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EC number: 616-995-5 | CAS number: 8018-01-7
- Life Cycle description
- Uses advised against
- Endpoint summary
- Appearance / physical state / colour
- Melting point / freezing point
- Boiling point
- Density
- Particle size distribution (Granulometry)
- Vapour pressure
- Partition coefficient
- Water solubility
- Solubility in organic solvents / fat solubility
- Surface tension
- Flash point
- Auto flammability
- Flammability
- Explosiveness
- Oxidising properties
- Oxidation reduction potential
- Stability in organic solvents and identity of relevant degradation products
- Storage stability and reactivity towards container material
- Stability: thermal, sunlight, metals
- pH
- Dissociation constant
- Viscosity
- Additional physico-chemical information
- Additional physico-chemical properties of nanomaterials
- Nanomaterial agglomeration / aggregation
- Nanomaterial crystalline phase
- Nanomaterial crystallite and grain size
- Nanomaterial aspect ratio / shape
- Nanomaterial specific surface area
- Nanomaterial Zeta potential
- Nanomaterial surface chemistry
- Nanomaterial dustiness
- Nanomaterial porosity
- Nanomaterial pour density
- Nanomaterial photocatalytic activity
- Nanomaterial radical formation potential
- Nanomaterial catalytic activity
- Endpoint summary
- Stability
- Biodegradation
- Bioaccumulation
- Transport and distribution
- Environmental data
- Additional information on environmental fate and behaviour
- Ecotoxicological Summary
- Aquatic toxicity
- Endpoint summary
- Short-term toxicity to fish
- Long-term toxicity to fish
- Short-term toxicity to aquatic invertebrates
- Long-term toxicity to aquatic invertebrates
- Toxicity to aquatic algae and cyanobacteria
- Toxicity to aquatic plants other than algae
- Toxicity to microorganisms
- Endocrine disrupter testing in aquatic vertebrates – in vivo
- Toxicity to other aquatic organisms
- Sediment toxicity
- Terrestrial toxicity
- Biological effects monitoring
- Biotransformation and kinetics
- Additional ecotoxological information
- Toxicological Summary
- Toxicokinetics, metabolism and distribution
- Acute Toxicity
- Irritation / corrosion
- Sensitisation
- Repeated dose toxicity
- Genetic toxicity
- Carcinogenicity
- Toxicity to reproduction
- Specific investigations
- Exposure related observations in humans
- Toxic effects on livestock and pets
- Additional toxicological data
Biodegradation in soil
Administrative data
Link to relevant study record(s)
- Endpoint:
- biodegradation in soil: simulation testing
- Type of information:
- experimental study
- Adequacy of study:
- key study
- Study period:
- August 2000 - Januar 2001
- Reliability:
- 1 (reliable without restriction)
- Qualifier:
- according to guideline
- Guideline:
- OECD Guideline 307 (Aerobic and Anaerobic Transformation in Soil)
- Version / remarks:
- 1999
- Deviations:
- no
- GLP compliance:
- yes
- Test type:
- laboratory
- Radiolabelling:
- yes
- Oxygen conditions:
- aerobic
- Soil classification:
- USDA (US Department of Agriculture)
- Year:
- 2 001
- Soil no.:
- #3
- Soil type:
- silt loam
- % Clay:
- 23.56
- % Silt:
- 56.12
- % Sand:
- 20.32
- % Org. C:
- 0.99
- pH:
- 5.8
- CEC:
- 15.49 meq/100 g soil d.w.
- % Moisture content:
- 55.35
- Soil no.:
- #2
- Soil type:
- loamy sand
- % Clay:
- 7.5
- % Silt:
- 15.4
- % Sand:
- 77.1
- % Org. C:
- 2.17
- pH:
- 5.7
- CEC:
- 11 meq/100 g soil d.w.
- Bulk density (g/cm³):
- 1 156
- % Moisture content:
- 50
- Soil no.:
- #1
- Soil type:
- sandy loam
- % Clay:
- 7.4
- % Silt:
- 26.5
- % Sand:
- 66.2
- % Org. C:
- 0.71
- pH:
- 6.5
- CEC:
- 11 meq/100 g soil d.w.
- Bulk density (g/cm³):
- 1 328
- % Moisture content:
- 37
- Details on soil characteristics:
- pH measured in CaCl2
soil 1 = Speyer 2.3/Germany
soil 2 = Speyer 2.2/Germany
soil 3 = Senozan/France
The soils have not been subfected to any pesticide and organic fertiliser treatment for the last five years.
Soil 1 and 2 were sieved through a 2 mm sieve by LUFA and stored ar RCC Ltd. at 4°C for about 6 weeks.
Soil 3 was freshly sampled by RCC Ltd. from the top 0 to 20 cm soil layer and sieved through a 2 mm sieve by RCC Ltd. prior to use. Sampling was performed according to the ISO/DIS 10381-6 guidelines.
Each soil was conditioned at room temperature for about 10 days prior to the start of the study. - Soil No.:
- #3
- Duration:
- 120 d
- Soil No.:
- #2
- Duration:
- 120 d
- Soil No.:
- #1
- Duration:
- 120 d
- Soil No.:
- #1
- Initial conc.:
- 3.61 mg/kg soil d.w.
