Dupont™ Asana® XL Insecticide Controls a Wide Range of Insect Pests That Have Economic Impact on Major Field, Vegetable, Tree Fruit and Nut Crops
DuPont™ Asana® XL insecticide
Technical Bulletin
DuPont™ Asana® XL insecticide controls a wide range of insect pests that have economic impact on major field, vegetable, tree fruit and nut crops. Table of Contents Introduction ...... 1 Formulation ...... 1 Pyrethroid Chemistry ...... 2 DuPont™ Asana® XL Insecticide Physical and Chemical Properties ...... 3 Mode of Action on Insects ...... 4 Symptoms ...... 4 Direct Contact ...... 4 Ingestion of Sprayed Foliage ...... 4 Partial Listing of Insects Controlled by Asana® XL ...... 5–7 Current U.S. Tolerances for Asana® XL ...... 8 Performance Characteristics ...... 9 Longer Residual Activity ...... 10–12 Improved Formulation ...... 13–14 Resistance to Washoff ...... 15 High Temperature Effectiveness ...... 16 Crop Safety ...... 16 Compatibility ...... 16 Mixes in Water ...... 16 Mixes in Vegetable Oils ...... 16 Tank Stability ...... 17 Ecological Effects ...... 18 Environmental Impact ...... 18 Environmental Hazards ...... 18 Toxicity to Fish ...... 18 Toxicity to Bees ...... 19 Environmental Fate ...... 19 Metabolism of Esfenvalerate in Plants and Animals ...... 19 Asana® XL Toxicology ...... 20 Acute Toxicity Studies ...... 21 Subchronic, Chronic and Neurotoxicity Studies ...... 21 Mutagenicity and Genetic Toxicity Studies ...... 21 Carcinogenicity ...... 21 Material Safety Information ...... 21 Health, Safety and Handling Information ...... 21 Hazardous Reactivity ...... 22 Fire and Explosion Data ...... 22 Special Fire Fighting Instructions ...... 22 Other Physical Hazards ...... 22 NFPA Rating ...... 22 Spills, Leaks or Releases ...... 23 Waste Disposal ...... 23 Shipping Information ...... 23 Returnable Bulk Container Systems ...... 24 Storage Conditions ...... 24 Personal Precautions, Symptoms and Treatment ...... 24 Health Hazards and Protection Information ...... 24 Effects of Overexposure/First Aid Response ...... 25 Ingestion ...... 25 Inhalation ...... 25 Eye Contact ...... 25 Skin Contact ...... 25 Medical Emergencies ...... 26 Introduction DuPont™ Asana® XL insecticide controls a wide range of insect pests that have economic impact on major field, vegetable, tree fruit and nut crops. Moreover, insect control is accomplished without phytotoxicity. The U.S. label includes more than 50 crops. Each gallon of Asana® XL is formulated with approximately 2 quarts of cottonseed oil. Research on this formulation has demonstrated that the addition of cottonseed oil extends residual activity and makes Asana® XL more resistant to washoff. For the grower, these attributes can contribute to improved financial returns. In addition, the low dosage rates and longer spray intervals minimize the amount of chemical introduced into the environment. Asana® XL is an environmentally sound insecticide. It is a synthetic version of pyrethrin, a naturally occurring insecticide derived from chrysanthemums. Formulation Asana® XL insecticide is formulated as an emulsifiable concentrate (EC) containing 0.66 pound of active ingredient (esfenvalerate) per gallon. Active ingredient — esfenvalerate (by weight): 8.4 percent Inert ingredients (by weight): 91.6 percent Environmental Protection Agency (EPA) Reg. No. 352-515
1 Pyrethroid Chemistry The insecticidal properties of pyrethrins, which are derived from the flowers of Chrysanthemum cinerariaefolium and several other members of the same genus, have been known for more than 100 years. Figure 1 shows the chemical structure of a major component in natural pyrethrins.
FIGURE 1: NATURAL PYRETHRIN
Pyrethrins boast several distinctions — low mammalian toxicity, high toxicity to a broad spectrum of insects at very low dosages and minor environmental impact. Commercial uses range from household to industrial insect control. Unfortunately, pyrethrins are costly and therefore are frequently formulated with a synergist (e.g., piperonyl butoxide) to reduce application rates. The rapid pho- todegradation of pyrethrins further limits their agricultural use. However, the desir- able properties of natural pyrethrins encouraged scientists to synthesize economi- cal, sunlight-stable, chemically related compounds (pyrethroids) that would exhibit similarly favorable low mammalian toxicity and high insecticidal activity. After the initial success of allethrin in 1949, scientists strived to improve pyrethroid chemistry. Worldwide efforts culminated in the commercial development of several compounds for agricultural use, including permethrin, cypermethrin, deltamethrin, tralomethrin and fenvalerate. Further investigation of fenvalerate chemistry led to the identification of the most insecticidally active isomer that would improve desired attributes. These attributes included much lower use rates for broader crop applications, no crop injury to sensi- tive crops, sunlight stability and effectiveness over wide temperature variations. This isomer, called esfenvalerate, is the insecticidal ingredient of DuPont™ Asana® XL. In today’s highly competitive pyrethroid market, some manufacturers promote their product as a “new generation” pyrethroid. This is a marketing tool that is used to make their product appear newer and better. Most of the pyrethroids currently on the market in the United States were patented before 1981 — more than 20 years ago!
