.2 Results
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
The toxicity of TI-435 to collembola was tested . Folsomia candida were exposed to nominal
concentrations of 0.01, 0.032, 0.1, 0.32 and 1.0 mg/kg dw artificial soil and effects on mortality and reproduction were observed.
5.2 Results and discussion
5.2.1 LC50 (mortality) 1.02 mg/kg dw soil (calculated)
5.2.2 LOEC (mortality) 1.0 mg/kg dw soil (nominal)
5.2.3 NOEC (mortality) 0.32 mg/kg dw soil (nominal)
5.2.4 LC50 (reproduction) 0.76 mg/kg dw soil (calculated)
5.2.5 LOEC (reproduction)
1.0 mg/kg dw soil (nominal)
5.2.6 NOEC (reproduction)
0.32 mg/kg dw soil (nominal)
5.3 Conclusion Validity criteria can be considered as fulfilled
5.3.1 Other Conclusions
5.3.2 Reliability 1
5.3.3 Deficiencies No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 7
Evaluation by Competent Authorities
Use separate "evaluation boxes" to provide transparency as to the comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ... (specify)
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 7 of 7
Sumitomo Chemical Takeda Agro Co. Ltd. TI-435 May 2008
Section A7.5.2.1/05 Annex Point IIIA XIII.3.2
Reproduction study with earthworms or other soil non-target macro-organisms
1 REFERENCE
Officialuse only
1.1 Reference (2000):
1.2 Data protection Yes 1.2.1 Data owner 1.2.2 Companies with
letter of access None
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study •
2.2 GLP Yes
2.3 Deviations None
3 METHOD
3.1 Test material TI-435 50% WDG
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
3.1.4 Composition of Product
3.1.5 Further relevant properties
3.1.6 Method of analysis
3.2 Reference substance
3.2.1
3.3 Testing procedure
3.3.1 Trial location and layout
RCC project no. 852224 Page 1 of 7
Sumitomo Chemical Takeda Agro Co. Ltd. TI-435 May 2008
Section A7.5.2.1/05 Annex Point IIIA XIII.3.2
Reproduction study with earthworms or other soil non-target macro-organisms
identification. Deeper living earthworms were extracted by evenly
RCC project no. 852224 Page 2 of 7
Sumitomo Chemical Takeda Agro Co. Ltd. TI-435 May 2008
Section A7.5.2.1/05 Annex Point IIIA XIII.3.2
Reproduction study with earthworms or other soil non-target macro-organisms
4 RESULTS
4.1 Results of test substance
RCC project no. 852224 Page 3 of 7
Sumitomo Chemical Takeda Agro Co. Ltd. TI-435 May 2008
Section A7.5.2.1/05 Annex Point IIIA XIII.3.2
Reproduction study with earthworms or other soil non-target macro-organisms
4.2 Results of toxic reference substance
RCC project no. 852224 Page 4 of 7
Sumitomo Chemical Takeda Agro Co. Ltd. TI-435 May 2008
Section A7.5.2.1/05 Annex Point IIIA XIII.3.2
Reproduction study with earthworms or other soil non-target macro-organisms
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
A supervised field trial was conducted over twelve months to determine the effects of TI-435 50% WDG on earthworms. TI-435 50% WDG was applied at a nominal rate of 75 g a.s./ha, 112 g a.s./ha and 225 g a.s./ha to plots two, three and four, respectively.
5.2 Results and discussion
Application of TI-435 50% WDG had no significant detrimental effect (to at least the 5% level) on the number of earthworms, or their biomass, following application at rates from 75 to 225 g a.s./ha, compared to the untreated control.
5.3 Conclusion Considering the results of the statistical analysis and the variability of earthworm abundance in natural soils, this study indicates that earthworm populations were not affected (to at least the 5% level) by the application of TI-435 50% WDG at rates from 75 to 225 g a.s./ha, compared to an untreated control, for a period up to one year after application.
