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Effects of neonics, synthetic
pyrethroids, glyphosate,
fungicides, and an adjuvant
on bees
Jody Johnson, Ph.D.
Pesticides and the Chesapeake Bay Watershed Conference,
Pearlstone Center, Reisterstown, MD
Oct 30 2018
Kingdoms of life
Ce
llula
r m
eta
bo
lism
Roche poster
Xenochemical targets
Insecticides-ex, neonics– sucking pests
Insecticides-Pyrethroids- target is insects/mosquitoes
Herbicide ex Glyphosate target is “weeds” that diminish crop production potential
Fungicides- target fungi that diminish bloom production of fruit or nut production
Adjuvants- no target, added to formulas and tank mixes for other reasons Ex organosilicons
Class of
neonicotinoids
http://en.wikipedia.org/wiki/(pesticide name) 2 20
2015
acetamiprid
dinitefuran
thiacloprid
clothianid
in
nitenpyram
thiamethoxam
Neonics used against
sucking pests
white grubs, billbugs, beetles, mealybugs, lice. flies,
ants,
Leafy vegetables, Fruiting Vegetables, Cole Crops,
Citrus Fruits, Pome Fruits (peach, pear), Grapes,
Cotton, and Ornamental Plants and Flowers
used in residential and commercial buildings, and for
professional turf management
Dinotefuran- used by vets in combo with pyriproxifen or
permethrin as flea/tick preventative for dogs & flea
preventative for cats. Ear mites, long star ticks and
gulf coast ticks can be controlled by formulas
combining neonics with other classes of active
ingredients.
S. Ahmed, 1M. S. Nisar, M. M. Shakir, M. Imran and K. Iqbal COMPARATIVE EFFICACY OF SOME NEONICOTINOIDS AND TRADITIONAL INSECTICIDES ON SUCKING INSECT PESTS AND THEIR NATURAL ENEMIES ON BT-121 COTTON CROP The Journal of Animal & Plant Sciences, 24(2): 2014, Page: 660-663 ISSN: 1018-7081
http://www.epa.gov/pesticides/chem_search/reg_actions/registration/fs_PC-099050_15-Mar-02.pdf 2 20 2015
http://www.capl.sci.eg/ActiveIngredient/Dinotefuran.html 2 20 2015
aphidwhitefly
Leafmining activity
Lace bug
Leaf
hopper
cockroaches
sawfly↑
Mole cricket
thrip
WIK
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Neuro-transmittersare recycled
Ne
on
ico
tin
oid
s
an
d p
yre
thro
ids
Neonics prematurely close Na channels
Pyrethroids keep the Na channels open too long
Neonicotinoid Insecticides Causing Bee
Losses A Synopsis of Recent Literature, with special reference to the situation in Germany, Klaus-Werner
Wenzel,
Scientists from three Italian universities found definite evidence at the molecular level, that clothianidin and imidacloprid negatively affect the transcription factor in honeybees, which controls the immune response; thus exposure to NN reduces a bee colony’s immune defenses. In order to demonstrate the impact of these molecular events in practice, using freshly emerged honeybees, the authors demonstrated increased replication of the Deformed Wing Virus genome (DWV). DI PRISCO, G., CAVALIERE, V., ANNOSCIA, D., VARRICCHIO, P., CAPRIO, E., NAZZI, F., GARGIOLO, G., PENNACCHIO, F. 2013. Neonicotinoid clothianidin diversely affects insect immunity and promotes replication of a viral pathogen in honey bees. Proceedings of the National Academy of Science USA, DOI: 10.1073/ PNAS1314923110
Recent Neonic papers
Bumble bees Bombus impatiens colonies exposed to turf with blooming white clove
treated with clothianidin and one other pesticide. Directly contaminated clover
nectar contained 171±44 ppb clothianidin. Sprays were applied at label rate and
lightly irrigated. After residues dried, confined colonies foraged for six days, and then
moved to non treated site to openly forage and develop. Colonies exposed to
clothianidin-treated weedy turf had delayed weight gain and produced no new
queens. Larson JL, Redmond CT, Potter DA (2013) Assessing Insecticide Hazard to Bumble Bees Foraging on Flowering Weeds in Treated
Lawns. PLoS ONE 8(6): e66375. https://doi.org/10.1371/journal.pone.0066375
Using data from recent residue surveys and toxicity of pesticides to honey and
bumble bees, and accounting for time-cumulative effects over time, especially with
dietary exposures, authors found that residues of pyrethroid and neonicotinoid
insecticides pose the highest risk by contact exposure of bees with contaminated
pollen. However, the synergism of ergosterol inhibiting fungicides with those two
classes of insecticides results in much higher risks in spite of the low prevalence of
their combined residues. More attention should be paid to specific residue mixtures that may result in synergistic toxicity to bees. Sanchez-Bayo F, Goka K (2014) Pesticide Residues and
Bees – A Risk Assessment. PLoS ONE 9(4): e94482. https://doi.org/10.1371/journal.pone.0094482
Pyrethroids
Pyrethrum-name of a
natural insecticide made
from the dried, crushed
flower heads of these two
chrysanthemums.