Pyrethroid insecticides Common name Brand names Esfenvalerate Asana® XL Bifenthrin Capture, Brigade, Empower, Discipline Cyfluthrin Baythroid, Renounce, Tempo, Aztec Cypermethrin Ammo, UP-Cyde, Fury*, Mustang*, Mustang Max*, Demon Cyhalothrin Karate**, Warrior**, ProAxis†, Silencer** Permethrin Pounce, Ambush, Waylay, Perm-UP Deltamethrin Decis * Fury, Mustang and Mustang Max are zeta-cypermethrin. ** Karate, Silencer and Warrior are lambda-cyhalothrin. † ProAxis is gamma-cyhalothrin. 2 DuPont™ Asana® XL insecticide Physical and Chemical Properties Trade Name ...... Asana® XL insecticide Common Name ...... Esfenvalerate (BSI, ISO) Chemical Name ...... (S)-cyano(3-phenoxyphenyl)methyl (S)-4-chloro-alpha-(1 methylethyl)- benzeneacetate CAS Registry Number ...... 66230-04-4
Structural Formula
FIGURE 2: ESFENVALERATE
ACID FRAGMENT ALCOHOL FRAGMENT
Empirical Formula ...... C25H22CINO3 Molecular Weight ...... 419.9 Concentration ...... 0.66 lb ai/gal Physical Form ...... Clear liquid Color ...... Straw to light amber Odor ...... Oily/aromatic Density ...... 7.8 lbs/gal at 20°C (68°F) 0.93 gm/ml at 20°C (68°F) pH ...... 5.14 (1% V emulsion in Type I reagent water) Emulsibility (Concentration – 0.025 lb ai/gal)
In Soft Water (32 ppm as CaCO3) ...... Good In Medium Hard Water (342 ppm as CaCO3) . .Good In Hard Water (900 ppm as CaCo3) ...... Good Miscibility with Vegetable Oils ...... Miscible and stable in nonvolatile, refined vegetable oils
1 Formulation Stability ...... Stable for more than 2 ⁄2 years at room temperature (18–24°C or 65–75°F); for four weeks at 54°C (130°F); for 26 weeks at 38°C (100°F), and ten weeks at 0°C (32°F) (based on standard duration stability tests). pH Stability ...... Stable to hydrolytic degradation at environ- mentally relevant pH (pH 5–9) log Kow (log Pow) ...... 6.5 Vapor Pressure ...... 1.5 x 10-9 mm Hg @ 25°C Water Solubility ...... 0.002 mg/L @ 25°C Koc ...... 251,700 mL/g 3 Mode of Action on Insects Symptoms Insects sprayed with DuPont™ Asana® XL exhibit symptoms such as the following:
■ Hyperexcitation
■ Tremors
■ Convulsions
■ Lethargy
■ Paralysis As the symptoms suggest, Asana® XL affects the insect’s nervous system. Asana® XL binds to the sodium channel in the nerve cell and locks the channel open. This results in repetitive firing of the nerves leading to the symptoms listed above. The insect is disoriented and its bodily functions fail because it cannot feed or move into protected areas. The exact type of symptoms that occur are linked to factors such as susceptibility of the insect species, the length of time between spraying and contact with the residue, and whether the exposure results from direct spraying, surface contact or ingestion.
Direct Contact Asana® XL can enter the insect directly through its cuticle, intersegmental membranes or other vulnerable areas, for example, the sensory structures on the exterior surface of the body. Direct contact with spray droplets is the most effective method of control because the insect is exposed to fresh, unaged residues. Insects not contacted by the spray are exposed to residual spray deposits on the treated crop foliage. Insects vary in the amount of contact they have with the plant during their normal activities. This may partially explain the variations that exist in the susceptibility of different species to Asana® XL.
Ingestion of Sprayed Foliage The primary route of insecticidal entry is through direct contact with Asana® XL residues during feeding. However, ingestion of treated crops adds to the intoxication process, serving as another means of exposure.
4 Partial Listing of Insects Controlled by Asana® XL The following chart provides a partial listing of the common and scientific names of the pests controlled. Please consult the package label for complete registration information.
Common name Scientific name Alfalfa caterpillar Colias eurytheme Alfalfa looper Autographa californica Apple aphid Aphis pomi Apple maggot Rhagoletis pomonella Armyworm Pseudaletia unipuncta Artichoke plume moth Platyptilia carduidactyla Aster leafhopper Macrosteles quadrilineatus Banded cucumber beetle Diabrotica balteata Banded sunflower moth Cochylis hospes Bean leaf beetle Cerotoma trifurcata Beet webworm Loxostege sticticalis Black cherry aphid Myzus cerasi Black cutworm Agrotis ipsilon Black vine weevil Otiorhynchus sulcatus Blueberry maggot Rhagoletis mendax Blueberry spanworm Itame argillacearia Boll weevil Anthonomus grandis grandis Cabbage looper Trichoplusia ni Celery looper Anagrapha falcifera Cherry fruit fly Rhagoletis cingulata Chinch bug Blissus leucopterus leucopterus Codling moth Cydia pomonella Colorado potato beetle Leptinotarsa decemlineata Corn earworm Helicoverpa zea (formerly Heliothis zea) Corn leaf aphid Rhopalosiphum maidis Corn rootworm (adult) Diabrotica spp. Corn silk fly Euxesta stigmatias Cotton bollworm Helicoverpa zea Cotton leafperforator Bucculatrix thurberiella Cotton leafworm Alabama argillacea Cranberry fruitworm Acrobasis vaccinii Cucumber beetle Acalymna spp. European corn borer Ostrinia nubilalis Filbertworm Cydia latiferreana Flea beetle Subfamily: Alticinae
5 Partial Listing of Insects Controlled by DuPont™ Asana® XL (continued) Common name Scientific name Fleahopper (cotton) Pseudatomoscelis seriatus Granulate cutworm Agrotis subterranea Grasshoppers Family: Acrididae (key genus Melanoplus) Green cloverworm Plathypena scabra Green fruitworm Lithophane antennata Green stink bug Acrosternum hilare Heliothis Heliothis virescens Hickory shuckworm Cydia caryana Imported cabbageworm Pieris rapae Japanese beetle (adult) Popillia japonica Lesser appleworm Grapholita prunivora Lesser peachtree borer Synanthedon pictipes Lygus bugs Lygus spp. Mexican bean beetle Epilachna varivestis Mullein plant bug Campylomma verbasci Nantucket pine tip moth Rhyacionia frustrana Navel orangeworm Amyelois transitella Oat-bird cherry aphid Rhopalosiphum padi Obliquebanded leafroller Choristoneura rosaceana Orange tortrix Argyrotaenia citrana Oriental fruit moth Grapholita molesta Painted lady butterfly (larvae) Vanessa cardui Pea aphid Acyrthosiphon pisum Pea weevil Bruchus pisorum Peachtree borer Synanthedon exitiosa Peach twig borer Anarsia lineatella Pear psylla Cacopsylla pyricola Pecan aphid (black/yellow) Melanocallis caryaefoliae/Monelliopsis pecanis Pecan nut casebearer Acrobasis nuxvorella Pecan phylloxera Phylloxera devastatrix Pecan spittlebug Clastoptera achatina Pecan weevil Curculio caryae Periodical cicada Magicicada septendecim Pickleworm Diaphania nitidalis Plum curculio Conotrachelus nenuphar Potato leafhopper Empoasca fabae Redbanded leafroller Argyrotaenia velutinana Rednecked peanutworm Stegasta bosqueella
