Modelli sul destino dei pesticidi nelle acque superficiali
Transcript of Modelli sul destino dei pesticidi nelle acque superficiali
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DefinizioniDefinizioni
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Le direttive comunitarie 95/36 e 91/414, recepite in Italia con il dec.lgs 194/95,
richiedono:- misure di EC;- calcoli di PEC- valutazione del rischio a breve e lungo termine.
per:- autorizzazione all’uso e al commercio.
Le direttive comunitarie 95/36 e 91/414, recepite in Italia con il dec.lgs 194/95,
richiedono:- misure di EC;- calcoli di PEC- valutazione del rischio a breve e lungo termine.
per:- autorizzazione all’uso e al commercio.
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l EPA - Office of Pesticide Programsn FIFRA (1988) - Federal Insecticide Fungicide
Rodenticide Actn FQPA (1996) - Food Quality Protection Act
l EPA - Office of Watern SDWA - Safe Drinking Water Actn WPCA - Water Pollution Control Actn CWA - Clean Water Act n Others
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waterplantswaterplants
suspended solidssuspended solids
sedsed. material. material liquid phaseliquid phase
water phasewater phase
sorptionsorption
sorptionsorption
volatilizationvolatilization
advection (up/downward seepage)advection (up/downward seepage)diffusiondiffusion
transport: advectiontransport: advectiondispersiondispersion
transformationtransformation
transport: advection, dispersion, diffusiontransport: advection, dispersion, diffusion
transformationtransformation
sorptionsorption
Processes in water and sediment
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Scarichi abusivi. Incredibile !
•• Inverted washed containersInverted washed containers•• Accounted for a loss of ~0.35 g activeAccounted for a loss of ~0.35 g active•• Need to dilute in 3.5 million litres of waterNeed to dilute in 3.5 million litres of water•• Equivalent to 10.5 Km standard streamEquivalent to 10.5 Km standard stream
Stoccaggio dei contenitori. Incredibile !
Cattiva manutenzione.
• 1 ml (50% 1 ml (50% aiai) drop = 0.5 g active) drop = 0.5 g active•• Foil seals typically contain ~2 Foil seals typically contain ~2 mlsmls = ~1 g active= ~1 g active•• Need to dilute in 10 million litres of waterNeed to dilute in 10 million litres of water•• Equivalent to 30 Km standard streamEquivalent to 30 Km standard stream
Incredibile !
•• Leakage from a pressure relief valveLeakage from a pressure relief valve•• Accounted for a loss of ~1.2g activeAccounted for a loss of ~1.2g active•• Need to dilute in 12 million litres of waterNeed to dilute in 12 million litres of water•• Equivalent to 36 Km standard streamEquivalent to 36 Km standard stream
Incredibile !
Trattamenti in aree non target. Incredibile !
Evidenze sperimentali
WHERE TO LOAD?
17 %
8 %
28 %
12 %
10 %25 %
Mud from tractorwheels
Tractor exteriorwashings
Spillage of containerwashings
Spillage whilemixing
Tank RinseWater
Foil Seals
Results from Year 1 Aventis Cherwell Study
Sources of farmyard pollution
SOURCE: CPA
Rassegne bibliografiche
Point sources 60% ?
Diffuse sources 40% ?
10%
50%
25%
5%5%1%
4%
Spray drift
Runoff
Leaching
Volatilisation
Drainflow
Farm yard
Roads/tracks
Questioni di “scala” ?
