Turfgrass Insecticides: Chemistry, Activity, and Environmental Impacts

David Held!Auburn University!

Overview:

•  Insecticides for people that hate chemistry!

•  Modes of Action, Exposure and Pest Spectrum

•  Impacts on beneficial and bees

•  Resistance and IRAC

Why do you need to know about turf insecticides?

• Insecticides largest and fastest growing pesticide in T&O market ($1.3 billion) Neonicotinoids>Pyrethroids> Chlorantraniliprole>Fipronil (~$61 million)

• Insecticide resistance concerns

Insecticides for people that hate chemistry!

Modes of Action, Exposure

and Pest Spectrum

Insects have significantly changed in the last 20 yr Four new chemical classes Increased efficacy Reduced mammalian toxicity

How do insecticides work? IRAC (Insecticide Resistance Action Committee)

29 categories (Numbers and letters)

http://www.irac-online.org/

TriazamateMethomyl

Aldicarb Carbofuran

Carbaryl

Thiodicarb

Benfuracarb Carbosulfan

Oxamyl

Methiocarb

Fenobucarb

O CH3

CH3

OCONHCH3

CH3NHCO

2N C

SCH3

CH3

CH3

CH3

C CHCH3S NOCONHCH

3

OCONHCH3

CH3NCO

2N C

SCH3

CH3

S

CH3NCO

2N C

SCH3

CH3

O

OCO

CH3

CH3

CH3

N S NCH2CH

2CO

2CH

2CH

3

CH(CH3)2

O CH3

CH3

OCO

CH3

N S N[(CH2)3CH

3]2

(CH3)2NCOC NOCONHCH

3

SCH3

OC

O

CH3NH

SCH3

CH3

CH3

O

CHCH2CH

3

CH3CH

3NHC

O

1A Carbamates

1B Organophosphates

Chlorpyrifos

Dimethoate Profenofos

MonocrotophosAcephate

Malathion

Methamidophos

Terbufos

Parathion-methyl

Diazinon

NCl

Cl Cl

OP(OCH2CH

3)2

S

CH3NHCOCH

2SP(OCH

3)2

S

O

CH3SP

OCH3

NHCOCH3

S

(CH3O)

2PS

CO2CH

2CH

3

CHCH2CO

2CH

2CH

3

O

NH2

CH3OPSCH

3

(E )

CONHCH3

O(CH3O)

2P

O

H

CC

CH3

S

P(OCH2CH

3)2(CH

3)3CSCH

2S

O2N OP(OCH

3)2

S

N

N

CH3

(CH3)2CH

OP(OCH2CH

3)2

S

SCH2CH2CH3

P

O

Br Cl

OCH2CH3

O

2B Phenylpyrazoles (Fiproles)2A Cyclodiene Organochlorines

Cl

Cl

Cl

Cl

Cl

ClCl

Cl

Chlordane

Cl

Cl

Cl

Cl

Cl

Cl

O

SO

O

Endosulfan

F3C N

Cl

Cl

N CN

SO

CF3NH2

Fipronil

NN

Cl Cl

CF3

H2N

CNCH3CH2SO

Ethiprole

3A Pyrethroids

PyrethrinsDeltamethrin

Lambda-cyhalothrin

Cypermethrin

Bifenthrin

Alpha-cypermethrin

Esfenvalerate

TefluthrinCyfluthrin

Zeta-

cypermethrin

EtofenproxCNOC

H

CO2

CH3

CH3

C

Br

Br

CH

HH

(Z)-(1R)-cis -

(Z)-(1S)-cis -(R)

(S)

CH3

CH3CH CC

F3C

ClH H

O2

C

CN

OH

CH3

CCH

CH3

C

F3C

ClH H

CNO2

CH

O

C CH

Cl

Cl

CH3

CH3

CO2CH O

CN

(Z)-(1R)-cis-

(Z)-(1S)-cis-

CH3

H2

CO2C

CH3

CH3CHC

F3C

Cl H H

CO2CCHC

F3C

Cl

CH3

CH3H H

CH3

H2

(1R)-cis -

(1S)-cis -(R)

(S)

CH3

CH3CH CC

Cl

ClH H

O2

CCN

O

H

CH3

CCH

CH3

C

Cl

Cl

H H

CNO

O2

C

H

OC

CNO

C

CH(CH3)2

Cl

O

H H

(Z)-(1S)-cis-

(Z)-(1R)-cis-

C CH

F3C

Cl

CH3

CH3

H H

F F

F F

CH3

CO2CH

2

CH3

CH3

CO2CH

2

F F

F F

CH3

HH

CH

F3C

ClC

OCH

CN

F

CH3

CH3

CHC

Cl

Cl

CO2

OCH

3

CH3

CO2CH

CHC

Cl

Cl

CN

CH3CH

2O

CCH3

CH2OCH

2

CH3

O

Pyrethrins

(Pyrethrum) DDT

Methoxychlor

Cl CH

CCl3

Cl

CH3O CH

CCl3

OCH3

R = -CH3 (chrysanthemates) or -CO2CH3 (pyrethrates)

R1 = -CH=CH2 (pyrethrin) or -CH3 (cinerin) or -CH2CH3 (jasmolin)

H

CH3 CH3

C

CH H

O

O H

CH3

O

CH2 C

CR1

H

H

C

CH3

R

3B DDT,

Methoxychlor

4A Neonicotinoids

Acetamiprid

N

C

CH3

CH3

N

CN

CH2

N

Cl

Clothianidin

N

Cl

CH2

NH

HN

CH3N

S

NO2

Dinotefuran

OHN

HN

CH3

NNO2

Imidacloprid

N

Cl CH2

N

NN

NO2

H

Nitenpyram

N

C

CH2CH3

CH3NH

C

NO2

CH2

N

Cl

H

Thiacloprid

S

N

N

Cl

CH2

N

CN

Thiamethoxam

S

N

CH2

N

O

N

Cl

N

CH3

NO2

4B Nicotine

N

CH3N

H

Nicotine

5 Spinosyns

Spinosad

O

O

OCH3

(CH3)2N

CH3

CH3CH2HH

H H

R

H

OOO

O

OCH3

OCH3

CH3OCH3

spinosyn A, R = H-

spinosyn D, R = CH3- Spinetoram

6 Avermectins, Milbemycins

Abamectin

O

CH3CH3

CH3

O

OO

OH

CH3

OH

O

OH

H

H

OCH3

OCH3

O

OCH3

HO

OCH3

CH3

H

H R

(i) R = -CH2CH3 (avermectin B1a)