5.3.1 Reliability 1
5.3.2 Deficiencies None
RCC project no. 852224 Page 5 of 7
Sumitomo Chemical Takeda Agro Co. Ltd. TI-435 May 2008
Section A7.5.2.1/05 Annex Point IIIA XIII.3.2
Reproduction study with earthworms or other soil non-target macro-organisms
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ... (specify)
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers and to applicant's summary and conclusion. Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 6 of 7
Sumitomo Chemical Takeda Agro Co. Ltd. TI-435 May 2008
RCC project no. 852224 Page 7 of 7
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 6
Section 7.5.2.2/01 Annex Point IIIA XIII.3.4
Long-term test with terrestrial plants
1 REFERENCE
Official
use only
1.1 Reference Brignole, A.J.; Porch, J.R. and Krueger, H.O. (2000a): TI-435 50%
WDG: A toxicity test to determine the effects of the test substance on
seedling emergence of ten species of plants.
Wildlife International, Ltd. Easton, Maryland 21601, USA; unpublished
report of project 197-126
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
US EPA OPPTS 850.4100 and 850.4225
2.2 GLP Yes
2.3 Deviations No
3 METHOD
3.1 Test material TI-435 50% WDG
3.1.1 Lot/Batch number IW016-046
3.1.2 Specification Not applicable, WDG formulation of TI-435
3.1.3 Purity Not applicable, WDG formulation of TI-435
3.1.4 Composition of
Product
49.3% TI-435 (active substance), 50.7% inerts
3.1.5 Further relevant
properties
None
3.1.6 Method of analysis The spray mixture of TI-435 50% WDG was diluted in
acetonitrile:NANOpure® water (10:90), as necessary, and analysed
by direct injection on the HPLC with UV detection.
LOQ: 1.0 mg a.s./L
3.2 Preparation of TS
solution for poorly
soluble or volatile
test substances
Not relevant. The active substance TI-435 is neither poorly soluble nor
volatile.
3.3 Reference
substance
No
3.4 Blank formulation Yes
Tan powder (TI-435 50WDG Blank Formulation)
3.5 Testing procedure
3.5.1 Preparation of
spray mixtures
The spray mixture for the test concentration (240 ppm a.s.) was
prepared by diluting 0.4875 g of the test substance to a volume of
1000 mL with reverse osmosis water. Accordingly, the spray mixture
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 6
Section 7.5.2.2/01 Annex Point IIIA XIII.3.4
Long-term test with terrestrial plants
for the formulation blank was prepared by diluting 0.4878 g of the
formulation blank to a volume of 1000 mL with reverse osmosis water.
3.5.2 Test plants
3.5.3 Test system
3.5.4 Test conditions The soil surfaces were sprayed with TI-435 50% WDG at the nominal
concentration of equivalent 225 g a.s./ha (spray volume equivalent to
940 L/ha), a formulation blank and a water control. For further details
see Table A7_5_1_3_01-3.
3.5.5 Test duration 15 days
3.5.6 Test parameter Emergence, growth and changes in general condition of seedlings
Observations on day 10 were made to document seedlings emergence.
Observations on day 14 were made to document seedling emergence
and growth, and to determine changes in general condition of seedlings.
The growth of emerged seedling was evaluated by assessing the height
and dry weight. Seedling condition was described by noting possible
signs of phytotoxicity (i.e. necrosis, leaf wrinkle, chlorosis, plant
lodging or plant stunting).
3.5.7 Sampling Analytical samples were collected immediately after spray mixtures
were prepared. Triplicate samples were collected from the 225 g a.s./ha
treatment group spray mixture in order to verify the test concentration
and homogeneity in the dosing solution. Single samples were collected
from the formulation blank and the negative control spray mixtures.
3.5.8 Method of analysis
of the plant material
Not relevant. Only height and dry weight of living seedlings were
determined at test termination.
3.5.9 Statistics A t-test was used to determine if the mean emergence, height or weight
of the treatment group differed significantly from the mean of the
pooled controls (water control and formulation blank). Dunnett’s test
was used in establishing the NOEC by determining significant
differences between the treatments and the water control.