Modelli contro Monitoraggio
Più modelli per più usi
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18 February 2002 4FO
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FOCUS
FOrum for the Co-ordination of pesticides fate models and their USe
• EU initiative (DG SANCO)§ Directive 91/414/EEC§ PECs based on community level validated models
• Support: Commission and ECPA• Participation:
§ Registration Authorities§ Academia & Research§ Industry
• Limited to exposure analysis
Models
Drift Drainage Run-off Fate
IDEFICSMOPEDPEDRIMOPSMDRIFTTABLES
- NL- UK- D
CHAIN_2D 1.1CRACK_P 1.0MACRO 3.1OPUS 1.63PESTLA 3.0PESTRAS 2.1
EPICGLEAMSOPUSPELMOPRZM2SWRRBWQ
ABIWASEXAMSSLOOT.BOXTOXSWAWASP
Drift
Transport model (MACRO)F
OC
US
Su
rfa
ce
Wa
ters
Macropores Micropores
Drainage+
leaching
Seepage and leaching
Solute application
Root water uptake
Precipitation+ irrigation
Interception
Transpiration
Infiltration
Runoff
Evaporation
Approach
Data set
Data evaluation
Exposure estimation
Emissionrates
Environmentaldistribution
Exposure levels, con-centrations, intakes
Hazard identificationDose-response assessment
Toxicity datasingle species
Extrapolation
No-effectlevels
Risk characterisation
(P)EC/PNEC, MOS, TER
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Approach (2)
• STEP 1: single application,fixed scenario
• STEP 2: multiple application,regional variation in Europe
• STEP 4: site specific calculation
• STEP 3: advanced modelling,specific European scenarios
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Approach, Step 1
Start
No specific climate,minor cropping differentiation, topographyand soil scenario
STEP 1Worst caseloading
Use safe?
no, to STEP 2
yes
No further work
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Approach, Step 2
No specific climate,minor croppingdifferentiation,interception,topographyand soil scenario
STEP 2Loadings based onsequential applicationpatterns
Use safe?
no, to STEP 3
yes
No further work
from STEP 1
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Approach, Step 3
Use safe?
no, to STEP 4
yes
No further work
Realistic worstcase scenario
STEP 3Loadings based onsequential applicationpatterns
from STEP 2
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Approach, Step 4
Specific and realisticcombinations ofcropping, soil,weather, fields, topographyaquatic bodies
STEP 4Loadings as in step 3considering the rangeof potential uses
from STEP 3
l
Concentration Range
Stima dell’esposizione
Step 1: Stima iniziale dell’esposizione in acqua(PECsw)
Step 2: Stima “ migliore” del PECsw
Step 3: Stima deterministicadel PECsw all’interno dei 10 scenari europei
FOCUS SW
Actual Range of Aquatic Exposure:
Step 4: Stima deterministica/ probabilistica del PECsw in condizioni reali
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• Step 1§ Arable: 2.8% § Vines: 8.0%§ Orchards: 29.2%§ Hops: 19.3%§ Aerial: 34.3%§ Seed treatment: 0%
0.0
5.0
10.0
15.0
20.0
25.0
30.0
1 2 3 4 5 6 7 8 >8Number of applications
Dri
ft (
% o
f in
-fie
ld a
pp
licat
ion
)
Orchards
Hops
Vines
Arable crops
Step 1 and 2: Drift Loadings
Orchards HopsVines Arable crops
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Percent of Application
Step/Location Aut Spr Sum
1 / all 10 10 10
2 / North 5 2 2
2 / South 4 4 3
Step 1 and 2: Runoff and Drainage Assumptions
North
South
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Standard assumptions for water body and sediment
Water depth (cm): 30
Sediment depth (cm): 5
Sediment OC (%): 5
Sed bulk density (g/ml): 0.8
Ratio of field:water body: 10
Step 1 and 2: Scenario Assumptions
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• Chemical properties- solubility- sorption coefficient- degradation rates in soil, water and sediment
• Additional data for metabolites- MW of parent and metabolite- maximum observed in soil studies- maximum observed in water/sediment studies
• Application data- rate per application- number of applications- type of crop- extent of canopy interception- region of use within EU
Step 1 and 2: Chemical Data
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4 Classes for each crop§ no interception§ minimal crop cover§ average crop cover§ full canopy
Step 2: Canopy Interception
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Drift events
Runoff event
Equilibrium sorption to sediment
Step 2: Example Results for Water
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rsStep 2: Example Results for Sediment
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rsStep 3 Calculations
PECsw and PECsed
SWASH (chem, appln, crop)
TOXSWA (aquatic fate)
MACRO (Drainage)
PRZM (runoff)
Drift Calc
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rsUser-defined inputs (entered in SWASH)
• Chemical dataparent / daughter relationshipschemical properties of parent / daughter
• Application datarate per applicationnumber of applicationsapplication window (earliest and latest dates)
• Crops and scenarioscrop type (23 different crops)scenarios (6 drainage and 4 runoff)appropriate scenarios are defined for crop