(ii) R = -CH3 (avermectin B1b)

Emamectinbenzoate

NH2

CH3

O

O

O

CH3

CH3

O

OO

OH

CH3

HO

O

H

H

OCH3

R

CH3HOCH3

CH3

OCH3

CH3O

CO2

B1a R = CH3CH2-

B1b R = CH3-

Milbemectin

CH3

CH3

O

O

CH3

R

OO

O CH3

OH

OH

H

H

H

H

Milbemycin A3: R = -CH3

Milbemycin A4: R = -CH2CH3

7A Juvenile hormone analogues 7B Fenoxycarb 7C Pyriproxyfen

CC

CC

CH2

CHCH2

CH2

CH2

CHCH3

CH3 CH3 CH3H

H H

CO2CH2CH3

Hydroprene Kinoprene

CC

CC

CH2CH

CH2CH2

CH2CH

CH3

CH3

CH3

CH3

H

H

H

CO2CH2C CH

Methoprene Fenoxycarb Pyriproxyfen

O OCH2CH2NHCO2CH2CH3

N OCH

CH3

CH2

O

O

CH2

C C

C C

CH3 CO2CH(CH3)2

H

H

H

CH

(CH2)3

CH3

(CH3)2C

OCH3

8A Alkyl halides 8B Chloropicrin 8C Sulfuryl fluoride

CH3Br Cl3C NO2S

O

O

F F

Chloropicrin

Sulfuryl

fluorideMethyl

bromide Tartar emeticBorax

Na B O . 10H OO O

SbO O

O

O

O OSb

O O

O

O

.2K+ .3H2O-

- -

- -

-

-

-3+ 3+

8D Borax 8E Tartar emetic

9B Pymetrozine 9C Flonicamid

N

CH

N

NNH

N

CH3

O N

CF3

CONHCH2CN

Pymetrozine Flonicamid

10A Clofentezine, Hexythiazox 10B Etoxazole

Cl

N N

NN

Cl

N

S

O

Cl

CH3

NH

C

O CH2CH3O

C(CH3)3

F

F

O

N

Clofentezine Hexythiazox Etoxazole

12C

Propargite

12D

Tetradifon12B Organotin

miticides

Diafenthiuron Azocyclotin

Cyhexatin

Fenbutatin oxide Propargite Tetradifon

O

CH(CH3)2

NHCSNHC(CH3)3

CH(CH3)2

Sn

N

N

N

OH

Sn

C CH2

CH3

CH3

CCH2

CH3

CH3

Sn O Sn

3 3

C(CH3)3

O

OSO2CH2C CH

Cl SO2

Cl

Cl

Cl

12A

Diafenthiuron

Bensultap

SO2 S CH2

CH

CH2S

N(CH3)2

SO2

CH2

CH2H2NCOS

CH

H2NCOS

N(CH3)2.HCl

S

SS

(CH3)2N

CH

CH2SSO3Na

CH2SSO3NaCH3

NCH3

Thiocyclam

Thiosultap-

sodium

Cartaphydrochloride

Chlorfenapyr DNOC

N

CH2OCH2CH3

CF3

BrCN

Cl

O2N

OH

CH3

NO2

14 Nereistoxin

analogues

N

N

S

NC(CH3)3

CH(CH3)2O

Buprofezin

N N

NH2N

NH2

NH

Cyromazine

HN N

O

OC(CH3)3

CH3

CH3

CH3

O

Chromafenozide

CH3O CH3

NH N

O

OC(CH3)3

CH3

CH3

HN N

O

OC(CH3)3Cl

HN N

O

OC(CH3)3 CH3

CH3

CH3CH2

Halofenozide

Methoxyfenozide

Tebufenozide18 Diacyl-

hydrazines

CF3CH

CH

C

CH

CH

NN

NH

NH

CH3

CH3

CF3

CH3 N

CH3

CH CH

CH3CH3

CH3N N

Amitraz Hydramethylnon

20A Hydramethylnon 20B Acequinocyl

O

O

O

(CH2)11CH3

COCH3

Acequinocyl

CCH

O

OO

CH3

CH2

O N

N

CF3

OCH

CH3

CH3

CH3

20C Fluacrypyrim

Fluacrypyrim

Fenazaquin

Fenpyroximate

Pyrimidifen

Pyridaben

Tebufenpyrad

Tolfenpyrad Rotenone

CH3O

OCH3

OO O

C

CH3

CH2

OH

H

CH2

C

NH

O

NN

CH3

CH3CH2 Cl O

CH3

CH2

C

NH

O

C(CH3)3

N N

CH3CH2

Cl

CH3

(CH3)3C CH2S

NN

Cl

O

C(CH3)3

N

N

CH3CH2 Cl

CH3

CH3

(CH2)2OCH2CH3

CH2

ONH

CH2

C

O

N

C

NN

CH3

O

CH3

H

O

CH2

O C(CH3)3

N

N

OCH2

CH2

C(CH3)3

21A METI acaricides and insecticides 21B Rotenone

Indoxacarb

O

N N

NO CO2CH3

CO2CH3Cl

OCF3

Metaflumizone

22A Indoxacarb 22B Metaflumizone 23 Tetronic & Tetramic acid derivatives

Spirodiclofen Spiromesifen

CCH2

C(CH3)3

O

O

OO

CH3

CH3 CH3

O

O

OC

O

Cl

Cl

CH3 CH2CH3

CH3

24A

Phosphine

AluminiumPhosphide

24B Cyanide

Cyanide

CN-

CalciumPhosphide

ZincPhosphide

Phosphine

Al P Zn P3 2

Ca P3 2

O

OH

CO2CH3

O

O

CH3OC

O

O OHC

CH3

CH3

O

CH3

O

OO

HO

CH3

H

O

CH3C

Azadirachtin Pyridalyl

DicofolChinomethionatBenzoximate

O

O O

NCl

Cl

CF3Cl

Cl

Cl C

OH

CCl3

ClN

N

S

SO

CH3

C

C

NOCH2CH3

OCH3

ClCH3O

O

O

Bifenazate

NHNH

OCH3

COOCH(CH3)2

AlF

F FF

FF3Na

Cryolite

15 Benzoylureas

Flucycloxuron

Flufenoxuron

Hexaflumuron

Lufenuron

Novaluron

Noviflumuron

Teflubenzuron

TriflumuronCH2

F

F

NHCONHCO

ONC

Cl

F

F

F

NHCONHCOOCF3

Cl

Cl F

F

NHCONHCO

Cl

CHF2CF2O

Cl

CF3CHFCF2O

Cl

F

FNHCONHCO

Cl

CF3OCHFCF2O

F

F

NHCONHCO

NH

C

O

NH

C

O

F

FCF3CHFCF2O

F

Cl

Cl

Cl

F

F

F

F

NHCONHCO

Cl

NHCONHCO

Cl

CF3O

Chlorfluazuron

Diflubenzuron

Cl

F

F

NHCONHCO

CONHCONH

F

F

O

N

CF3

ClCl

Cl

Bistrifluron

Insecticide Resistance Action Committee

The Key to Resistance Management

Guidance on the use of Sub-Groups:

