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UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

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Page 1: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy
Page 2: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Paladin® Soil FumigantPaladin Soil Fumigant

• Registration – July 9 2010Registration July 9, 2010– Arkema

• World’s largest producer of thiochemicals• World s largest producer of thiochemicals

• Development & MarketingUnited Phosphorus Inc– United Phosphorus, Inc.

• Global supplier of proprietary and post patent crop protection technologiespatent crop protection technologies

Page 3: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Paladin® Soil FumigantPaladin Soil Fumigant

• Product Information• Product Information– Active Ingredient

• Dimethyl disulfide– Molecular formula

• C2H6 S2

– Molecular weightg• 94.2

Page 4: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Paladin® Soil FumigantPaladin Soil Fumigant• Physical & Chemical Properties

C l– Color• Yellow

– Physical Statei id• Liquid

– Specific Gravity• 1.062 (68°F)

– Vapor pressure• 22.5 mmHg (68°F)

– Vapor pressure referenceWater = 17 5» Water = 17.5

» Ethanol = 67.5» Propane = 16,500

Page 5: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Paladin® Soil FumigantPaladin Soil Fumigant• P.Chem. (continued)

– Solubility in water• 2.7 g/L (68°F)

– Flash point• closed cup (65.3°F)

– ReferenceReference» Ethanol (70%) = 61.9°F

– Odor • Garlic-like

– 8-10 ppb threshold

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Paladin® Soil FumigantPaladin Soil Fumigant

• Signal WordSignal Word– Warning

• Only currently registered fumigant• Only currently registered fumigant with this signal wording

• Restricted Use PesticideRestricted Use Pesticide– Certified applicators only

• Nasal irritationNasal irritation

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Paladin® Soil Fumigant

M d f A ti

g

• Mode of Action– Causes mitochondrial dysfunction

d ti ti f K ATP h land activation of K-ATP channelsBlocks cytochrome oxydase

Complex IVComplex IVActs on K-ATP channelshyperpolarizationyp p

Page 8: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Paladin® Soil FumigantPaladin Soil Fumigant• Toxicological Informationg

– Oral • Moderately toxic (rat)

LD50 = 290 500 mg/kg– LD50 = 290-500 mg/kg– Dermal

• Slightly toxic (rabbit)LD50 >2 000 /k– LD50 >2,000 mg/kg

– Inhalation• Practically nontoxic (rat)

– 4 h LC50 = 5.24 mg/l (1310 ppm)– 24 h NOAEL = 0.05 mg/l (12 ppm)

» Signs: Degeneration of nasal epithelium

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Paladin® Soil FumigantPaladin Soil Fumigant• Toxicological InformationToxicological Information

– Eyes • Slightly to moderately irritating g y y g

(rabbit)– Index: 7-20/110

– Skin Irritation– Skin Irritation• Slightly irritating (rabbit)

– Index: 1.5-2.5/8.0 (4 h)

– Skin sensitization• No skin allergy observed (guinea pig)

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Paladin® Soil FumigantPaladin Soil Fumigant

• Toxicological Information• Toxicological Information (cont.)

Genetic toxicity– Genetic toxicity– Developmental toxicity– Reproductive toxicity

• No effects observed

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Paladin® Soil FumigantPaladin Soil Fumigant

• Ecological Effects• Ecological Effects– Chemical fate

• Not readily biodegradable– 28 d < 10%

– Atmospheric half-life• Hours

– ozone depleting potential» zero

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Paladin® Soil FumigantPaladin Soil Fumigant• Ecological Effectsg

– Algae • Slightly toxic

– Pseudokirchneriella subcapitata » 72 h EC50 = 14-26 mg/l

– Skeletonema costatum » 96 h EC50 = 1.2-3.9 mg/l

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Paladin® Soil FumigantPaladin Soil Fumigant• Ecological Effectsg

– Aquatic toxicity• Moderately toxic

– Zebra fish 96 h LC50 = 5 mg/l• Highly toxic

Trout 96 h LC50 = 0 97 mg/l– Trout 96 h LC50 = 0.97 mg/l

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Paladin® Soil FumigantPaladin Soil Fumigant• Ecological Effectsg

