MRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

1 Reference Gould, T., and Jerkins, E. (2015) Determination of the Residues of Imidacloprid, 5

- Hydroxy Imidacloprid, and Imidacloprid Olefin in Bee Relevant Matrices Collected from Tomatoes Following Application of Imidacloprid Over Two Successive Years: Fin al Report. Project Number: E BNTN012. Unpublished study prepared by Bayer CropScience 466pg. MRID 49665201, CDPR study ID 285680,
Data Volume 51950

- 0899, Tracking ID#270950



### 1. ST UDY INFORMATION

Chemical: Imidacloprid PC Code 129099

Test Material : Admire Pro Systemic Protectant (SC) Purity : 43.50% a.i. w.w.

Study Type: Non

- Guideline field residue study on tomatoes to establish imidacloprid and

meta bolite levels in pollen, nectar , and leaves after at plant soil drip/drench application followed by two foliar spray applications in each of two successive years and three different soil types (fine, medium, and coarse).

Sponsor: Bayer CropScience
2T.W. Alexander Drive
Research Triangle Park, NC

USA 27709 Experiment Start and

End Date: July 2, 2013

- April 9, 2015

Sponsor Study

ID: E BNTN01 2

Study Location s : 9 Field Trials in the
cities of : Fresno, Guadalupe,

Kerman
, Porterville, Sanger, San Joaquin, San Luis Obispo, California Study Completion

Date: June 2 9, 2015

GLP Status: GLP

- compliant; protocol reviewed by EPA, PMRA, CDPR

. [ CDPR study ID 254887 , Data Volume 51950

- 0 757 , Tracking ID# 2 41047 .]



### 2. REVIEWER INFORMATION Primary Reviewer s : California Department of
Pesticide Regulation John Troiano, Ph.D. , Research Scientist III, Environmental Monitoring
Branch Richard Bireley , Senior Environmental Scientist (Specialist), Ecotoxicology Group, Pesticide Registration Branch
Denise Alder , Senior Environmental Scientist (Specialist), Lead Reevaluation Coordinator, Pesticide Registration Branch Russell Darling , Environmental Scientist, Reevaluation Coordinator, Pesticide Registration Branch



### 3. EXECUTIVE SUMMARY

A total of nine field trials were conducted to measure the magnitude of imidacloprid residues in transplanted tomato pollen and in/on transplanted tomato leaves following three applications of Admire Pro Systemic Protectant , EPA Reg. No. 264

- 827 in each of two successive years. Admire Pro Systemic Protectant is a suspension concentrate formulation containing 550 g/L imidacloprid. Five trials have one year of data and four trials have two years of data.MRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

2 Trials NT017

- 13ZB and NT039

- 13ZA through NT042

- 13ZA were started/restarted in 2014, so only one year of data from these trials are reported here.

Across all reported trials and years, treated plot s received one soil (in

- furrow) drip/drench application of

Admire Pro five to seven days after tomato transplantation followed by two eq uivalent Admire Pro foliar spray applications per planting season. Individual soil application rates ranged from 0.37 to 0.38 lb imidacloprid/A per application (0.42 to 0.43 kg/ha). The interval between the soil and first foliar applications was 48 to 78 d ays. Individual foliar application rates ranged from 0.058 to 0.062 lb imidacloprid/A/application (0.066 to 0.070 kg/ha). All foliar applications were made to flowering tomato plants, after the first two sampling events were complete. The interval between foliar applications was
four to five days. The foliar spray volumes ranged from 50 to 101 gal/A, with the exception of the second foliar spray in 2013 to trial NT018

- 13ZA (48 gal/A). Total seasonal application rates were 0.50 lb imidacloprid/A (0.56 kg/ha)

.

All applications were made using ground

- based equipment. The adjuvant Dyne

- Amic (0.25 or 0.5 % v/v) was used in all foliar applications, with the exception of the first foliar application in trial NT017

- 13ZB and both foliar applications in trial NT039

- 1 3ZA.

One bee tunnel was erected on untreated plot UTC, and two bee tunnels were erected on treated plot TRTD, except in trials NT013

- 13ZA, NT040

- 13ZA, and NT041

- 13ZA, when only one TRTD tunnel was
erected. Bumble bee (Bombus impatiens) colonies (1 to 3 per tunnel) were placed in each tunnel for the collection of pollen. One sample was collected per bee tunnel, yielding two TRTD samples and one UTC sample at each sampling interval, except in trials NT013

- 13ZA, NT040

- 13ZA, and NT041

- 13ZA, when two replicate samples were collected from the single erected TRTD tunnel.

Tomato leaf and pollen samples were collected at four sampling intervals: two samples were collected after the soil application, approximately 14 days apart (31 to 68 and 45 to 77 days after the soil application, respectively), and two samples were collected after the last foliar application, approximately 14 days apart (2 to 8 and 16 to 22 days after the last foliar application, respectively). At each interval, fresh bumble b ee colonies were placed in each bee tunnel, and the bumble bees were allowed to forage from the tomato flowers for several days. Then, bumble bees carrying pollen were collected from the tunnels, and the pollen was removed from the bees. To ensure a large enough pollen sample for analysis, some trials collected bees over mul tiple days (up to seven ) per sampling event.
Multi

- day pollen samples from the same sampling interval and bee tent were composited together into one sample vial.

During the described sa mpling intervals, composite samples of tomato leaves were collected from within the tunnels of the treated plots. Composite samples of tomato pollen and leaves were collected from the control plot tunnel of each trial on the same days and using the same me thods as samples collected from the treated plots.

The residues of Admire Pro Systemic Protectant (imidacloprid, 5

- hydroxy imidacloprid, and imidacloprid olefin) were quantitated by high performance liquid chromatography/triple stage quadrupole mass
spect rometry (LC/MS/MS) and LC/high resolution mass spectrometry (LC/HRMS) using stable isotopically labeled internal standards. The individual analyte residues were summed to give a total imidacloprid residue.MRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

3 Storage stability studies indicate that the imida cloprid residues would have been stable during frozen storage for at least for at least 1

, 080 days (36 months) in tomato leaves prior to analysis. Transit stability samples showed that imidacloprid residues were stable in pollen for the duration of the stu dy. The maximum storage period of frozen samples in this study for Admire Pro Systemic Protectant was 561 days for tomato leaves and 560 days for tomato pollen.