- Based on:
- test mat.
- Parameter followed for biodegradation estimation:
- CO2 evolution
- radiochem. meas.
- Soil No.:
- #3
- Temp.:
- 20°C
- Microbial biomass:
- Start = 587 mg OC/kg soil End = 393mg OC/kg soil (20°C); 487 mg OC/kg soil (10°C)
- Soil No.:
- #2
- Temp.:
- 20°C
- Microbial biomass:
- Start = 401 mg OC/kg soil End = 406 mg OC/kg soil
- Soil No.:
- #1
- Temp.:
- 20°C
- Microbial biomass:
- Start = 142 mg OC/kg soil End = 93 mg OC/kg soil
- Details on experimental conditions:
- The test item was applied to the soils at a concentration of 3.61 mg Mancozeb/kg soil dry weight (corresponding to a field rate of about 2.7 kg a.s./ha Mancozeb; assuming a uniform distribution in the 5 cm top soil and a bulk density of 1.5 g/cm3. The soil samples were incubated at 20 ± 2 °C and for one soil at 10 ± 2 °C. All soils were maintained at a moisture content of about 40 % of the soils maximum water holding capacity (MWC).
Samples from all three soils were taken for analysis immediately after treatment and after 1, 7, 14, 28 (duplicates), 63 and 120 (duplicates) days of incubation. Volatiles and 14CO2 were collected. All samples were subjected to exhaustive solvent extractions, and the extracts were analysed by HPLC and TLC. The total radioactivity balance and the distribution of radioactivity in each incubation sample were established on each sampling day. - Soil No.:
- #3
- % Recovery:
- 95.9
- St. dev.:
- 4
- Remarks on result:
- other: incubation at 10°C
- Soil No.:
- #3
- % Recovery:
- 95.3
- St. dev.:
- 2.6
- Remarks on result:
- other: incubation at 20°C
- Soil No.:
- #2
- % Recovery:
- 99.2
- St. dev.:
- 3.1
- Remarks on result:
- other: incubation at 20°C
- Soil No.:
- #1
- % Recovery:
- 100.2
- St. dev.:
- 3.4
- Remarks on result:
- other: incubation at 20°C
- Parent/product:
- parent
- Key result
- Soil No.:
- #3
- % Degr.:
- 58.4
- Sampling time:
- 120 d
- Remarks on result:
- other: degradation at 10 °C
- Parent/product:
- parent
- Key result
- Soil No.:
- #3
- % Degr.:
- 61.6
- Sampling time:
- 120 d
- Remarks on result:
- other: parent degrades on DAT 0 with a value of 63.6 % to 2.0 % on DAT 120; degradation at 20°C
- Parent/product:
- parent
- Key result
- Soil No.:
- #2
- % Degr.:
- 67.5
- Sampling time:
- 120 d
- Remarks on result:
- other: parent degrades on DAT 0 with a value of 69.7 % to 2.2 % on DAT 120; degradation at 20°C
- Parent/product:
- parent
- Key result
- Soil No.:
- #1
- % Degr.:
- 80.8
- Parameter:
- radiochem. meas.
- Sampling time:
- 120 d
- Remarks on result:
- other: parent degrades on DAT 0 with a value of 85.2 % to 4.3 % on DAT 120; degradation at 20°C
- Key result
- Soil No.:
- #3
- DT50:
- 0.027 d
- Type:
- other: Single First Order (SFO)
- Temp.:
- 10 °C
- Remarks on result:
- other: re-analysis of the degradation kinetics according to FOCUS degradation kinetics (Hardy, 2015)
- Key result
- Soil No.:
- #3
- DT50:
- 0.027 d
- Type:
- other: Single First Order (SFO)
- Temp.:
- 20 °C
- Remarks on result:
- other: re-analysis of the degradation kinetics according to FOCUS degradation kinetics (Hardy, 2015)
- Key result
- Soil No.:
- #2
- DT50:
- 0.027 d
- Type:
- other: Single First Order (SFO)
- Temp.:
- 20 °C
- Remarks on result:
- other: re-analysis of the degradation kinetics according to FOCUS degradation kinetics (Hardy, 2015)
- Key result
- Soil No.:
- #1
- DT50:
- 0.043 d
- Type:
- other: Single First Order (SFO)
- Temp.:
- 20 °C
- Remarks on result:
- other: re-analysis of the degradation kinetics according to FOCUS degradation kinetics (Hardy, 2015)
- Transformation products:
- yes
- No.:
- #3
- No.:
- #2
- No.:
- #1
- Details on transformation products:
- Metabolite EBIS was detected at maximum amounts, 1.5 hours after application, of 29.1 %, 29.1 %, 24.8 % and 24.8 % of the applied radioactivity in soil extracts from soils I, II, III incubated at 20 °C and soil III incubated at 10 °C, respectively. Thereafter EBIS disappeared with a DT50 value of 0.6 days or less in all soils at 20 °C and 1.3 days at 10 °C.
