pyrethroids and water quality · • dpr plans to put synthetic pyrethroid products into...
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Pyrethroids and Water Quality
Frank Spurlock
Environmental MonitoringCDPR
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Pyrethroids and Water Quality
I. Overview: use, properties, aquatic toxicity
II. Recent pyrethroid monitoring
III. What is reevaluation?
IV. Synthetic pyrethroids reevaluation
V. DPR activities
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PUR Synthetic Pyrethroid Use - Σ 26 AIs
year
LBS
- 10
00s
2004200220001998199619941992
1000
900
800
700
600
500
Statewide Use
2004 TOP 7permethrincypermethrinbifenthrincyfluthrinfenpropathrinλ-cyhalothrinesfenvalerate
all > 30000 lbsin 2004
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Pyrethroid Properties hydrophobicity
log
KO
W
all_othersPyrethsOCsOPs
7
6
5
4
3
2
1
0
-1
-2
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Pyrethroid Properties soil persistence
log
aero
bic
soil
half
-lif
e (d
)
all_othersPyrethsOCOP
4
3
2
1
0
-1
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Pyrethroid Properties relative acute aquatic toxicity
log
LC50
(u
g/L)
all_othersPyrethsOPOC
7
6
5
4
3
2
1
0
-1
-2
Daphnia magna LC50
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Pyrethroid Use and Properties: Summary
• Use steadily increasing - 2004 total use ~ twice 1992 total use
• Highly hydrophobic - associated with suspended and bed sedimentsat equilibrium
• Only moderately persistent - based on aerobic soil half-life data
• High aquatic toxicity - based on laboratory aqueous acute toxicity data- bioavailability effects -
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Recent Pyrethroid Monitoring • Pyrethroids detected in sediment, both urban/ag sites
(Weston et al. 2004, 2005; DPR monitoring)
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Recent Pyrethroid Monitoring • Pyrethroids detected in sediment, both urban/ag sites
• Detections frequent, geographically widespread
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Recent Pyrethroid Monitoring • Pyrethroids detected in sediment, both urban/ag sites
• Detections frequent, geographically widespread
• Urban detections included bifenthrin, cyfluthrin, cypermethrin,deltamethrin, λ - cyhalothrin
• Ag detections included bifenthrin, esfenvalerate, λ - cyhalothrin,permethrin, resmethrin, fenpropathrin
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Recent Pyrethroid Monitoring • Pyrethroids detected in sediment, both urban/ag sites
• Detections frequent, geographically widespread
• Urban detections included bifenthrin, cyfluthrin, cypermethrin,deltamethrin, λ - cyhalothrin
• Ag detections included bifenthrin, esfenvalerate, λ - cyhalothrin,permethrin, resmethrin, fenpropathrin
• Acute toxicity to native sediment-dwelling amphipod Hyalella aztecain bioassays, correlated with pyrethroid concentrations
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Recent Pyrethroid Monitoring • Pyrethroids detected in sediment, both urban/ag sites
• Detections frequent, geographically widespread
• Urban detections included bifenthrin, cyfluthrin, cypermethrin,deltamethrin, λ - cyhalothrin
• Ag detections included bifenthrin, esfenvalerate, λ - cyhalothrin,permethrin, resmethrin, fenpropathrin
• Acute toxicity correlated with pyrethroid concentrations
• Other potential sediment toxicants (OCs, chlorpyrifos) generally far below concentrations sufficient to cause toxicity
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Example: H. azteca mortality vs. pyrethroid concentrations (TUs)
mor
talit
y
0
50
100
urban dataWeston et al.
(2005)
~0.25”
0.1 1 10 100
Σ toxic units predicted from pyrethroid concentrations
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Reevaluation
•DPR plans to put synthetic pyrethroid products into reevaluation
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What is Reevaluation?
•DPR plans to put synthetic pyrethroid products into reevaluation
•Mechanism for obtaining additional post-registration
data for products from pesticide registrants, e.g.....
spatial and temporal extent of off-site residues
sources - types of uses
mitigation practices
toxicity data
other
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What is Reevaluation?
• DPR plans to put synthetic pyrethroid products into reevaluation
• DPR’s mechanism for obtaining additional post-registration data
• Occurs when “a pesticide may have caused, or is likely to cause,
a significant adverse impact”, e.g.
* public or worker health hazard* residue over-tolerance* undesireable phytotoxicity* environmental contamination* fish or wildlife hazard* or numerous other impacts ................
(CCR 6220 et seq.)
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What is Reevaluation?
• DPR plans to put synthetic pyrethroid products into reevaluation
•DPR’s mechanism for obtaining additional post-registration data
• Occurs when a potential significant adverse impact
• Various possible outcomes:
* no action
* restricted material
* label amendments
* cancellation
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Synthetic Pyrethroid Reevaluation
• May potentially include products with following AIs:
ALLETHRIN FENPROPATHRINS-BIOALLETHRIN FENVALERATE
D-TRANS ALLETHRIN FLUCYTHRINATEESBIOTHRIN IMIPROTHRIN
D-ALLETHRIN LAMBDA CYHALOTHRINBIFENTHRIN PERMETHRINCYFLUTHRIN PHENOTHRIN
BETA-CYFLUTHRIN PRALLETHRINCYPERMETHRIN RESMETHRIN
(S)-CYPERMETHRIN TAU-FLUVALINATEDELTAMETHRIN TETRAMETHRINESFENVALERATE TRALOMETHRINETOFENPROX
Final product list not yet determined - will probably excludevarious pressurized and impregnated formulations
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Synthetic Pyrethroid Reevaluation
• numerous products - not finalized
•Possible data requirements:
physical-chemical properties - soil/aquatic half-lives, KOC,...
sediment toxicity data - H. azteca, C. tentans
monitoring data - source ID ag/urban; spatial/temporal extent?
mitigation measure studies/effectiveness
Final data requirements not yet determined
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Synthetic Pyrethroid Reevaluation
• numerous products - not finalized
• data requirements - not finalized
• Extended process: ~ years
> 125 registrants, > 700 products
other reevaluations in progress:
diazinon dormant spray, chlorpyrifos,
VOC TGA data, VOC product reformulation
==> already ~ 1000 products in reevaluation
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Synthetic Pyrethroid Reevaluation
• numerous products - not finalized
• data requirements - not finalized
• extended process: ~ years
• DPR research:
- monitoring
- sediment bioavailability research/measurement techniques
(Jay Gan, UCR)
- analytical method development (USGS, CDFA)
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Questions?R1 R2 R3
cyfluthrinCCl2 CN F
cypermethrinCCl2 CN H
cyhalothrinCClCF3 CN H
permethrinCCl2 H H
OCHO
CHCR1O R2
CH3H3C R3
OCHO
CO
HCCH
H3C CH3
ClCN
CH2O
CHCO CH3
Cl
CF3
CH3H3C
fenvaleratebifenthrin