### 4. STUDY VALIDITY

Guideline Followed: Non

- guideline study (protoco l was reviewed by U.S. EPA/PMRA/CDPR )
Guideline Deviations: N/A
Other Deviations: N/A

Classification: Quantitative
Rationale: The data from the study will provide a basis for developing a quantitative assessment of exposure levels to bees that can be used in a
risk assessment scenario. Reparability: N/A



### 5. MATERIALS AND METHODS

Test Material Characterization

Test item: Admire Pro Systemic Protectant (Imidacloprid) 550 g a.i./L SC CAS #: 138261

- 41

- 3 Description: Suspension concentrate (SC) Purity: 43.50% w/w Lot No./Batch No. Batch No. NK41CX0578 Density: 1.41

– 1.54 g/mL

Material Source: Bayer CropScience Cert. # 213CJ2446 Material Receipt

Date: Not Reported Analysis

Date: 12/03/2012 Expiration Date: 12/03/2014 Solubility: 0.51 to 0.61 g/L

Storage of Test

Mat erial : Ambient (35

- 86oF) except trials NT0 10

- 13Z A and

NT 016

- 13Z A when the temperature briefly reached

9 5 oF ; trial NT017

- 13ZB when the temperature briefly reached 90oF; and, trial NT018

- 13ZA when the temperature
reached as low as 32oF and as high a s 90oF

. Sample Storage: - 27 oC to

- 7 oC

- 16oF to 19 oF

5A. S TUDY D ESIGN

This study requirement was part of the imidacloprid special review at the California Department of Pesticide Regulation (CDPR). The study design and protocol were approved by CDPR prior to study initiation. This study was conducted using GLP standards and following an approved protocol. The study initiation date was June 21, 2013. The experimental start date was July 02, 2013 (first application), and the experimental end date was April 09, 2015 (last analysis).

Nine trials in California were conducted for this study, representing all three soil texture categories (fine, medium, and coarse). Each trial, includes two treated plots, both to be planted and treated for twoMRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

4 consecutive years. To date, Bayer CropScience has collected at least one year of residue data from all nine trial sites (five coarse texture fields, one medium, and three fine). Two years of data collection are complete at four sites (two coarse texture sites, one medium, and one fine). Bayer CropScience continues work on a second year of data collection on five sites in the 2015 growing season (three coarse texture sites and two fine) which is anticipated in January 2016

.

Indeterminate (continuously flowering and fruiting) tomato varieties representing those commonly grown in the area of the trials and agronomic practices typical for commercial production of tomato were used at all trial locations. Once bloom began, the tomato plots wer e sampled at four intervals. The plots were sampled twice at early bloom approximately 14 days apart, prior to any foliar sprays, to

assess the residues in bee

- relevant matrices resulting from the at

- plant soil application. The flowering

tomatoes were then given two foliar applications of imidacloprid. The tomatoes were sampled twice more after the last foliar application, approximately 14 days apart, to assess the residues resulting from the soil application at planting plus two additional at

- bloom foliar applications.

Homogenization and analysis of the samples from this study were performed by Bayer CropScience in Research Triangle Park (RTP), NC. Final report preparation was performed by Critical Path Services, LLC, located in RTP, NC.

All raw data asso ciated with this study are retained along with the protocol, protocol amendments, and final report under Notebook Number EBNTN012 at Bayer CropScience, 2 T. W. Alexander Drive, RTP, NC

27709.

5 B

. A PPLICATION T IMING AND R ATES

The full study report provides (1) Chronological listing of significant study dates ( Appendix 1 ); (2) Field report summaries for each trial detailing the actual amount of test substance applied, plot sizes, dates of treatment, dates of sample collection, maintenance chemicals, climatic data, and irrigation data ( Appendix 2 ); and (3) Quality assurance statements for each trial ( Appendix 3 ). Information on application timing is provided in Table 1. Soil and meteorological characteristics of the study sites are provided in Table 2 and Table 3

. Table 4 provides the sampling dates and tomato developmental stages.

BBCH or Biologische Bundesanstalt, Bundessortenamt und CHemische Industrie, identifies the specific phenological development stages of tomato . Plot TRTD received one soil (in

- furrow) drip/drench

a pplication of Admire Pro five to seven days after tomato transplantation followed by two equivalent Admire Pro foliar applications per planting season. Individual soil application rates ranged from 0.3 7 to

0.38 lb imidacloprid/ A per application (0. 42 to 0.43 kg/ha). The interval between the soil and first foliar applications was 48 to 78 days. Individual foliar application rates ranged from 0.058 to 0.062 lb imidacloprid/A/application ( 0.06 6 to 0.0 7 0 kg / ha ). All foliar applications were made to flowering tomato plants, after the first two sampling events were complete. The interval between foliar applications was four to five days. The foliar spray volumes ranged from 50 to 101 gal/A, with the exception of the
second foliar spray in 2013 to trial NT018

- 13ZA (48 gal/A). Total seasonal application rates were 0.50 lb imidacloprid/A (0.56 kg/ha).

Temperature and precipitation data were recorded for each trial and are summarized in Appendix 2 of the study rep ort EBNTN01 2 . Temperatures recorded during the field phase of the study were similar to average historical records except in trial NT013

- 13ZA, which had a slightly warmer spring 2014

.MRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

5 Recorded rainfall was slightly lower than historical records in trials N T010

- 13ZA, NT016

- 13ZA, and

NT018

- 13ZA. However, there were no significantly unusual weather conditions that would affe ct the conclusions of the study

. CDPR requested that the trial sites be distributed as three coarse, three medium, and three fine textured soils [per USDA’s Soil Survey Geographic database (SSURGO) mapping units] . There are nine trial sites in this tomato study design: three in fine texture soils, one in medium, and five in coarse; three sandy loams (as determined by SSURGO and shown in the general texture description of were considered coarse textured. One to two years of data for each site are presented in this report. The three fine texture sites have one to two years of data (trial NT016

- 13ZA has two years of
data and trials NT039

- 13ZA an d NT040

- 13ZA each have one year, for four total trial years of data). The medium texture site has two years of data (trial NT013

- 13ZA). The five coarse texture sites have one to two years of data (trial NT017

- 13ZB, NT041

- 13ZA, and NT042

- 13ZA each have one year of data; trials

NT010

- 13ZA and NT018

- 13ZA have two years of data). Therefore, there are four trial years in fine texture soils, two trial years in medium soil, and seven trial years in coarse soils. See Table 3 for more site specific soil information

.MRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

6 Table 1 . Summary of soil and foliar application rates and timing *.MRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

7 a V a l ues f or s p r a y v o l u m e, r ate, a nd t ot a l r ate h a v e be e n r oun d ed u s i ng v a l u es p r o v i ded i n Appendix 2.

b N A = Not a p p l i c a b l e.

c T r i a l s N T 017

- 13 Z B a nd N T 039

- 1 3 Z A t h r ou g h N T 042

- 1 3 Z A we r e s ta r t e d/ r e s ta r t e d i n 2 01 4

, s o o n l y

one y e ar of te s t s ub s t a n c e ap p li c a t i on da t a a r e r epo r te d.

d N R = Not r e po r t e d; t h e B B CH at t h i s a p p li c a t i on w as not r e p o r ted b y t h e P rincipal F ield I nvestigator

.
* Table 4 of the study report.MRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

8 5C. S TUDY S ITE L OCATION AND C HARACTERISTICS

Table 2. Soil and meteorological characteristics of the study sites*.