Metabolite ETU was detected in all three soils. Maximum amounts of 22.0 %, 24.8 % and 14.7 % of the applied radioactivity were present at incubation day 1 in soils I, II and III, respectively incubated at 20 °C. For soil III incubated at 10 °C the maximum amount of ETU was detected on day 7 with 11.9 %. The DT50 values for ETU were 18.2 days, 4.4 days, and 10.7 days for soils I to III incubated at 20 °C and 23.1 days for soil III incubated at 10 °C.
Metabolite EU was detected at maximum amounts of 18.5 % (soil I, day 7), 11.8 % (soil II, day 1), 11.7 % (soil III at 20 °C, day 1) and 11.6 % (soil III at 10 °C, day 7). Thereafter, EU disappeared with a DT50 value of 2.7 days or less in all soils. Kinetic analysis indicates that EU is formed mainly from EBIS (via other transient metabolites) in this study, as well as potentially directly from ETU. - Evaporation of parent compound:
- yes
- Details on results:
- The total mean recoveries were 100.2 % ± 3.4 %, 99.2 % ± 3.1 %, 95.3 % ± 2.6 % and 95.9 % ± 4.0 % of the applied radioactivity for soils I, II, III incubated at 20 °C and soil III incubated at 10 °C, respectively. Individual recoveries ranged from 90.3 % to 106.1 % for soils I to III.
Immediately after treatment (DAT 0), 85.2 %, 69.7 % and 63.6 % of the applied radioactivity could be extracted from soils I, II and III, respectively. With increasing incubation time, the amount of extractable radioactivity decreased continuously amounting to 10.6 %, 5.2 %, 4.5 % and 10.3 % on DAT 28 in soils I, II, III incubated at 20 °C and soil III incubated at 10 °C, respectively. At the end of incubation (DAT 120) the corresponding extracted radioactivity amounted to 4.3 %, 2.2 %, 2.0 % and 5.2 % of the applied radioactivity, respectively.
The amount of non-extractable radioactivity increased for all soils to a maximum value and thereafter decreased until the end of incubation. The following maximum amounts were attained: 59.1 % (soil l/20 °C/DAT 28), 69.8 % (soil II/20 °C/DAT 28), 70.7 % (soil III/20 °C/DAT 7) and 66.7 % (soil III/10 °C/DAT 63). The maximum of bound residues in soil III was observed later for the incubation at 10 °C than at 20 °C. Therefore, the amounts of bound residues decreased on incubation DAT 120 to 49.0 %, 58.0 %, 52.0 % and 62.0 % for the four parts, respectively. The incubation at 10 °C ended at a higher amount of bound residue than the corresponding incubation at 20 °C.
Additional organic matter fractionation was performed with selected samples of soil non-extractables from DAT 120. The results show that 38.1 %, 45.9 %, 40.8 % and 38.5 % the applied radioactivity in the soils I to III incubated at 20 °C and in soil III incubated at 10 °C, respectively, were bound to the immobile humic acids and humin fractions. Similarly, the radioactivity associated with the fulvic acids fraction amounted to 14.0 %, 15.2 %, 11.9 % and 23.3 % of the applied radioactivity in the four parts, respectively.
The mineralization of [14C]-Mancozeb was high in all soils. The amount of 14CO2 evolved increased continuously with incubation time. Maximum mean values of 49.6 %, 41.8 %, 44 % and 33 % of the applied radioactivity were evolved as 14CO2 from soils I to III incubated at 20 °C and from soil III incubated at 10 °C, respectively, at the end of incubation. Volatile radioactivity other than 14CO2 did not exceed 0.1 % of the radioactivity applied.
Metabolite EBIS was detected at maximum amounts, 1.5 hours after application, of 29.1 %, 29.1 %, 24.8 % and 24.8 % of the applied radioactivity in soil extracts from soils I, II, III incubated at 20 °C and soil III incubated at 10 °C, respectively. Thereafter EBIS disappeared with a DT50 value of 0.6 days or less in all soils at 20 °C and 1.3 DAT at 10 °C.
Metabolite ETU was detected in all three soils. Maximum amounts of 22.0 %, 24.8 % and 14.7 % of the applied radioactivity were present at incubation DAT 1 in soils I, II and III, respectively incubated at 20 °C. For soil III incubated at 10 °C the maximum amount of ETU was detected on DAT 7 with 11.9 %. The DT50 values for ETU were 18.2 DAT , 4.4 DAT , and 10.7 days for soils I to III incubated at 20 °C and 23.1 DAT for soil III incubated at 10 °C.
Metabolite EU was detected at maximum amounts of 18.5 % (soil I, DAT 7), 11.8 % (soil II, DAT 1), 11.7 % (soil III at 20 °C, DAT 1) and 11.6 % (soil III at 10 °C, DAT 7). Thereafter, EU disappeared with a DT50 value of 2.7 DAT or less in all soils. Kinetic analysis indicates that EU is formed mainly from EBIS (via other transient metabolites) in this study, as well as potentially directly from ETU.
Highly transient metabolite M11 was detected at maximum amounts of 20.3 % (soil I, DAT 0.06), 16.6 % (soil II, DAT 0.06), 20.3 % (soil III at 20 °C, DAT 0.06) and 20.3 % (soil III at 10 °C, DAT 0.06). Thereafter, M11 rapidly disappeared with a DT50 value of 2-6 hours in all soils; with no residues >LOD remaining on DAT 1 in soils I and III (20°C). Evaluation of the time series data indicates that M11 rapidly forms significant levels of NER. Chromatographically, M11 appears less polar than EBIS [longer retention time by reverse phase HPLC].