– Aquatic invertebrates• Moderately toxic

– Daphnia 48 h EC50 = 1.8 mg/l– Mysid shrimp 96 h LC50 = 5 mg/l

• Slightly toxic• Slightly toxic– Oysters 96 h LC50 = 14 mg/l

Page 15: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Dimethyl DisulfideDimethyl Disulfide

• Industrial UsesIndustrial Uses – Oil refining

• Activates catalysts which remove• Activates catalysts which remove sulfur

– Petrochemicals• Coke inhibiting agent

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Dimethyl DisulfideDimethyl Disulfide

• Food UsesFood Uses– FDA approved additive

• Flavor Use for onion garlic & savory• Flavor Use for onion, garlic & savory flavor in cheese, meat

– 0.02-10 ppm

Page 17: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Dimethyl DisulfideDimethyl Disulfide• Environmental Occurrence

– Water• Salt• Brackish• Fresh

S di t• Sediment• Soil• Atmosphere

• Sulfur cycle

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Dimethyl Disulfide

• Biological PresenceBiological Presence – Bacteria– FungiFungi– Animals– Plants

• Cole crops, bulb crops, • tomatoes, others

Page 19: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

FORMULATIONSFORMULATIONS

Page 20: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

ACTIVE INGREDIENT………..98.8%For Shank Injection

Raised Beds, Broadcast/Flatfume Applications

Page 21: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

ACTIVE INGREDIENT 93 8%ACTIVE INGREDIENT………..93.8%Emulsifiable Concentrate for Preplant Soil Chemigation

Page 22: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

CropsFruiting VegetablesTomatoesPeppersEggplant

Cucurbit CropsCucumbersCucumbersSquash (all)Melons (all)

Small Fruit CropsStrawberriesBlueberries

Field Grown Ornamentals

Forestry Nursery Cropsy y p

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P tPestsWeeds such as-Nutsedge (purple & yellow), Chickweed, Lambsquarters, Purslane, grasses

Soil Borne Plant Pathogens such as-Verticillium, Fusarium, Pythium, Sclerotinia, Rhizoctonia

Nematodes such as-Root Knot (Southern, Northern and Colombia), Stubby Root, Lesion, Stunt, Sting

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RATESRATES

Page 25: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

CropsPests1

Broadcast Application RateFruiting PALADIN® PALADIN ® ECVegetablesTomatoesPeppersEggplant

gallons pounds gallons pounds

Weeds such as-Nutsedge (purple &ggp

Cucurbit CropsCucumbersSquash (all)

Nutsedge (purple & yellow), Chickweed, Lambsquarters, Purslane, grasses

51.3 455 54.2 479

Soil Borne PlantMelons (all)

Small Fruit CropsStrawberries

Soil Borne Plant Pathogens such as-Verticillium, Fusarium, Pythium, Sclerotinia, Rhizoctonia

40-51.3 355-455 42.3-54.2 347-479

StrawberriesBlueberries

Field Grown Ornamentals

Nematodes2 such as-Root Knot (Southern, Northern and 35-51.3 310-455 37-54.2 326-479

1Use the higher rate of product when there is a combination of these pests

Ornamentals

Forestry Nursery Crops

Colombia), Stubby Root, Lesion, Stunt, Sting

35 51.3 310 455 37 54.2 326 479

2Use the higher rate for cyst forming nematodes

Page 26: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

BUFFER ZONESBUFFER ZONES

Page 27: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Paladin® Soil FumigantBuffer zones

• Buffer zones determined by1. Area treated2. Application method

– Broadcast– Raised bed

3. Application rate of Paladin

Page 28: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Paladin® Soil FumigantBroadcast/Flat Fume Shank Applications

Example1 Buffer Zones for low/high or 100 pounds PaladinExample1 Buffer Zones for low/high or ≈100 pounds, Paladin1-40 Acres (10 acre increments)

buffer zones < 250 feet = blue, >250 ft = red

Application Rate Application Block size (Acres

Lb /A G l/A1 10 20 30 40

Lbs/A Gal/ABuffer zone in feet

199 22.4 25 170 275 355 430290 32.7 30 230 360 455 550380 42.9 40 275 415 525 635455 51.3 55 305 455 575 690455 51.3 55 305 455 575 690

1The Paladin product label contains detailed tables for determining buffer zone distances with broadcast applications.