4 RESULTS
4.1 Results test
substance
4.1.1 Applied initial
concentration
Analysis of the spray mixture showed that the test concentration was in
the range of 218 - 234 ppm a.s.,
4.1.2 Phytotoxicity rating There were no apparent adverse treatment-related effects on any of the
plant species tested.
4.1.3 Plant height The heights of treated plants at test termination (day 14) were in the
range of 96 - 106% of the pooled controls.
4.1.4 Plant dry weights The dry weights of treated plants at test termination (day 14) were in the
range of 94 - 113% of the pooled controls.
4.1.5 Emergence The emergence of treated plants at test termination (day 14) was in the
range of 78 - 110% of the pooled controls.
4.1.6 Number of dead
plants
None for all species
4.1.7 Effect data For effect data see Table A7_5_1_3_01-4.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 6
Section 7.5.2.2/01 Annex Point IIIA XIII.3.4
Long-term test with terrestrial plants
Differences in seedling emergence and growth between the 225 g a.s./ha
treatment group means and the pooled control means were minor and
not statistically significant (p>0.05). Therefore, the application of
TI-435 50% WDG at a rate equivalent to 225 g a.s./ha was determined
to be the NOEC for emergence and growth of all species tested.
4.1.8 Concentration /
response curve
4.1.9 Other effects None for all species and treatment groups
4.2 Results of controls
4.2.1 Applied initial
concentration
Analysis of the formulation blank and of the water control showed that
neither contained TI-435.
4.2.2 Number/
percentage of plants
showing adverse
effects
Neither seedlings of the formulation blank nor seedlings of the water
control showed adverse effects.
4.3 Test with
reference
substance
Not performed
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
Toxic effects of TI-435 50% WDG on seedling emergence and growth
of of plants were tested according to US EPA OPPTS
850.4100 and 850.4225. No deviations from the guidelines occurred.
5.2 Results and
discussion
5.2.1 NOEC 225 g a.s./ha for emergence and growth of all species tested
5.3 Conclusion There were no observed treatment-related effects on any of the test
species.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 6
Section 7.5.2.2/01 Annex Point IIIA XIII.3.4
Long-term test with terrestrial plants
Evaluation by Competent Authorities
Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2005-05-25
Materials and Methods Applicant's version is not acceptable for long term testing because the submitted
study is an acute plant test
Results and discussion Applicant's version can not be adopted for long term testing because the
submitted study is an acute plant test .
Conclusion Applicant's version can not be adopted for long term testing because the
submitted study is an acute plant test .
Reliability -Not applicable due to study concept.
Acceptability Not acceptable; the performed test is an acute plant test and can not be submitted
as long-term study. No data were submitted for Section A7.5.2.2 Long-term test
with terrestrial plants. A long term test with terrestrial plants is not required.
Remarks
COMMENTS FROM ... (specify)
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 6
_5_1_3_01-1: Test plants
Family Species Common name Source (seed)
Dicotyledonae Leguminosae Phaseolus
vulgaris
Pinto bean Meyer Seed Co.,
Baltimore, MD
Compositae Lactuca sativa Lettuce Territorial Seed Co.,
Cottage Grove, OR
Cruciferae Brassica olearaea Cabbage Meyer Seed Co.,
Baltimore, MD
Leguminosae Glycine max Soybean Johnny’s Selected
Seeds, Albion, ME
Solanaceae Lycopersicon
esculentum
Tomato Meyer Seed Co.,
Baltimore, MD
Cruciferae Raphanus sativus Radish Meyer Seed Co.,
Baltimore, MD
Monocotyledonae Liliaceae Allium cepa Onion Territorial Seed Co.,
Cottage Grove, OR
Gramineae Lolium perenne Ryegrass Meyer Seed Co.,
Baltimore, MD
Gramineae Zea mays Field corn Johnny’s Selected
Seeds, Albion, ME
Gramineae Triticum aestivum Wheat Arrowhead Mills
Inc., Hereford, TX
Table A7_5_1_3_01-2: Test system
Criteria Details
Test type Greenhouse
Container type Plastic pots (16 cm diameter, 11 cm-deep)
Seed germination potential Not stated
Identification of the plant species Seeds were impartially assigned to pre-labelled
growth pots on the day of test initiation.