New chromatographic evaluations have been made with standards not available during study conduct [TDIT and TCIT], comparing them to historical HPLC data within the study report (in relation to the renewal). TCIT and TDIT have previously been postulated as transient intermediates in the degradation pathway for metiram, but these did not correspond chromatographically with M11. M11 corresponds to the same metabolite in the hydrolysis study at pH4, but this could not be ionised by LC/MS or GC/MS by Völkel, W. (2001b). The highly transient nature of M11 (DT50 <6 hours) and non-polar nature indicate that M11 will not be a risk to groundwater or surface water. Consideration of M11 in the soil risk assessment is taken into account using a conservative DT50 for mancozeb of 0.6 days based on CS2 formation, which adequately covers the decline in total mancozeb + M11 residues of 0.04 - 0.08 days [ Hardy, IAJ (2015)].
Additionally, at least twelve unknown radioactive fractions were detected in all three soils. None of these metabolites exceeded 7.4 % of the applied radioactivity and none >5 % at two consecutive timepoints. - Conclusions:
- The degradation of [14C]-Mancozeb was investigated in three typical use soils, incubated at 20 °C under aerobic conditions for a period of up to 120 days. Additionally one soil (soil III) was also incubated at 10 °C. [14C]-Mancozeb was rapidly eliminated initially by hydrolysis to the degradates EBIS, ETU and EU with a half-life of less than 0.1 days. Kinetic re-evaluation according to FOCUS Kinetics requirements results in calculated DT50 values of up to 0.043 days for mancozeb, 0.42 days for EBIS, 15.3 days for ETU and 8.0 days for EU at 20°C (at 10°C, the corresponding DT50 values were 0.027, 0.95, 34.1 and 5.8 days).
- Executive summary:
The summary below taken from the updated RAR Volume 3 CA B8 version December 2018.
Mancozeb disappeared rapidly from the soils I, II and III. Its half llfe in any of these soils was less than 1 hour.
The metabolic pathway of Mancozeb in the soils used was similiar in all three soils. [14C]-Mancozeb was rapidly degraded to the major metabolites EBIS (M1), ETU (M2) and EU (M3) and finally to carbon dioxide. An intermediate degradation product M11 was detected, however, it disappeared rapidly in less than 1 day.
The amount of radioactive carbon dioxide evolved from soils I to III incubated at 20°C and soil III incubated at 10°C accounted for up to 49.6%, 41.8%, 44.0% and 33.0% of the applied radioactivity, respectively.Metabolite EBIS (M1) was detected at maximum amounts, 1.5 hours after application, of 29.1%, 29.1%, 24.8% and 24.8% of the applied radioactivity in soil extracts from soils I, II, III incubated at 20°C and soil III incubated at 10°C, respectively. Thereafter EBIS disappeared with a DT-50 value of 0.6 days or less in all soils at 20°C and 1.3 days at 10°C.
Metabolite ETU (M2) was detected in all three soils. Maximum amounts of 22.0%, 24.8% and 14.7% of the applied radioactivity were présent at incubation day 1 in soils I, II and III, respectively incubated at 20°C. For soil III incubated at 10°C the maximum amount of ETU was detected on day 7 11.9%. The DT-50 values for ETU were 18.2 days, 4.4 days, and 10.7 days for soils I to III incubated at 20°C and 23.1 days for soil III incubated at 10°C.
Metabolite EU (M3) was detected at maximum amounts of 18.5% (soil I, day 7), 11.8% (soil II, day 1), 11.7% (soil III at 20°C, day 1) and 11.6% (soil III at 10°C, day 7). Thereafter, EU disappeared with a DT-50 value of 2.7 days or less in all soils.
M11, an unknown intermediate, appeared only immediately after application at concentrations above 10%. It reached values of 20.3% (soils I, III at 20°C and at 10°C) and 16.6% (soil II) of the radioactivity applied 1.5 hours after application. Thereafter, it degraded rapidly, and it can therefore be concluded that its half-life is below 1 day.
Additionally, at least twelve unknown radioactive fractions were detected in ail three soils. None of these metabolites exceeded 7.4% of the applied radioactivity. Additionally, at least twelve unknown radioactive fractions were detected in all three soils. None of these metabolites exceeded 7.4% of the applied radioactivity and none >5% at two consecutive timepoints.
The non-extractable radioactivity amounted to a maximum of 59.1% (day 28), 69.8% (day 28) and 70.7% (day 7) in soils I, Il and III, respectively, incubated at 20°C and to 66.7% (day 63) in soil III incubated at 10°C. Thereafter, the mineralisation to 14C02 continued and the non-extractable radioactivity decreased to 49.0% (soil I), 58.0% (soil II), 52.0% (soil lll/20°C) and 62.0% (soil lll/10°C) after 120 days of incubation. The organic matter fractionation of the bound residues showed that the major part was bound to immobile humic acids and humin fractions amounting to 38.1%, 45.9%, 40.8% and 38.5% the applied radioactivity in the soils I to III incubated at 20°C and in soil III incubated at 10°C, respectively. The corresponding radioactivity associated with the fulvic acid fraction accounted for 14.0%, 15.2%, 11.9% and 23.3% of the applied radioactivity, respectively.