Pyrethrum is a mix of 6
cmpds.
Chrysanthemum cinerariifolium
Chrysanthemum coccineum
Pyrethrin
Pyrethroids are axonic excitotoxins, the toxic effects of which
are mediated through preventing the closure of the voltage-
gated sodium channels in the axonal membranes. The sodium
channel is a membrane protein with a hydrophilic interior.
“Twenty insecticides (numbers 2 to 21 in Table 1 ) are highly toxic
chemicals, including thiamethoxam, clothianidin, three organophosphates
(acephate, chlorpyrifos, and dimethoate), and most pyrethroids tested. Ten pesticides (numbers 22 to 31) are moderately toxic, including
imidacloprid and a few carbamate insecticides. The remaining 11
pesticides (numbers 32 to 42) are slightly toxic chemicals to honey bees,
including acetamiprid, spiromesifan and novaluron.” Spray Toxicity and Risk Potential of
42 Commonly Used Formulations of Row Crop Pesticides to Adult Honey Bees (Hymenoptera: Apidae)
Yu Cheng Zhu John Adamczyk Thomas Rinderer Jianxiu Yao Robert Danka Randall Luttrell Jeff Gore, Journal of Economic
Entomology, Volume 108, Issue 6, 1 December 2015, Pages 2640–2647, https://doi.org/10.1093/jee/tov269
Pollen collected by HBs in maize- and soybean-dominated landscapes is
contaminated with multiple agricultural pesticides, including NNs. Highest
levels of contamination in pollen are pyrethroid insecticides targeting
mosquitoes and other nuisance pests. HBs collect most of their pollen from non-cultivated plants. Long, EY & Krupke, CH, Non-cultivated plants present a season-long route of pesticide
exposure for honey bees Nature Communications volume7, Article number: 11629 (2016), Published: 31 May 2016
Effects of pyrethroids
Herbicides
2-4 D meristem cell elongation kills plant by overgrowth
Dicamba ties up glutathione, a biochemical with many uses and involved in many pathways
A plant growth regulator (PGR), aminoethoxyvinylgycine hydrochloride (AEG) (ReTain® active ingredient) inhibits ethylene biosynthesis that delays bloom senescence for increasing fruit set. Although a PGR, AEG can have negative effects on animal physiology, including developmental and metabolic effects.
3,6-dichloro-2-methoxybenzoic
acid
2,4-Phenoxyacetic acid
Both 2-4D and dicamba kill
Monocots (grasses) and
Dicots (broadleaf plants)
Glyphosate (Round Up) Monsanto
patent that expired in (1974-2000)
Glyphosate non-selectively kills most plants & some
bacteria, fungi, & protists (5 kingdoms-not animals!)
Glyphosate specifically inhibits the enzyme 5-
enolpyruvylshikimate 3-phosphate synthase in the
shikimic acid pathway. This growth pathway’s
purpose is to biosynthesize folates and aromatic
amino acids (phenylalanine, tyrosine, tryptophan).
Folates are needed to make DNA & help cells
divide. Amino acids build proteins.
Effects of glyphosate- depends on who
you ask Four out of 8 species of beneficial microbiota needed to process food
and fight against pathogens in HB guts were reported diminished by
field relevant doses of glyphosate. Erick V. S. Motta, Kasie Raymann,
Nancy A. Moran. Glyphosate perturbs the gut microbiota of honey
bees. Proceedings of the National Academy of Sciences, 2018;
201803880 DOI: 10.1073/pnas.1803880115
When glyphosate was sprayed on large areas of vegetation directly
adjacent to beehives it was found to have no acute or chronic effects
on adult honeybees or brood production – even at concentrations
three times higher than usual application rates 4.Glyphosate Task Force
has many representatives from agrochemical industry.
https://www.glyphosate.eu/impact-glyphosate-honeybees accessed
10 23 2018
Cascade effects
Fungicides are surface or plant protectants.