! Represent distinct structural classes believed to have the same mode of action.

! Provides differentiation between compounds that may bind at the same target site.

! Are structurally different such that risk of metabolic cross-resistance is lower than for close chemical analogs.

! Are likely to be metabolized by different enzymes - may bind differently enough within the target site that the chance of

selection for metabolic/target-site resistance is reduced compared to close analogs.

! 3A & 3B - If there are no other alternatives, compounds may be rotated in situations where cross-resistance mechanisms (e.g.

kdr) are known to be absent in the insect populations to be treated. DDT is no longer used in agriculture and therefore this is

only applicable for the control of human disease vectors such as mosquitoes, because of a lack of alternatives.

!10A - Clofentezine & Hexythiazox are grouped because they commonly exhibit cross-resistance even though they are structurally

distinct, and the target site for neither compound is known.

! 22A & 22B - Although these compounds are believed to have the same target site, they have been sub-grouped because they

are chemically distinct, and current evidence indicates that the risk of metabolic cross-resistance is low.

! In the absence of other alternatives, it may be possible to rotate compounds between sub-groups if it is clear that cross-

resistance mechanisms do not exist in the target populations.

! Not all of the current groupings are based on knowledge of a shared target protein. For further information please refer to the

IRAC Mode of Action Classification document.

!1A & 1B - If there are no other alternatives, compounds may be rotated in situations where cross-resistance mechanisms are

known to be absent in the insect populations to be treated.

More information on IRAC and the Mode of Action Classification is available from:

www.irac-online.org or enquiries@irac-online.org

Structures, reproduced from the Pesticide Manual, are with permission from the British Crop Protection Council Poster Version 2, October 2009. Based on the Mode of Action Classification - Version 6.3The poster is for educational purposes only. Details presented are accurate to the best of our knowledge at the time of publication but IRAC or its member companies cannot accept

responsibility for how this information is used or interpreted. Advice should always be sought from local experts or advisors and health and safety recommendations followed.

N

CF3

NH

NH

OO

CF3

NC

NH

O O

NH

F

FCl

FF

F

F FF

B.t.

israelensisB.t.

aizawai

B.t.

aizawai

B.

sphaericus

B.t.

kurstaki

B.t.

tenebrionis

Cry1Ab

Cry1Ac

Cry1Fa

Cry2Ab

mCry3A

Cry3Ab

Cry3Bb

Cry34/35Ab1

Spirotetramat

NH

O

O

O

O

CH2

CH3

OCH

3

CH3

CH3

O

O

O

O

O

N

O

O

O

O

O

HH

H H

H

R

5 6

C5 C6, R = HC5 C6, R = CH3

-=

NN

N

(CH3)3C

CON(CH3)2

SCH2CO

2C

2H

5

13 Pyrroles, Dinitrophenols

16 Buprofezin 17 Cryomazine

19 Amitraz

25 Cyenopyrafen

Cyenopyrafen

Cyflumetofen

Chlorantraniliprole28

Diamides

NH

CH3

O

ClO

NN

N

Cl

BrNH

CH3

SOO

I

O

NH

NH

O

CF3

CF3

F

Flubendiamide

CF3

CC

O

NC

C(CH3)3

O

O

H2C CH2

O CH3

CC

CN

C(CH3)3

N

N

OH3C

CH3H3C

C(CH3)3

O

Group 1: Acetylcholinesterase (AChE) inhibitors (Only major representatives of the groups are shown)

Group 2: GABA-gated chloride channel antagonists

Group 3: Sodium channel modulators (Only major representatives of group 3A are shown)

Group 4: Nicotinic acetylcholine receptor (nAChR) agonists

Group 5: Nicotinic acetylcholinereceptor (nAChR) allosteric modulators

Group 6: Chloride channel activators

Group 7: Juvenile hormone mimics

Group 8: Miscellaneous non-specific (multi-site) inhibitors

Group 9: Selective homopteran feeding blockers

Group 10: Mite growth inhibitors

Group 11: Microbial disruptors of insect midgut membranes and derived toxins

Group 12: Inhibitors of mitochondrial ATP synthase

Group 13: Uncouplers of oxidative phos-phorylation via disruption of proton gradient