T r ial

ID a T r ial Lo ca t i o n ( Ci t y , C ount r y/ S t a t e , Y ea r , G P S
C oo r d i n a t es b ) S o il C h a r a c t e r i s t ics c M e t e o r o l og ical Da t a d

Variety OM ( % ) p H C E C ( me q /

100 g

s o il) %

S a n d %

S ilt %
Cl a y T y p e T ot al

Rai nf all ( i n ) T e mp . Ra ng e ( ° F )

NT010

- 13ZAv Porterville, CA, 2013

- 2014 (36.005,

- 119.0721) 1.2 7.7 13.7 58 36 6 Sandy
Loam 4.56 29 97 Garden Delight

NT013

-

13ZA Fresno, CA, 2013

- 2014 (36.7362,

- 119.87476) 0.7 7.7 9.1 71 20 9 Sandy

Loam 3.62 30 102 Big Beef

NT016

-

13ZA Porterville, CA, 2013

- 2014 (36.0348,

- 118.9964) 1.7 7.0 29.4 44 21 35 Clay

Loam 4.62 29 97 Garden Delight

NT017

-

13ZB Guadalupe, CA, 2014 (N34.96917, W120.60196) 0.6 7.4 28.6 75 14 11 Sandy

Loam 0.01 51 74 Sungold

NT018

-

13ZA Sanger, CA, 2013

- 2014 (36.739659,

- 119.576766) 0.8 7.1 4.9 78 12 10 Sandy

Loam 4.34 28 100 Cherry

Tomato

NT039

-

13ZA San Luis Obispo, CA, 2014 (35.306478,

- 120.677548) 2.8 7.5 32.7 46 21 33 Sandy Clay

Loam 0 50 78 Naomi
NT040

-

13ZA San Joaquin, CA, 2014 (36.59885,

- 120.20671) 1.4 8.4 62.0 11 24 65 Clay 0.0 52 105 Naomi

NT041

-

13ZA Kerman, CA, 2014 (36.79380,

- 120.05320) 0.4 5.4 4.6 79 18 3 Sandy

Loam 0.11 58 98 Naomi

NT042

-

13ZA Sanger, CA, 2014 (36.70034,

- 119.461982) 0.4 6.7 4.5 62 29 9 Sandy

Loam 0.48 56 97 Cherry

Tomato (Golden

Gem)

a Site conditions listed are for the TRTD plot. For UTC plot conditions, see Appendix 2 of the study
report.
b GPS coordinates are in the form (latitude, longitude).

c These soil characteristics are based on analyses of soil samples collected from within approximately 500 ft of the treated plot. Abbreviations used: %OM = percent organic matter; CEC = cation exchange capacity.
d Data is for the interval of the month of first applica tion through the month of last sampling. Meteorological data were obtained from nearby government weather stations.
* Combined table from Table 3A and Table 8 of the study report.

Table 3 . S SURGO soil characteristics of the study sites*.

T r ial

ID T r ial

Lo ca t i o n G e n e r al T ex tu r e Des c r i pt i o n ( SS UR GO ) C ompon e n t % a CD P R
T ex tu r e Ca t e go r y D r ai n a g e Class H y d r o l og ic

G r ou p R unoff P a r t i cle

S i z e

N T 010

-

13 Z A P o r te r v i l l e,
CA T u j unga l o a m y

s and,
0

- 2% s l o pes 85 Coa rs e S o m e w h at

e xc e ss iv e l y

d r a i n ed A Neg l i g i b le N A bMRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

9 T r ial

ID T r ial

Lo ca t i o n G e n e r al T ex tu r e Des c r i pt i o n ( SS UR GO ) C ompon e n t % a CD P R
T ex tu r e Ca t e go r y D r ai n a g e Class H y d r o l og ic

G r ou p R unoff P a r t i cle

S i z e

N T 013

- 13 Z A Fr e s no, CA Ra m ona l oam 80 Me d i um W e ll
d r a i n ed C L o w F i ne
Loa m y

N T 016

- 13 Z A P o r te r v i l l e,
CA Cente r v i l l e c l a y , 2

- 9% s l o pes 80 F i ne W e ll
d r a i n ed D NA F i ne

N T 017

- 13 Z B G uad a l u p e,
CA Mo c ho s a n d y l oa m , 0

- 3% s l o pes 85 Coa rs e W e ll
d r a i n ed A Neg l i g i b le F i ne
Loa m y

N T 018

- 13 Z A S a n ge r , C A De l h i l oa m y s and,
0

- 3% s l o pes 85 Coa rs e S o m e w h at

e xc e ss iv e l y

d r a i n ed A V e r y L o w NA

N T 039

- 13 Z A S an L u i s O b i s po, CA S a l i n as s il t y cl a y l oa m , 0

- 2% s l o pe 85 F i ne W e ll

D r a i n ed C Me d i um F i ne l oa m y N T 040

- 13 Z A S an
J oaq u i n, C A Me rc ed cl a y ,
s li g h t l y s a l i n e 85 F i ne V e r y P o o r l y
D r a i n ed C Me d i um F i ne

N T 041

- 13 Z A K e r m an, CA Han f o r d c oa rs e

s an d y l o am 85 Coa rs e W e ll
d r a i n ed A V e r y L o w Coa rs e

l oa m y

N T 042

- 13 Z A S a n ge r , C A Han f o r d f i ne s a n d y l oa m , g r a v e l l y

s ub s t r atum 85 Coa rs e W e ll

D r a i n ed A V e r y L o w Coa rs e

l oa m y

a Major component of the soil as a percentage of to ta l soil

. b NA = Not a p p l i c a b l e.

5D. S AMPLE C OLLECTION , H ANDLING , P ROCESSING

Tomato Plant Matrices.

Composite samples (one per each bee tunnel) of tomato leaves and pollen were collected from plots UTC and TRTD in years one and two of the study, except in trials NT017

- 13ZB and NT039

- 13ZA through

NT042

- 13ZA, which were started/restarted in 2014 and have o nly completed one year of the study. All tomato leaf and pollen samples were collected from within the erected bee tunnels on both plots at four sampling intervals. The first and second samples were collected at early bloom approximately 14 days apart, pr ior to any foliar sprays (31 to 68 and 45 to 77 days after the soil application, respectively). The third and fourth samples were collected after the last foliar application, approximately 14 days apart (2 to 8 and 16 to 22 days after the last foliar appli cation, respectively). UTC samples were collected at the same sampling intervals and via the same methods as the TRTD samples.

All samples were protected from sunlight and placed in field coolers containing ice substitute. Upon
arrival at the site facilit y, all composite leaf samples were placed directly into frozen storage. All composite pollen samples were placed directly into frozen storage after their removal from the bumble bees (used as a sampling device).