Number of replicates 4
Numbers of plants per replicate per dose 10
Date of planting October 12, 1999
Plant density 10 seeds per pot put into 10 single holes in the soil
surface (surface: 201 cm²)
Date of test substance application October 12, 1999
High of plants at application Application was performed directly after planting the
seeds.
Date of phytotoxicity rating or harvest See 3.5.6
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 6
Table A7_5_1_3_01-3: Test conditions
Criteria Details
Test type Seedling emergence and growth
Method of application A pressurised spray applicator was used to spray the soil
surface in pots.
Number of applications: 1
Application levels 225 g a.s./ha (spray volume equivalent to 940 L/ha)
Dose rate 225 g a.s./ha
Substrate characteristics sand soil composed of industrial quartz sand, kaolinite clay
and peat (ratio 50:4:5)
soil analysis showed 91% sand, 2% silt, 7% clay, 2.4%
organic matter and a pH of 7.8
limestone (to buffer the pH) and a slow-release fertiliser
were added
Watering of the plants Water lost through transpiration and evaporation replaced by
subirrigation with well water
Temperature 23 to 28°C
Photoperiod 12 hours
Light regime 411 to 7518 kW/m2 light intensity
(natural sunlight not supplemented with artificial lighting)
Relative humidity 21 to 89%
Wind volatility Not relevant, test performed in greenhouse.
Observation periods and duration of test Observations were made on day 10 (seedlings emergence)
and day 14 (seedling emergence, growth and changes in
general condition of seedlings).
Test duration: 15 days
Pest control No
Any other treatments and procedures No
Table A7_5_1_3_01-4: Emergence and effective phytotoxicity of treated seeds (225 g a.s./ha) on day 14
Plant Absolute numbers Per cent relative to pooled controls
Plant
height [cm]
Plant dry
weight [mg]
Emergence Plant
height [%]
Plant dry
weights [%]
Emergence
[%]
Pinto bean 20.2 245 9.75 102 110 99
Cabbage 5.1 9.2 9.5 106 98 107
Field corn 40.0 176 9.75 97 101 103
Lettuce 4.3 3.6 9.25 103 113 97
Onion 7.2 2.9 8.75 105 98 101
Radish 6.0 22 8.25 97 111 94
Ryegrass 8.0 2.1 10.0 99 95 110
Soybean 26.1 313 10.0 97 94 100
Tomato 4.2 6.9 5.75 106 100 78
Wheat 25.5 26 9.75 96 104 100
Table A7_5_1_3_01-5: Validity criteria for terrestrial plant toxicity according to EPA OPPTS 850.4100
Fulfilled Not fulfilled
Adverse effect > 25% on one or more plant species (EPA) x
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 1 of 6
Section 7.5.2.2/02 Annex Point IIIA XIII.3.4
Long-term test with terrestrial plants
1 REFERENCE
Official
use only
1.1 Reference Brignole, A.J.; Porch, J.R. Krueger, H.O. and Kendall, T.Z. (2000b): TI-
435 50% WDG: A toxicity test to determine the effects of the test
substance on vegetative vigor of ten species of plants.
Wildlife International, Ltd. Easton, Maryland 21601, USA; unpublished
report of project 197-127
1.2 Data protection Yes
1.2.1 Data owner Sumitomo Chemical Takeda Agro Co., Ltd.
1.2.2 Companies with
letter of access
None
1.2.3 Criteria for data
protection
Data on existing a.s. submitted for the first time for entry into Annex I.
