### Test Material: Nicosulfuron

MRID 48354304

Title: Sarff, P. 2004. Aerobic aquatic metabolism of 14 

### C-nicosulfuron (DPXV9360) in two water/sediment systems.

EPA PC Code: 129008

OCSPP Guideline: 835.4300

For Cambridge Environmental

Primary Reviewer: Lynne Binari Signature:

Date: 2/16/12

Secondary Reviewer: Kathleen Ferguson Signature:

Date: 2/16/12

QC/QA Manager: Joan Gaidos Signature:

Date: 2/16/12Nicosulfuron (PC 129008) MRID 48354304

Page 3 of 33 

### sediment, extractable [ 14 

### C]residues were 14.2-14.8% of the a pplied at day 0, a maximum 26.0% at 60 days and 21.5-22.4% at study term ination, while nonextractable [ 14 

### C]residues increased from 1.0-1.1% at day 0 to 19.4-20.1% at study termination. For both systems, total evolved CO 2 

### and other volatile compounds were each <1% of applied.

Table 1. Results Summary

Total System Observed

DT 50 (days) Calculated

Half-life

(days) Model

Parameters Transformation Products (% of Applied) 1

Major Minor

Catalonia, Spain lake

water-silt loam sediment (20°C, water pH 8.2, sediment pH 7.8) ca . 80 82.5 C 0 = 101.8
k = -0.0084

r 2 = 0.9970 (2-parameter

SFO 2 ) IN-37740 (maximum 29.1% at 102 days)

Nonextractable sediment

residues (maximum 17.7% at 102 days) IN-V9367 (maximum 5.3% at 102 days) IN-77799 (maximum 3.0%

at 102 days) IN-HYY21 (maximum 6.6%

at 102 days)

CO 2 (maximum 0.297% at 102 days)

North Dakota lake

water-sand sediment (20°C, water pH 8.3, sediment pH 8.2) ca . 95 101.9 C 0 = 96.2
k = -0.0068

r 2 = 0.9976 (2-parameter SFO) IN-37740 (maximum 20.3% at 60 days)

Nonextractable sediment

residues (maximum 20.1% at 102 days) IN-V9367 (maximum 4.1% at 102 days) IN-77799 (maximum 2.3% at 102 days) IN-HYY21 (maximum 3.2% at 102 days)

CO 2 (maximum 0.668% at 102 days)
1 IN-37740, IN-77799 and IN-HYY21 contained both the pyridine and pyrimidine labels, while IN-V9367 contained only the pyridine label. 2 SFO means “single first-order” kinetics model.



### I. Materials and Methods

A. Materials

1. Test Materials: [Pryidine-2- 14 

### C]- and [pyrimidine-2- 14 

### C]-nicosulfuron (pp. 19-20). Pyridine-2- 14 

### C Specific activity: 62.9 μCi/mg

N O CH 3

O CH 3 N N H

O N H

S O

O

N N C H 3

C H 3 O

* 

### Radiochemical purity: ≥ 96.7% (pp. 19, 25; Figure 5, p. 73) Chemical purity: Not reported.

Lot No.: 2385-050

Pyrimidine-2- 14 

### C Specific activity: 62.2 μCi/mg

N N O CH 3

O CH 3 N N H

O N H

S O

O N C H 3

C H 3 O * 

### Radiochemical purity: ≥ 95.1% (pp. 19, 25; Figure 6, p. 74) Chemical purity: Not reported.

Lot No.: 2406-007Nicosulfuron (PC 129008) MRID 48354304

Page 4 of 33 

### Solubility in water: 370 mg/L at pH 4.6 (p. 21) 390 mg/L at pH 5.1-5.6 9,000 mg/L at pH 6.3 15,000 mg/L at pH 6.6 18,000 mg/L at pH 7.2 >250,000 mg/L at pH 9.0

2. Reference Compounds: The following standards were used in the analysis:

Table 2. Reference Compounds 1

Applicant’s
Code Name Chemical Name Purity (%) Lot No.

Nicosulfuron (DPX-V9360) 2-[[[[(4,6-Dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-N,Ndimethyl-3-pyridinecarboxamide 97.9 116

IN-V9367 2-(Aminosulfonyl)-N,N-dimethyl-3-pyridinecarboxamide 99.7 3

IN-37740 2-[[(3,4-Dihydro-6-methoxy-4-oxopyrimidin-2- yl]aminocarbonyl]aminosulfonyl]-N,N-dimethyl-3-pyridinecarboxamide -- 2 4

-- IN-J0290 4,6-Dimethoxy-2-pyrimidinamine 99.1 3
IN-H1043 2-Amino-6-hydroxy-4(1H)-pyrimidinone 97.0 7

IN-74427 2-[(4,6-Dimethoxy-2-pyrimidinyl)-amino]-N,N-dimethyl-3- pyridinecarboxamide 99.4 2

IN-W9807 2-[[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]-Nmethyl-3-pyridinecarboxamide 97.2 3

IN-64554 Isothiaxolo[5,4-B]pyridin-3(2H)-one,1,1-dioxide 99.5 2

IN-GDC42 2-[[[[(Aminocarbonyl)amino]carbonyl]amino]sulfonyl]-N,N-dimethyl-3- pyridinecarboxamide -- --

IN-77799 2-[(Aminocarbonyl)[4-methoxy-6-(methyldioxy)-2-pyrimidinyl]amino]- N,N-dimethyl-3-pyridinecarboxamide -- --

IN-69188 1-(4,6-Dimethoxypyrimidin-2-yl)pyrido[2,3-d]pyrimidine-2,4-dione -- --
IN-H9235 2-Amino-4-hydroxy-6-methoxypyrimidine -- --

IN-HYY21 2-[[[[(Aminoiminomethyl)amino]carbonyl]amino]sulfonyl]-N,N-dimethyl3-pyridinecarboxamide -- --
Data obtained from pp. 19, 21-22; Figure 1, pp. 65-69 of the study report. 1 Reference compounds supplied by DuPont Agricultural Products, Wilmington, Delaware. (p. 21). 2 Information not reported.



### 3. Water-sediment: Water-sediment system description a nd characterization are summarized in

Table 3 and Tables 4a-4b , respectively.

Table 3. Water-Sediment Collection and Storage

Description Estany de Banyoles (Lake of Banyoles) Golden Lake

Geographic location Estany de Banyoles, Catalonia, Spain Golden Lake, Steele County,
North Dakota.

Soil series Not reported.

Pesticide use history at the collection site Not reported.

Collection date Not reported.

Collection procedures Water: Not reported.

Sediment: Not reported.Nicosulfuron (PC 129008) MRID 48354304

Page 5 of 33 Description Estany de Banyoles (Lake of Banyoles) Golden Lake

Storage conditions Sediment stored at ca . 4°C in darkness. Storage conditions of the water

were not described.

Storage length Approximately one month; specific intervals/dates were not reported.

Preparation Water: ca. 2-mm sieved.

Sediment: ca . 2-mm sieved.
Data obtained from pp. 23, 36 of the study report.