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Paladin® Soil FumigantRaised Bed Shank Applications

E l 1 B ff Z f l /hi h 50 d P l di

Application

Example1 Buffer Zones for low/high or ≈50 pounds, Paladin1-40 Acres (10 acre increments)

buffer zones 25 feet = blue, <100 ft = green; <200 ft = yellow, 200 ft or greater =red

Application Rate Application Block size (Acres

Lbs/A Gal/A1 10 20 30 40

Lbs/A Gal/ABuffer zone in feet

112 12.8 25 25 25 25 30152 17.2 25 25 40 75 105152 17.2 25 25 40 75 105200 22.5 25 35 90 130 170251 28.3 25 65 125 170 215300 34.0 25 80 150 200 250

1The Paladin product label contains detailed tables for determining buffer zone distances with raised bed applications.

Page 30: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Calculating Prepared / Raised BedA li ti A tApplication Amounts

Bed top Width (inches)x Broadcast

rate1 =Effective

broadcast equivalent rate

Row spacing (center to center in inches))

Example calculation for Paladin

30”x 455 lb = 284 lb

48”

1From the rate table in the Paladin product label use instructions

Page 31: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

PERSONAL PROTECTIVE EQUIPMENT (PPE)

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Paladin® Soil Fumigant PPEPPE

• Handlers with potential contact with pPaladin liquid– Loose fitting or well ventilated long

sleeved shirt and long pantssleeved shirt and long pants– Chemical resistant footwear– Socks– Full face shield or safety glasses– If odor detected,

H lf f ll f i if i i t• Half or full face air-purifying respirator– May be removed if no odor detected

» two consecutive air sampling events at 15 minute intervalsminute intervals

Page 33: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Paladin® Soil Fumigant PPEPPE

• Handlers with no potential forHandlers with no potential for contact with Paladin liquid

Loose fitting or well ventilated long– Loose fitting or well ventilated long sleeved shirt and long pants

– SocksSocks– If odor detected,

• Half or full face air-purifying respiratorHalf or full face air purifying respirator– May be removed if no odor detected

» two consecutive air sampling events at 15 minute intervals15 minute intervals

Page 34: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

TARPSbarrier mulch films

Page 35: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Paladin® Soil Fumigant TARPSTARPS

• Low density polyethylene (LDPE)Low density polyethylene (LDPE)– Approximately four times more

permeable than higher densitypermeable than higher density barrier films (Tarps).

• Only VIF films are approved forOnly VIF films are approved for use with Paladin

Page 36: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Paladin® Soil Fumigant TARPSTARPS

• High Barrier Tarps (VIF) required and listed th P l di l b lon the Paladin labels

– Olefinas Embossed VIF– Klerks VIF – Pliant Blockade (1 25 mil)– Pliant Blockade (1.25 mil)

• black or white– XL Blockade (0.00125)– Pliant Metalized black VIF

C lit M t li d (1 25 il)– Canslit Metalized (1.25 mil) • high barrier black or white

– FilmTec VIF (1.25 mil)– Ginegar VIF Embossed– Cadillac VIF – Guardian VIF (1.2 mil)– Mid-South Extrusion VIF– Bromostop (1 38 mil)– Bromostop (1.38 mil)

Page 37: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Paladin® Soil Fumigant TARPSTARPS

• Tarp installationTarp installation– Immediately after application

• Kept in place• Kept in place– Minimum of 12 days

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Paladin® Soil FumigantPlant Back Intervals

• Application to planting interval determined by average low soil temp1 at an 8” depthaverage low soil temp1 at an 8 depth

Soil Temperature

Application to planting interval (days)

71° F and higher 21 days61° - 70° F 28 days55° - 60° F 35 days

• Circumstances such as heavy soils & high soil moisture can also lengthen the plant back interval.

50° - 54° F 42 days

moisture can also lengthen the plant back interval. See also Paladin label.

1The soil temperature at the depth of injection must not be less than 45º F or exceed 90º F at the beginning of the applicationor exceed 90 F at the beginning of the application

Page 39: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

FMPsfumigation management plans

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Paladin® Soil FumigantFMP

SITE SPECIFIC FUMIGATION

FMPs

• SITE-SPECIFIC FUMIGATION MANAGEMENT PLAN (FMP)

–Prior to the start of fumigation the Certified–Prior to the start of fumigation, the Certified Applicator supervising the application must verify that a site-specific FMP exists for each

li ti bl kapplication block.–Each site-specific FMP must contain date of completing registrant training program.completing registrant training program.