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study Yes
US EPA OPPTS 850.4150
2.2 GLP Yes
2.3 Deviations No
3 METHOD
3.1 Test material TI-435 50% WDG
3.1.1 Lot/Batch number IW016-046
3.1.2 Specification Not applicable, WDG formulation of TI-435
3.1.3 Purity Not applicable, WDG formulation of TI-435
3.1.4 Composition of
Product
49.3% TI-435 (active substance), 50.7% inerts
3.1.5 Further relevant
properties
None
3.1.6 Method of analysis The spray mixture of TI-435 50% WDG was diluted in
acetonitrile:NANOpure® water (10:90), as necessary, and analysed by
direct injection on the HPLC with UV detection.
LOQ: 1.0 mg a.s./L
3.2 Preparation of TS
solution for poorly
soluble or volatile
test substances
Not relevant. The active substance TI-435 is neither poorly soluble nor
volatile.
3.3 Reference
substance
No
3.4 Blank formulation Yes
Tan powder (TI-435 50WDG Blank Formulation)
3.5 Testing procedure
3.5.1 Preparation of
spray mixtures
The spray mixture for the test concentration (240 ppm a.s.) was
prepared by diluting 0.4868 g of the test substance to a volume of
1000 mL with reverse osmosis water. Accordingly, the spray mixture
for the formulation blank was prepared by diluting 0.4867 g of the
formulation blank to a volume of 1000 mL with reverse osmosis
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 2 of 6
Section 7.5.2.2/02 Annex Point IIIA XIII.3.4
Long-term test with terrestrial plants
water.
3.5.2 Test plants See Table A7_5_1_3_02-1
3.5.3 Test system See Table A7_5_1_3_02-2
3.5.4 Test conditions A spray application of TI-435 50% WDG at a nominal concentration of
equivalent to 225 g a.s./ha (spray volume equivalent to 940 L/ha), a
formulation blank and a water control was made to the plant foliage.
For further details see Table A7_5_1_3_02-3.
3.5.5 Test duration 15 days
3.5.6 Test parameter Plant growth and condition (phytotoxicity)
Plant growth was evaluated by assessing the height and dry weight.
Plant condition was described by noting possible signs of
phytotoxicity (i.e. necrosis, leaf wrinkle, chlorosis, plant lodging or
plant stunting). Plant heights and condition were observed on day 0
(prior to application), days 7 and 14. Shoot dry weights were
determined at test termination.
3.5.7 Sampling Analytical samples were collected immediately after spray mixtures
were prepared. Triplicate samples were collected from the 225 g
a.s./ha treatment group spray mixture in order to verify the test
concentration and homogeneity in the dosing solution. Single samples
were collected from the formulation blank and the negative control
spray mixtures.
3.5.8 Method of analysis
of the plant material
Not relevant. Only height and dry weight of plants were determined.
3.5.9 Statistics For each species, an assessment was made as to whether the test
concentration was a NOEC. Plant growth was assessed by comparing
treatment group means for shoot height and dry weight. Evaluation of
plant condition was also used in determining treatment related effects.
Although group mean plant scores were calculated, statistical
comparison of the means was not performed since condition is a
qualitative measurement (relative not quantitative differences).
A t-test was used to determine if the mean height or dry weight of the
treatment group differed significantly from the mean of the pooled
controls (water control and formulation blank).
4 RESULTS
4.1 Results test
substance
4.1.1 Applied initial
concentration
Analysis of the spray mixture showed that the test concentration was in
the range of 225 - 239 ppm a.s., i.e. 93.8 – 99.4% of nominal (mean:
96.8%).
4.1.2 Phytotoxicity rating There were no apparent adverse treatment-related effects on any of the
10 plant species tested.
4.1.3 Plant height The heights of treated plants at day 7 and at day 14 were in the range of
96 - 105% and 97 - 105% of the pooled controls, respectively.
4.1.4 Plant dry weights The dry weights of treated plants at day 14 were in the range of 91 -
109% of the pooled controls.
4.1.5 Number of dead
plants
None for all species
4.1.6 Effect data For effect data see Table A7_5_1_3_02-4.
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 3 of 6
Section 7.5.2.2/02 Annex Point IIIA XIII.3.4
Long-term test with terrestrial plants
Differences between treatment group means and the pooled control
means were minor and not statistically significant (p>0.05). Therefore,
the application of TI-435 50% WDG at 225 g a.s./ha was determined to
be the NOEC for vegetative vigor in all species tested.