### Table 4a. Properties of the Water-S ediment: Estany de Banyoles

Parameter (unit) Field Sampling/Post Handling Stage of Test Procedure 1

Prior to Test 2 During Test End of Test

Water Temperature (oC) -- pH 8.2 8.26, 7.83 7.38-8.13 7.17, 7.34 TOC (mg/L) 2.0 -- -- --

O 2 (mg/L) -- 8.10, 8.30 5.10-8.50 5.85, 5.83 Redox potential (mV) +187, +182 +163 to +266 +213, +249

Sediment Sampling Depth (cm) -- Soil Texture (USDA) Silt loam

% Sand 43

% Silt 52 % Clay 5 pH (1:1, soil:water ratio) 7.8 7.78, 7.70 7.33-7.98 7.48, 7.48

Organic matter (%) Walkley-Black: 2.1

Furnace method: 1.6 Organic carbon (%, Wa lkely-Black with heat) 1.2 --
--
CEC (meq/100 g) 5.6

Soil moisture content (%) At 0 bar: 70.1

At 1/3 bar: 24.2

At 1.0 bar: 9.4

at 15 bar: 4.4 Bulk density (g/cm 3 ) 0.86 Microbial biomass (μg/g dry wt.) 3 -- 52.9 17.3 Redox potential (mV) +177, +177 +161 to +252 +215, +248 Data obtained from pp. 36-37; Table 1, pp. 48-49; Table 4A, p. 53; Table 4C, p. 54 of the study report. Soil texture was confirmed using USDA-NRCS technical support tools. -- = Not reported. 1 Treated systems, combined labels (T able 4A, p. 53; Table 4C, p. 54). 2 Day 0 posttreatment. 3 Fumigation-extraction method (pp. 36-37).



### Table 4b. Properties of the Water-Sediment: Golden Lake

Parameter (unit) Field Sampling/Post Handling Stage of Test Procedure 1

Prior to Test 2 During Test End of Test

Water Temperature (oC) -- pH 8.3 8.07, 8.28 7.74-8.52 8.43, 8.51 TOC (mg/L) 12.2 -- -- --

O 2 (mg/L) -- 5.44, 6.98 4.50-7.85 5.50, 5.50Nicosulfuron (PC 129008) MRID 48354304

Page 6 of 33 Parameter (unit) Field Sampling/Post Handling Stage of Test Procedure 1

Prior to Test 2 During Test End of Test
Redox potential (mV) +151, +28 +70 to +155.6 +142.5, +132.5

Sediment Sampling Depth (cm) -- Soil Texture (USDA) Sand

% Sand 88

% Silt 8 % Clay 4 pH (1:1, soil:water ratio) 8.2 7.18, 7.03 6.96-8.36 7.62, 8.02 Organic matter (%, Walkley-Black) 1.6 Organic carbon (%, Wa lkely-Black with heat) 0.9 --
--
CEC (meq/100 g) 11.7

Soil moisture content (%) At 0 bar: 45.7

At 1/3 bar: 12.3

At 1.0 bar: 9.2

at 15 bar: 7.2 Bulk density (g/cm 3 ) 1.10 Microbial biomass (μg C/g) 3 34.2 54.2 Redox potential (mV) -5, +42 -34 to +161.4 +151.4, +133.4 Data obtained from pp. 36-37; Table 1, pp. 48-49; Table 5A, p. 55; Table 5C, p. 56 of the study report. Soil texture was confirmed using USDA-NRCS technical support tools. -- = Not reported. 1 Treated systems, combined labels (T able 5A, p. 55; Table 5C, p. 56). 2 Day 0 posttreatment. 3 Fumigation-extraction method (pp. 36-37).



### B. Study Design

1. Experimental Conditions: Experimental conditions are summarized in Table 5

.

Table 5. Experimental Design

Parameter Details Duration of the test (days) 102

Water Type and size of filter used: ca . 2-mm Amount of sediment and water per treatment

Water: 160 mL total volume

Sediment: ca . 40 g dry wt.
Water/sediment ratio: 4:1 (160 mL:40 g dry wt.).
Control conditions (if used) Sterile controls were not used.

Pre-treatment acclimation 20 ± 2°C in darkness Estany de Banyoles: 21 days.
Golden Lake: 13 days.
Application rates
Nominal: 0.15 mg a.i./L

Actual: Estany de Banyoles: Pyridine label: 0.152 mg a.i./L Pyrimidine label: 0.153 mg a.i./L.

Golden Lake: Pyridine label: 0.141 mg a.i./L Pyrimidine label: 0.139 mg a.i./L
Number of replicates
Controls (if used): Sterile controls were not used.Nicosulfuron (PC 129008) MRID 48354304

Page 7 of 33 Parameter Details

Treatment: Per system and label type, twelve water-sediment systems were treated to allow for a single system per label/system type at each of ten sampling intervals, two reserves.
Test apparatus

Type/material/volume: Glass gas-washing bottles (250 mL), containing the watersediment system, connected in series (sample train per system/label type) to a continuous flow-through (moistened air, flow rate not reported) volatiles trapping system. The test apparatus is illustrated in Figure 2, p. 70.

Details of traps for CO 2 and other volatiles (if any): In sequence as follows: ethylene glycol (one trap) to collect organic volatiles and 1N KOH solution (two traps) to collect CO 2 ; trapping solution volumes not reported.
If no traps were used, is the system closed/open? Volatiles traps were used.

Identity and final concentration (based on water volume) of co-solvent 10mM ammonium

acetate Estany de Banyoles: 0.04-0.06% by
volume.
Golden Lake: 0.18-0.19% by volume.
Test material application method

Volume of the

test solution
used/treatment: Estany de Banyoles: 59.9 μL/160 mL for [pyridine-2- 14 C]-label, 89.2 μL/160 mL for [pyrimidine-2- 14 C]-label

Golden Lake: 304 μL/160 mL for [pyridine-2- 14 C]-label, 283 μL/160 mL for [pyrimidine-2- 14 C]-label
Application method ( e.g. , mixed/not mixed): Test solution applied to surface of water layer using a Rainin EDP Plus automatic pipet.

Any indication of the test material adsorbing to the walls of the test apparatus? Not indicated. Water-sediment transferred to centrifuge bottles using water phase for processing, with system material balances of 94.8-101.9% of applied at day 0 posttreatment.
Experimental conditions
Temperature (  C): 20 ± 2  C, range not reported

Continuous darkness: Yes

Other details (if any) Per label type, a water sample (160 mL) was treated in the same manner as the water-sediment systems to be used as a dose control.

Per system type, one untreated wa ter-sediment system (160 mL:40 g dry wt.) was prepared and maintained to monitor system parameters (dissolved oxygen, pH, redox potential) throughout the
incubation.

Per system type, two untreated water-sediment systems (1,600 mL:400 g dry wt.) were prepared in 3-L metabolism vessels

connected to a continuous air-f low system and maintained for biomass determinations at study initiation and termination.

Per label type, one silt loam sediment (Estany de Banyoles) system (160 mL:40 g dry wt.) was treated at a nominal 1 mg a.i./L (10x rate) and maintained for possible transformation product identification analyses.

The nominal test application rate of 0.15 μg a.i./g water used in this study was reported as equivalent to a field use rate of 450 g a.i./ha as applied to a 1 ha body of water of 30-cm depth. This rate was reported as c a . 10-fold the maximum field use rate, but was required to allow for detection of 1% of the applied radioactivity. Data obtained from pp. 19, 23-28; Table 2, p. 50; Tables 6-7, pp. 57-60; Figure 2, p. 70 of the study report.Nicosulfuron (PC 129008) MRID 48354304

Page 8 of 33 

### No supplementary studies were described.

2. Sampling: Sampling details are summarized in Table 6

.

Table 6. Sampling Details

Criteria Details

Sampling intervals (days) Estany de Banyoles: 0, 3, 7, 14, 21, 31, 45, 59, 75 and 102

Golden Lake: 0, 3, 7, 14, 21, 29, 47, 60, 75 and 102

Sampling method Per system and label type, a single sample was collected at each sampling interval

Method of collection of CO 2 and organic volatile compounds Volatiles traps were collected a nd/or replaced at each sampling interval after day 0.

Sampling intervals/times for

Sterility check (if used): Sterile controls were not used.