Composite samples were placed into labeled (study number and sample number) containers for shipment. All samples were frozen within four hours of their collection. Samples were shipped and remained frozen until receipt at Bayer CropScience (RTP, NC).MRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

10 During the described sampling intervals, duplica te composite samples (one per bee tunnel) of tomato leaves were collected from the treated plots (one day of sampling only).

All composite leaf samples were collected by hand from different areas of the tomato plants (top and middle, left and right). Each composite sample of leaves contained a target of 150 g collected from any number of healthy

- appearing plants located inside the bee tunnel.

Tomato Pollen Samples and Bee Handling

.

Details on the pollinator portions of the study are located in Appendix 5 . One bee tunnel was erected on untreated plot UTC, and two bee tunnels were erected on treated plot TRTD, except in trials NT013

- 13ZA, NT040

- 13ZA, and NT041

- 13ZA, when only one TRTD tunnel was erected. Bumble bee ( Bombus impatiens ) colonies (1 to 3 per tunnel) were placed in each tunnel for the collection of pollen. One sample was collected per bee tunnel, yielding two TRTD samples and one UTC sample at each sampling interval, except in trials NT013

- 13ZA, NT040

- 13ZA, and NT041

- 13ZA, when two replicate sa mples were collected from the single erected TRTD tunnel.

At each testing location, the control and treated plots were divided into sampling subplots for the
construction of bee

- tight, ventilated mesh

- covered tents (tunnels). When the tomato bloom was
suf ficient to support pollen sampling after the first (soil) application, the tunnels were erected. The tunnels were 100 to 210 feet long and 20 to 40 feet wide, and each tunnel enclosed four to eight rows of tomato plants. In some trials, the tunnel was remo ved after sampling interval two to allow for the foliar applications and re

- erected prior to sampling interval three.

Normally developed, apparently healthy bumble bees ( Bombus impatiens ) were used for pollen
collection. One to three bumble bee colonies w ere placed in each bee tunnel. Bumble bee colonies were contained in Class A research hives, Class C garden hives, or boxed colonies. In all trials, the bumble bee colonies were allowed access to sugar water feeders or nectar/syrup bags.

Fresh bumble bee colonies were placed in each bee tunnel prior to each sampling event; the bumble bees were allowed to forage from the tomato flowers for several days. Bumble bees were observed for visible pollen collected in the pollen basket on their legs. Bees with poll en were collected using nets or vacuums and placed in containers with dry ice at the field. The bees were transported to the site facility for pollen removal. All available pollen was collected from the bees using an appropriate tool such as
tweezers or fo rceps, and the pollen samples were placed in 40

- mL amber glass containers.

To ensure a large enough pollen sample for analysis, some trials collected bees over multiple days (up to

seven ) per sampling event (see Appendix 2 ). Multi

- day pollen samples from the same sampling interval and bee tent were composited together into one sample vial. Bumble bee colonies were removed from the tents after the end of the sampling event.

Bumble bee colonies were removed from the tents after the end of the sampling event

.MRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

11 Table 4. Sampling dates and tomato develop mental stages for plant residue analysis*

Pollen and Leaf Sampling

Year 1 Year 2 Year 1 Year 2

BBCH † Dates ‡ BBCH † Dates ‡ BBCH † Dates ‡ BBCH † Dates ‡

Fresno = NT013

- 13ZA Sanger 1 = NT018

- 13ZA

XX 3 62

- 68 DASA,

- 16 to

- 10

DA1FA XX 31

- 33 DASA,

- 17 to

- 15 DA1FA 71 55 DASA,

- 17 DA1FA 61 52

- 54 DASA,

- 20 to

- 18 DA1FA

XX 75

- 77 DASA,

- 3 to

- 1

DA1FA XX 45

- 47 DASA,

- 3 to

- 1 DA1FA 83 70

- 71 DASA,

- 2 to

- 1

DA1FA 71 69 DASA,

- 3 DA1FA

XX 2

- 8 DA2FA XX 4 DA2FA 1 85 6 DA2FA 72 7 DA2FA

XX 17

- 20 DA2FA XX 19

- 21 DA2FA 85 20 DA2FA 86 20 DA2FA Guadalupe = NT017

- 13ZB Sanger 2 = NT0 42

- 13ZA

69 46 DASA,

- 15 DA1FA TBC 2 XX 36

- 38 DASA,

- 16 to

- 14

DA1FA TBC

72 59 DASA,

- 2 DA1FA TBC XX 49

- 51 DASA,

- 3 to

- 1

DA1FA TBC

74 8 DA2FA TBC XX 5

- 6 DA2FA TBC

79 19

- 20 DA2FA TBC XX 16

- 18 DA2FA TBC

Kerman = NT041

- 13ZA San Joaquin = NT0 40

- 13ZA

XX 33

- 37 DASA,

- 17 to

- 13

DA1FA TBC XX 35

- 37 DASA,

- 17 to

- 15

DA1FA TBC

XX 49 DASA,

- 1 DA1FA 1 TBC XX 50 DASA,

- 2 DA1FA 1 TBC

XX 4

- 7 DA2FA TBC XX 4

- 6 DA2FA TBC

XX 19

- 21 DA2FA TBC XX 19

- 22 DA2FA TBC
Porterville 1 = NT010

- 13ZA San Luis Obispo = NT0 39

- 13ZA

XX 44

- 45 DASA,

- 13 to

- 12

DA1FA XX 61 DASA,

- 14 DA1FA XX 50 DASA,

- 14 DA1FA 1 TBC

XX 54

- 56 DASA,

- 3 to

- 1

DA1FA XX 72

- 73 DASA,

- 3 to

- 2 DA1FA XX 61

- 63 DASA,

- 3 to

- 1

DA1FA TBC

XX 4 DA2FA 1 XX 4

- 6 DA2FA XX 5

- 6 DA2FA TBC

XX 20

- 21 DA2FA XX 17

- 19 DA2FA XX 17

- 18 DA2FA TBC
Porterville 2 = NT016

- 13ZA

XX 48

- 50 DASA,

- 13 to

- 11

DA1FA XX 59

- 61 DASA,

- 16 to

- 14

DA1FA

XX 59 DASA,

- 2 DA1FA 1 XX 72

- 73 DASA,

- 3 to

- 2 DA1FAMRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

12 Pollen and Leaf Sampling

Year 1 Year 2 Year 1 Year 2

BBCH † Dates ‡ BBCH † Dates ‡ BBCH † Dates ‡ BBCH † Dates ‡

XX 5 DA2FA 1 XX 4

- 6 DA2FA

XX 20 DA2FA XX 17

- 19 DA2FA † BBCH = B iologische Bundesanstalt, B undessortenamt und CH emische Industrie growth stage scale for tomato. ‡ DASA = Days after the soil (in

- furrow) application; DA1FA = days after the first foliar application;

DA2 FA = days after the second foliar (and last) application. A negative number designates days prior to the indicated application. Ranges indicate that samples were collected over several days and composited together to create a large enough volume for analysis.