The results show that [14C]-Mancozeb was very rapidly eliminated from the test soils at both 20°C and 10°C. This rapid degradation implies that Mancozeb is initially degraded by hydrolysis. The major degradates, EBIS, ETU and EU, are themselves eliminated by subsequent biotransformation to carbon dioxide.
Incorporation into the organic matter of soil also played a significant role.
Reference
Characterisation of the extractable radioactivity from soil I (Speyer 2.3)
|
%Applied radioactivity |
|||||||||
Time (d) |
0 |
0.06 |
1 |
7 |
14 |
28 |
28 |
63 |
120 |
120 |
Mancozeb |
92.0 |
33.2 |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
EBIS |
4.6 |
29.1 |
4.9 |
1.2 |
1.2 |
0.6 |
<LOD |
0.1 |
0.2 |
<LOD |
ETU |
1.3 |
<LOD |
22.0 |
13.0 |
14.9 |
6.1 |
5.3 |
3.9 |
2.5 |
2.0 |
EU |
1.3 |
<LOD |
14.2 |
18.5 |
1.1 |
1.2 |
0.7 |
1.0 |
0.5 |
0.4 |
M11 |
0.8 |
20.3 |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
NER |
np |
18.0 |
41.3 |
55.3 |
56.9 |
59.2 |
58.9 |
53.8 |
48.4 |
49.5 |
CO2 |
np |
np |
<0.1 |
2.8 |
22.5 |
28.0 |
28.4 |
39.3 |
46.8 |
52.4 |
Total |
103.2 |
np |
95.0 |
103.1 |
98.8 |
97.7 |
97.8 |
100.1 |
99.6 |
106.1 |
np not performed LOD 0.1%
Characterisation of the extractable radioactivity from soil II (Speyer 2.2)
|
%Applied radioactivity |
|||||||||
Time (d) |
0 |
0.06 |
1 |
7 |
14 |
28 |
28 |
63 |
120 |
120 |
Mancozeb |
92.0 |
18.0 |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
EBIS |
4.6 |
29.1 |
2.8 |
1.6 |
0.7 |
|
0.2 |
0.2 |
<LOD |
0.1 |
ETU |
1.3 |
6.0 |
24.8 |
8.6 |
4.0 |
2.7 |
2.4 |
2.0 |
1.3 |
1.3 |
EU |
1.3 |
<LOD |
11.8 |
1.4 |
1.2 |
0.4 |
0.2 |
0.1 |
0.6 |
0.6 |
M11 |
0.8 |
16.6 |
1.7 |
<LOD |
0.3 |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
NER |
np |
31.8 |
50.6 |
69.7 |
67.9 |
67.3 |
72.2 |
61.7 |
56.4 |
59.5 |
CO2 |
np |
np |
<0.1 |
12.1 |
18.5 |
24.9 |
25.4 |
33.5 |
41.1 |
42.4 |
Total |
101.5 |
np |
96.6 |
95.6 |
96.4 |
97.3 |
103.0 |
98.7 |
99.6 |
104.1 |
np not performed LOD 0.1%
Characterisation of the extractable radioactivity from soil III (Senozan) – 20oC
|
%Applied radioactivity |
|||||||||
Time (d) |
0 |
0.06 |
1 |
7 |
14 |
28 |
28 |
63 |
120 |
120 |
Mancozeb |
92.0 |
18.4 |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
EBIS |
4.6 |
24.8 |
7.6 |
2.8 |
0.7 |
0.2 |
0.2 |
0.3 |
<LOD |
<LOD |
ETU |
1.3 |
<LOD |
14.7 |
10.4 |
5.8 |
2.9 |
2.7 |
1.1 |
0.9 |
0.7 |
EU |
1.3 |
<LOD |
11.7 |
2.4 |
0.7 |
0.7 |
0.6 |
0.6 |
0.8 |
0.9 |
M11 |
0.8 |
20.3 |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
M19 |
<LOD |
<LOD |
7.4 |
3.1 |
0.3 |
0.2 |
<LOD |
<LOD |
<LOD |
<LOD |
NER |
np |
30.7 |
48.6 |
70.7 |
59.0 |
58.7 |
60.4 |
57.6 |
51.9 |
52.1 |
CO2 |
np |
np |
<0.1 |
3.5 |
22.4 |
29.5 |
28.7 |
37.1 |
44.9 |
43.0 |
Total |
94.3 |
np |
97.0 |
95.8 |
91.0 |
93.0 |
93.3 |
97.6 |
98.8 |
97.1 |
np not performed LOD 0.1%
Characterisation of the extractable radioactivity from soil III (Senozan) – 10oC
|
%Applied radioactivity |
|||||||||
Time (d) |
0 |
0.06 |
1 |
7 |
14 |
28 |
28 |
63 |
120 |
120 |
Mancozeb |
92.0 |
18.4 |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
EBIS |
4.6 |
24.8 |
14.5 |
0.8 |
1.7 |
0.8 |
1.3 |
0.8 |
<LOD |
<LOD |
ETU |
1.3 |
<LOD |
3.3 |
11.9 |
6.3 |
5.5 |
5.7 |
2.6 |
1.6 |
1.5 |
EU |
1.3 |
<LOD |
8.0 |
11.6 |
1.7 |
1.1 |
0.6 |
0.7 |
0.8 |
0.9 |
M11 |
0.8 |
20.3 |
<LOD |
2.0 |
<LOD |
<LOD |
0.6 |
<LOD |
<LOD |
<LOD |
M19 |
<LOD |
<LOD |
<LOD |
5.9 |
3.2 |
<LOD |
<LOD |
<LOD |
<LOD |
<LOD |
M23 |
<LOD |
<LOD |
6.9 |
<LOD |