Group 14: Nicotinic acetylcholine receptor (nAChR) channel blockers

Group 15: Inhibitors of chitin biosynthesis, type 0

Group 17: Moulting disruptor, Dipteran

Group 18: Ecdysone receptor agonistsGroup 16: Inhibitors of

chitin biosynthesis,type 1

Group 19: Octopaminereceptor agonists

Group 20: Mitochondrial complex III electron transport inhibitors

Group 21: Mitochondrial complex I electron transport inhibitors

Group 22: Voltage-dependentsodium channel blockers

Group 23: Inhibitors of acetylCoA carboxylase

Group 24: Mitochondrial complex IV electron transport inhibitorsGroup 25: Mitochondrial

complex II electron transport inhibitors

Group 28: Ryanodine

receptor modulatorsGroup UN: Compounds of unknown or uncertain mode of action

Mode of Action Classification

PH3

2 4 7 2

Terms  Dendrite:      Cell  body:      Axon:        Axon  terminal:      Synapse:      Neurotransmi9er:  

Terms  Dendrite:    Source  of  the  signal  or  input    Like  a  keyboard  or  mouse  

Terms  Dendrite:  source      Cell  body:    Computer    Sends  signal  out  to  printer  or  monitor    

Terms  Dendrite:  source      Cell  body:  computer    Axon:  the  middle,  like  a  wire,  connects  the  cell  body  to  the  axon  terminal    

Terms  Dendrite:  source      Cell  body:  computer    Axon:  the  middle,  like  a  wire,  connects  cell  body  to  axon  terminal    Axon  terminal:  printer;  where  an  electrical  signal  becomes  chemical  (ink  in  the  printer;  neurotransmi9er  in  nerve  cells)    

Synapse;  the  space  in  the  printer  where  the  paper  feeds  

Sodium  channels  along  the  axon;  conductors  of  the  signal  in  the  

printer  cable  

Dendrite  

Axon  terminal;  the  printer  in  our  analogy  

Illustrated  parts  of  one  nerve  cell  

v  

Axon  

Dendrite  

Nerve    leading  to  wings  

Nerve    leading  to  brain  

Nerve    leading  to  leg  muscles  

Nerve    leading  to  gut  

Receptors  on  other  nerve  cells  

Nerve  cells  communicate  with  chemicals  called  neurotransmi9ers  (analagous  to  ink)  

Neurotransmi9er  

Synapse  

Electrical  signal  moves  along  the  Axon  

Dendrite  

v  

v  

v  

v  v  

v  

Neurotransmi9er  released  into  the  

Synapse  

Enzymes  in  the  synapse  remove  the  neurotransmi9er  like  the  printer  pulling  in  a  new  piece  of  paper  

Signal  moves  along  the  axon  of  another  nerve  cell  

Binds  to  another  nerve  cell  

The  receptors  are  now  ready  to  get  another  signal  

v  

Synapse  

Axon  

Nerve    leading  to  leg  muscles  

Receptors  

InsecKcides  target  the  nervous  system  internally  within  the  axon  

And  at  receptors  (channels)  where  nerve  cells  try  to  communicate  with  other  nerve  cells  or  muscles  

IRAC Group

Mode of action

Chemical Class

Active ingredient

Trade names

1 Acetylcholinesterase inhibitor

Between nerve cells

A. Carbamate carabaryl Sevin B.

Organophosphate acephate Orthene

trichlorofon Dylox chlorpyrifos Dursban

2 GABA-chloride channel antagonists Nerve cell to muscle

cells

A. Organochlorines

chlordane Chlordane

B. Phenylpyrazoles

fipronil TopChoice

3 Sodium channel modulators

Poison nerve cells internally (axon)

A. Pyrethroids\pyrethrins

bifenthrin Talstar delatamethrin Deltagard

Lambda-cyhalothrin

Scimitar

B. DDT DDT DDT 5 Nicotinic

acetylcholine receptor activators

Between nerve cells

Spinosyns Spinosad Conserve

IRAC Group

Mode of action

Chemical Class

Active ingredient

Trade names

4 Nicotinic acetylcholine

receptor agonists

A. Neonicotinoids

Clothianidin Arena Aloft

Dinotefuran Zylam Imidacloprid Merit

Allectus Thiamethoxam Meridian

18 Ecdysone receptor agonists

(metamorphosis)

Diacylhydrazines Halofenozide Mach2*

22 Voltage-dependent sodium channel

blockers

A. Indoxacarb Indoxacarb Provaunt Advion

28 Ryanodine receptor

modulators (muscles)

Diamides or anthranilic diamides

Chlorantraniliprole Acelepryn

Cyantraniliprole Ference, Mainspring

Source: www.irac-online.org

Routes of Exposure Pyrethroids: Contact only

Fipronil: Contact or Ingestion (bait)

Neonicotinoids: Contact, Ingestion, Systemic

Indoxacarb: Ingestion, contact, translaminar

Diamides: Ingestion mainly (Systemic), Contact

Turf Pest Spectrum Pyrethroids: caterpillars, chinch bugs, surface active insects\mites

Fipronil: ants, mole crickets

Neonicotinoids: grubs, billbugs, caterpillar activity (Zylam and clothianidin)

Provaunt: caterpillars, mole crickets

Diamides: caterpillars, billbugs, grubs

Expected residual against foliage feeders

Pyrethroids 7-10 d residual

Acelepryn 6-8 wk residual

Mach 2 and Provaunt 2-4 wk

Preventive control of soil pests

Typically 1-2 apps per year

Mole crickets: mid May-July

White grubs: May-June

Curative control of soil pests

Shorter residual insecticides

Baits, Dylox, all OP’s and carbamates

Reducing Impacts on Bees and other

Beneficials

Overview

What  are  beneficials?    Impacts  of  insecKcides  on  beneficials  

Bees aren’t the only beneficials

Pollinators                                  Predators                                Parasitoids                                    Pathogens\Nematodes    

Applying milky spore powder has never been experimentally shown to control white grubs!

Predators

Ants                Predatory  wasps                                  Spiders                                                True  bugs      

Pest vs Predatory beetles?

