Modelli sul destino dei pesticidi nelle acque superficiali

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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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Questioni di “gocce”

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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

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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 datarate per applicationnumber of applications- type of crop- extent of canopy interception- region of use within EU

Step 1 and 2: Chemical Data

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rsSTEP 2: Crop inte rc e ption

4 Classes for each crop§ no interception§ minimal crop cover§ average crop cover§ full canopy

Step 2: Canopy Interception

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rsStep 1: Example Results

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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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rsTabular Illustration of

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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rsTabular Illustration of

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


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


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)

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

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


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

Documents

Modelli sul destino dei pesticidi nelle acque superficiali