6 Partial Listing of Insects Controlled by Asana® XL (continued)
Common name Scientific name Rindworm [complex] – Diaphania spp./and some species of Considered any caterpillar Family: Noctuidae that feeds on melon rinds Rosy apple aphid Dysaphis plantaginea Saltmarsh caterpillar Estigmene acrea Sap beetle [dusky] (adult) Carpophilus lugubris Sorghum midge Contarinia sorghicola Southern armyworm Spodoptera eridania Southern green stink bug Nezara viridula Southwestern corn borer Diatraea grandiosella Soybean aphid Aphis glycines Spittle bug Family: Cercopidae Spotted tentiform leafminer Phyllonorycter blancardella Squash bug Anasa tristis Squash vine borer Melittia cucurbitae Stalk borer Papaiema nebris Stink bug Family: Pentatomidae Sugarcane borer Diatraea saccharalis Sunflower beetle Zygogramma exclamationis Sunflower maggot Strauzia longipennis Sunflower moth Homoeosoma electellum Sunflower seed weevil Smicronyx spp. Sunflower stem weevil Cylindrocopturus adspersus Tarnished plant bug Lygus lineolaris Tentiform leafminer [spotted] Phyllonorycter blancardella Threecornered alfalfa hopper Spissistilus festinus Tobacco budworm Heliothis virescens Tobacco hornworm Manduca sexta Tomato fruitworm Helicoverpa zea Tomato hornworm Manduca quinquemaculata Tomato pinworm Keiferia lycopersicella Tufted apple bud moth Platynota idaeusalis Variegated leafhopper Erthroneura variabilis Velvetbean caterpillar Anticarsia gemmatalis Walnut aphid Chromaphis juglandicola Walnut husk fly Rhagoletis completa Western bean cutworm Loxagrotis albicosta Western cherry fruit fly Rhagoletis indifferens White apple leafhopper Typhocyba pomaria Woollybear caterpillar Family: Arctiidae 7 Current U.S. Tolerances for DuPont™ Asana® XL The following chart provides the current EPA-established tolerances for residues of Asana® XL in or on raw agricultural commodities (RAC’s). Tolerances are indicated in parts per million (ppm) of all isomers. RAC PPM RAC PPM Almond hulls 15.0 Kiwi 0.5 Almonds 0.2 Kohlrabi 2.0 Apples 2.0 Muskmelons 1.0 Artichokes 1.0 Mustard greens 5.0 Beans, dried 0.25 Peanuts 0.02 Beans, snap 2.0 Peanut hulls 0.1 Broccoli 2.0 Pears 2.0 Blueberries 3.0 Peas 1.0 Cabbage 10.0 Peas, dried 0.25 Caneberries 3.0 Pecans 0.2 Cantaloupes 1.0 Peppers 1.0 Carrots 0.5 Potatoes 0.02 Cauliflower 0.5 Pumpkins 1.0 Collards 10.0 Radish, roots 0.3 Corn, grain 0.02 Radish, tops 8.0 Corn, fodder 50.0 Sorghum, grain 5.0 Corn, forage 50.0 Sorghum, forage and fodder 10.0 Corn, sweet Soybeans 0.05 Kernels and cobs 0.1 Stone fruits 10.0 Cottonseed 0.2 Sugar beet, pulp 2.5 Cucumbers 0.5 Sugar beet, root 0.5 Currants 3.0 Sugar beet, tops 5.0 Eggplant 1.0 Sugarcane 2.0 Elderberries 3.0 Summer squash 0.5 English walnuts 0.2 Sunflower seeds 1.0 Filberts 0.2 Tomatoes 1.0 Gooseberries 3.0 Turnip, roots 0.5 Head lettuce 5.0 Turnip, tops 20.0 Honeydew melons 1.0 Watermelons 1.0 Huckleberries 3.0 Winter squash 1.0
8 Performance Characteristics Insects exposed to Asana® XL stop feeding almost immediately, thus preventing further damage to the crop. However, the lethal effects of Asana® XL may not be apparent until 72 hours after application. Because of this performance characteristic, premature evaluation of Asana® XL treatments can lead to the erroneous conclusion that insect control has not been achieved. Conduct post-treatment scouting 72 hours after an application to avoid unnecessary retreatment. Some insects are known to develop resistance to products used repeatedly for control. For example, Heliothis virescens (tobacco budworm) has developed some resistance to pyrethroid insecticides in certain areas. The use of Asana® XL should conform to resistance management strategies established in the use area. Due to resistance in some areas, a pyrethroid alone may not provide adequate control. If you experience difficulty with insect control while using this product, consult your local DuPont representative, agricultural advisor or university Extension specialist for specific control recommendations. The judicious use of pesticides demands adopting a sensible integrated pest management (IPM) approach. Consider the condition and stage of crop growth in conjunction with the levels of insects present — both pests and beneficial species. In some crops, beneficial insects are able to keep pest populations below the economic threshold. Frequent and detailed observations are needed to determine when economic thresholds are exceeded and chemical control is required. The combination of label information and detailed scouting will indicate if and when Asana® XL needs to be applied and the appropriate rate. It is generally accepted that variable rates of Asana® XL may be used, depending upon timing and insect pressure. Rigid spray schedules are not recommended because they are not sound economical or ecological practices. Rational timing of Asana® XL treatments and use of a sufficient dosage, within label recommendations, to bring pest populations under control are essential. Insect control objectives should be set at a level that achieves the maximum economic return while minimizing environmental impact. For cotton, sweet corn, cole crops and other crops that require multiple applications over a period of several weeks to control insect populations, make the initial one or two applications of Asana® XL at intermediate to high labeled rates. This practice establishes a residual deposit on the plants that will control heavy insect infestations. After insect populations are under control, the use of lower labeled rates usually controls light to moderate infestations. Also consider rotating to an insecticide in a different class of chemistry (such as DuPont™ Lannate®, Avaunt® or Steward®) with a different mode of action to minimize the potential for developing insect populations that are resistant to pyrethroids.†
† DuPont™ Lannate®, Avaunt® and Steward® are not labeled for use on all crops mentioned above. You must refer to the product label for each product for a complete listing of crop/pest combinations controlled or suppressed.
