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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
Paladin® Soil FumigantPaladin Soil Fumigant
• Product Information• Product Information– Active Ingredient
• Dimethyl disulfide– Molecular formula
• C2H6 S2
– Molecular weightg• 94.2
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
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
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
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
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
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)
Paladin® Soil FumigantPaladin Soil Fumigant
• Toxicological Information• Toxicological Information (cont.)
Genetic toxicity– Genetic toxicity– Developmental toxicity– Reproductive toxicity
• No effects observed
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
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
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
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
Dimethyl DisulfideDimethyl Disulfide
• Industrial UsesIndustrial Uses – Oil refining
• Activates catalysts which remove• Activates catalysts which remove sulfur
– Petrochemicals• Coke inhibiting agent
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
Dimethyl DisulfideDimethyl Disulfide• Environmental Occurrence
– Water• Salt• Brackish• Fresh
S di t• Sediment• Soil• Atmosphere
• Sulfur cycle
Dimethyl Disulfide
• Biological PresenceBiological Presence – Bacteria– FungiFungi– Animals– Plants
• Cole crops, bulb crops, • tomatoes, others
FORMULATIONSFORMULATIONS
ACTIVE INGREDIENT………..98.8%For Shank Injection
Raised Beds, Broadcast/Flatfume Applications
ACTIVE INGREDIENT 93 8%ACTIVE INGREDIENT………..93.8%Emulsifiable Concentrate for Preplant Soil Chemigation
CropsFruiting VegetablesTomatoesPeppersEggplant
Cucurbit CropsCucumbersCucumbersSquash (all)Melons (all)
Small Fruit CropsStrawberriesBlueberries
Field Grown Ornamentals
Forestry Nursery Cropsy y p
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
RATESRATES
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
BUFFER ZONESBUFFER ZONES
Paladin® Soil FumigantBuffer zones
• Buffer zones determined by1. Area treated2. Application method
– Broadcast– Raised bed
3. Application rate of Paladin
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.
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.
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
PERSONAL PROTECTIVE EQUIPMENT (PPE)
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
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
TARPSbarrier mulch films
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
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)
Paladin® Soil Fumigant TARPSTARPS
• Tarp installationTarp installation– Immediately after application
• Kept in place• Kept in place– Minimum of 12 days
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
FMPsfumigation management plans
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.
EfficacyEfficacy
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
Combinations of Paladin® Soil Fumigant With Chloropicrin
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
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
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
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
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
Paladin® Soil FumigantPaladin Soil Fumigant
• Experimental Use Permit• Experimental Use Permit–On farm evaluation of Paladin
• 2007 to 2010
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%
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Vicia
Weeds
Ralston
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Am Am C D E Ge Ip M
Poly Se S R Ver
Root
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
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