Appearance of mouthparts

OP,  Carbamates,  Pyrethroids  Kill  if  contact  with  fresh  residue  Short  term  reducKons  (≤  1MAT)  on  insect  predators,  earthworms,  parasitoids    Acephate,  bifenthrin  compaKble  with  some  beneficial  nematodes  

 Sources: Cockfield and Potter 1984, Braman and Pendley 1993, Kunkel et al. 1999, Barabara and Buss 2005, Larson et al. 2011

Acelepryn  (chlorantraniliprole)  &  

Halofenozide  

 Low  toxicity  to  parasitoids,  predators,  earthworms,  ants,  beneficial  nematodes    

   Sources: Kunkel et al. 1999, Mannion et al. 2000, Koppenhoffer and Fuzzy

2008, Brugger et al. 2009, Gradish et al. 2010, Larson et al. 2013, 2014

Fipronil  (TopChoice)    Toxic  to  ants  (labeled),  predatory  beetles,  true  bugs,  wasps    Minimal  impact  on  earthworms    CompaKble  with  beneficial  nematodes  

   

Sources: Balanca and de Visscher 1997, Elzen 2001, Mostert et al. 2002, Barabara and Buss 2005, NPIC 2009

Provaunt  (indoxacarb)    Toxic  to  true  bugs,  sublethal  effects  on  some  predatory  beetles  (bait)    Minimal  impact  on  earthworms      Sources: Balanca and de Visscher 1997, Elzen 2001, Mostert et al. 2002, NPIC 2009

NeonicoKnoids  Effects  on  individuals    If  hit  by  spray,  contact  mortality    Sublethal  effects:  consuming  tainted  nectar,  pollen,  or  insects  consumed  aYer  being  killed  by  the  treatment      Sources: Kunkel et al. 1999, Rogers and Potter 2003, Peck and Olmstead

2010, Larson et al. 2011, 2013, 2014

NeonicoKnoids  Effects  on  individuals    Effects  common  at  lower  than  label  rates  (1/8-­‐1/2x;  sublethal)  

   

Sources: Kunkel et al. 1999, Rogers and Potter 2003, Peck and Olmstead 2010, Larson et al. 2011, 2014

NeonicoKnoids  Popula7on  level    Mainly  short-­‐term  impacts  on  different  groups  (predatory  beetles,  earthworms)      

Sources: Kunkel et al. 1999, Peck and Olmstead 2010, Larson et al. 2011, 2013, 2014

NeonicoKnoids  Preda7on\Parasi7sm      ReducKons  in  parasiKsm  (sublethal)    May  or  may  not                                          reduce  predaKon    Some  may  increase  thatch  

Sources: Kunkel et al. 1999, Peck and Olmstead 2010, Larson et al. 2011, 2013, 2014

What  about  Pre-­‐mix  products?  zeta-­‐cypermethrin,  bifenthrin  and  imidacloprid  

Clothianidin  +  bifenthrin  (AloY)    

Thiamethoxam  +  Fungicide  (Caravan)  

Pre-­‐mix  products  and  beneficials  

Larson  et  al.  2011,  2014  Compared  mix  to  each  component  of  AloY  

Impacts  similar  to  those  known  for  the  insecKcide  components  

   

Reasons  for  Bee  Decline  Complex  set  of  stressors  and  pathogens  

•  Parasi5c  mites  •  Viruses,  Bacteria,  other  Pathogens    •  Poor  nutri5on      • GeneKcs  •  Pes5cides  

Bee  Effects  by  Chemical  Class  • OP’s  (Dursban),  carbamates  (Sevin),  Pyrethroids  – Most  toxic  by  contact  

• Fipronil  (TopChoice)  – Contact,  ingesKon  toxicity  – Affect  orientaKon  and  learning  (ingesKon)  

• Chlorantraniliprole  (Acelepryn)  – No  direct  toxicity  reported  

 

 

Sources: Gels et al. 2002, NPIC 2009, Larson et al. 2013

• Indoxacarb  (Provaunt)  – Toxic  on  contact,  not  by  ingesKon  

• Halofenozide  (IGR)    – PracKcally  non-­‐toxic  to  bees  

 

 Sources: Dias 2006

Bee  Effects  by  Chemical  Class  

• NeonicoKnoids  – First  new  class  scruKnized  for  bee  effects  – Individual  acKve  ingredients  vary    

 

 

Sources: Gels et al. 2002, Larson et al. 2013

Bee  Effects  by  Chemical  Class  

Insec5cide   Oral  LD50   Contact  LD50  Imidacloprid   3.7-­‐40.9  ng  \bee   59.7-­‐242.6  ng  \bee  Dinotefuran   23  ng  \bee   47  ng  \bee  

Acetamiprid   14530  ng  \bee   8090  ng  \bee  

Thiamethoxam   5  ng  \bee  (192  ppb)   24  ng  \bee  

Clothianidin   3  ng  \bee   22-­‐44  ng  \bee  

• NeonicoKnoids  – First  new  class  scruKnized  for  bee  effects  – Individual  acKve  ingredients  vary  – CombinaKons  products  (+pyrethroids)  – Influenced  by  formulaKon,  irrigaKon,  mowing  

 

 

Sources: Gels et al. 2002, Larson et al. 2013

Bee  Effects  by  Chemical  Class  

Bad  News  InsecKcides  use  in  weedy  turf  will  have  bee  impacts!  

One  exposure  to  clothianidin  can  have  season  long  impacts  

Can  be  translocated  into  nectar  in  woody  plants  (e.g.,  Oregon)  

   

Good  News  Mowing  flowering  weeds  before  applicaKon  significantly  reduces  bee  hazard  

Post-­‐treatment  irrigaKon  removes  hazard  (pyrethroids,  Provaunt)  

Acelepryn  had  no  adverse  effects  New  labeling  to  guide  insecKcide  use  

Conclusion  and  Discussion  InsecKcides  are  oYen  needed  PoliKcs  are  unavoidable  and  immutable    Imidacloprid  got  fast  track  registraKon    It’s  always  something…  

Follow  label  and  avoid  hazards  to  bees  

   

InsecKcide  Resistance  

What  is  resistance?  

Ability  of  an  individual(s)  to  tolerate  or  avoid  selec7on  factors  that  would  otherwise  be  lethal  to  the  majority  of  individuals  in  a  normal  popula7on  

•     Process  of  selecKon  

•     NOT  the  same  as  product  failures!  