Fungicides are designed to kill cells by various mechanisms (coding changes, cancer causing)
Fungistatic compounds arrest growth but do not necessarily kill the fungi.
Propiconazole
(a.i. in Tilt) is a
demethylation
inhibitor (ranked 36/286
highest use
pesticide in MD 2014)
Membranes
Propiconazole
Cholesterol (Honey bee) ergosterol (fungus)
During the biosynthesis of cholesterol, three demethylations occur, one on the
C14 named 14α-demethylation and two on the C4 named 4α-demethylations
(Cabrera-Vivas et al 2003)
P450’s
Propiconazole inhibits microsomal cytochrome P450s from midguts
of Spodoptera eridania sixth-instar caterpillars. (Brattsen et al. 1994).
Cyprodinil (a.i. in Vanguard)-ranked 148/286 highest
pesticide use in MD 2014
Interrupts methionine (amino acid) synthesis
may activate aryl hydrocarbon receptors (which regulate gene expression) and may induce nuclear translocation of AHR
may act as an endocrine disruptor
may disrupt the ERK pathway (an extracellular signaling pathway that is complex and can have affects on kidney function, the immune system, and the nerve system)
source: Fang et al. 2013 Toxicology 304, 32-40
We worry because
1)There are reported effects in HBs (Johnson et al.2013, Pettis et al 2013, Brattsten et al.1994)
2)The fungicide’s mode of action may share common biochemistry with the animal kingdom. (Radice et al.1998)
3)The fungicide may interfere in an unanticipated way with the animal’s biochemistry (Iwasa et al.2004, Brattsten et al.1994)
4)Beneficial fungi utilized by HB to make bee bread may be negatively impacted (Yoder et al. 2013)
Microbes in general produce enzymes, vitamins, antimicrobials, organic acids, lipids that help with conversion of pollen to bee bread and stabilization of bee bread.Molds ( fungi) produce beneficial enzymes involved in lipid, protein and carbohydrate metabolismYeasts (fungi)ferment glucose and sucrose, source of vitamins and enzymesBacillus(bacteria)-proteolytic enzymes and carbohydrates, production of antibiotics and fatty acidsAspergilli (fungus), penicillia (fungus) & Mucorales (fungus) used for antibiotic, organic acid, enzymes and lipid production Molds (fungi) such as Mucorales including Mucor spinosus, Rhizopus arrhizus and rhizopus spp. And the aspergillus Asp. Tamarii are antagonists to chalkbrood ( Ascosphaeraapis)Gilliam M, FEMS Microbiology Letters 155 (1997) 1-10 Identification and roles of non-pathogenic microflora associated with honeybees
Honey bees use these traits in microbes:
Feb 2018
study in
almond
orchard
NORTH
All foragers returning Only pollen bearing foragers Foragers visiting sprayed areas
Conclusion; honey bee foragers avoided fungicide sprayed blooms
Why? physical reasons(difficult to land on flowers?)
chemical reasons (fungicide burned bee feet/disguised
fragrance?
biological reasons (fungicides sickened/disoriented bees?)
I can’t answer these questions yet.
Adjuvant= pharmacological
agent added to a pesticide or
drug to increase delivery efficiency or effect
Ex. molasses is used as a “sticker”
Ex. water repellent to delay washing effect of rainfall on leaves
Ex. anti-abrasive that keeps coating on seeds so the active ingredient does not wear away in tumbling out to boom ports
Adjuvants are not monitored or regulated by EPA. Any farmer can add them to their tank mixes. Adjuvants have many different names depending on the country.
Pesticide products contain proprietary
information and are required by our EPA to
follow many regulations—many background
studies that drive up the cost of the eventual
product. For example, studies may be required
on several organisms ( ex , mice, catfish,
songbird, ducks, eggs, chickens, bees, small
aquatic organisms). Not all ingredients are listed
on the publicly available Safety Data Sheets.
Adjuvants are not regulated and sometimes not
listed. Farmers are allowed to add adjuvants to
tank mixes without fines. Adjuvants are not
regulated in trade, go by different names in
different countries, and the amount of use is not
specified
Organosilicones: Emerging adjuvant of
concernOrganosilicones (OSS) are often added as an adjuvant to
chemical mixing tanks, and may be sprayed with other
pesticides on a variety of fruit crops. OSS are implicated in a
synergistic relationship with viruses to kill honey bee (Apis
mellifera) larvae, has had negative impacts on newly
emerged bumble bees, Bombus impatiens, and appears to decrease nest tube formation and egg laying in alfalfa leaf
cutting bees (Megachile rotundata).