9 Longer Residual Activity Although a number of factors can affect pyrethroid performance (e.g., rainfall and temperature), research studies have documented that the ultraviolet (UV) rays in sunlight are the primary cause of pyrethroid breakdown. Compared to other pyrethroid products, the chemical structure of DuPont™ Asana® XL offers an advantage in the area of photostability. All pyrethroids consist of an alcohol fragment or moiety that is combined with an acid fragment. The reaction of the alcohol fragment (ending in –OH) with the acid fragment (carboxyl or COOH) releases water and forms a very stable ester molecule. The structure of the alcohol moiety is similar in most commercial pyrethroid products. However, there are important differences between Asana® XL and other pyrethroids in terms of the chemical structure of the acid fragment. Specifically, the arrange- ment of the Asana® XL molecule makes it much more stable and less vulnerable to UV degradation. Permethrin (Ambush and Pounce), Cypermethrin (Cymbush and Ammo), Baythroid, Capture, Decis, Fury, Karate, Mustang and Warrior all bond the alcohol fragment with a vinyl substituted cyclopropyl acid. This vinyl cyclopropyl acid fragment of the molecule is characterized by a carbon-to-carbon double bond. This chemistry, while insecticidally active, is susceptible to UV degradation. Because of the instability of the vinyl cyclopropyl double bond region when exposed to sunlight, the molecule breaks apart at this point. The UV-chemical reaction then denatures the pyrethroid molecule. In Asana® XL, the acid-alcohol bond is achieved using an isopropyl benzyl acid. This unit lacks the carbon-to-carbon double bond present in Ambush, Pounce, Baythroid, Capture, Decis, Fury, Karate, Mustang, Warrior and Cypermethrin. Although the acid fragment of the molecule is still vulnerable to sunlight breakdown, the process is much slower due to the lack of the double bond. Figure 3 shows the results of a DuPont trial that compared the photostability of Asana® XL and competitive pyrethroids. The chemical half-life of Asana® XL is almost twice as long as any of its competitors when they are applied to glass plates and exposed to artificial sunlight.
FIGURE 3: 100 ® STABILITY OF ASANA® XL ASANA XL INSECTICIDE AND COMPETI- CAPTURE TIVE PYRETHROIDS EXPOSED 80 BAYTHROID TO ARTIFICIAL (XENON ARC) KARATE SUNLIGHT (APPLIED AT 60 INSECTICIDALLY EQUIVALENT RATES). 40 ESTIMATED HALF-LIFE, DAYS
ASANA® XL 13.5 20 CAPTURE 7.8 BAYTHROID 4.0 KARATE 2.5 0 PERCENTAGE OF APPLIED A.I. REMAINING PERCENTAGE 0 2468101214 EXPOSURE TIME, DAYS (24 HOURS) 10 Figures 4 and 5 show the results of laboratory/greenhouse trials conducted with a number of commercial pyrethroid formulations to determine comparative residual activity. In Figure 4, paired soybean plants were treated at insecticidally equivalent rates. After the spray deposits had dried, half the plants were bioassayed at 24 hours after treatment. A second set of plants was held for 7 days and then bioassayed. All plants were bioassayed for control of corn earworm (Helicoverpa zea) larvae. The loss of activity after 7 days was calculated by comparing the toxicity of the deposit remaining on the plant 24 hours after application versus the toxicity of the deposit on the plants held for 7 days. The results were expressed as the percent of active residue remaining after 7 days for each product. Warrior was the most affected after 7 days, losing at least 75 percent of its original activity. Asana® XL was least affected after 7 days with more than 50 percent of the original activity remaining.
FIGURE 4: PYRETHROID RESIDUAL RESIDUAL ACTIVITY Corn Earworm LC50 OF ASANA® XL AND COM- Percent active residue remaining at 7 days PETITIVE PYRETHROIDS ON CORN EARWORM.
ASANA® XL
CAPTURE
AMMO
FURY
BAYTHROID
WARRIOR
0 1020304050
STINE HASKELL RESEARCH CENTER 2001 DATA
11 Figure 5 shows the results for a similar trial conducted with cabbage looper (Trichoplusia ni) on cabbage plants. In this trial Pounce and Ammo were the most affected after 7 days, losing more than 90 percent of their original activity. DuPont™ Asana® XL was least affected, retaining more than 25 percent of its original activity.
FIGURE 5:
RESIDUAL ACTIVITY PYRETHROID RESIDUAL
® OF ASANA XL AND Cabbage Looper LC50 COMPETITIVE PYRETHROIDS Percent active residue remaining at 7 days ON CABBAGE LOOPER.
ASANA® XL
WARRIOR
FURY
CAPTURE
BAYTHROID
AMMO
POUNCE
0 10203040
STINE HASKELL RESEARCH CENTER 2001 DATA
12 Improved Formulation In efforts to improve photostability, DuPont researchers experimented with a number of different formulations, trying to block the effects of the sun’s rays. They discovered that formulating it with cottonseed oil (CSO), which has a sunscreen-like effect, could extend the residual life of Asana® XL. The fatty acids in cottonseed oil absorb UV light, protecting Asana® XL from certain wavelengths that break it down. Other ingredients that act as a sunscreen also are included in the formulation. As noted in Figure 6, DuPont research shows the Asana® XL formulation with cottonseed oil is much more resistant to sunlight breakdown than an earlier formulation of the same compound (Asana® 1.9) or conventional EC formulations of similar products.