1 Leaf sampling ONLY. No pollen data, insufficient sample weight.

2 TBC = To Be Collected; the samples will be collected when the second year of the trial is performed.

3 B BCH XX indicates no growth stage reported in the field data summary.
*Combination of Appendix 1 and Appendix 5 of the study report.

Sample Storage

.

Composite samples were placed into labeled (study number and sample number) containers for shipment. All samples were frozen within four hours of their collection. Samples were shipped and remained frozen until receipt at Bayer CropScience (RTP, NC).

5E. A NALYTICAL M ETHODS

The analytical methods 1

- 2 used in this study measured the residues of imidacloprid, 5

- hydroxy
imid acloprid, and imidacloprid olefin in tomato leaves and pollen . These data are reported in Appendix 4 of the full study report titled, “ Analytical Report for EBNTN012 Determination of the Residues of Imidacloprid, 5

- Hydroxy Imidacloprid, and Imidacloprid O lefin in Bee Relevant Matrices Collected from Tomato Plants Following Soil and Foliar Applications of Admire Pro Over Two Successive
Years.”

All neat analytical reference standards were stored frozen prior to dilution. All reference standard
solutions were prepared in parent equivalents and corrected for purity during initial preparation. The reference standard solutions were stored refrigerated or frozen and have been shown to be stable for the length of stora ge time required for this study

.

For the t omato leaves a 2.5 g sample was weighed into a 50

- mL polypropylene conical centrifuge tube,
and 10 mL HPLC

- grade water was added. The tube was mixed manually for 1 min, followed by adding 20 mL of acetonitrile and mechanical shaking (HS501 digital, IKA

- We rke, Wilmington, NC) for an additional 1 min. Then, 3 g of MgSO4 and 1.5 g of NaCl were added. The sample was amended with a mixed internal standard solution, capped, and shaken for 1 min. For leaf samples which were found to contain high residues of imida cloprid (>2 ppm), the sample was amended with a 10X mixed internal standard solution before the salts were added. The sample was centrifuged. For low imidacloprid residue samples, 20 mL of organic supernatant was transferred into a separate 50

- mL polypropy lene conical centrifuge tube containing 0.3 g of Bondesil

- PSA and 1.8 g of MgSO4. For high imidacloprid residue samples, 2.0 mL of organic supernatant and 18.0 mL of acetonitrile were transferred into a separate 50

- mL polypropylene conical centrifuge tube containing 0.3 g of Bondesil

- PSA and 1.8 g of MgSO4, which was capped and shaken for 1 min. The sample extract was centrifuged, and a 1.25 mL aliquot of supernatant was transferred into a clean culture tube. The sample aliquot was evaporated toMRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

13 near drynes s on the Turbo

- Vap (Biotage, Charlotte, NC). The solid was reconstituted with 1.25 mL of
9:1 H2O:MeOH and transferred into a 2

- mL sample vial for LC/MS/MS analysis.

For pollen, a 0.1 g sample was weighed into a 2

- mL centrifuge tube containing 2.8 mm stee l balls. If the available pollen amount was less than 0.1 g but greater than 0.025 g for a sample, the sample was considered sufficient for analysis. A 1 mL portion of methanol/water (3:1 v/v) was added, and the mixture was homogenized with a bead mixer at 5000 beats/min for 1 min on a Precellys homogenizer (Bertin Technologies, Rockville, MD). The isotopically labeled internal standards were added and mixed, and the mixture was centrifuged at 12,000 rpm for 2 min. The supernatant was transferred into a cle an culture tube containing 2.5 mL of water and was evaporated to an aqueous remainder, then applied to a

3

- mL ChemElut SPE cartridge. After 10 to 15 min, the cartridge was washed with 4 mL of hexane/ethyl acetate (1:1 v/v) three times into a clean culture tube. The combined eluates were evaporated to dryness. The analytes were dissolved from the tube with 0.5 mL of MeOH/H2O (1:4 v/v). The solution was transferred into a 2 mL sample vial for analysis by LC/high resolution mass spectrometry (LC/HRMS).

Quanti tation of each analyte was based on the daughter ion transitions of the analyte and the respective internal standard analog. The responses of the LC/MS/MS and LC/HRMS systems to each analyte and its internal standard were measured in samples and in standar ds, and a relative response was calculated (as the ratio of the analyte and the stable isotopically labeled internal standard responses). The relative response of the analyte in each sample was compared to the relative response of the analyte in the standa rds

.

The relative responses of imidacloprid and its analytes were measured over the range of 0.00012 to 0.040 ppm (0.0006 to 0.200 ppm sample equivalent). The analyte relative responses were fit to a linearity curve calculated using linear regression anal ysis with 1/x weighting (Thermo Finnigan X Calibur

2.7.0.20 or 2.2 SP1.48 ). Correlation coefficients were calculated with the same software.

All data are reported in parent equivalents, and the individual measured residues of imidacloprid,

5

- hydroxy imida cloprid, and imidacloprid olefin are summed to give a total imidacloprid residue.

The methods for determining imidacloprid, 5

- hydroxy imidacloprid, and imidacloprid olefin residues in/on tomato leaves and pollen were validated by measuring the recovery of these analytes from control matrices fortified at their respective LOQs. Additional recoveries at higher fortification levels validated the method for the highest residues observed in individual matrices. Concurrent recoveries of imidacloprid, 5

- hydroxy i midacloprid, and imidacloprid olefin from fortified samples were measured with each set of samples to verify method performance.

5F. Q UALITY A SSURANCE R ESULTS

The responses of the LC/HRMS and LC/MS/MS systems to imidacloprid, 5

- hydroxy imidacloprid, and imidacloprid olefin were linear in solvent over the range of 0.00012 to 0.040 ppm (0.0006 to 0.200 ppm sample equivalent). The coefficients of determination were >0.99. The response data are located in Appendix 4

.

Control interferences for tomato matrices are discussed in this paragraph; no total imidacloprid residue was calculated for the UTC samples, so the levels of imidacloprid as an individual analyte are described. Imidacloprid (parent) residues in UTC tomato pollen ranged from below the analyte LOD to 0.060 ppmMRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

14 (trial NT018

- 13ZA). Imidacloprid residues in UTC tomato leaves ranged from below the analyte LOD to 0.031 ppm (trial NT017

- 13ZB).

The recovery data for imidacloprid (parent), 5

- hydroxy imidacloprid, and imidacloprid olefin residues are

summar ized in Table 5

.

All recoveries were corrected for any interferences in corresponding controls. The overall means of the recoveries for each matrix at each fortification level were within the acceptable range of 70 to 120%, and the standard deviation values were below 20%. The analytical data summaries are located in Appendix 4

.