Water level maintenance: None required

Redox potential, dissolved oxygen and pH in the water layer, and redox potential and pH in sediment: Measured in treated systems coll ected at each sampling interval. Probes were placed in the water phase or just below surface for

sediment.

Sample storage before analysis Water and sediment were separated and the sediment extracted the day of sampling.

Water layer and sediment extract samples were stored frozen until analysis. Water samples were typically analyzed within one week and sediment extract samples within ca . 1 month; extraction and analysis dates were not provided.

Storage stability experiments reportedly showed nicosulfuron to be stable for up to six months; however, supporting data were not provided. Repeat analyses of se lected water layer and sediment extract samples conducted up to ca . 18 months after initial analyses found quantitatively similar product profiles.

Other observation (if any 

### ) None.
Data obtained from pp. 27-28, 43; Table 2, p. 51; Figures 20-21, pp. 106-107 of the study report.



### 3. Analytical Procedures:

Separation of the water and sediment: The water layer was separated from the sediment by centrifugation, decanted and analyzed by LSC (p. 28).

Extraction/clean up/concentration methods: Sample processing is illustrated in Figure 3 (p. 71).

Water samples were filtered (0.2-μm) and analyzed directly using LSC and HPLC (pp. 28-29).

Sediment was extracted three times with acetone:0.1M ammonium carbonate (4:1, v:v; 160 mL; p. 29). For each extraction, the sample and extrac tion solvent were shaken for 30 minutes, then centrifuged. Extracts were combined and a subsampl e was concentrated to near dryness by rotary evaporation. Resulting residues were reconstituted in acetone, filtered (0.45-μm), concentrated toNicosulfuron (PC 129008) MRID 48354304

Page 9 of 33 

### dryness under nitrogen, then reconstituted in wate r:methanol (95:5, v:v) and re-filtered. Aliquots were analyzed using LSC and HPLC.

Determination of unextracted residues: Extracted sediment was air-dried, homogenized using mortar and pestle, then analyzed by LSC followi ng combustion (p. 29). Oxid izer efficiency was reported as 95-105% (p. 30).

Determination of volatile compounds: Trapping solutions were an alyzed using LSC (p. 28).

Total radioactivity measurement: Total [ 14 

### C]residues were determined by summing the

concentrations of residues measured in the water layer, sediment extracts, extracted sediment and trapping solutions (pp. 32-33).

Derivatization method A derivatization method was not employed.

Identification and quantification of parent and transformation compounds: Water layer and sediment extract samples were analyzed by HPLC using a Supelco Discovery C18 column eluted with a gradient mobile phase of (A) 0.1% formic acid in water and (B) methanol (pp. 30-31; Figure 4, p. 72). Column recoveries were reported as "approximately 90-110%"; HPLC results were not corrected for column recovery (p. 38).

Identifications of parent compound and a major transformation product were confirmed using the water layer from the high dose (10x) pyridine label treated silt loam (Estany de Banyoles) system (pp. 29, 32, 41-42). An aliquot of the water layer wa s concentrated under n itrogen, filtered (0.45- μm, then 0.2-μm), and analyzed using LC/MS/MS w ith electrospray ionizati on in positive ion mode (p. 32).

Detection limits (LOD, LOQ) for the parent and transformation products: Limits of detection (LOD) and quantitation (L OQ) are summarized in Table 7

.

Table 7. Limits of Detection (LOD) and Quantita tion (LOQ), Expressed as Percentage of the Applied Radioactivity

Sample Type LOD LOQ
HPLC analyses

Aqueous 0.22-0.25 0.87-0.96
Organic 0.00030-0.00071 0.0012-0.0027

LSC analyses

KOH trap 0.023-0.026 0.085-0.094

Ethylene glycol trap 0.0088-0.0097 0.034-0.037

Aqueous phase 0.056-0.062 0.22-0.24

Organic extracts 0.35-0.39 1.4-1.5

Soil combustions 0.098-0.11 0.35-0.39
Data obtained from Table 3, p. 52 of the study report.Nicosulfuron (PC 129008) MRID 48354304

Page 10 of 33 

### II. Results and Discussion

A. Findings:

Total mass balances and distribution of radioactivity are presented in Tables 8a, 8b, 8c, and 8d

.

The incubation temperature and flood level were reportedly maintained throughout the experiment, except on one occasion when the incubation temperature exceeded 20 ± 2°C (maximum 26.3°C) for approximately 5 hours; the specific interval the deviation occurred was not reported (p. 36). At study termination in the treated silt loam (Estany de Banyoles ) system, dissolved oxygen, redox potentials and pH in the water layer were 5.83-5.85 mg/L, +213 to +249 mV, and 7.17-7.34, respectively, with redox potentials and pH in the sediment of +215 to +248 mV and 7.48 (n = 2), respectively (Table 4A, p. 53; Table 4C, p. 54). At study termination in th e treated sand (Golden Lake) system, dissolved oxygen, redox potentials and pH in the water layer were 5.50 mg/L (n = 2), +132.5 to +142.5 mV, and 8.43-8.51, respectively, with re dox potentials and pH in the sediment of +133.4 to +151.4 mV and 7.62-8.02, respectively (Table 5A, p. 55; Table 5C, p. 56). The physical/chemical properties in the treated systems were comparable to those measured in untreated control systems (Tables 4A-5D, pp. 53-56). Sediments were viable at initia tion and termination (p. 37).

Overall [ 14 

### C]residue recoveries for pyridine- and pyr imidine-label treated systems averaged 102.0  3.6% (range 97.8-106.6%) and 97.9 ± 4.1% (range 93.0- 107.3%) of the applied, respectively, for the silt loam sediment system and 99.2  3.7% (range 94.5-105.4%) a nd 100.5 ± 3.7% (range 94.8- 105.6%), respectively, for the sand sediment syst em (Tables 6-7, pp. 57-60; DER Attachment 2).

Recoveries of total residues di d not decrease over time.

### Table 8a. Transformation of [Pyridine-2- 14 

### C]Nicosulfuron, Expressed as Percentage of the Applied Radioactivity, in Aerobi c Lake Water-Silt Loam Sediment

Compound Sampling Intervals (days posttreatment)

0 3 7 14 21 31 45 59 75 102

Nicosulfuron (DPX-V9360) 101.3 94.3 93.5 94.0 91.8 81.6 70.7 67.2 53.4 42.1

IN-37740 0 0 0 4.4 7.2 13.1 17.5 24.4 26.4 29.1

IN-V9367 0 0 0 0 0 0 2.4 3.1 3.4 5.3

IN-77799 0 0 0 0 0 0 1.0 2.3 1.9 2.8

IN-HYY21 0 0 0 0 0 0 0 0 0 0.8

Unknowns 1 0.6 3.4 4.0 2.8 3.1 5.1 2.6 4.4 8.2 8.7

Extracted residues 19.5 25.2 23.7 24.6 25.6 25.1 23.9 27.4 23.2 26.1

Nonextractable

residues 0 0.189 0.248 0.485 0.831 1.41 3.55 6.52 10.5 17.7

CO 2 2 -- 0.018 0.018 0.018 0.022 0.026 0.026 0.026 0.050 0.102

Other volatile compounds -- 0 0 0 0 0 0 0 0 0

Total recovery 101.9 97.8 97.8 101.8 102.9 101.2 97.8 107.9 103.8 106.6
Data obtained from Table 6, p. 57; Table 8, p. 61 of the study report. -- = not analyzed. 1 Unassigned [ 14 C]residues with no individual unidentified HPLC peak detected at >2.1% (day 102) of applied in the water layer or >2.1% (day 102) in the sediment (Table 8, p. 61). 2 All samples were connected to the same set of volatile traps.