FIGURE 6:
100 ASANA® XL STABILITY OF ASANA® XL ASANA® 1.9 INSECTICIDE AND COMPETITIVE AMMO PYRETHROIDS ON GLASS PLATES 80 SCOUT EXPOSED TO NATURAL SUN- CYMBUSH LIGHT (APPLIED AT INSECTICI- 60 BAYTHROID DALLY EQUIVALENT RATES). ESTIMATED HALF-LIFE, DAYS 40 ASANA® XL 7.5 ASANA® 1.9 2.3 CYMBUSH 0.5 20 AMMO 1.1 BAYTHROID 0.5 0 SCOUT 0.9 PERCENTAGE OF APPLIED A.I. REMAINING PERCENTAGE 024681012 EXPOSURE TIME, DAYS (24 HOURS)
13 Figure 7 shows the results of a DuPont laboratory/greenhouse trial conducted with six commercial pyrethroid formulations to determine comparative UV (ultraviolet) light stability. Paired cotton plants were treated at insecticidally equivalent rates. After the spray deposits had dried, half the plants were held in a dark growth chamber while the other half were exposed to 24 hours of high-intensity, simulated sunlight (equivalent to three days exposure in the field). All plants were then bioassayed for control of tobacco budworm larvae (Heliothis virescens). The loss of activity was calculated by comparing the toxicity of the deposit remaining on the plant exposed to simulated sunlight versus the toxicity of the deposit on the plants held in the dark. The results are expressed as the percent of original activity remaining after 24 hours of simulated sunlight for each product. Baythroid and Warrior were most affected by exposure to simulated sunlight, losing at least 30 percent of their original activity. DuPont™ Asana® XL was least affected by the simulated sunlight with more than 85 percent of the original activity remaining. Similar results have been reported from comparative photostability tests on cotton plant leaves exposed to natural sunlight. The improved residual performance of Asana® XL helps growers reduce the number of spray applications, with the benefits of lower labor, equipment and chemical costs.
FIGURE 7:
ASANA® XL RESISTANCE TO PYRETHROID UV STABILITY UV DEGRADATION Percent of original activity remaining INSECTICIDAL ACTIVITY OF after 24 hours in UV chamber THE DEPOSIT REMAINING ON THE PLANT AFTER EXPOSURE TO 24 HOURS OF SIMULATED ASANA® XL SUNLIGHT.
CAPTURE
FURY
AMMO
BAYTHROID
WARRIOR
50 60 70 80 90 100
STINE HASKELL RESEARCH CENTER 2001 DATA
14 Resistance to Washoff Another important criterion for the Asana® XL formulation is resistance to washoff. Ongoing field and laboratory tests have verified that adding cottonseed oil to the formulation not only increases photostability but also helps the insecticide adhere to plant foliage. As individual spray droplets of Asana® XL dry, a protective film of cottonseed oil and Asana® XL forms. This protective film, which is extremely resistant to water, ensures that the insecticidally active pyrethroid residues will remain on the plant. Once the spray deposit has dried, Asana® XL resists washoff from rainfall, dew or irrigation better than competitive pyrethroids formulated with petroleum-based solvents. Figure 8 shows the results of a laboratory/greenhouse trial conducted with six commercial pyrethroid formulations to determine resistance to washoff. Paired cotton plants were treated at insecticidally equivalent rates. After the spray deposits had dried, half the plants were exposed to a 2-inch simulated rainfall (applied at 1 inch per hour). All plants were then bioassayed for control of tobacco budworm larvae (Heliothis virescens). The loss of activity was calculated by comparing the toxicity of the deposit remaining on the plant exposed to rainfall versus the toxicity of the deposit on the plant not exposed to rainfall. The results are expressed as the percent of original activity remaining after 2 inches of simulated rainfall for each product. Fury and Warrior were most affected by washoff, losing more than 65 percent of their efficacy. Asana® XL was least affected by the simulated rainfall with more than 50 percent of the original activity remaining. Field entomologists have also observed that the insect control properties of Asana® XL are maintained even if treatments are followed by sprinkler irrigation or heavy rainfall.
FIGURE 8:
PYRETHROID WASHOFF ASANA® XL RESISTANCE Percent of original activity remaining after TO WASHOFF 2 inches simulated rainfall INSECTICIDAL ACTIVITY OF THE SPRAY DEPOSIT REMAINING ON THE PLANT AFTER ASANA® XL EXPOSURE TO A 2-INCH SIMULATED RAINFALL.
CAPTURE
BAYTHROID
AMMO
WARRIOR
FURY
10 20 30 40 50 60
STINE HASKELL RESEARCH CENTER 2001 DATA 15 High Temperature Effectiveness In field applications on cotton, DuPont™ Asana® XL has demonstrated outstanding activity over a wide range of temperatures and climatic conditions. Observations indicate that even at high temperatures Asana® XL maintains its effectiveness.
Crop Safety Asana® XL has been shown to be noninjurious to a wide range of field, tree and vegetable crops when used in accordance with the label. Multiple applications, even at maximum labeled rates, are not phytotoxic to leaves or fruit.
Compatibility Mixes in Water Asana® XL may be tank mixed in a water carrier with most other pesticides, including DuPont™ Avaunt®, Lannate®, Steward® and Vydate® insecticides, or with certain herbicides when insect populations require control concurrent with the need for weed control. Laboratory evaluations indicate that most other pesticides likely to be tank mixed in a water carrier will be compatible with Asana® XL. Always check all applicable labels and conduct a test for physical compatibility before making and applying field mixtures. To conduct a test for compatibility, add proportionate amounts of Asana® XL and each ingredient of the intended tank mixture to a pint or quart jar. After capping the jar, shake it and allow the mixture to stand for 15 minutes. If precipitates form that are not readily redispersed, the mixture is incompatible and should not be used.
Mixes in Vegetable Oils The growing practice of ultra-low-volume (ULV) oil application techniques has raised questions about pesticide tank-mix compatibility in vegetable oils. To date, laboratory evaluations show that most pesticides sold as emulsible concentrates will be compatible with Asana® XL in vegetable oil. Mixtures of solid formulations, water-dispensable suspensions and certain solution formulations in water-miscible solvents are likely to generate mixing, homogeneity and spraying problems with Asana® XL in vegetable oil. This is a function of the solid pesticide formulations and oil and is not a problem brought about by the presence of Asana® XL in the mixture. Again, it is good practice to perform the standard physical compatibility test described above before mixing large volumes in a spray tank.