The limit of quantitation (LOQ) is defined as the lowest fortification level of an analyte at which acceptable recovery has been achieve d. The LOQ for a total residue is the highest of the LOQ values assigned to the individual analytes for a particular matrix.

The limit of detection (LOD) is defined as the lowest concentration of an analyte that can be determined to be statistically diffe rent from a blank. The LODs were determined from method validation data obtained from control samples fortified at the respective analyte LOQs. The LODs were calculated by multiplying the standard deviation of recovery measurements at the LOQ by t0.99 [whe re t0.99 is the

one

- tailed t

- statistic at the 99% confidence level for the number of replicates (n)].8 The LOD for the total imidacloprid residue in each matrix is the highest LOD value of any one individual analyte for that particular matrix.

Table 2 . Limits of quantification and detection for imidacloprid and metabolites*.

*From page 11 of the study report.



### 6. RESULTS:

6. A. C OMPARISON OF C ONCENTRATIONS M EASURED FOR P ARENT AND D EGRADATES Comparison of the relative concentrations measured for parent imidacloprid and degradation products in pollen and leaves are presented in Table 7 and Table 8

. The LOD of values for pollen were very low ranging from 0.3 ppb to 0.5 ppb. The LOD for leaves ra nged from 0.7 to 2.2 ppb. Data reported as below the LOD were assigned one

- half the LOD value. Comparison of the contribution of each chemical to the total residue indicates that parent imidacloprid represented the majority of the total residue measured

in each plant part. For pollen, parent imidacloprid comprised 90% or greater of the total residue for the
first three sampling intervals and was at 88% at the last sampling interval. For leaves, parent imidacloprid comprised 95% of the total residue for the first three sampling intervals and was at 90% for the last sampling interval. Since the degradation products comprised a small portion of the measured residue and since they are considered as toxic as parent imidacloprid, the following discussions will
foc us on comparing total imidacloprid residue measured in plant tissues.MRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

15 6. B

. M AGNITUDE OF R ESIDUES IN B EE

- R ELEVANT M ATRICES Figure 1 explains the statistical aspects relayed in the Box

- and

- Whisker plots used to compare the
distribution of concentrations cal culated for comparison of total imidacloprid residue at each sampling interval. For each data set analyzed, the box graphic presents values for the mean, median, minimum, maximum, and 25th and 75th percentiles. The LOD of values were very low ranging from 0.3 ppb to 2.2 ppb so data reported as below the LOD were assigned one

- half the LOD value.

Pollen. Comparison of overall statistics for total imidacloprid residue indicated much greater concentrations in all plant parts at the third sampling interval than at the other three sampling intervals ( Figure 2 ). The soil application occurred at planting. Two samplings were conducted at 14 day intervals after the soil application and before two foliar applications. The first sampling occurred at a mean of
48 d ays after the soil application with a range of values from 31 to 65 days. The second sampling interval that was also made prior to foliar applications occurred at a mean of 62 days after the soil application with a range of 45 to 77 days. Mean total imidac loprid residues in pollen, which is relevant to potential bee exposure, was 66 and 39 ppb for sampling intervals 1 and 2, respectively ( Table 7 ). After the second sampling interval plants received two additional foliar applications at approximately 5 day i ntervals. Concentrations measured at the third sampling interval that occurred around 6 days after the second foliar application increased nearly tenfold to a mean of 493 ppb with the 90th percentile value at 1,003 ppb. The fourth and final sampling inter val occurred around 19 days after the second foliar application where mean total imidacloprid resid ue concentration were found to drop back down to 88 ppb.

6.C. M AGNITUDE OF R ESIDUES IN L EAVES For leaves the same pattern was measured as for pollen where mean total imidacloprid values were 163, 143, 1527, and 131 ppb for intervals 1, 2, 3, and 4, respectively ( Table 8 ). The tenfold increase at the third sampling interval indicated a strong relationship between residues measured in leaves and
their effect on levels measured in pollen. The sharp decrease in concentration between intervals 3 and 4 does not appear to be due to wash

- off from rainfall or irrigation because drench/drip irrigation was indicated at each site and there was essentially no recorded ra infall during the interval between foliar applications and sampling of plant tissues.

6. D. S ITE S PECIFIC T RENDS Temporal patterns in residue concentration for each site are depicted in Figure 3 and Figure 4 for pollen and leaves, respectively. For pollen data, three sites lacked data for sampling interval 3. Based on the pattern noted in section 6.B, this is obviously an important interval so graphs are not presented for sites where data was missing for this interval. Data were also not available for sampl ing interval 2 at the San Joaquin and Kerman sites and for interval 1 at the San Luis Obispo site, but they are presented because they have data for interval 3 and conformed to the noted trend. The general pattern of mean concentrations r ising nearly tenfo ld at the third sampling interval was observed at all sites ( Figure 3 ). A sharp decline in concentration between intervals 3 and 4 was also predominant except for the San Luis Obispo site where there was only a slight dec rease at interval 4.

For leaves, a steep rise at the third sampling interval was reflected at 8 of the 13 curves ( Figure 4 ). Curves not reflective of the predominant pattern were indicated at 2 sites (Sanger 1 2014 and Fresno 2013). Pollen data for these two sites do indicate a significant rise in concentration at the third sampling interval. The lack of a similar pattern between leaves and pollen for these two sites indicate a large variability in distribution of concentration in leaf tissue. This might be due to variability in application methodology.MRID 4 966520 1 CDPR IMI Soil and Foliar Tomato Study

16 6.E. Potential Carry

- over of Residues The site specific curves provide comparison for levels measured between 2013 and 2014 for only one site, the Sanger site, for pollen and at 4 sites, the Sanger, Porterville, and Fresno sites for leaves ( Figure 3 and Figure 4 ). For leaves the values in 2013 are either equal to or greater than the values measured in 2014. For pollen the values are similar between the two years. Although the data are sparse there is no indication of a carry

- over effect of re sidues between each year.