### Table 8b. Transformation of [Pyrimidine-2- 14 

### C]Nicosulfuron, Expressed as Percentage of the Applied Radioactivity, in Aerobi c Lake Water-Silt Loam Sediment

Compound Sampling Intervals (days posttreatment)

0 3 7 14 21 31 45 59 75 102

Nicosulfuron (DPX-V9360) 97.3 91.1 96.5 100.5 89.4 80.4 66.9 61.6 49.4 38.7

IN-37740 0 1.7 0 5.7 8.1 13.0 17.6 23.8 24.3 22.2

IN-77799 0 0 0 0 0 0 0.9 2.0 1.9 3.0

IN-HYY21 0 0 0 0 0 0 0 0 0 6.6

Unknowns 1 0 0.5 0.3 0.6 1.4 1.9 7.7 6.5 7.8 10.0

Extracted residues 20.0 20.6 21.7 25.4 24.8 23.6 25.0 26.2 22.1 24.4

Nonextractable

residues 0 0 0.249 0.581 0.872 1.74 3.65 7.07 9.51 17.5

CO 2 2 -- 0 0 0 0.007 0.020 0.020 0.108 0.177 0.297

Other volatile compounds -- 0 0 0 0 0 0 0 0 0

Total recovery 97.3 93.3 97.0 107.3 99.8 97.0 96.7 101.0 93.0 96.1
Data obtained from Table 6, p. 58; Table 8, p. 62 of the study report. -- = not analyzed. 1 Unassigned [ 14 C]residues with no individual unidentified HPLC peak detected at >1.6% (day 102) of applied in the water layer or >2.4% (day 102) in the sediment (Table 8, p. 62). 2 All samples were connected to the same set of volatile traps.Nicosulfuron (PC 129008) MRID 48354304

Page 12 of 33 

### Table 8c. Transformation of [Pyridine-2- 14 

### C]Nicosulfuron, Expressed as Percentage of the Applied Radioactivity, in Aero bic Lake Water-Sand Sediment

Compound Sampling Intervals (days posttreatment)

0 3 7 14 21 29 47 60 75 102

Nicosulfuron (DPX-V9360) 93.3 90.9 95.0 88.1 88.3 73.9 68.6 57.3 54.5 45.6

IN-37740 0 0 0 3.1 5.9 8.5 14.1 20.3 18.7 18.7

IN-V9367 0 0 0 0 0 0 0 3.9 3.8 4.1

IN-77799 0 0 0 0 0 0 0 1.9 1.6 2.3

IN-HYY21 0 0 0 0 0 0 0 0 0 3.2

Unknowns 1 3.9 1.1 4.5 1.7 2.3 6.5 7.1 5.9 8.4 5.6

Extracted residues 14.2 18.5 17.1 19.0 22.6 20.6 23.1 24.0 25.9 21.5

Nonextractable

residues 1.0 3.3 5.2 4.3 8.9 5.6 8.0 9.2 14.5 19.4

CO 2 2 -- 0 0 0 0.008 0.015 0.039 0.067 0.109 0.199

Other volatile compounds -- 0 0 0 0 0 0 0 0

Total recovery 98.1 95.2 104.7 97.2 105.4 94.5 97.8 98.4 101.6 99.2
Data obtained from Table 7, p. 59; Table 9, p. 63 of the study report. -- = not analyzed. 1 Unassigned [ 14 C]residues with no individual unidentified HPLC peak detected at >2.8% (day 75) of applied in the water layer or >0.9% (day 102) in the sediment (Table 9, p. 63). 2 All samples were connected to the same set of volatile traps.



### Table 8d. Transformation of [Pyrimidine-2- 14 

### C]Nicosulfuron, Expressed as Percentage of the Applied Radioactivity, in Aero bic Lake Water-Sand Sediment

Compound Sampling Intervals (days posttreatment)

0 3 7 14 21 29 47 60 75 102

Nicosulfuron (DPX-V9360) 90.1 98.1 92.7 86.7 88.8 79.1 76.1 65.5 62.8 48.3

IN-37740 0 0 0 0.6 5.6 7.9 14.2 14.2 12.2 18.7

IN-77799 0 0 0 0 0 0 0 1.6 1.3 2.2

IN-HYY21 0 0 0 0 0 0 0 0 2.2 2.4

Unknowns 1 3.5 1.4 6.3 4.5 2.8 4.3 4.4 10.4 8.5 7.4

Extracted residues 14.8 17.3 19.3 20.5 25.5 23.5 25.2 26.0 24.3 22.4

Nonextractable

residues 1.1 1.8 6.6 4.4 7.2 8.8 8.8 10.8 9.1 20.1

CO 2 2 -- 0.003 0.010 0.016 0.033 0.082 0.199 0.198 0.373 0.668

Other volatile compounds -- 0 0 0 0 0 0 0 0 0

Total recovery 94.8 101.4 105.6 96.2 104.2 100.3 103.6 102.7 96.6 99.8
Data obtained from Table 7, p. 60; Table 9, p. 64 of the study report. -- = not analyzed. 1 Unassigned [ 14 C]residues with no individual unidentified HPLC peak detected at >1.7% (day 75) of applied in the water layer or >1.1% (day 102) in the sediment (Table 9, p. 64). 2 All samples were connected to the same set of volatile traps.Nicosulfuron (PC 129008) MRID 48354304

Page 13 of 33 

### B. Transformation of Parent Comp ound and Transformation Products: Transformation kinetics of the parent compound and transfor mation product information are summarized in Tables

9 and 10 , respectively. Degradation patte rns were comparable between the foreign (Spain) silt loam sediment system and the domestic (N orth Dakota) sand sediment system.

Based on nonlinear (SigmaPlot v. 9.0, exponential, one compartment/two parameter) regression analysis and using individual total system data for each sampling interval, nicosulfuron dissipated

with reviewer-calculated ha lf-lives of 83 days in the silt loam sediment system and 102 days in the sand sediment system (DER Attachment 2).

Using first-order kinetics (one compartment/two-parameter single first-order and first-order multicompartment), the study author similarly estimated half-lives of 83 and 102 days in the silt loam sediment (Estany de Banyoles) and sand sedime nt (Golden Lake) systems, respectively, and

estimated DT 90 

### values of 276 and 340 days, respectivel y (p. 42; Figure 16, pp. 99-100; Figure 18, pp. 103-104).

Table 9. Transformation Kinetics of Nicosulfuron (Combined Labels) in Aerobic WaterSediment Systems

Total System Observed DT 50 (days) 1 Observed DT 90 (days) 1 Calculated

Half-life 2

(days) Kinetics Model Model

Parameters

Catalonia, Spain lake watersilt loam sediment (20°C, water pH 8.2, sediment pH 7.8) ca . 80 >102 82.5 2-Parameter, Single

first-order C 0 = 101.8
k =- 0.0084

r 2 = 0.9970

North Dakota lake watersand sediment (20°C, water pH 8.3, sediment pH 8.2) ca . 95 >102 101.9 2-Parameter, Single
first-order C 0 = 96.2
k = -0.0068

r 2 = 0.9976

1 Based on mean nicosulfuron levels at each interv al and 100% application to water layer at time 0. 2 Calculated by the reviewer using SigmaPlot v 9.0 (expone ntial; one compartment/two parameter) and data obtained from Tables 8-9, pp. 61-64 of the study report (DER Attachment 2).