•     Must  pass  through  to  next  generaKon  

What  is  resistance?  

What  favors  resistance?  MulKple  generaKons  per  year  PesKcide  applied  before  maKng  Limited  dispersal  (non-­‐flight)  Repeated  applicaKons  with  similar  modes  of  acKon    

How  do  you  manage  resistance?  

Integrate  controls  Spot  treat  whenever  possible  Go  to  IRAC    

TriazamateMethomyl

Aldicarb Carbofuran

Carbaryl

Thiodicarb

Benfuracarb Carbosulfan

Oxamyl

Methiocarb

Fenobucarb

O CH3

CH3

OCONHCH3

CH3NHCO

2N C

SCH3

CH3

CH3

CH3

C CHCH3S NOCONHCH

3

OCONHCH3

CH3NCO

2N C

SCH3

CH3

S

CH3NCO

2N C

SCH3

CH3

O

OCO

CH3

CH3

CH3

N S NCH2CH

2CO

2CH

2CH

3

CH(CH3)2

O CH3

CH3

OCO

CH3

N S N[(CH2)3CH

3]2

(CH3)2NCOC NOCONHCH

3

SCH3

OC

O

CH3NH

SCH3

CH3

CH3

O

CHCH2CH

3

CH3CH

3NHC

O

1A Carbamates

1B Organophosphates

Chlorpyrifos

Dimethoate Profenofos

MonocrotophosAcephate

Malathion

Methamidophos

Terbufos

Parathion-methyl

Diazinon

NCl

Cl Cl

OP(OCH2CH

3)2

S

CH3NHCOCH

2SP(OCH

3)2

S

O

CH3SP

OCH3

NHCOCH3

S

(CH3O)

2PS

CO2CH

2CH

3

CHCH2CO

2CH

2CH

3

O

NH2

CH3OPSCH

3

(E )

CONHCH3

O(CH3O)

2P

O

H

CC

CH3

S

P(OCH2CH

3)2(CH

3)3CSCH

2S

O2N OP(OCH

3)2

S

N

N

CH3

(CH3)2CH

OP(OCH2CH

3)2

S

SCH2CH2CH3

P

O

Br Cl

OCH2CH3

O

2B Phenylpyrazoles (Fiproles)2A Cyclodiene Organochlorines

Cl

Cl

Cl

Cl

Cl

ClCl

Cl

Chlordane

Cl

Cl

Cl

Cl

Cl

Cl

O

SO

O

Endosulfan

F3C N

Cl

Cl

N CN

SO

CF3NH2

Fipronil

NN

Cl Cl

CF3

H2N

CNCH3CH2SO

Ethiprole

3A Pyrethroids

PyrethrinsDeltamethrin

Lambda-cyhalothrin

Cypermethrin

Bifenthrin

Alpha-cypermethrin

Esfenvalerate

TefluthrinCyfluthrin

Zeta-

cypermethrin

EtofenproxCNOC

H

CO2

CH3

CH3

C

Br

Br

CH

HH

(Z)-(1R)-cis -

(Z)-(1S)-cis -(R)

(S)

CH3

CH3CH CC

F3C

ClH H

O2

C

CN

OH

CH3

CCH

CH3

C

F3C

ClH H

CNO2

CH

O

C CH

Cl

Cl

CH3

CH3

CO2CH O

CN

(Z)-(1R)-cis-

(Z)-(1S)-cis-

CH3

H2

CO2C

CH3

CH3CHC

F3C

Cl H H

CO2CCHC

F3C

Cl

CH3

CH3H H

CH3

H2

(1R)-cis -

(1S)-cis -(R)

(S)

CH3

CH3CH CC

Cl

ClH H

O2

CCN

O

H

CH3

CCH

CH3

C

Cl

Cl

H H

CNO

O2

C

H

OC

CNO

C

CH(CH3)2

Cl

O

H H

(Z)-(1S)-cis-

(Z)-(1R)-cis-

C CH

F3C

Cl

CH3

CH3

H H

F F

F F

CH3

CO2CH

2

CH3

CH3

CO2CH

2

F F

F F

CH3

HH

CH

F3C

ClC

OCH

CN

F

CH3

CH3

CHC

Cl

Cl

CO2

OCH

3

CH3

CO2CH

CHC

Cl

Cl

CN

CH3CH

2O

CCH3

CH2OCH

2

CH3

O

Pyrethrins

(Pyrethrum) DDT

Methoxychlor

Cl CH

CCl3

Cl

CH3O CH

CCl3

OCH3

R = -CH3 (chrysanthemates) or -CO2CH3 (pyrethrates)

R1 = -CH=CH2 (pyrethrin) or -CH3 (cinerin) or -CH2CH3 (jasmolin)

H

CH3 CH3

C

CH H

O

O H

CH3

O

CH2 C

CR1

H

H

C

CH3

R

3B DDT,

Methoxychlor

4A Neonicotinoids

Acetamiprid

N

C

CH3

CH3

N

CN

CH2

N

Cl

Clothianidin

N

Cl

CH2

NH

HN

CH3N

S

NO2

Dinotefuran

OHN

HN

CH3

NNO2

Imidacloprid

N

Cl CH2

N

NN

NO2

H

Nitenpyram

N

C

CH2CH3

CH3NH

C

NO2

CH2

N

Cl

H

Thiacloprid

S

N

N

Cl

CH2

N

CN

Thiamethoxam

S

N

CH2

N

O

N

Cl

N

CH3

NO2

4B Nicotine

N

CH3N

H

Nicotine

5 Spinosyns

Spinosad

O

O

OCH3

(CH3)2N

CH3

CH3CH2HH

H H

R

H

OOO

O

OCH3

OCH3

CH3OCH3

spinosyn A, R = H-

spinosyn D, R = CH3- Spinetoram

6 Avermectins, Milbemycins

Abamectin

O

CH3CH3

CH3

O

OO

OH

CH3

OH

O

OH

H

H

OCH3

OCH3

O

OCH3

HO

OCH3

CH3

H

H R

(i) R = -CH2CH3 (avermectin B1a)

(ii) R = -CH3 (avermectin B1b)