6. F. L EAF AND N ECTAR C ONCENTRATION IN R ELATION TO S OIL T YPE Originally, the proposed study design suggested sampling sites located in coarse, medium, and fine

textured soils with three replicates assigned to each soil type. The r eported soils in this study were biased towards coarse soils where, in 2013 t wo sites were located in coarse

- textured soil, one in a
medium

- textured soil and one in the fine

- textured category. In 2014, three were located in the fine

textured category, one site in medium

- textured soil, and five sites in the coarse

- textured category. In Figure 5 the concentration of total imidacloprid residue in pollen is plotted in relation to levels measured in corresponding leaf samples. Data for both years are plotted wit h data for interval 1 indicated as black markers, interval 2 as red markers, interval 3 as blue markers, and interval 4 as orange markers. Soil texture categories are represented with circles indicating coarse

- textured soil, squares for
medium

- texture soil , and triangles for fine

- textured soil. Levels measured in pollen from fine

- textured soil sites approximate levels measured in coarse

- textured soils, especially for sampling interval 3. Although more representative sampling of the soil groups is needed to provide a definitive relationship between method of pesticide application and concentration in plant tissue due to soil type, data at interval 3 provide an initial indication that foliar applications greatly increased levels in all plants parts irrespectiv e of soil type.MRID 4 9665201 CDPR IMI Soil and Foliar Tomato Study

17 Table 7 . Magnitude of imidacloprid and related metabolites in tomato pollen (ppb).

Interval 1 Interval 2 Interval 3 Interval 4

Olefin 5

- OH IMI Total Olefin 5

- OH IMI Total Olefin 5

- OH IMI Total Olefin 5

- OH IMI Total

N 12 12 12 12 10 10 10 10 10 10 10 10 13 1 3 13 13

Mean 1.1 2.7 62.1 66 0.4 1.5 37.1 39 6.0 22.5 464.3 492.9 1.8 7.0 78.7 88

SD 1.4 2 .7 54.0 58.0 0.4 1.2 29.5 30.8 1.8 12.2 291.8 302.7 1.6 10.1 75.9 86.0

CV (%) 127% 103% 87% 88% 107% 94% 80% 79% 31% 54% 63% 61% 86% 144% 96% 99%

Min. 0.2 0.3 6.6 7.0 0.2 0.3 2.6 3.0 3.0 9.7 232.9 249.1 0.2 1.0 21.8 22.9

Median 0.5 1.4 38.6 40.9 0.2 1.2 29.4 30.8 6.4 16.8 364.8 387.1 0.9 4.4 60.6 68.4

75 th 1.7 4.3 102.3 108.3 0.4 2.1 48.2 51.6 7.9 30.2 426.1 458.9 3.6 6.9 79.1 87.3

90 th 2.4 6.6 121.9 130.8 1.0 4.0 83.4 87.6 8.0 40.0 955.9 1003 3.9 9.7 119.6 132.9

Max. 4.6 8.7 185.1 198.4 1.4 4.8 103.3 106.6 8.1 49.3 1212.3 1268.4 4.4 39.4 312.2 353.9

% of
Total 1.7% 4.1% 94.2% 0.9 % 3.8 % 95.1 % 1.2 % 4.6 % 94.2% 2.1 % 8.0 % 89.8 %

N OTES : IMI= imidacloprid, olefin = imidacloprid olefin, 5

- OH = 5 hydroxy imidacloprid, Total = sum of IMI, olefin and 5

- OH (in bold). SD=standard deviation, CV =
coefficient of variation.

Table 8 . Magnitude of imidacloprid and related metabolites in tomato leaves (ppb).

Interval 1 Interval 2 Interval 3 Interval 4

Olefin 5

- OH IMI Total Olefin 5

- OH IMI Total Olefin 5

- OH IMI Total Olefin 5

- OH IMI Total

N 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13

Mean 7.2 8.1 147.6 163 6.2 5.7 131.1 143 38.1 71.0 1417.5 1527 7.2 8.6 115.1 131

SD 7.0 11.3 148.6 165.7 4.6 5.3 100.2 109.4 21.8 46.8 1213.3 1276.1 4.2 5.9 86.8 95.8

CV (%) 97% 141% 101% 102% 74% 92% 76% 76% 57 % 66% 86% 84% 58% 68% 75% 73%

Min. 0.5 0.4 1.7 2.5 0.8 0.4 18.6 20.7 7.6 12.3 221.9 241.8 2.3 1.7 39.1 43.1

Median 4.5 4.4 111.5 121.1 6.3 3.4 102.2 114.6 29.6 56.2 863.6 942.8 6.2 7.4 67.5 82.3

75 th 9.6 6.3 159.2 173.5 9.0 9.0 231.9 253.7 54.0 107.7 2794.2 2968.2 9.5 11.3 129.1 150.0

90 th 16.4 26.5 388.1 445.8 13.3 13.3 266.4 293.4 69.2 121.3 3311.5 3502.3 9.7 16.3 268.6 292.1

Max. 24.7 38.3 517.2 568.4 13.5 16.5 284.0 306.6 78.0 163.6 3348.9 3566.5 18.5 22.0 324.7 365.2

% of
Total 4.4 % 5.0 % 90.7 % 4.3 % 4.0 % 91.6 % 2.5 % 4.7 % 92.8 % 5.5% 6.6% 87.9%

N OTES : IMI= imidacloprid, olefin = imidacloprid olefin, 5

- OH = 5 hydroxy imidacloprid, Total = sum of IMI, olefin and 5

- OH (in bold). SD=standard deviation, CV =
coefficient of variation.MRID 4 9665201 CDPR IMI Soil and Foliar Tomato Study

18 

### 7. STUDY STRENGTHS, LIMITATIONS AND CONCLUSIONS

The data from this study provide an expected distribution of the concentration of imidacloprid residues that bees are exposed to in pollen in tomato flowers grown under actual agronomic practices in California. Relating concentrations measured in flower pa rts to bee health is possible by comparing the concentrations measured in bee relevant plant parts to target values that define acute or chronic exposure scenarios. The data set is incomplete as the year two results from five trials have not been reported yet. Based on the data received, results would represent a minimal exposure assessment to foliar applications because samples were not taken during the period of foliar application. Therefore, there is some uncertainty with respect as to how reflect ive the values obtained at the four sampling
interval s represent maximum exposure scenarios.

In the context of documenting the magnitude of imidacloprid residues in bee

- related matrices of

tomato , the following strengths are observed with this study.

1. Data provide quantitative values of total imidacloprid residues expected in pollen, and leaves of tomato plants grown under California conditions.

2. Measurements were taken at four time intervals in an attempt to quantify levels expected in plant tissues: First a nd second intervals reflected concentrations following a period of time after a soil application at planting, and third and fourth intervals reflected concentrations after the final foliar application.

Limitations noted in this study include:

1. The study di d not follow the residue data protocol calling for three replicates each in fine, medium and coarse soils resulting in uncertainty in regards to the effects of soil type on imidacloprid uptake in tomato.

2. The values most likely reflect a minimal exposure b ecause bee relevant tissue was not sampled during the period of foliar application.

3. Data were available for two years at only one site for pollen and four sites for leaf data

. Thus,
d ata to determine whether or not carry

- over occurred was not maximal.

4. Data were missing for pollen sampling at interval 3 at three sites. Highest concentrations were measured at this sampling interval so characterization of the distribution for the third sampling interval across all sites is incomplete.

5. Data are inadequate t o c ompare the residues among coarse, medium, and fine textured soil types because data from coarse soils was disproportionately represented compared to the medium and fine soil types.