16 Tank Stability Asana® XL should be applied as soon as possible following preparation to avoid the possibility of product degradation. However, equipment breakdown, sudden rain, high winds and other environmental factors can delay or interrupt insecticide applications. When a job must be postponed, the unused spray solution is left sitting in the equipment until the situation improves enough to continue with the application. This can extend into a period of days, during which time the tank mix can decompose and be ineffective when spraying is resumed. The chemical stability of a pesticide in a tank mix is primarily dependent on the temperature and the tank mix pH. The pH of the tank mix is not necessarily the same as the source water since most formulations contain chemicals that will change the pH. Knowing the pH and temperature of the tank mix during the delay, the following graph can be used to determine the approximate percent of Asana® XL remaining after the delay. Asana® XL exhibits excellent tank stability under a wide range of tank pH (see Figure 9). In addition, spray tank temperature does not affect Asana® XL stability appreciably over the standard tested range of 32º F to 113º F. Many insecticides do not exhibit this degree of stability. The graph only represents the activity of Asana® XL in water and does not apply to any added tank-mix partner. In all cases, tank mixes should be thoroughly agitated before spraying is resumed. This information is intended as a guide for understanding the tank stability of Asana® XL and is not to be used to determine if, or how much, pesticide should be added to an existing tank mix after a time delay, or as a guide to determine how far in advance a tank mix can be prepared.
FIGURE 9: ® STABILITY OF ASANA XL TANK STABILITY
100 SUMMARY OF PERCENT ASANA® XL REMAINING IN 96 TANK DEPENDENT UPON pH. 92
88 XL REMAINING ® 84 pH=9 80 pH=7 76 pH=5
PERCENT ASANA 72 0 1 2 3 DAYS
17 Ecological Effects Environmental Impact Toxicological and environmental fate data indicate that esfenvalerate has a minimal environmental impact on both man and the environment when applied at recommended use rates in accordance with label directions. Phytotoxicity from esfenvalerate has not been observed in any plant studies. The compound is chemically very stable and degrades to known and understood metabolites. Esfenvalerate binds very tightly to soil, and its binding properties increase proportionally to the organic content of the soil (average Koc=251,700). The compound is very insoluble in water (less than 2 ppb). These factors make it highly unlikely that DuPont™ Asana® XL will move into groundwater or wash off-site to surface waters.
Environmental Hazards Asana® XL is a restricted-use pesticide because it is extremely toxic to fish and aquatic invertebrates. Use with care when applying in the vicinity of any body of water. Do not apply directly to water or when weather conditions favor drift from treated areas. Do not apply Asana® XL by ground within 25 feet, or by air within 150 feet of lakes, reservoirs, rivers, permanent streams, marshes, natural ponds, estuaries or commercial fish-farm ponds. Increase the buffer zone to 450 feet when ultra-low volume (ULV) application is made. Do not contaminate water when disposing of equipment wash waters. Do not apply to blooming crops if bees are visiting the treatment area. Apply this product only as specified on the label.
Toxicity to Fish Although laboratory tests have demonstrated that Asana® XL is extremely toxic to fish and aquatic invertebrates, these tests were conducted under conditions where the concentrations of Asana® XL were maintained throughout the test. Under natural conditions, the level of Asana® XL is likely to decrease rapidly due to the very high binding affinity of Asana® XL for organic matter in water, soil or sediment, thereby decreasing its availability to fish and zooplankton. Rapidly diminishing concentrations of Asana® XL mitigate the level and duration of potential toxicity of fish and aquatic invertebrates in aquatic habitats. Large-scale field mesocosm studies using quarter-acre ponds have confirmed that under natural conditions, toxicity of Asana® XL to fish and aquatic invertebrates is lower than predicted from laboratory studies. When ponds containing natural assemblages of algae, invertebrates and fish were treated with repeated applications of Asana® XL simulating both drift (up to 20 percent of the maximum field use rate) and runoff (up to 37 percent of the maximum field use rate), no detrimental effects were observed for algae or fish. The populations of some aquatic invertebrates in the ponds were negatively affected, but the effects were transient and longer-term effects were only seen for sediment-dwelling invertebrates and then only at the highest concentrations tested.
18 Toxicity to Bees Asana® XL is highly toxic to bees directly exposed to applications. However, once the foliar residues have dried, the hazard is insignificant. Thus, Asana® XL can be used on a blooming crop if applied when bees are not actively foraging. The best time for treatment is either early morning or evening. Due to the bee repellent effect, bee visitations can be expected to drop slightly for one day and then return to normal. By following these application guidelines, growers will see effective insect control with little or no interruption of bee activity to pollination-dependent crops. Research has confirmed that bees do not carry Asana® XL back to the hive in quantities that either weaken the hive or predispose it to loss during the winter. In addition, dried spray residues of Asana® XL will not become resuspended or dissolved in dew, unlike some other pesticides, further reducing the hazard of Asana® XL to bees.
Environmental Fate Water: Esfenvalerate is stable in acid or neutral water but degrades via hydrolysis in alkaline water. When aqueous solutions were exposed to light, it degraded rapidly with a half-life of 4 days in summer and 13 to 15 days in winter. Soil: In soils, the rate of degradation is dependent on the nature of the soil. Light further assists the degradation of esfenvalerate in soil. Half-lives averaging 10 days were observed in soil photolysis experiments. Due to its affinity for organic material, there is no leaching of this compound in soil.
Metabolism of Esfenvalerate in Plants and Animals The metabolism of esfenvalerate has been extensively studied in plants and animals. In plants, esfenvalerate showed very little systemic absorption and translocation after foliar application. Esfenvalerate that does enter the plant, degrades by photolytic decarboxylation reaction, ester cleavage and subsequent conjugation of the cleaved products with glucose. In animals, esfenvalerate is extensively metabolized and rapidly excreted. The major metabolic reaction is ester cleavage and hydroxylation at the alcohol moiety.