### Transformation Products: One major transformation product and three minor products were identified by HPLC, with iden tification of the major product c onfirmed using LC/MS/MS (pp. 41- 42; Figure 1, pp. 65-66, 68-69; Figure 4, p. 72; Figures 9-14, pp. 80-96):

 

### 2-[[(3,4-dihydro-6-methoxy-4-oxopyrimidin-2 -yl]aminocarbonyl]aminosulfonyl]-N,Ndimethyl-3-pyridinecarboxamide (IN-37740);

 

### 2-[(aminocarbonyl)[4-methoxy-6- (methyldioxy)-2-pyrimidinyl ]amino]-N,N-dimethyl-3- pyridinecarboxamide (IN-77799);

 

### 2-[[[[(aminoiminomethyl)amino]carbonyl ]amino]sulfonyl]-N,N-dimethyl-3- pyridinecarboxamide (IN-HYY21); and

 

### 2-(aminosulfonyl)-N,N-diemthyl-3 -pyridinecarboxamide (IN-V9367).Nicosulfuron (PC 129008) MRID 48354304

Page 14 of 33 

### Table 10. Transformation Products of Nicosu lfuron (Combined Labels) in Aerobic WaterSediment Systems 1

Transformation products Lake Water-Silt Loam Sedimen t Lake Water-Sand Sediment

% Applied

Maximum Final Maximum Final
IN-37740 29.1 at 102 days 29.1 at 102 days 20.3 at 60 days 18.7 at 102 days

IN-V9367 5.3 at 102 days 5.3 at 102 days 4.1 at 102 days 4.1 at 102 days

IN-77799 3.0 at 102 days 3.0 at 102 days 2.3 at 102 days 2.3 at 102 days

IN-HYY21 6.6 at 102 days 6.6 at 102 days 3.2 at 102 days 3.2 at 102 days
Data obtained from Tables 8-9, pp. 61-64 of the study report. 1 IN-37740, IN-77799 and IN-HYY21 contained both the pyridine and pyrimidine labels, while IN-V9367 contained only the pyridine label.



### Transformation Pathway: A transformation pathway was provi ded by the study author and is illustrated below (pp. 42-43; Figure 19, p. 105). Based on the study results, nicosulfuron degrades to one major transformation product, IN-37740, se veral minor products, minor levels of CO 2 

### and significant levels of sediment bound residues. Th e primary pathway was demethylation of the pyrimidinyl methoxy group to form IN-37740. Cleavag e of the pyrimidine ring of IN-37740 yields IN-HYY21, while hydrolysis of the sulfonylurea urea bridge forms IN-V9367. Another minor pathway was contraction of the su lfonylurea bridge through loss of SO 2 

### to yield IN-77799.Nicosulfuron (PC 129008) MRID 48354304

Page 15 of 33 

### III. Study Deficiencies and Reviewer's Comments

1. For the sand sediment system, average mass balances determined by the reviewer differed from those reported by the study author. For the pyridine and pyrimidine labels, the reviewer determined average recoveries of 99.2  3.7% and 100.5 ± 3.7%, respectively, whereas the study author reported recoveries of 99.0 ± 4.3% and 100.9 ± 4.1%, respecti vely (p. 39; Table 7, pp. 59-60; DER Attachment 2). No explanation for the discrepancies could be determined.

2. The study was conducted for an insufficient length of time. The patterns of formation and

decline of the transformation products were not established at study termination. The major transformation product, IN-37740, was detected at a maximum 29.1% of the applied at study termination in the silt loam system, and was de tected at a maximum 20.3% at 60 days in the sand system declining only to 18.7% at study te rmination (Tables 8-9, pp. 61-64). Additionally, all three minor products, IN-V9360, IN-77799 and HYY21, were detected at maximum concentrations at study termination.

3. Nonextractable [ 14 

### C]residues were detected at maximums of 17.5-20.1% of the applied at study termination, but were not characterized thr ough organic matter fractionation (Tables 6-7, pp. 57- 60).

4. Per treatment type (water-sediment system, label) , a single treated sample was collected at each sampling interval for analysis. Duplicate repl icate samples should be taken at each sampling interval for analysis to allow for a better assessment of the study results.

5. The pesticide use histories for the source sites for the test waters a nd sediments were not reported. The water and sediment we re not analyzed for pesticides to establish that they were not contaminated prior to treatment.

6. The length of storage and storage conditions of the collected water and sediment prior to preparation of test systems for pre-treatment accl imation was not adequately addressed. Current OCSPP guidelines specify if storag e is necessary, sediment and water should be sieved and stored together, water-logged (6- 10 cm water layer), in the dark, at 4 ± 2°C for a maximum of 4 weeks. Water and sediment were reportedly used within approximately one month after collection; however, specific intervals/dates were not provided (p. 36) . Sediment was reported

as stored at ca . 4°C in darkness (p. 23). Storage cond itions of the water were not described.

7. The amount of sediment utilized per test system was 40 g (dry wt.) for these experiments; sediment layer depths were not reported (p. 24). Current OCSPP guidelines recommend a minimum amount of 50 g of sediment (dry wt. ba sis) per incubation vessel is utilized, with a sediment layer depth of 2.5 ± 0.5 cm. The water: sediment volume ratio of the test systems was 4:1, within OCSPP guidelines.

8. All samples from a given treatment were connected in series to the same set of volatile traps (p. 24). The reported concentration of CO 2 

### was adjusted based on the number of samples in the chamber at the time of sampling (p. 33). It is pr eferred that sample vessels be connected to individual volatile traps so that more preci se material balances for each sample can be

calculated.Nicosulfuron (PC 129008) MRID 48354304

Page 16 of 33 

### IV. References

1. U.S. Environmental Protection Agency. 2008. Fate, Transport and Tr ansformation Test - Guidelines, OPPTS 835.4300, Aerobic Aquatic Meta bolism. Office of Prevention, Pesticides and Toxic Substances, Washi ngton, DC. EPA 712-C-08-018.