Emamectinbenzoate

NH2

CH3

O

O

O

CH3

CH3

O

OO

OH

CH3

HO

O

H

H

OCH3

R

CH3HOCH3

CH3

OCH3

CH3O

CO2

B1a R = CH3CH2-

B1b R = CH3-

Milbemectin

CH3

CH3

O

O

CH3

R

OO

O CH3

OH

OH

H

H

H

H

Milbemycin A3: R = -CH3

Milbemycin A4: R = -CH2CH3

7A Juvenile hormone analogues 7B Fenoxycarb 7C Pyriproxyfen

CC

CC

CH2

CHCH2

CH2

CH2

CHCH3

CH3 CH3 CH3H

H H

CO2CH2CH3

Hydroprene Kinoprene

CC

CC

CH2CH

CH2CH2

CH2CH

CH3

CH3

CH3

CH3

H

H

H

CO2CH2C CH

Methoprene Fenoxycarb Pyriproxyfen

O OCH2CH2NHCO2CH2CH3

N OCH

CH3

CH2

O

O

CH2

C C

C C

CH3 CO2CH(CH3)2

H

H

H

CH

(CH2)3

CH3

(CH3)2C

OCH3

8A Alkyl halides 8B Chloropicrin 8C Sulfuryl fluoride

CH3Br Cl3C NO2S

O

O

F F

Chloropicrin

Sulfuryl

fluorideMethyl

bromide Tartar emeticBorax

Na B O . 10H OO O

SbO O

O

O

O OSb

O O

O

O

.2K+ .3H2O-

- -

- -

-

-

-3+ 3+

8D Borax 8E Tartar emetic

9B Pymetrozine 9C Flonicamid

N

CH

N

NNH

N

CH3

O N

CF3

CONHCH2CN

Pymetrozine Flonicamid

10A Clofentezine, Hexythiazox 10B Etoxazole

Cl

N N

NN

Cl

N

S

O

Cl

CH3

NH

C

O CH2CH3O

C(CH3)3

F

F

O

N

Clofentezine Hexythiazox Etoxazole

12C

Propargite

12D

Tetradifon12B Organotin

miticides

Diafenthiuron Azocyclotin

Cyhexatin

Fenbutatin oxide Propargite Tetradifon

O

CH(CH3)2

NHCSNHC(CH3)3

CH(CH3)2

Sn

N

N

N

OH

Sn

C CH2

CH3

CH3

CCH2

CH3

CH3

Sn O Sn

3 3

C(CH3)3

O

OSO2CH2C CH

Cl SO2

Cl

Cl

Cl

12A

Diafenthiuron

Bensultap

SO2 S CH2

CH

CH2S

N(CH3)2

SO2

CH2

CH2H2NCOS

CH

H2NCOS

N(CH3)2.HCl

S

SS

(CH3)2N

CH

CH2SSO3Na

CH2SSO3NaCH3

NCH3

Thiocyclam

Thiosultap-

sodium

Cartaphydrochloride

Chlorfenapyr DNOC

N

CH2OCH2CH3

CF3

BrCN

Cl

O2N

OH

CH3

NO2

14 Nereistoxin

analogues

N

N

S

NC(CH3)3

CH(CH3)2O

Buprofezin

N N

NH2N

NH2

NH

Cyromazine

HN N

O

OC(CH3)3

CH3

CH3

CH3

O

Chromafenozide

CH3O CH3

NH N

O

OC(CH3)3

CH3

CH3

HN N

O

OC(CH3)3Cl

HN N

O

OC(CH3)3 CH3

CH3

CH3CH2

Halofenozide

Methoxyfenozide

Tebufenozide18 Diacyl-

hydrazines

CF3CH

CH

C

CH

CH

NN

NH

NH

CH3

CH3

CF3

CH3 N

CH3

CH CH

CH3CH3

CH3N N

Amitraz Hydramethylnon

20A Hydramethylnon 20B Acequinocyl

O

O

O

(CH2)11CH3

COCH3

Acequinocyl

CCH

O

OO

CH3

CH2

O N

N

CF3

OCH

CH3

CH3

CH3

20C Fluacrypyrim

Fluacrypyrim

Fenazaquin

Fenpyroximate

Pyrimidifen

Pyridaben

Tebufenpyrad

Tolfenpyrad Rotenone

CH3O

OCH3

OO O

C

CH3

CH2

OH

H

CH2

C

NH

O

NN

CH3

CH3CH2 Cl O

CH3

CH2

C

NH

O

C(CH3)3

N N

CH3CH2

Cl

CH3

(CH3)3C CH2S

NN

Cl

O

C(CH3)3

N

N

CH3CH2 Cl

CH3

CH3

(CH2)2OCH2CH3

CH2

ONH

CH2

C

O

N

C

NN

CH3

O

CH3

H

O

CH2

O C(CH3)3

N

N

OCH2

CH2

C(CH3)3

21A METI acaricides and insecticides 21B Rotenone

Indoxacarb

O

N N

NO CO2CH3

CO2CH3Cl

OCF3

Metaflumizone

22A Indoxacarb 22B Metaflumizone 23 Tetronic & Tetramic acid derivatives

Spirodiclofen Spiromesifen

CCH2

C(CH3)3

O

O

OO

CH3

CH3 CH3

O

O

OC

O

Cl

Cl

CH3 CH2CH3

CH3

24A

Phosphine

AluminiumPhosphide

24B Cyanide

Cyanide

CN-

CalciumPhosphide

ZincPhosphide

Phosphine

Al P Zn P3 2

Ca P3 2

O

OH

CO2CH3

O

O

CH3OC

O

O OHC

CH3

CH3

O

CH3

O

OO

HO

CH3

H

O

CH3C

Azadirachtin Pyridalyl

DicofolChinomethionatBenzoximate

O

O O

NCl

Cl

CF3Cl

Cl

Cl C

OH

CCl3

ClN

N

S

SO

CH3

C

C

NOCH2CH3

OCH3

ClCH3O

O

O

Bifenazate

NHNH

OCH3

COOCH(CH3)2

AlF

F FF

FF3Na

Cryolite

15 Benzoylureas

Flucycloxuron

Flufenoxuron

Hexaflumuron

Lufenuron

Novaluron

Noviflumuron

Teflubenzuron

TriflumuronCH2

F

F

NHCONHCO

ONC

Cl

F

F

F

NHCONHCOOCF3

Cl

Cl F

F

NHCONHCO

Cl

CHF2CF2O

Cl

CF3CHFCF2O

Cl

F

FNHCONHCO

Cl

CF3OCHFCF2O

F

F

NHCONHCO

NH

C

O

NH

C

O

F

FCF3CHFCF2O

F

Cl

Cl

Cl

F

F

F

F

NHCONHCO

Cl

NHCONHCO

Cl

CF3O

Chlorfluazuron

Diflubenzuron

Cl

F

F

NHCONHCO

CONHCONH

F

F

O

N

CF3

ClCl

Cl

Bistrifluron

Insecticide Resistance Action Committee

The Key to Resistance Management

Guidance on the use of Sub-Groups:

! Represent distinct structural classes believed to have the same mode of action.

! Provides differentiation between compounds that may bind at the same target site.

! Are structurally different such that risk of metabolic cross-resistance is lower than for close chemical analogs.

! Are likely to be metabolized by different enzymes - may bind differently enough within the target site that the chance of

selection for metabolic/target-site resistance is reduced compared to close analogs.