<LOD |
<LOD |
<LOD |
1.5 |
1.2 |
1.4 |
NER |
30.7 |
np |
52.2 |
61.1 |
65.1 |
64.3 |
64.6 |
66.7 |
62.0 |
61.9 |
CO2 |
np |
np |
<0.1 |
<0.1 |
7.9 |
15.7 |
16.1 |
25.5 |
31.7 |
34.2 |
Total |
94.3 |
np |
97.9 |
97.7 |
92.6 |
90.3 |
90.9 |
99.6 |
98.7 |
101.4 |
np not performed LOD 0.1%
DT50 values of Mancozeb and its metabolites EBIS, ETU
and EU according to Hardy, 2015
|
DT50 [days] |
|||
|
Soil I – 20°C |
Soil II – 20°C |
Soil III – 20°C |
Soil III – 10°C |
Mancozeb |
0.043 |
0.027 |
0.027 |
0.027 |
EBIS |
0.29 |
0.24 |
0.42 |
0.95 |
ETU |
15.3 |
4.6 |
8.8 |
34.1 |
EU |
8.0 |
2.1 |
2.3 |
5.8 |
Description of key information
The degradation of [14C]-Mancozeb was investigated in three typical use soils, incubated at 20 °C under aerobic conditions for a period of up to 120 days. Additionally one soil (soil III) was also incubated at 10 °C. [14C]-Mancozeb was rapidly eliminated initially by hydrolysis to the degradates EBIS, ETU and EU with a half-life of less than 0.1 days. Kinetic re-evaluation according to FOCUS Kinetics requirements results in calculated DT50 values of up to 0.043 days for mancozeb, 0.42 days for EBIS, 15.3 days for ETU and 8.0 days for EU at 20°C (at 10°C, the corresponding DT50 values were 0.027, 0.95, 34.1 and 5.8 days).
Key value for chemical safety assessment
- Half-life in soil:
- 0.043 d
- at the temperature of:
- 20 °C
Additional information
The degradation of [14C]-Mancozeb was first investigated within the soil degradation study by Völkel (2001) in three typical use soils (sandy loam, loamy sand, silt loam), incubated at 20 °C under aerobic conditions for a period of up to 120 days. Additionally one soil (soil III) was also incubated at 10 °C. [14C]-Mancozeb was rapidly eliminated initially by hydrolysis to the degradates EBIS, ETU and EU with a half-life of less than 0.1 days.
The data by the study of Völkel, 2001 were re-assessed according to to FOCUS Kinetics guidance to derive DT50 values and formation fractions for mancozeb and its metabolites EBIS, ETU and EU by Hardy, 2015.
The results of the kinetic modelling evaluations indicate a modified degradation pathway for mancozeb and its metabolites in these soils. Initial evaluations with the linear pathway mancozeb-EBIS-ETU-EU were not successful and were not able to adequately fit the data, as the apparent slow decline of ETU in these soils is not consistent with the rapid formation/decline of EU (assuming a direct pathway only from ETU). An additional pathway from EBIS-EU significantly improved the fits but indicated minimal transfer from ETU-EU, thus the pathway was simplified with formation of EU only from EBIS.
Trigger endpoints
DegT50 (days) DegT90 (days)
Soil 1 0.043 0.141
Soil 2 0.027 0.088
20°C
Soil 3 0.027 0.090
10°C
Soil 3 0.027 0.090
Modelling endpoints
DegT50 (days) DegT90 (days)
Soil 1 0.043 0.036
Soil 2 0.027 0.027
Soil 3 0.027 0.024
The behaviour of mancozeb has been investigated in eight soils under laboratory conditions at 20-23oC [Randazzo (1986); Bieber and Kröhn (1989); Todt and Conradt (1989), summarised in the original Monograph (Annex I Inclusion) and Völkel (2001). In the Bieber and Kröhn (1989) study, 14C-mancozeb was used to follow the degradation of mancozeb in a silt loam soil. The CS2 evolution method was used in the Randazzo (1986) and Todt and Conradt (1989) studies, thus the calculated DT50 values represent the sum of CS2 liberating components as conservative over-estimates for mancozeb.