2. U.S. Environmental Protection Agency. 1982. Pest icide Assessment Guidelines, Subdivision N, Chemistry: Environmental Fate, Section 162-4, Aerobic Aquatic Me tabolism Studies. Office of Pesticide and Toxic Substances, Washington, DC. EPA 540/9-82-021.Nicosulfuron (PC 129008) MRID 48354304Page 17 of 33DER ATTACHMENT 1. Nicosulfuron and Its Environmental Transformation Products.ACode Name/SynonymChemical NameChemical StructureStudy TypeMRIDMaximum%AR (day)Final %AR(study length)PARENTNicosulfuron(DPX-V9360)IUPAC:2-[(4,6-Dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-N,NdimethylnicotinamideCAS:2-[[[[(4,6-Dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-N,N-dimethyl-3-pyridinecarboxamideCAS No.:111991-09-4Formula:C15H18N6O6SMW:410.411 g/molSMILES:c1(c(nccc1)S(=O)(=O)NC(=O)Nc2nc(cc(n2)OC)OC)C(=O)N(C)CSOOOO CH3O CH3NNNHNHONCH3CH3N835.4300Aerobic aquaticmetabolism48354304Lake water-siltloam sediment:101.3% (0 d)42.1% (102 d)Lake water-sandsediment: 93.3%(0 d)48.3% (102 d)MAJOR (>10%) TRANSFORMATION PRODUCTSIN-37740CAS:2-[[(3,4-Dihydro-6-methoxy4-oxopyrimidin-2-yl]aminocarbonyl]aminosulfonyl]-N,N-dimethyl-3-pyridinecarboxamideFormula:C14H16N6O6SMW:396.38 g/molSMILES:c1(c(nccc1)S(=O)(=O)NC(N/C2=N/C(=C\C(N2)=O)OC)=O)C(N(C)C)=O835.4300Aerobic aquaticmetabolism48354304Lake water-siltloam sediment:29.1% (102 d)29.1% (102 d)Lake water-sandsediment: 20.3%(60 d)18.7% (102 d)Pyridinesulfonamide(IN-V9367)CAS:2-(Aminosulfonyl)-N,Ndimethyl-3-pyridinecarboxamideCAS No.:112006-75-4835.4300Aerobic aquaticmetabolism48354304Lake water-siltloam sediment:5.3% (102 d)5.3% (102 d)Nicosulfuron (PC 129008) MRID 48354304Page 18 of 33Code Name/SynonymChemical NameChemical StructureStudy TypeMRIDMaximum%AR (day)Final %AR(study length)Formula:C8H11N3O3SMW:229.259 g/molSMILES:c1(cccnc1S(=O)(=O)N)C(=O)N(C)CLake water-sandsediment: 4.1%(102 d)4.1% (102 d)UnextractedresiduesNANA835.4300Aerobic aquaticmetabolism48354304Lake water-siltloam sediment:17.7% (102 d)17.7% (102 d)Lake water-sandsediment: 20.1%(102 d)20.1% (102 d)MINOR (<10%) TRANSFORMATION PRODUCTSIN-77799(DPX-V9360 Ipsoprecursor)CAS:2-[(Aminocarbonyl)[4-methoxy-6-(methyldioxy)-2-pyrimidinyl]amino]-N,N-dimethyl3-pyridinecarboxamideFormula:C15H18N6O4MW:346.34 g/molSMILES:NC(N(c1nc(cc(n1)OC)OC)c2ncccc2C(N(C)C)=O)=O835.4300Aerobic aquaticmetabolism48354304Lake water-siltloam sediment:3.0% (102 d)3.0% (102 d)Lake water-sandsediment: 2.3%(102 d)2.3% (102 d)IN-HYY21CAS:2-[[[[(Aminoiminomethyl)amino]carbonyl]amino]sulfonyl]-N,Ndimethyl-3-pyridinecarboxamideFormula:C10H14N6O4SMW:314.33 g/molSMILES:c1(c(nccc1)S(=O)(=O)NC(NC(=N)N)=O)C(N(C)C)=O835.4300Aerobic aquaticmetabolism48354304Lake water-siltloam sediment:6.6% (102 d)6.6% (102 d)Lake water-sandsediment: 3.2%(102 d)3.2% (102 d)Nicosulfuron (PC 129008) MRID 48354304Page 19 of 33Code Name/SynonymChemical NameChemical StructureStudy TypeMRIDMaximum%AR (day)Final %AR(study length)Carbon dioxideCarbon dioxideFormula:CO2MW:44 g/molSMILES:C(=O)=O835.4300Aerobic aquaticmetabolism48354304Lake water-siltloam sediment:0.297% (102 d)0.297% (102 d)Lake water-sandsediment:0.668% (102 d)0.668% (102 d)REFERENCE COMPOUNDS NOT IDENTIFIEDIN-74427(DPX-V9360 Ipsoproduct)CAS:2-[(4,6-Dimethoxy-2-pyrimidinyl)-amino]-N,N-dimethyl3-pyridinecarboxamideFormula:C14H17N5O3MW: 303.323 g/molSMILES:c1(c(nccc1)Nc2nc(cc(n2)OC)OC)C(N(C)C)=O835.4300Aerobic aquaticmetabolism48354304 NA NAO,O-Bisdesmethylpyrimidine amine(IN-H1043)CAS:2-Amino-6-hydroxy-4(1H)-pyrimidinoneCAS No.:56-09-7Formula:C4H5N3O2MW:127.103 g/molSMILES:n1c(nc(cc1O)O)N835.4300Aerobic aquaticmetabolism48354304NANAN-Desmethyl DPXV9360(IN-W9807)CAS:2-[[[[(4,6-Dimethoxypyrimidin-2yl)amino]carbonyl]-amino]sulfonyl]-N-methyl-3-pyridinecarboxamideFormula:C14H16N6O6SMW:396.384 g/molSMILES:c1(c(nccc1)S(=O)(=O)NC(Nc2nc(cc(n2)OC)OC)=O)C(NC)=O835.4300Aerobic aquaticmetabolism48354304NANANicosulfuron (PC 129008) MRID 48354304Page 20 of 33Code Name/SynonymChemical NameChemical StructureStudy TypeMRIDMaximum%AR (day)Final %AR(study length)O,O-Desmethylpyrimidine amine(IN-H9235)CAS:2-Amino-4-hydroxy-6-methoxypyrimidineFormula:C5H7N3O2MW:141.130 g/molSMILES:c1c(nc(nc1OC)N)O835.4300Aerobic aquaticmetabolism48354304 NA NAPyrimidine amine(IN-J0290)CAS:4,6-Dimethoxy-2-pyrimidinamineCAS No.:36315-01-2Formula:C6H9N3O2MW:155.15 g/molSMILES:Nc1nc(cc(n1)OC)OC835.4300Aerobic aquaticmetabolism48354304 NA NAPyridine saccharinanalog(IN-64554)CAS:Isothiaxolo[5,4-b]pyridin3(2H)-one,1,1-dioxideCAS No.:138417-40-0Formula:C6H4N2O3SMW:184.17 g/molSMILES:c12cccnc1S(NC2=O)(=O)=O835.4300Aerobic aquaticmetabolism48354304 NA NAIN-GDC42CAS:2-[[[[(Aminocarbonyl)amino]carbonyl]amino]sulfonyl]-N,N-dimethyl-3-pyridinecarboxamideFormula:C10H13N5O5SMW:315.309 g/molSMILES:c1(ncccc1C(=O)N(C)C)S(NC(NC(N)=O)=O)(=O)=O835.4300Aerobic aquaticmetabolism48354304 NA NANicosulfuron (PC 129008) MRID 48354304Page 21 of 33Code Name/SynonymChemical NameChemical StructureStudy TypeMRIDMaximum%AR (day)Final %AR(study length)IN-69188CAS:1-(4,6-Dimethoxypyrimidin2-yl)pyrido[2,3-d]pyrimidine-2,4-dioneFormula:C10H13N5O5SMW:315.309 g/molSMILES:c1(ncccc1C(=O)N(C)C)S(NC(NC(N)=O)=O)(=O)=O835.4300Aerobic aquaticmetabolism48354304 NANAAAR means “applied radioactivity”. MW means “molecular weight”. NA means "not applicable".1 Expressed as percentage of recovered radioactivity.Nicosulfuron (PC 129008) MRID 48354304Page 22 of 33Attachment 2: Statistics Spreadsheets and GraphsChemical: NicosulfuronMRID: 48354304PC: 129008Guideline: 835.4300Silt Loam (Estany de Banyoles) systems: Total system, labels combinedLinearNonlinearHalf-life (days): 78.0 Half-life (days): 82.5r2: 0.9970Days Nicosulfuron (DPX-V9360)Posttreatment(% ofapplied)Ln (%applied)0 101.3 4.61810 97.3 4.57783 94.3 4.54653 91.1 4.51207 93.5 4.53807 96.5 4.569514 94.0 4.543314 100.5 4.610221 91.8 4.519621 89.4 4.493131 81.6 4.401831 80.4 4.387045 70.7 4.258445 66.9 4.203259 67.2 4.207759 61.6 4.120775 53.4 3.977875 49.4 3.9000102 42.1 3.7400102 38.7 3.6558Nicosulfuron (PC 129008) MRID 48354304Page 23 of 33Data obtained from Table 8,pp. 61-62 of the study report.SUMMARY OUTPUTRegression StatisticsMultiple R 0.98236497R Square 0.965040935Adjusted RSquare 0.963098765Standard Error 0.057612993Observations 20ANOVAdf SS MS FSignificanceFRegression 1 1.649298636 1.649298636 496.8879111 1.4698E-14Residual 18 0.059746625 0.003319257Total 19 1.70904526CoefficientsStandardError t Stat P-value Lower 95% Upper 95% Lower 95.0% Upper 95.0%Intercept 4.636218892 0.019194999 241.5326505 4.68832E-33 4.595891696 4.676546088 4.595891696 4.676546088X Variable 1-0.008885003 0.000398592 -22.29098273 1.4698E-14-0.009722413-0.008047592-0.009722413-0.008047592Nicosulfuron (PC 129008) MRID 48354304Page 24 of 33Chemical: NicosulfuronMRID: 48354304PC: 129008Guideline: 835.4300Sand (Golden Lake) systems: Total system, labels combinedLinearNonlinearHalf-life (days): 100.0 Half-life (days): 101.9r2: 0.9976Days Nicosulfuron (DPX-V9360)Posttreatment(% ofapplied)Ln (%applied)0 93.3 4.53580 90.1 4.50093 90.9 4.50983 98.1 4.58607 95.0 4.55397 92.7 4.529414 88.1 4.478514 86.7 4.462521 88.3 4.480721 88.8 4.486429 73.9 4.302729 79.1 4.370747 68.6 4.228347 76.1 4.332060 57.3 4.048360 65.5 4.182175 54.5 3.998275 62.8 4.1400102 45.6 3.8199102 48.3 3.8774Data obtained from Table 9,pp. 63-64 of the study report.SUMMARY OUTPUTNicosulfuron (PC 129008) MRID 48354304Page 25 of 33Regression StatisticsMultiple R 0.974304231R Square 0.949268735Adjusted RSquare 0.946450332Standard Error 0.054907877Observations 20ANOVAdf SS MS FSignificanceFRegression 1 1.015442404 1.015442404 336.8107893 4.22579E-13Residual 18 0.054267749 0.003014875Total 19 1.069710153CoefficientsStandardError t Stat P-value Lower 95% Upper 95% Lower 95.0% Upper 95.0%Intercept 4.56943354 0.018268529 250.1259751 2.4992E-33 4.531052785 4.607814294 4.531052785 4.607814294X Variable 1-0.006934738 0.000377865 -18.35240554 4.22579E-13-0.007728603-0.006140872-0.007728603-0.006140872Nicosulfuron (PC 129008) MRID 48354304