Page 41: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

EfficacyEfficacy

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Paladin® Soil FumigantPaladin Soil Fumigant

• Field Trials• Field Trials–2004 to 2010

• efficacy and crop safety assessments

–Approximately »250 field trials»250 field trials»15 countries

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Combinations of Paladin® Soil Fumigant With Chloropicrin

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Paladin® Soil Fumigant April 13, 2009 52 DAT

With and without ChloropicrinEquivalent rates of DMDS active ingredient

Paladin51 GPA

UTC Paladin® Pic 60 GPA UTC51 GPA 60 GPA

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Paladin® Soil FumigantAverage of three trials 2008 & 2009

BURIED BAG ASSAYS Dr. Gary E. Vallad University Of Florida, IFAS, Gulf Coast REC

F. oxysporum f.sp. lycopersici (causal agent of Fusarium wilt of tomato)

Control Paladin (99:1) 51 gpa

Paladin+Pic (79:21) 60gpa MeBr (67:33) 175 gpa

3

4

1

2

0Average CFU/g soil

(cfu) per gram of soil for each bag was calculated and log transformed

Page 46: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

2009 University of Georgia F ll R t K t N t d T i lFall Root Knot Nematode Trial

25

15

20

5

10

0Nem Counts / 100 cm3

Paladin Pic 60 GPA GA 3 WayPaladin Pic 60 GPA GA 3 WayMtBr/ pic 50/50 MIDAS 50/50

UTC Nematode Count/100cm3 786.5

Page 47: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Evaluation of Paladin and Paladin Pic With and Without soil applied herbicide (napropamide – (Devrinol)) Dr. Andrew MacRae UFL

Grass Control

20

NoHerb Napropamide (Devrinol)

16

18

20

Average Weed Count Per Plot

10

12

14

4

6

8

0

2

Non-treated Control Paladin @ 51.4 gal/A Paladin Pic @ 60 gal/A Methyl Bromide 67:33@ 175 lbs/A

Devrinol=Devrinol+ # compound for nut sedge control

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Evaluation of Paladin and Paladin Pic With and Without soil applied herbicide (napropamide – (Devrinol)) Dr. Andrew MacRae UFLherbicide (napropamide (Devrinol)) Dr. Andrew MacRae UFL

Broadleaf Control

NoHerb Napropamide (Devrinol)

60

70

NoHerb Napropamide (Devrinol)

Average Weed

40

50Count Per Plot

20

30

0

10

Non-treated Control Paladin @ 51 4 gal/A Paladin Pic @ 60 gal/A Methyl Bromide 67:33 @Non treated Control Paladin @ 51.4 gal/A Paladin Pic @ 60 gal/A Methyl Bromide 67:33 @175 lbs/A

Devrinol=Devrinol+ # compound for nutsedge control

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Paladin® Soil FumigantPaladin Soil Fumigant

• Experimental Use Permit• Experimental Use Permit–On farm evaluation of Paladin

• 2007 to 2010

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Efficacy % of MB / StandardPaladin EUP Trials 2007 - 2009

250%

PaladinPic Vs MB / Standard

50 GPA PaladinPic 60 GPA PaladinPic

100%

150%

200%

250%

% of MB /Standard

0%

50%

100%

Amaranth

Ambrosia

Cyperu

s Digi

taria

Eleusin

eGera

nium

Ipomoe

aMeli

lotus

olygo

num

Rumex

Ses

bania

Solanu

m

Vicia

Weeds

Ralston

ia Vert

icilliu

mot

Galling

Am Am C D E Ge Ip M

Poly Se S R Ver

Root

Page 51: UPI Paladin fumigant IR-4 update FUW 2010.pptir4.rutgers.edu/FoodUse/FUWorkshop/Industry Talks/201… ·  · 2010-09-29... 1.5-2.5/8.0 (4 h) – Skin sensitization • No skin allergy

Last comment…Last comment…• Could everyone please take a y p

deep breath and exhale slowly• Everyone exhaling has justEveryone exhaling has just

produced a small quantity of DMDSDMDS