Soil characteristics
Randazzo, 1986:
Classification | Silt loam |
Sand content | 16.0 % |
Silt content | 58.0 % |
Clay content | 26.0 % |
Organic matter content | 2.0 % |
Moisture capacity | 27.4 % |
pH | 6.1 |
Cation exchange capacity | 11.9 meq/100 g |
Bieber and Kröhn, 1989:
Classification | silt loam |
Vegetation | pasture, sheep grazing |
Organic carbon | 1.7 % |
pH | 6.8 |
Water capacity | 48.3 g/100 g soil |
Soil particles < 0.002 mm | 21.4 % |
0.002-0.006 mm | 4.6 % |
0.006-0.02 mm | 9.5 % |
0.02-0.063 mm | 54.2 % |
0.063-0.2 mm | 10.3 % |
Microbial biomass | 27.5 mgC/100 g soil |
Todt and Conradt, 1989:
| Soil N° 1 | Soil N° 2 | Soil N° 3 |
Origin | Offenbach-Queich Südpfalz | Neustadt-Lachen Pfalz | Neustadt-Lachen Pfalz |
Characteristics | Sand | Sand | Loamy sand |
Current culture | Potato | Stone-fruit | Wine |
Organic carbon (%) | 1.1 | 1.34 | 0.83 |
% particles < 0.002 mm | 10.6 | 5.5 | 12.9 |
0.002-0.006 | 4.3 | 4.7 | 5.2 |
0.006-0.02 | 9.4 | 11.7 | 13.7 |
0.02-0.063 | 19.0 | 20.0 | 23.5 |
0.063-0.2 | 20.9 | 24.2 | 11.7 |
0.2-0.63 | 33.1 | 31.2 | 30.1 |
0.63-2 | 2.7 | 2.7 | 2.9 |
pH | 6.3 | 6.8 | 7.2 |
Microbial biomass (mg micro-C/100 g soil) at start of experiment | 38 | 46 | 27 |
Microbial biomass (mg micro-C/100 g soil) at end of experiment | 24 | 26 | 18 |
Völkel, 2001:
| Soil I | Soil II | Soil III |
| Speyer 2.3 | Speyer 2.2 | Senozan |
Texture (USDA) | Sandy loam | Loamy sand | Silt loam |
Sand (%) | 66.2 | 77.1 | 20.32 |
Silt (%) | 26.5 | 15.4 | 56.12 |
Clay (%) | 7.4 | 7.5 | 23.56 |
Organic carbon (%) | 0.71 | 2.17 | 0.99 |
pH [CaCl2] | 6.5 | 5.7 | 5.8 |
CEC (meq/100g soil) | 11 | 11 | 15.49 |
MWHC (%w/w) | 37 | 50 | 55.35 |
pF 2.5 (%w/w) | - | - | 24.19 |
Biomass (mg OC/kg soil) |
|
|
|
Start | 142 | 401 | 587 |
End | 93 | 406 | 393 (20oC) |
Materials and methods
Bieber and Kröhn, 1989:
Radio labelled [14C]-Mancozeb (specific radioactivity: 1.029 MBq/mg, ETU content < 0.1%) was used together with un-labelled Mancozeb technical (purity: 87.7 %).
[14C]Mancozeb was applied in solution in acetone at ca. 4 mg a.i./kg soil (ca. 3kg a.i./ha) in the degradation experiment - up to 30 mg [14C]Mancozeb in the experiments for metabolite identification. The temperature was 20-21°C.
Sampling was performed at 0, 1, 3, 16, 24, 40, and 48 hours and 1, 2, 4 and 8 week. The analysis of CS2 was determined according to the DFG-method S15 (xanthogenate, 302 nm, 2 cm cuvettes, S15-5).
Metabolites were identified by Thin Layer Chromatography with reference chemicals (ETU, DIDT, EMI, EU, TCIT, Sulphur, Jaffe's base) using 2 different solvents mixtures: acetonitrile: water = 85: 15 (v/v) and methanol: toluene = 1: 1(v/v). Compounds (metabolites) are identified by GC/MS and radioactivity was determined by Liquid Scintillation Spectrometry.
Todt and Conradt, 1989:
Technical Mancozeb (Purity:87.7%) has been used with BBA standards soils provided by Lufa Speyer.
Mancozeb was applied at a rate of 3.0 - 5.3 mg a.i./kg soil (applied in solution in acetone). Sampling was performed at 0, 1, 2, 6, 24, 48 hours and 1, 2, 4 and 8 weeks. Mancozeb was analysed by CS2 according to the DFG-method S15 (xanthogenate, 302 nm, 2 cm cuvettes, S15-5).
Völkel, 2001:
For details please refer to the key study under point 5.2.3 Biodegradation in soil - aerobic.
Kinetic evaluation:
Kinetic modelling following the appropriate FOCUS Kinetics (2006) flowchart was carried out using CAKE v3.1 by Hardy, 2015.
Results and discussion
The geometric mean normalised DegT50 is rounded up to 0.1 days for model input.
For PECsoil calculations, a conservative DT50 is selected as 0.6 days - mean un-normalised SFO DT50 of the 20 and 10ppm silt loam soils based on CS2 liberation. This DT50 value is highly conservative for mancozeb and ensures that the soil exposure/risk assessment covers any transient unidentified components in soil.