! 3A & 3B - If there are no other alternatives, compounds may be rotated in situations where cross-resistance mechanisms (e.g.

kdr) are known to be absent in the insect populations to be treated. DDT is no longer used in agriculture and therefore this is

only applicable for the control of human disease vectors such as mosquitoes, because of a lack of alternatives.

!10A - Clofentezine & Hexythiazox are grouped because they commonly exhibit cross-resistance even though they are structurally

distinct, and the target site for neither compound is known.

! 22A & 22B - Although these compounds are believed to have the same target site, they have been sub-grouped because they

are chemically distinct, and current evidence indicates that the risk of metabolic cross-resistance is low.

! In the absence of other alternatives, it may be possible to rotate compounds between sub-groups if it is clear that cross-

resistance mechanisms do not exist in the target populations.

! Not all of the current groupings are based on knowledge of a shared target protein. For further information please refer to the

IRAC Mode of Action Classification document.

!1A & 1B - If there are no other alternatives, compounds may be rotated in situations where cross-resistance mechanisms are

known to be absent in the insect populations to be treated.

More information on IRAC and the Mode of Action Classification is available from:

www.irac-online.org or enquiries@irac-online.org

Structures, reproduced from the Pesticide Manual, are with permission from the British Crop Protection Council Poster Version 2, October 2009. Based on the Mode of Action Classification - Version 6.3The poster is for educational purposes only. Details presented are accurate to the best of our knowledge at the time of publication but IRAC or its member companies cannot accept

responsibility for how this information is used or interpreted. Advice should always be sought from local experts or advisors and health and safety recommendations followed.

N

CF3

NH

NH

OO

CF3

NC

NH

O O

NH

F

FCl

FF

F

F FF

B.t.

israelensisB.t.

aizawai

B.t.

aizawai

B.

sphaericus

B.t.

kurstaki

B.t.

tenebrionis

Cry1Ab

Cry1Ac

Cry1Fa

Cry2Ab

mCry3A

Cry3Ab

Cry3Bb

Cry34/35Ab1

Spirotetramat

NH

O

O

O

O

CH2

CH3

OCH

3

CH3

CH3

O

O

O

O

O

N

O

O

O

O

O

HH

H H

H

R

5 6

C5 C6, R = HC5 C6, R = CH3

-=

NN

N

(CH3)3C

CON(CH3)2

SCH2CO

2C

2H

5

13 Pyrroles, Dinitrophenols

16 Buprofezin 17 Cryomazine

19 Amitraz

25 Cyenopyrafen

Cyenopyrafen

Cyflumetofen

Chlorantraniliprole28

Diamides

NH

CH3

O

ClO

NN

N

Cl

BrNH

CH3

SOO

I

O

NH

NH

O

CF3

CF3

F

Flubendiamide

CF3

CC

O

NC

C(CH3)3

O

O

H2C CH2

O CH3

CC

CN

C(CH3)3

N

N

OH3C

CH3H3C

C(CH3)3

O

Group 1: Acetylcholinesterase (AChE) inhibitors (Only major representatives of the groups are shown)

Group 2: GABA-gated chloride channel antagonists

Group 3: Sodium channel modulators (Only major representatives of group 3A are shown)

Group 4: Nicotinic acetylcholine receptor (nAChR) agonists

Group 5: Nicotinic acetylcholinereceptor (nAChR) allosteric modulators

Group 6: Chloride channel activators

Group 7: Juvenile hormone mimics

Group 8: Miscellaneous non-specific (multi-site) inhibitors

Group 9: Selective homopteran feeding blockers

Group 10: Mite growth inhibitors

Group 11: Microbial disruptors of insect midgut membranes and derived toxins

Group 12: Inhibitors of mitochondrial ATP synthase

Group 13: Uncouplers of oxidative phos-phorylation via disruption of proton gradient

Group 14: Nicotinic acetylcholine receptor (nAChR) channel blockers

Group 15: Inhibitors of chitin biosynthesis, type 0

Group 17: Moulting

disruptor, DipteranGroup 18: Ecdysone receptor agonists

Group 16: Inhibitors of

chitin biosynthesis,

type 1

Group 19: Octopaminereceptor agonists

Group 20: Mitochondrial complex III electron transport inhibitors

Group 21: Mitochondrial complex I electron transport inhibitors

Group 22: Voltage-dependentsodium channel blockers

Group 23: Inhibitors of acetylCoA carboxylase

Group 24: Mitochondrial complex IV electron transport inhibitorsGroup 25: Mitochondrial

complex II electron transport inhibitors

Group 28: Ryanodine

receptor modulatorsGroup UN: Compounds of unknown or uncertain mode of action

Mode of Action Classification

PH3

2 4 7 2

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