Page 26 of 33 Chemical: Nicosulfuron

MRID:
48354304
PC: 129008
Guideline: 835.4300 Silt Loam (Estany de Bany oles) systems: Total system, labels combined Nonlinear Regression

Data Source: Data 1 in 129008 48354304 835.4300 Silt loam.JNB Equation: Single, 2 Parameter

R Rsqr Adj Rsqr Standard Error of Estimate

0.9985 0.9970 0.9967 4.6163

Coefficient Std. Error t P VIF

a 101.7947 1.7407 58.4806 <0.0001 1.7757
b 0.0084 0.0005 16.1711 <0.0001 1.7757

Analysis of Variance:

DF SS MS Regression 2 129416.6872 64708.3436
Residual 18 383.5828 21.3102

Total 20 129800.2700 6490.0135

Statistical Tests:

PRESS 470.7657

Durbin-Watson Statistic 0.7604 Failed

Normality Test Passed (P = 0.9919)

K-S Statistic = 0.0938 Significance Level = 0.9919

Constant Variance Test Passed (P = 0.7000)

Power of performed test wi th alpha = 0.0500: 1.0000

Regression Diagnostics:
Row Predicted Residual Std. Res. Stud. Res. Stud. Del. Res.

1 101.7947 -0.4947 -0.1072 -0.1157 -0.1125

2 101.7947 -4.4947 -0.9737 -1.0513 -1.0545

3 99.2758 -4.9758 -1.0779 -1.1491 -1.1601

4 99.2758 -8.1758 -1.7711 -1.8881 -2.0490<

5 96.0139 -2.5139 -0.5446 -0.5730 -0.5620

6 96.0139 0.4861 0.1053 0.1108 0.1077

7 90.5614 3.4386 0.7449 0.7723 0.7633

8 90.5614 9.9386 2.1529 2.2322< 2.5509<

9 85.4186 6.3814 1.3824 1.4231 1.4681

10 85.4186 3.9814 0.8625 0.8879 0.8824

11 78.5742 3.0258 0.6555 0.6740 0.6634

12 78.5742 1.8258 0.3955 0.4067 0.3971 Chemical: Nicosulfuron

MRID:Nicosulfuron (PC 129008) MRID 48354304

Page 27 of 33 48354304
PC: 129008
Guideline: 835.4300 Silt Loam (Estany de Bany oles) systems: Total system, labels combined

13 69.9033 0.7967 0.1726 0.1790 0.1741

14 69.9033 -3.0033 -0.6506 -0.6748 -0.6642

15 62.1894 5.0106 1.0854 1.1420 1.1523

16 62.1894 -0.5894 -0.1277 -0.1343 -0.1306

17 54.4101 -1.0101 -0.2188 -0.2343 -0.2280

18 54.4101 -5.0101 -1.0853 -1.1619 -1.1740

19 43.4253 -1.3253 -0.2871 -0.3144 -0.3064

20 43.4253 -4.7253 -1.0236 -1.1209 -1.1295

Influence Diagnostics: Row Cook's Dist Leverage DFFITS

1 0.0011 0.1422 -0.0458

2 0.0916 0.1422 -0.4293

3 0.0902 0.1201 -0.4287

4 0.2434 0.1201 -0.7572

5 0.0176 0.0968 -0.1840

6 0.0007 0.0968 0.0353

7 0.0224 0.0698 0.2090

8 0.1868 0.0698 0.6985

9 0.0606 0.0564 0.3591

10 0.0236 0.0564 0.2158

11 0.0130 0.0541 0.1587

12 0.0047 0.0541 0.0950

13 0.0012 0.0704 0.0479

14 0.0173 0.0704 -0.1829

15 0.0697 0.0966 0.3768

16 0.0010 0.0966 -0.0427

17 0.0040 0.1274 -0.0871

18 0.0986 0.1274 -0.4487

19 0.0098 0.1661 -0.1367

20 0.1251 0.1661 -0.5041

95% Confidence: Row Predicted Regr. 5% Regr. 95% Pop. 5% Pop. 95%

1 101.7947 98.1377 105.4517 91.4297 112.1597

2 101.7947 98.1377 105.4517 91.4297 112.1597

3 99.2758 95.9141 102.6374 89.0112 109.5403

4 99.2758 95.9141 102.6374 89.0112 109.5403

5 96.0139 92.9966 99.0313 85.8569 106.1709

6 96.0139 92.9966 99.0313 85.8569 106.1709

7 90.5614 88.0000 93.1229 80.5304 100.5925

8 90.5614 88.0000 93.1229 80.5304 100.5925

9 85.4186 83.1143 87.7229 75.4501 95.3870

10 85.4186 83.1143 87.7229 75.4501 95.3870

11 78.5742 76.3177 80.8306 68.6167 88.5317

12 78.5742 76.3177 80.8306 68.6167 88.5317

13 69.9033 67.3292 72.4775 59.8691 79.9376

14 69.9033 67.3292 72.4775 59.8691 79.9376

15 62.1894 59.1753 65.2034 52.0333 72.3454

16 62.1894 59.1753 65.2034 52.0333 72.3454 Chemical: Nicosulfuron

MRID:
48354304
PC: 129008Nicosulfuron (PC 129008) MRID 48354304

Page 28 of 33 Guideline: 835.4300 Silt Loam (Estany de Bany oles) systems: Total system, labels combined