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rsFixed scenario parameters
• Agronomic datacropping dates (planting, maturation, harvest) growth data (root depth, plant height, canopy)
• Soil dataproperties of soil profiletopographical data (slope, field dimensions)
• Climatic data (daily)precipitation (and irrigation, if appropriate)evapotranspirationtemperature
• Water body typesditch, pond and streamdynamic hydrology with upstream catchments
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rsExtent of FOCUS runoff scenarios
R2
R4R3
R1
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rsExtent of FOCUS drainage scenarios
D2
D4D3
D1
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rsExtent of FOCUS drainage scenarios (continued)
D6D5
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rsCalculated scenario parameters
• Application datesspecific application dates are calculated by Pesticide Application Tool (PAT) within PRZM:
- avoids application on days with precipitation- ensures precipitation within 10 days of appln
• Simulation datesdepending upon the date of the first application, a specific simulation period is selected for simulation:
- 12 months for PRZM- 16 months for MACRO
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rsCalculations performed by PRZM and MACRO
• PRZM results represent edge-of-field runoff and erosion containing water, soil and chemical; MACRO results represent tile drainage from beneath treated fields
• Most scenarios have available runoff or drainage data from field experiments for comparison
• For selected year, outputs include:§ hourly runoff or drainage volume§ hourly chemical concentration
• Output files are transferred to TOXSWA for simulation of aquatic fate
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rsSimulation of Metabolites in Step 3
• PRZM can simulate up to a maximum of parent plus two metabolites in a single run
• MACRO can simulate a parent and one metabolite
• TOXSWA can currently only handle one chemical at a time, resulting in multiple runs for parent and metabolites
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0.0
0.2
0.4
0.6
0.8
1.0
1.2
100 120 140 160 180 200 220 240
Julian Day
Con
c of
pes
ticid
e in
runo
ff (p
pb)
Graphical Illustration of TOXSWA Results
Drift from application
Runoff or drainage loading events
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TOXSWA Results
Tabl es: Maxi mum exposur e concent r at i ons i n wat er l ayer ======================================================
I n segment f r om 0. 0 t o 30. 0 m i n wat er body. ( Act ual concent r at i ons PECsw as wel l as PECsed r ef er t o moment ar y concent r at i ons occur r i ng 1, 2 et c days af t er t he gl obal maxi mum concent r at i on. Ti me Wei ght ed Aver age Exposur e Concent r at i ons ( TWAEC) have been cal cul at ed f or a movi ng t i me f r ame and have been al l ocat ed t o t he l ast day of t he per i od consi der ed)
Act ual concent r at i ons i n wat er l ayer i n µg. L- 1
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -Concent r at i on Dat e Daynr
Gl obal max 0. 373 20- May- 1984 11: 00 81 ( i nc l . susp. sol 0. 373) PECsw1 0. 360 21- May- 1984 11: 00 82 PECsw2 0. 350 22- May- 1984 11: 00 83 PECsw4 0. 332 24- May- 1984 11: 00 85 PECsw7 0. 330 27- May- 1984 11: 00 88 PECsw14 0. 305 03- Jun- 1984 11: 00 95 PECsw21 0. 243 10- Jun- 1984 11: 00 102 PECsw28 0. 194 17- Jun- 1984 11: 00 109 PECsw42 0. 127 01- Jul - 1984 11: 00 123 PECsw50 0. 095 09- Jul - 1984 11: 00 131 PECsw100 0. 015 28- Aug- 1984 11: 00 181 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
output from a 30m wide pond
actual water concentration
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TOXSWA Results (continued)
Tabl es: Maxi mum exposur e concent r at i ons i n wat er l ayer ======================================================
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
Maxi mum Ti me Wei ght ed Aver aged Exposur e Concent r at i ons i n wat er l ayer i n µg. L- 1
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -Concent r at i on Dat e Daynr
TWAECsw1 0. 367 21- May- 1984 10: 00 82 TWAECsw2 0. 361 22- May- 1984 09: 00 83 TWAECsw4 0. 351 24- May- 1984 09: 00 85 TWAECsw7 0. 342 27- May- 1984 09: 00 88 TWAECsw14 0. 332 03- Jun- 1984 07: 00 95 TWAECsw21 0. 313 10- Jun- 1984 05: 00 102 TWAECsw28 0. 290 17- Jun- 1984 03: 00 109 TWAECsw42 0. 251 18- Jun- 1984 08: 00 110 TWAECsw50 0. 238 26- Jun- 1984 03: 00 118 TWAECsw100 0. 177 29- Jul - 1984 08: 00 151
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
TWA water concentration
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Tabular Illustration of TOXSWA Results (continued)
Tabl es: Maxi mum exposur e concent r at i ons i n sedi ment
===================================================
I n t he t op 5. 00 cm sedi ment l ocat ed under t he wat er body segment f r om 0. 0 t o 30. 0 m, expr essed as µg subst ance per kg dr y sedi ment .