4.1.7 Concentration /
response curve
4.1.8 Other effects None for all species and treatment groups
4.2 Results of controls
4.2.1 Applied initial
concentration
Analysis of the formulation blank and of the water control showed that
neither contained TI-435.
4.2.2 Number/
percentage of plants
showing adverse
effects
Neither plants of the formulation blank nor plants of the water control
showed adverse effects.
4.3 Test with
reference
substance
Not performed
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and
methods
Toxic effects of TI-435 50% WDG on vegetative vigor of
plants were tested according to US EPA OPPTS 850.4150. No
deviations from the guideline occurred.
5.2 Results and
discussion
There were no apparent adverse treatment-related effects on any of the
10 plant species tested after application of equivalent 225 g a.s./ha.
Differences between treatment group means and the pooled control
means were minor and not statistically significant (p>0.05).
5.2.1 NOEC 225 g a.s./ha for vegetative vigor of all species tested
5.3 Conclusion There were no observed treatment-related effects on any of the test
species.
5.3.1 Reliability 1
5.3.2 Deficiencies No
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 4 of 6
Section 7.5.2.2/02 Annex Point IIIA XIII.3.4
Long-term test with terrestrial plants
Evaluation by Competent Authorities
Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date 2005-05-25
Materials and Methods Applicant's version is not acceptable for long term testing because the submitted
study is an acute plant test.
Results and discussion Applicant's version can not be adopted for long term testing because the
submitted study is an acute plant test
Conclusion Applicant's version can not be adopted for long term testing because the
submitted study is an acute plant test .
Reliability Not applicable due to study concept.
Acceptability Non acceptable;the performed test is an acute plant test and can not be submitted
as acute and longterm study. No data were submitted for Section A7.5.2.2/02
Long-term test with terrestrial plants. A long term test with terrestrial plants is
not required.
Remarks
COMMENTS FROM ... (specify)
Date Give date of comments submitted
Materials and Methods Discuss additional relevant discrepancies referring to the (sub)heading numbers
and to applicant's summary and conclusion.
Discuss if deviating from view of rapporteur member state
Results and discussion Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Reliability Discuss if deviating from view of rapporteur member state
Acceptability Discuss if deviating from view of rapporteur member state
Remarks
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 5 of 6
Table A7_5_1_3_02-1: Test plants
Family Species Common name Source (seed)
Dicotyledonae Leguminosae Phaseolus
vulgaris
Pinto bean Meyer Seed Co.,
Baltimore, MD
Compositae Lactuca sativa Lettuce Territorial Seed Co.,
Cottage Grove, OR
Cruciferae Brassica olearaea Cabbage Meyer Seed Co.,
Baltimore, MD
Leguminosae Glycine max Soybean Johnny’s Selected
Seeds, Albion, ME
Solanaceae Lycopersicon
esculentum
Tomato Meyer Seed Co.,
Baltimore, MD
Cruciferae Raphanus sativus Radish Meyer Seed Co.,
Baltimore, MD
Monocotyledonae Liliaceae Allium cepa Onion Territorial Seed Co.,
Cottage Grove, OR
Gramineae Lolium perenne Ryegrass Meyer Seed Co.,
Baltimore, MD
Gramineae Zea mays Field corn Johnny’s Selected
Seeds, Albion, ME
Gramineae Triticum aestivum Wheat Arrowhead Mills
Inc., Hereford, TX
Table A7_5_1_3_02-2: Test system
Criteria Details
Test type Greenhouse
Container type Plastic pots (11 cm diameter, 10 cm-deep)
Seed germination potential Not stated
Identification of the plant species Seedlings were randomly assigned to the treatment
and control groups and labelled with the species
name, project number, treatment group, replicate
designation and plant number.