17 54.4101 50.9480 57.8723 44.1122 64.7080

18 54.4101 50.9480 57.8723 44.1122 64.7080

19 43.4253 39.4728 47.3779 32.9524 53.8983

20 43.4253 39.4728 47.3779 32.9524 53.8983

Fit Equation Description: [Variables] x = col(1) y = col(2) reciprocal_y = 1/abs(y) reciprocal_ysquare = 1/y^2
'Automatic Initial Parameter Estimate Functions F(q)=if(size(x)>1, if(total(abs(y))>0, ape(x,log(abs(y)),1,0,1), -306), 0) asign(q)=if(mean(q)>=0,1,-1) [Parameters] a = if(F(0)[1]< 307, if(F(0)[1]>-307, asign(y)*10^F(0)[1], asign(y)*10^(-307)), asign(y)*10^307) ''Auto {{previous: 101.795}} b = if(x50(x,y)-min(x)=0, 1, -ln(.5)/(x50(x,y)-min(x))) ''Auto {{previous: 0.00835211}} [Equation] f = a*exp(-b*x) fit f to y ''fit f to y with weight reciprocal_y ''fit f to y with weight reciprocal_ysquare [Constraints]

b>0 [Options]
tolerance=1e-10 stepsize=1

iterations=200

Number of Iterations Performed = 6Nicosulfuron (PC 129008) MRID 48354304

Page 29 of 33Nicosulfuron (PC 129008) MRID 48354304

Page 30 of 33 Chemical: Nicosulfuron
MRID: 48354304
PC: 129008
Guideline: 835.4300 Sand (Golden Lake) systems: Total system, labels combined Nonlinear Regression

Data Source: Data 1 in 129008 48354304 835.4300 Sand.JNB Equation: Single, 2 Parameter

R Rsqr Adj Rsqr Standard Error of Estimate

0.9988 0.9976 0.9974 4.0320

Coefficient Std. Error t P VIF

a 96.1846 1.4840 64.8142 <0.0001 1.8173
b 0.0068 0.0004 15.6654 <0.0001 1.8173

Analysis of Variance:

DF SS MS Regression 2 124110.8779 62055.4390
Residual 18 292.6321 16.2573

Total 20 124403.5100 6220.1755

Statistical Tests:

PRESS 358.6015

Durbin-Watson Statistic 2.3731 Passed

Normality Test Passed (P = 0.9866)

K-S Statistic = 0.0980 Significance Level = 0.9866

Constant Variance Test Passed (P = 0.7576)

Power of performed test wi th alpha = 0.0500: 1.0000

Regression Diagnostics:
Row Predicted Residual Std. Res. Stud. Res. Stud. Del. Res.

1 96.1846 -2.8846 -0.7154 -0.7694 -0.7604

2 96.1846 -6.0846 -1.5091 -1.6230 -1.7071

3 94.2475 -3.3475 -0.8302 -0.8832 -0.8775

4 94.2475 3.8525 0.9555 1.0164 1.0174

5 91.7252 3.2748 0.8122 0.8540 0.8473

6 91.7252 0.9748 0.2418 0.2542 0.2475

7 87.4726 0.6274 0.1556 0.1614 0.1570

8 87.4726 -0.7726 -0.1916 -0.1987 -0.1933

9 83.4171 4.8829 1.2110 1.2469 1.2678

10 83.4171 5.3829 1.3350 1.3746 1.4120

11 79.0120 -5.1120 -1.2678 -1.3023 -1.3298

12 79.0120 0.0880 0.0218 0.0224 0.0218

13 69.9324 -1.3324 -0.3304 -0.3426 -0.3340 Chemical: NicosulfuronNicosulfuron (PC 129008) MRID 48354304

Page 31 of 33 MRID: 48354304
PC: 129008
Guideline: 835.4300 Sand (Golden Lake) systems: Total system, labels combined

14 69.9324 6.1676 1.5297 1.5857 1.6615

15 64.0309 -6.7309 -1.6694 -1.7544 -1.8726

16 64.0309 1.4691 0.3644 0.3829 0.3737

17 57.8377 -3.3377 -0.8278 -0.8863 -0.8807

18 57.8377 4.9623 1.2307 1.3177 1.3472

19 48.1602 -2.5602 -0.6350 -0.7020 -0.6917

20 48.1602 0.1398 0.0347 0.0383 0.0372

Influence Diagnostics: Row Cook's Dist Leverage DFFITS

1 0.0464 0.1355 -0.3010

2 0.2064 0.1355 -0.6757

3 0.0513 0.1163 -0.3183

4 0.0680 0.1163 0.3691

5 0.0385 0.0955 0.2753

6 0.0034 0.0955 0.0804

7 0.0010 0.0703 0.0432

8 0.0015 0.0703 -0.0532

9 0.0468 0.0567 0.3109

10 0.0568 0.0567 0.3463

11 0.0467 0.0522 -0.3120

12 1.3838E-005 0.0522 0.0051

13 0.0044 0.0695 -0.0913

14 0.0939 0.0695 0.4540

15 0.1609 0.0946 -0.6054

16 0.0077 0.0946 0.1208

17 0.0575 0.1276 -0.3369

18 0.1270 0.1276 0.5153

19 0.0547 0.1818 -0.3260

20 0.0002 0.1818 0.0176

95% Confidence: Row Predicted Regr. 5% Regr. 95% Pop. 5% Pop. 95%

1 96.1846 93.0668 99.3024 87.1581 105.2112

2 96.1846 93.0668 99.3024 87.1581 105.2112

3 94.2475 91.3587 97.1363 85.2975 103.1975

4 94.2475 91.3587 97.1363 85.2975 103.1975

5 91.7252 89.1075 94.3429 82.8590 100.5915

6 91.7252 89.1075 94.3429 82.8590 100.5915

7 87.4726 85.2266 89.7185 78.7089 96.2363

8 87.4726 85.2266 89.7185 78.7089 96.2363

9 83.4171 81.3993 85.4349 74.7091 92.1251

10 83.4171 81.3993 85.4349 74.7091 92.1251

11 79.0120 77.0771 80.9469 70.3228 87.7011

12 79.0120 77.0771 80.9469 70.3228 87.7011

13 69.9324 67.6994 72.1653 61.1720 78.6927

14 69.9324 67.6994 72.1653 61.1720 78.6927

15 64.0309 61.4251 66.6367 55.1682 72.8937

16 64.0309 61.4251 66.6367 55.1682 72.8937

17 57.8377 54.8112 60.8642 48.8423 66.8331

18 57.8377 54.8112 60.8642 48.8423 66.8331 Chemical: Nicosulfuron
MRID: 48354304
PC: 129008Nicosulfuron (PC 129008) MRID 48354304

Page 32 of 33 Guideline: 835.4300 Sand (Golden Lake) systems: Total system, labels combined

19 48.1602 44.5486 51.7719 38.9515 57.3690

20 48.1602 44.5486 51.7719 38.9515 57.3690

Fit Equation Description: [Variables] x = col(1) y = col(2) reciprocal_y = 1/abs(y) reciprocal_ysquare = 1/y^2
'Automatic Initial Parameter Estimate Functions F(q)=if(size(x)>1, if(total(abs(y))>0, ape(x,log(abs(y)),1,0,1), -306), 0) asign(q)=if(mean(q)>=0,1,-1) [Parameters] a = if(F(0)[1]< 307, if(F(0)[1]>-307, asign(y)*10^F(0)[1], asign(y)*10^(-307)), asign(y)*10^307) ''Auto {{previous: 96.1846}} b = if(x50(x,y)-min(x)=0, 1, -ln(.5)/(x50(x,y)-min(x))) ''Auto {{previous: 0.00678172}} [Equation] f = a*exp(-b*x) fit f to y ''fit f to y with weight reciprocal_y ''fit f to y with weight reciprocal_ysquare [Constraints]

b>0 [Options]

tolerance=1e-10 stepsize=1
iterations=200

Number of Iterations Performed = 7Nicosulfuron (PC 129008) MRID 48354304

Page 33 of 33