19 DuPont™ Asana® XL Toxicology EPA Toxicity Acute Toxicology1,2 Asana® XL Category Acute Oral LD50 Rat 458 mg/kg (moderately toxic) II Acute Dermal LD50 Rabbit >2000 mg/kg (moderately toxic) III Acute Inhalation LC50 Rat >2.93 mg/L (4 hours — moderately toxic) III Eye Contact Rabbit minimally irritating IV Skin Contact Rabbit not an irritant IV Guinea pig not a sensitizer
Avian Asana® Technical (mg/kg) Mallard duck LD50 >2250 (very low to slightly toxic) Bobwhite quail LD50 381 (moderately toxic)
Aquatic Asana® Technical (ug/L, ppb) Rainbow trout LC50 0.26 (96 hours — extremely toxic) Bluegill sunfish LC50 0.26 (96 hours — extremely toxic) Carp LC50 1.34 (48 hours — extremely toxic) Daphnia magna LC50 0.90 (48 hours — extremely toxic)
1 LD50 is the dose of chemical per kilogram of body weight that is lethal to 50 percent of the animals tested. 2 LC50 is the concentration of material in air or water that is lethal to 50 percent of the animals tested.
20 Acute Toxicity Studies Asana® XL is moderately toxic via oral, dermal and inhalation exposures. Exposure to near lethal concentrations has produced neurological effects in laboratory animals. Such exposures are not reached when the product is used in accordance with the product label. Contact with the concentrate produced minimal eye irritation that had reversed in three days. It is not a primary skin irritant nor a sensitizer. However, contact with skin has resulted in a transient burning or prickling sensation that may last from a few minutes to approximately 24 hours. This sensation is usually not accompanied by visible irritation or a rash and is common to many pyrethroid insecticides. Vitamin E oil or cream has been shown to offer relief from this effect.
Subchronic, Chronic and Neurotoxicity Studies Esfenvalerate has been thoroughly evaluated in laboratory toxicity tests. Esfen- valerate does not produce any significant target organ toxicity in animals following repeated dosing by feeding or application to the skin. It has not been demonstrated to be a reproductive toxin or a developmental toxin in laboratory animals. These tests were also negative for neurological lesions or significant effects on other tissues.
Mutagenicity and Genetic Toxicity Studies Esfenvalerate does not produce genetic damage. It was negative in all tests for this effect, including gene mutation tests in S. typhimurium (Ames Test), E. coli and in Chinese hamster ovary (CHO) cells; in vitro chromosome aberration test in CHO cells; mouse micronucleus test; and the unscheduled DNA assay in HeLa cells.
Carcinogenicity Lifetime studies in rodents with fenvalerate or esfenvalerate were negative for carcinogenic effects. Esfenvalerate has been classified by the EPA as: evidence of noncarcinogenicity for humans.
Material Safety Information Consult the Material Safety Data Sheet (MSDS) for more information.
Health, Safety and Handling Information Only certified applicators or persons working under their direct supervision can use Asana® XL. Only those uses covered by the certified applicator’s certification are permitted. Safety in handling, storing and applying Asana® XL is the responsibility of each individual who works with it. Prior to using Asana® XL, refer to the product label for more information on its use. In addition, observe the precautions outlined in the following sections whenever you are working with Asana® XL.
21 Hazardous Reactivity Instability: Stable at normal temperatures and storage conditions. Decomposition: Hydrogen cyanide may be formed by thermal decomposition or reaction with alkaline materials. Polymerization: Polymerization will not occur. Incompatibility: Avoid heat, flame and contact with strong oxidizing agents.
Fire and Explosion Data The flash point for DuPont™ Asana® XL is 150º F (TCC). Heating can release vapors that can be ignited. Hazardous gases/vapors produced in fire are toxic and may include hydrogen cyanide. Extinguishing media are water spray, water fog, dry
chemical and CO2. Special Fire Fighting Instructions ■ Evacuate personnel to a safe area.
■ Wear self-contained breathing apparatus.
■ Wear full protective equipment.
■ Use water spray; cool tank/container with water spray.
Other Physical Hazards ■ Use explosion-proof ventilation as required to control vapor concentrations.
■ Keep liquid and vapor away from heat, sparks or flame. Hot surfaces may ignite liquid product even in the absence of sparks or flame.
■ Extinguish pilot lights and cigarettes; turn off other sources of ignition prior to use and until all vapors are gone.
■ Do not cut, drill, grind, or weld on or near container. Emptied containers can contain explosive vapors.
NFPA Rating Health 1 Flammability 2 Reactivity 0
22 Spills, Leaks or Releases* Small Spills
■ Soak up with absorbent material and place in nonleaking containers for proper disposal.
■ Do not use alkaline absorbent because Asana® XL can react to form hydrogen cyanide.
■ Use diking to ensure that water sources are not contaminated. Large Spills
■ Eliminate potential sources of ignition.
■ Wear appropriate respirator and other protective clothing.
■ Shut off source of leak only if safe to do so.
■ Dike and contain. Remove with vacuum trucks or pump to storage/salvage vessels.
■ Soak up residue with an absorbent such as clay, sand or other suitable material. Place in nonleaking containers and seal tightly for proper disposal.
■ Do not use alkaline absorbent because Asana® XL can react to form hydrogen cyanide.
■ Flush area with water to remove trace residue; dispose of flush solution as described above. * Note: Review the sections on “FIRE AND EXPLOSION DATA” and “HEALTH HAZARDS” before proceeding with clean up. CAUTION — COMBUSTIBLE!
In case of a significant spill, call CHEMTREC: 1-800-424-9300 Waste Disposal ■ Place in a disposal facility approved under Resource Conservation and Recovery Act (RCRA) Regulations for hazardous waste.
■ Use nonleaking containers, seal tightly and label properly. Improper disposal of excess pesticide, spray mixture, or rinsate is a violation of federal law. If these wastes cannot be disposed of according to label instructions, contact your State Pesticide or Environmental Control Agency or the hazardous waste representative at the nearest EPA Regional Office for guidance.
Shipping Information Asana® XL is classified by the Department of Transportation (DOT) as: Pesticide Liq- uid, Toxic, N.O.S. (esfenvalerate), 6.1., UN 2902, PG111. If shipped by water or bulk (more than 119 gallons per single package), add: Marine Pollutant.