An Inert Pesticide Adjuvant Synergizes Viral Pathogenicity and Mortality in Honey Bee Larvae JD Fine, DL Cox-Foster, CA Mullin - Scientific Reports, 2017 - ncbi.nlm.nih.gov
Christopher A Mullin Effects of ‘inactive’ ingredients on bees, Current Opinion in Insect Science, Volume
10, August 2015, Pages 194-200 https://doi.org/10.1016/j.cois.2015.05.006
Made
by
Julia Fines
work: The virus,
Black Wing Cell
virus, is greatly
potentiated in
honey bee
larvae. The
synergist
seems to be
the
organosilicone,
Sylgard 309
Ref: An Inert Pesticide Adjuvant Synergizes Viral Pathogenicity and Mortality in Honey Bee LarvaeJD Fine, DL Cox-Foster, CA Mullin -Scientific Reports, 2017 -ncbi.nlm.nih.gov
Limit the use or decrease the dose of the pesticides?
Transform the pesticides by chemically changing the
structure/formula?
Change the application method?
Change the degradation time on a pesticide?
Change the industry approach on xenochemicals?
Abandon xenochemicals as a strategy?
How do we solve this?
Thank you for inviting me to speak.
Contact: [email protected]
Fungicides
Group Target site of action Chemical family Active ingredient /trade name
1 Inhibition of tubulinformation
Benzimidazoles benomyl (Benlate) and thiophanate-methyl(Topsin M)
2 Affect cell division, DNA &RNA synthesis , metabolism
dicarboximides iprodione (Rovral) and vinclozolin (Ronilan)
3 Demethylation inhibitor Triazoles myclobutanil (Nova),
fenbuconazole (Indar)propiconazole (Orbit), section 18's only
4 Affects RNA synthesis acylamines metalaxyl (Ridomil),
9 anilinopyrimidine anilinopyrimidine cyprodinil (one of the active ingredients inSwitch)
11 Quinone outside inhibitors strobilurins azoxystrobin (Quadris and Abound) andpyraclostrobin (Cabrio)
12 phenylpyrroles phenylpyrroles fludioxinil (the other active ingredient inSwitch)
17 hydroxyanilide hydroxyanilide fenhexamid (Elevate)
M Multi site activity Phosphates, organics, dithiocarbamates, chloroalkythios, chloronitriles,guanidines
fosetyl-Al (Aliette), fungicides containingcopper or sulfur as the active ingredient, thiram(Thiram), ziram (Ziram), captan (Captan orCaptec), and dodine (Syllit)
http://www.umass.edu/fruitadvisor/nesfpmg/update.pdf 5/20/08
Insecticides and Miticideshttp://www.umass.edu/fruitadvisor/nesfpmg/update.pdf 5/20/08
Group Target site of action Chemical
family
Active ingredient/trade name
1A The acteylcholine esteraseInhibitors, (interrupt the transmission of nerve impulses).
carbamates carbaryl (Sevin), methomyl (Lannate)
1B Ditto above organophosphates
azinphos-methyl (Guthion), chlorpyrifos(Lorsban), diazinon, malathion, naled(Dibrom), and phosmet (Imidan)
2A GABA-gated chloridechannel antagonists (causerepetitive nervousdischarges).
Chlorinated cyclodiones
endosulfan (Thiodan, Phaser)methoxychlor
3 Sodium channel modulators,which also results inrepetitive nervous discharges, leading to paralysis
Syntheticpyrethroid, pyrethrins
fenpropathrin (Danitol), bifenthrin(Brigade),esfenvalerate (Asana) and one of the activeingredients in Pyrellin.
5 acetylcholine receptor
modulator
spinosyns Spinosyns (SpinTor, Success)
6 Chloride channel activators(interfere with insect nervereceptors)
avermectins abamectin (AgriMek)
Insecticides and Miticides (Con’t)
http://www.umass.edu/fruitadvisor/nesfpmg/update.pdf 5/20/08
Grou
p
Target site of action Chemical family Active
ingredient/trade
name
10 Mite growth inhibitors with
unknown or non-specific
target sites of action
hexythiazox (Savey)
11 Microbial disruptors of
insect
midgut membranes.