Degradation parameters and trigger endpoints for mancozeb
Soil | Best-fit model | Chi2 | Model parameters | Trigger endpoints | |
DegT50 | DegT90 | ||||
Silt loam (20ppm) | DFOP | 3.1 | k1 [d-1]: 7.818 | 0.105* | 1.35* |
Silt loam (10ppm) | FOMC | 7.0 | α 0.6848 | 0.159* | 2.53* |
Marsh | FOMC | 8.8 | α 0.5977 | 0.017 | 0.35 |
Silty sand 1 | DFOP | 11.3 | k1 [d-1]: 46.42 | 0.027* | 29.6* |
Silty sand 2 | DFOP | 10.3 | k1 [d-1]: 24.82 | 0.039* | 33.3* |
Humic loamy sand | FOMC | 11.5 | α 0.3084 | 0.055* | 11.4* |
Speyer 2.3 | SFO | 1.01 | k [d-1]: 16.3080 | 0.043 | 0.141 |
Speyer 2.2 | SFO | 1.01 | k [d-1]: 26.1120 | 0.027 | 0.088 |
Senozan | SFO | 1.01 | k [d-1]: 25.7520 | 0.027 | 0.090 |
* Total of CS2 liberating components, thus conservative for mancozeb
Degradation parameters and modelling endpoints for mancozeb – 14C studies
Soil | Best-fit model | Chi2 | t-test | Modelling endpoints | |
DegT50 | Normalised DegT50 | ||||
Marsh | FOMC | 8.8 | N/A | 0.106 | 0.082 |
Speyer 2.3 | SFO | 1.01 | 5.00E-04 | 0.043 | 0.036 |
Speyer 2.2 | SFO | 1.01 | 5.52E-04 | 0.027 | 0.027 |
Senozan | SFO | 1.01 | 5.48E-04 | 0.027 | 0.024 |
Geometric mean |
|
|
|
| 0.037 |
a Reference conditions: 20oC, pF2
Degradation parameters and modelling endpoints for mancozeb - CS2 liberation studies
Soil | Best-fit model | Chi2 | t-test | Modelling endpoints | |
DegT50 | Normalised DegT50 | ||||
Silt loam (20ppm) | SFO | 13.7 | 1.03E-04 | 0.595c | 0.69c,d* |
Silt loam (10ppm) | SFO | 11.5 | 2.66E-04 | 0.638c | 0.74c,d* |
Silty sand 1 | DFOPb | 11.3 | 0.008107 | 0.015 | 0.015* |
Silty sand 2 | DFOPb | 10.3 | 1.78E-04 | 0.028 | 0.028* |
Humic loamy sand | DFOPb | 13.3 | 0.001329 | 0.048 | 0.048* |
a Reference conditions: 20oC, pF2
b DFOP k1 degradation rate selected as representing mancozeb degradation in the CS2 liberation study.
c Conservative SFO fit that includes other CS2 liberating components
d geometric mean of the two silt loam soils = 0.70 days
* CS2 liberation studies
Degradation parameters and modelling endpoints for mancozeb
Soil | Best-fit model | Chi2 | t-test | Modelling endpoints | |
DegT50 | Normalised DegT50 | ||||
Silt loam (20ppm) | SFO | 13.7 | 1.03E-04 | 0.595c | 0.69c,d* |
Silt loam (10ppm) | SFO | 11.5 | 2.66E-04 | 0.638c | 0.74c,d* |
Silty sand 1 | DFOPb | 11.3 | 0.008107 | 0.015 | 0.015* |
Silty sand 2 | DFOPb | 10.3 | 1.78E-04 | 0.028 | 0.028* |
Humic loamy sand | DFOPb | 13.3 | 0.001329 | 0.048 | 0.048* |
Marsh | FOMC | 8.8 | - | 0.106 | 0.082 |
Speyer 2.3 | SFO | 1.01 | 5.00E-04 | 0.043 | 0.036 |
Speyer 2.2 | SFO | 1.01 | 5.52E-04 | 0.027 | 0.027 |
Senozan | SFO | 1.01 | 5.48E-04 | 0.027 | 0.024 |
Geometric mean |
|
|
|
| 0.05d,e |
a Reference conditions: 20oC, pF2
b DFOP k1 degradation rate selected as representing mancozeb degradation in the CS2 liberation study.
c Conservative SFO fit that includes other CS2 liberating components
d geometric mean of the two silt loam soils (0.7 days) calculated first
e rounded to 0.1 days for model input
* CS2 liberation studies
Degradation parameters for total mancozeb + M11 residues
Soil | DT50 | DT50 | Chi2 | t-test | Visual |
Speyer 2.3 | 0.076 | 1.8 | 0.1 | 0.001128 | Good |
Speyer 2.2 | 0.042 | 1.0 | 2.7 | 1.78E-06 | Good |
Senozan | 0.048 | 1.1 | 0.1 | 0.001018 | Good |
Formation/decline degradation parameters for M11 residues
Soil | DT50 | DT50 | t-test | ffm | Visual |
Speyer 2.3 | 0.095 | 2.3 | 1.07E-04 | 0.44 | Good |
Speyer 2.2 | 0.257 | 6.2 | 6.22E-05 | 0.24 | Good |
Senozan | 0.102 | 2.5 | 6.19E-05 | 0.35 | Good |
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