Overall, considering the strengths and limitations of this study, the f ollowing conclusions can be drawn:

1. At approximately 48 days after soil application of approximately 0.3 8 lb ai/A maximum concentration of total imidacloprid residue was 198 ppb in pollen.

2. For samples taken approximately six days after two foliar application s of approximately 0.06 8 lb ai/A, maximum total imidacloprid residue w as 1,268 ppb in pollen.

3. Mean total imidacloprid residue for samples taken 48 days after the soil application was 66 ppb

in pollen.

4. Mean total imidacloprid residue w as 493 ppb in pollen when sampled 6 days after the second foliar application.

5. For the limited data available, t here was no evid ence of year to year carryover.

6. Generally, residues were highe st when sampling occurred following six days after the second foliar application.MRID 4 9665201 CDPR IMI Soil and Foliar Tomato Study

19 

### 8. STUDY VALIDITY/CLASSIFICATION The data from this study provide an expected distribution of the concentration of imidacloprid residues that bees are exposed to in pollen of tomato plants grown under actual agronomic practices in
Cali fornia. Relating concentrations measured in flower parts to bee health is possible by comparing the concentrations measured in bee relevant plant parts to target values that define acute or chronic exposure scenarios. These data, however, would represent a minimal exposure assessment to foliar applications because samples were not taken during the period of foliar ap plication. Therefore, there is uncertainty with respect as to how reflective the values obtained at the four sampling interval s represent maxim um exposure scenarios. The study is considered scientifically sound and useful for risk assessment purposes. The study is classified as ACCEPTABLE for quantitative use in risk assessment



### 9. REFERENCES

1 . Brungardt, J. 2010. An Analytical Method for the De termination of Residues of Imidacloprid and its Metabolites Imidacloprid Olefin and 5

- Hydroxy Imidacloprid in Bee Relevant Matrices Using LC/MS/MS. Bayer Method No. NT

- 005

- P10

- 01.

2 . Miller, A. 2014. An Analytical Method for the Determination of Residues of Imidacloprid and its Metabolites Imidacloprid Olefin and 5

- Hydroxy Imidacloprid in Bee Relevant Matrices Using LC/MS/MS. Bayer CropScience Report Number: NT

- 006

- A13

- 01.

3 . Office of Pesticide Programs, US EPA. 2000. Assigning values to nondetected/nonq uantified pesticide residues in human health food exposure assessments. EPA Docket #OPP

- 00570A.MRID 4 9665201 CDPR IMI Soil and Foliar Tomato Study

20 Figure 1. Explanation of statistical meaning of the Box

- and

- Whisker plots.



## Maximum Observation

Minimum Observation Median Value (50%) Mean Value

25% Quartile 75% QuartileMRID 4 9665201 CDPR IMI Soil and Foliar Tomato Study

Page 21 of 24 Figure 2 . Relative concentration of total imidacloprid residues measured in tomato ( A) p ollen and ( B)

l eaves compared between sampling intervals. Data were averaged o ver all sites.



## A. Pollen B. Leaves

Interval: 1 2 3 4 Interval: 1 2 3 4MRID 4 9665201 CDPR IMI Soil and Foliar Tomato Study

Page 22 of 24 Figure 3. Trend in total imidacloprid residue measured in pollen at each site. Within each panel markers denote the site, for example Sanger site 1 is solid circles and Sanger site 2 are open squares. Black dashed lines are data collected in 2013 and gree n solid lines are data collected in 2014. Note the difference in scale for Fresno and Guadalupe graphs.Total Imidacloprid Residue (ppb)



## Days After Imidacloprid Soil Application 0 100 200 300 400 500 Sanger1 - 2013 Sanger1 - 2014 Sanger2 - 2014

0 100 200 300 400 500

20 30 40 50 60 70 80 90 100 110 San Luis Obispo - 2014 San Joaquin - 2014

Kerman - 2014 0 100 200 300 400 500 Porterville1 - 2014

Porterville2 - 2014



### Specific Site Information: Sanger1=NT018

- 13ZA Sanger2=NT042

- 13ZA

Fresno=NT013

- 13ZA Guadalupe=NT017

- 13ZB Specific Site Information:
Porterville1=NT010

- 13ZA
Porterville2=NT016

- 13ZA San Luis Obispo=NT039

- 13ZA San Joaquin=NT040

- 13ZA

Ker m an=NT041

- 13ZA 0 500 1000 1500

20 30 40 50 60 70 80 90 100 110 Fresno - 2013

Guadalupe - 2014MRID 4 9665201 CDPR IMI Soil and Foliar Tomato Study

Page 23 of 24 Figure 4

. Trend in total imidacloprid residue measured i n leaf tissue at each site. Within each panel markers denote the site, for example Sanger site 1 is solid circles and Sanger site 2 are open squares. Black dashed lines are data collected in 2013 and green lines are data collected in 2014. Note the
differe nces in scale between the graphs.Total Imidacloprid Residue (ppb)



## Days After Imidacloprid Soil Application 0 1000 2000 3000 4000 Sanger1 - 2013 Sanger1 - 2014 Sanger2 - 2014

0 500 1000 1500

20 30 40 50 60 70 80 90 100 110 Fresno - 2013

Fresno - 2014
Guadalupe - 2014

0 500 1000 1500

20 30 40 50 60 70 80 90 100 110 San Luis Obispo - 2014

San Joaquin - 2014

Kerman - 2014 0 1000 2000 3000 4000 Porterville1 - 2013

Porterville1 - 2014

Porterville2 - 2013

Porterville2 - 2014



### Specific Site Information: Sanger1=NT018

- 13ZA

Sa nger2=NT042

- 13ZA

Fresno=NT013

- 13ZA Guadalupe=NT017

- 13ZB Specific Site Information:
Porterville1=NT010

- 13ZA
Porterville2=NT016

- 13ZA San Luis Obispo=NT039

- 13ZA San Joaquin=NT040

- 13ZA

Ker m an=NT041

- 13ZAMRID 4 9665201 CDPR IMI Soil and Foliar Tomato Study

Page 24 of 24 Figure 5

. Relationship between concentration of total imidacloprid residues measured in tomato leaves
and pollen parsed out by soil type. Numbers after the texture category indicate data for interval 1, 2, 3,

or 4 where black markers are from sampling interval 1, red markers from interval 2, and blue markers
from interval 3. Circles are coarse

- texture soils, squares are medium

- textured soils, and triangles are
fine

- textured soils.

0.00 500.00 1000.00 1500.00

0 500 1000 1500 2000 2500 3000 3500 Coarse -1 Medium -1 Fine -1

Coarse -2 Medium -2 Fine -2

Coarse -3 Medium -3 Fine -3

Coarse -4 Medium -4 Fine -4Pollen Total Imidacloprid Residue (ppb)



## Leaf Total Imidacloprid Concentration