23 Returnable Bulk Container Systems To assist in the task of proper handling and disposal of containers, DuPont offers DuPont™ Asana® XL in 14- and 110-gallon returnable container systems. The 14-gallon stainless steel container is equipped with a Micromatic Macro-Valve dry-break male fitting. The 110-gallon plastic returnable tank is equipped with a Micromatic Drum Valve dry-break male fitting. Both systems are evacuated using customer-owned pump and meter systems. For low volume users, the Tuthill/Sotera Series 35 volumetric hand pump is recommended. For high volume users, the Murray Tru-Force 12-volt electric pump/meter system is recommended. Other pump/meter systems have also been used successfully. Due to the Asana® XL formulation, all pump systems should use Viton gaskets for maximum longevity. After the 14- or 110-gallon container is empty, simply return it to DuPont through an approved agrichemical supplier. This eliminates the time-consuming and expensive decontamination and disposal process now faced by consumers.
Storage Conditions ■ Store Asana® XL in a secure, dry and temperate area in the original container.
■ Keep the container closed when not in use.
■ Do not use or store around the home or near food or feed.
■ Avoid contact with water.
® 1 Asana XL insecticide is shelf-stable for more than 2 ⁄2 years under normal storage conditions. This period is accurate both with respect to retention of active component and maintenance of acceptable emulsibility properties. Personal Precautions, Symptoms and Treatment Health Hazards and Protection Information Warning! Asana® XL may be fatal if swallowed and harmful if inhaled. (Please see page 21 for Acute Toxicity Study information)
■ Avoid breathing vapors or mist; do not get in eyes, on skin or on clothing.
■ Use Asana® XL only with adequate ventilation. Wear goggles or a face shield, protective clothing and rubber gloves (as specified by the label) when handling.
■ Wash thoroughly with soap and water after handling and before eating, drinking, chewing gum, using tobacco or using the toilet.
■ Wash contaminated clothing before reuse; discard shoes if contaminated.
■ Do not consume food, drink or tobacco in areas where they may become contaminated.
24 Effects of Overexposure/First Aid Response Ingestion Reactions may initially include nonspecific discomfort, such as nausea, vomiting, headache or weakness; temporary nervous system effects, such as muscular weakness, tremors and incoordination may also occur. IF SWALLOWED: Call poison control center or doctor immediately for treatment advice. Do not induce vomiting unless told to do so by the poison control center or doctor. Do not give anything by mouth to an unconscious person. If vomiting occurs spontaneously, keep head below hips to prevent aspiration of liquid into the lungs. Aspiration of vomitus into the lungs must be avoided because even a small amount may result in aspiration pneumonitis. Get medical attention.
Inhalation May result in difficulty breathing. IF INHALED: Move person to fresh air. If person is not breathing, call 911 or an ambulance, then give artificial respiration, preferably by mouth-to-mouth, if possible. Call a poison control center or doctor for further treatment advice.
Eye Contact Reactions may initially include eye irritation with discomfort, tearing or blurring of vision. IF IN EYES: Hold eye open and rinse slowly and gently with water for 15 to 20 minutes. Remove contact lenses, if present, after the first 5 minutes, then continue rinsing eye. Call a poison control center or doctor for treatment advice.
Skin Contact Reactions may initially include a transient (several minutes up to approximately 24 hours), persistent burning or prickling sensation, usually not accompanied by visible irritation or rash. IF ON SKIN OR CLOTHING: Take off contaminated clothing. Rinse skin immediately with plenty of water for 15 to 20 minutes. Call a poison control center or doctor for treatment advice. Note to Physician — Wash with soap and water immediately. After drying, apply vitamin E cream or oil (12,000 international units of vitamin E per fluid ounce, available at drug stores and supermarkets). If vitamin E cream or oil is not available, liberally apply vegetable oil over any painful areas; the oil or cream may be used repeatedly until relief is achieved. Relief may come within minutes; symptoms usually disappear after several hours. Contains xylene range aromatic solvent — vomiting may cause aspiration pneumonia.
25 Medical Emergencies For medical emergencies involving DuPont™ Asana® XL insecticide and related formulations of any other DuPont agrichemical product, call toll free: 1-800-441-3637. This is a 24-hour DuPont product information and emergency response number in Wilmington, Del. Caller should state, “This is a medical emergency.” The caller will be placed in contact with a poison control center. Caller should be prepared to state the name of the DuPont product involved and the attending physician’s name, address and phone number.
26 Notes Notes
Asana® XL, Lannate®, Vydate®, Ambush, Ammo, Aztec, Baythroid, Brigade, Capture, Cymbush, Decis, Discipline, Empower, Fury, Karate, Mustang, Mustang Max, Perm-UP, Pounce, ProAxis, Renounce, Silencer, Tempo, UP-Cyde, Warrior and Waylay are restricted-use pesticides. This reference guide is not intended as a substitute for the product label for the products referenced herein. Product labels for the referenced products contain important precautions, directions for use and product warranty and liability limitations that must be read before using the product. Applicators must be in possession of the product label at the time of application. Always read and follow all label directions and precautions for use. The DuPont Oval Logo, DuPont™, The miracles of science™, Asana®, Avaunt®, Lannate®, Steward® and Vydate® are trademarks or registered trademarks of DuPont or its affiliates. Ambush, Cymbush, Karate and Warrior are trademarks or registered trademarks of Syngenta Crop Protection. Ammo, Brigade, Capture, Fury, Mustang and Pounce are registered trademarks of FMC Corporation. Aztec, Baythroid, Decis, Renounce, Scout and Tempo are trademarks or registered trademarks of Bayer CropScience. Empower is a trademark of Helena Chemical Company. Discipline is a registered trademark of AMVAC Chemical Corporation. ProAxis is a registered trademark of Pytech Chemicals Gmbh. Silencer is a trademark of Makhteshim Chemical Works LTD. Copyright © 2002-2006 E.I. du Pont de Nemours and Company. All Rights Reserved. 2/06 Reorder No.: K-09355 (Replaces H-95335)