Bt microbials with
various subgroups
depending on the
strain
Bt (Dipel, others)
12 Inhibition of oxidative
phosphorylation
Organotin miticides fenbutatin oxide, aka
hexakis (Vendex)
18 Ecdysone agonist
disruptor
(disrupts insect molting)
Benzoic acid
hydrazide
tebufenozide
(Confirm)
20 Site II electron transport
inhibitors
dicofol (Dicofol and
Kelthane)
21 Site I electron transport
inhibitors
botanical rotenone (the other
ingredient in Pyrellin)
Yes, by misapplication
(human error) Chris Krupke’s
presentation at NAPPC 2011
Yes by wind drift
Yes by volatility (fume off)
Yes, by dissolution into
streams , less so in soils.
Impacts
Non-target area: 68.9 ± 6.2% of target area
(Received 0.561 – 1.744 g/ha)
Spatial
interpolationsLegend
HP_Dose
Value
High : 2.77779
Low : 0
2.8 g/ha
0 g/ha
Predicted Dose(g/ha)
This work is from Franklin Egan, his advisor
David Mortensen, and John Tooker from Penn
State Univ. who presented this work at NAPPC
meeting Oct 2010 on dicamba
From pollen to bee bread, biochemical changes include addition of lipids ( from bees and/ or microbes), 115 fold increase in free organic acids ( indicates active fermentation and creates a preservative effect), availability of amino acids ( better nutritional value)Bees exploit these traits in microbes:Microbes in general produce enzymes, vitamins, antimicrobials, organic acids, lipids that help with conversion of pollen to bee bread and stabilization of bee breadSpecifically – molds-produce enzs involved in lipid, protein and carbohydrate metabolismYeasts (fungi)ferment glucose and sucrose, source of vitamins and enzymesBacillus(bacteria)-proteolytic enzymes and carbohydrates, production of antibiotics and fatty acidsAspergilli (fungus), penicillia (fungus) & Mucorales (fungus) used for antibiotic, organic acid, enzymes and lipid production Molds (fungi) such as Mucorales including Mucor spinosus, Rhizopus
arrhizus and rhizopus spp. And the aspergillus Asp. Tamarii are antagonists to chalkbrood ( Ascosphaera apis)Gilliam M, FEMS Microbiology Letters 155 (1997) 1-10 Identification and roles of non-pathogenic microflora associated with honeybees
http://www.umass.edu/fruitadvisor/nesfpmg/update.pdf 5/20/08This website has an incredible amount of information on all the pesticides in a tabular form. Down load it into this power point presentation
Adjuvants
An adjuvant is added to a pesticide product or pesticide spray mixture to enhance the pesticide’s performance and/or the physical properties of the spray mixture.
Examples of adjuvants include surfactants, oils, compatibility agents, buffering and conditioning agents, defoaming agents, deposition agents, drift control agents, and thickeners.
http://extension.psu.edu/pests/pesticide-education/applicators/fact-sheets/pesticide-safety/spray-adjuvants
Neonicotinoid Insecticides Causing Bee
Losses A Synopsis of Recent Literature, with special reference to the situation in Germany, Klaus-Werner
Wenzel,
After extensive reviews by the “Worldwide Integrated Assessment of the Impact of Systemic Pesticides on
Biodiversity and Ecosystems” of the Task Force on Systemic Pesticides (TFSP) and Policy Report of the European
Academies Science Advisory Council (EASAC) examining 1120 peer-reviewed scientific papers, the examining
groups confirmed that HBs, other pollinators, biodiversity in general, and food security are damaged by NN.
EASAC recommended that NN should be removed from the natural environment and a return to traditional
crop rotation would be a major step. EASAC is supported by the 29 National Science Academies of the EU and
Switzerland. The US EPA continues to partner with the pesticide industry. In 2003 for instance, the EPA licensed BAYER’s clothianidin (“Poncho”); it did this against the written, formal advice of its own Scientific Division and
then ignored several petitions for retraction of that license, from environmental NGOs. After EU’s ban on
neonicotinoids in 2013, the official response by the EPA was that: ‘there is no reliable evidence of damage to
bees being caused by NN’; furthermore, the EPA only agreed to ‘reassess’ NNs by 2019. To reaffirm its loyalty to the pesticide industry, the EPA then issued an unlimited license for Sulfoxaflor, a fourth generation
neonicotinoid which is equally deadly to bees. Sulfoxaflor was released to the market by DOW CHEMICAL in
early 2014 without any independent risk-assessment or testing; only the manufacturer’s test data was used.
However, on Sept., 12th, 2015 , a US court ordered the EPA to revoke its biased and scientifically unjustifiable
licence for Sulfoxaflor (43)