Act ual concent r at i ons i n sedi ment i n µg. kg- 1 DW
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -Concent r at i on Dat e Daynr
Gl obal max 0. 699 03- Jun- 1984 20: 30 95 PECsed1 0. 699 04- Jun- 1984 21: 00 96 PECsed2 0. 697 05- Jun- 1984 21: 00 97 PECsed4 0. 690 07- Jun- 1984 21: 00 99 PECsed7 0. 674 10- Jun- 1984 21: 00 102 PECsed14 0. 623 17- Jun- 1984 21: 00 109 PECsed21 0. 566 24- Jun- 1984 21: 00 116 PECsed28 0. 504 01- Jul - 1984 21: 00 123 PECsed42 0. 364 15- Jul - 1984 21: 00 137 PECsed50 0. 298 23- Jul - 1984 21: 00 145 PECsed100 0. 079 11- Sep- 1984 21: 00 195 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
actual sediment concentration
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Tabular Illustration of TOXSWA Results (continued)
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Maxi mum Ti me Wei ght ed Aver aged Exposur e Concent r at i ons i n sedi ment i n µg. kg- 1 DW
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -Concent r at i on Dat e Daynr
TWAECsed1 0. 699 04- Jun- 1984 08: 30 96 TWAECsed2 0. 699 04- Jun- 1984 21: 00 96 TWAECsed4 0. 699 05- Jun- 1984 23: 00 97 TWAECsed7 0. 696 07- Jun- 1984 20: 00 99 TWAECsed14 0. 686 13- Jun- 1984 03: 30 105 TWAECsed21 0. 673 17- Jun- 1984 05: 00 109 TWAECsed28 0. 657 21- Jun- 1984 23: 00 113 TWAECsed42 0. 620 02- Jul - 1984 11: 00 124 TWAECsed50 0. 595 09- Jul - 1984 11: 00 131 TWAECsed100 0. 457 04- Aug- 1984 02: 30 157 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
The r un t i me was: 0 mi nut es and 39 seconds
TWA sediment concentration
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Trigge ring Ste p 4
• In principle, Step 4 is triggered by failing Step 3 scenarios(how many, when for Annex 1?)
• Step 3 contains a number of inherent conservatisms, andStep 4 will refine these uncertainties
• Due to the nature of the process, mitigation is not possible until Step 4 (failure triggers move to next level of risk assessment). Why?§ Step 1 and 2 extreme worst-case§ Step 3 reasonable worst-case§ Only sensible to begin mitigating a reasonable worst-case§ Step 2 mitigation likely to be difficult to apply (RO/DR)
• Step 4 covers mitigation and/or refined exposure calculation
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Options for Ste p 4
• Three approaches are proposed:§ Further refinement of the generic chemical input
and fate parameters used at Step 3.§ Developing label mitigation measures and
applying these to Step 3 scenarios.§ Developing a new range of landscape and/or
scenario input parameters that are location orregion specific.
• Need to consider all options for effects andexposure refinement along with mitigation options at Step 4 - “ higher-tier risk assessment”
How do download focus model?
http://viso.ei.jrc.it/focus/
USA approach
§ Computer Simulation Includes 3 Tiers of Increasing Complexity• Tier 1: GENEEC (Ecological) & FIRST
(Drinking Water)• Tier 2 : �< * ����(EXAMS + PRZM +
AgDrift)EXAMS - Surface Water Concentrations PRZM – Pesticide, Runoff & Soil Erosion from the FieldAgDrift - Off-site Spray Drift from the Field
• Tier 3: WARP (Daily Water Concentrations at 7000 Surface Drinking Water Facilities)
How do download USA model?
http://www.epa.gov/oppefed1/models/water/index.htmhttp://www.epa.gov/oppefed1/models/water/index.htm