Number of replicates 6
Numbers of plants per replicate per dose 5 plants, each in a separate pot
Date of planting September 27 to October 7, 1999
Plant density 1 plant per pot
Date of test substance application October 15, 1999
High of plants at application Pinto bean: 14.4 cm, cabbage: 8.3 cm, field corn:
18.6 cm, lettuce: 4.98 cm, onion: 8.4 cm, radish:
8.8 cm, ryegrass: 11.5 cm, soybean: 13.4 cm,
tomato: 5.4 cm, wheat: 18.9 cm (mean values)
Date of phytotoxicity rating or harvest See 3.5.6
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
RCC project no. 852224 Page 6 of 6
Table A7_5_1_3_02-3: Test conditions
Criteria Details
Test type Vegetative vigor
Method of application pressurised spray applicator
spray of plant foliage
Number of applications: 1
Application levels 225 g a.s./ha (spray volume equivalent to 940 L/ha)
Dose rate 225 g a.s./ha
Substrate characteristics sand soil composed of industrial quartz sand, kaolinite clay
and peat (ratio 50:4:5)
soil analysis showed 91% sand, 2% silt, 7% clay, 2.4%
organic matter and a pH of 7.8
limestone (to buffer the pH) and a slow-release fertiliser
were added
Watering of the plants Water lost through transpiration and evaporation replaced by
subirrigation with well water
Temperature 23 to 28°C
Photoperiod 12 hours
Light regime 411 to 7149 kW/m2 light intensity
(natural sunlight not supplemented with artificial lighting)
Relative humidity 21 to 89%
Wind volatility Not relevant, test performed in greenhouse.
Observation periods and duration of test Plant heights and condition were observed on day 0 (prior to
application), days 7 and 14. Shoot dry weights were
determined at test termination.
Test duration: 15 days
Pest control No
Any other treatments and procedures No
Table A7_5_1_3_02-4: Plant heights and dry weights of treated plants (225 g a.s./ha)
Plant Absolute numbers Per cent relative to pooled controls
Plant height
at day 7
[cm]
Plant height
at day 14
[cm]
Plant dry
weight at
day 14 [mg]
Plant height
at day 7
[%]
Plant height
at day 14
[%]
Plant dry
weight at
day 14 [%]
Pinto bean 19.2 26.1 1.43 96 98 101
Cabbage 12.7 16.8 0.85 105 104 101
Field corn 44.4 66.9 1.02 100 100 96
Lettuce 9.0 13.1 0.16 103 105 91
Onion 13.8 16.0 0.022 96 100 100
Radish 11.6 14.6 0.179 99 101 104
Ryegrass 15.9 21.4 0.068 100 100 96
Soybean 22.7 31.1 1.34 98 97 98
Tomato 10.2 18.1 0.709 100 98 95
Wheat 31.2 34.9 0.226 101 101 109
Table A7_5_1_3_02-5: Validity criteria for terrestrial plant toxicity according to
EPA OPPTS 850.4150 (vegetative vigor test)
Fulfilled Not fulfilled
Adverse effect > 25% on one or more plant species (EPA) x
Sumitomo Chemical clothianidin (TI-435) August 2008
RCC project no. 852224 Page 1 of 6
Section A7.5.4.1 (01) Annex Point IIIA XIII.3.1
Acute toxicity to honeybees and other beneficial arthropods, e.g. predators
1 REFERENCE
Official use only
1.1 Reference (2000):
1.2 Data protection Yes
1.2.1 Data owner
1.2.2 Companies with letter of access
1.2.3 Criteria for data protection
2 GUIDELINES AND QUALITY ASSURANCE
2.1 Guideline study
2.2 GLP Yes
2.3 Deviations
3 MATERIALS AND METHODS
3.1 Test material
3.1.1 Lot/Batch number
3.1.2 Specification
3.1.3 Purity
3.1.4 Composition of Product
3.1.5 Further relevant properties
3.1.6 Method of analysis
3.2 Preparation of TS solution for poorly soluble or volatile test substances
3.3 Reference substance
3.4 Testing procedure
3.4.1 Preparation of test solutions
3.4.2 Test organisms
3.4.3 Test system
3.4.4 Test conditions
Sumitomo Chemical clothianidin (TI-435) August 2008
RCC project no. 852224 Page 2 of 6
Section A7.5.4.1 (01) Annex Point IIIA XIII.3.1
Acute toxicity to honeybees and other beneficial arthropods, e.g. predators
3.4.5 Duration of the test 77 days
3.4.6 Test parameter Behaviour Mortality Metamorphosis
Body weight of adult beetles
4 RESULTS
4.1 Limit Test
4.2 Test substance
4.3 Controls
Sumitomo Chemical clothianidin (TI-435) August 2008
RCC project no. 852224 Page 3 of 6
Section A7.5.4.1 (01) Annex Point IIIA XIII.3.1
Acute toxicity to honeybees and other beneficial arthropods, e.g. predators
4.4 Reference substance
5 APPLICANT'S SUMMARY AND CONCLUSION
5.1 Materials and methods
The effect of TI-435 on larvae of Poecilus cupreus was tested under extended laboratory conditions. The larvae were exposed to the test substance mixed into soil at concentrations of 0.02, 0.03, 0.04, 0.06 and 0.08 mg a.s./kg soil (dry weight).
he following test parameters were assessed: behaviour,
mortality, metamorphosis (number of successful metamorphoses and time period to metamorphosis) and body weight of adult beetles.
5.2 Results and discussion
X
5.3 Conclusion An LC50 of 0.046 mg a.s./kg soil (dry weight) was calculated (95% confidence limits: 0.036 - 0.062 mg/kg dry soil).
5.3.1 Reliability 1
5.3.2 Deficiencies None that affected the integrity of the findings.
Evaluation by Competent Authorities
Use separate "evaluation boxes" to provide transparency as to the comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
COMMENTS FROM ...
Sumitomo Chemical clothianidin (TI-435) August 2008
RCC project no. 852224 Page 4 of 6
Date
Materials and Methods
Results and discussion
Conclusion
Reliability
Acceptability
Remarks
Sumitomo Chemical clothianidin (TI-435) August 2008
RCC project no. 852224 Page 5 of 6
Sumitomo Chemical clothianidin (TI-435) August 2008
RCC project no. 852224 Page 6 of 6
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.5.1 Annex Point IIA VII.7.5
Bioconcentration, further studies
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ X ] Limited exposure [ ] Other justification [ ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. Clothianidin August 2006
Section A7.5.5 Annex Point IIA VII.7.5
Bioconcentration, terrestrial
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ X ] Limited exposure [ ] Other justification [ ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.6 Annex Point IIIA XIII.3
Effects on other terrestrial non-target organisms
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ X ] Limited exposure [ ] Other justification [ ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.7.1.1 Annex Point IIIA XIII.3.4
Effect on mammals – acute oral toxicity
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ ] Limited exposure [ ] Other justification [ X ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.7.1.2 Annex Point IIIA XIII.3
Effect on mammals – short term toxicity
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ ] Limited exposure [ ] Other justification [ X ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1
Sumitomo Chemical Takeda Agro Co., Ltd. TI-435 February 2004
Section A7.5.7.1.3 Annex Point IIIA XIII.3
Effect on mammals – effects on reproduction
JUSTIFICATION FOR NON-SUBMISSION OF DATA Officialuse only
Other existing data [ ] Technically not feasible [ ] Scientifically unjustified [ ] Limited exposure [ ] Other justification [ X ]
Detailed justification:
Undertaking of intended data submission [ ]
-
Evaluation by Competent Authorities Use separate "evaluation boxes" to provide transparency as to the
comments and views submitted
EVALUATION BY RAPPORTEUR MEMBER STATE
Date
Evaluation of applicant's justification
Conclusion
Remarks
COMMENTS FROM OTHER MEMBER STATE (specify)
Date Give date of comments submitted
Evaluation of applicant's justification
Discuss if deviating from view of rapporteur member state
Conclusion Discuss if deviating from view of rapporteur member state
Remarks
RCC project no. 852224 Page 1 of 1