The Danish Pesticide Leaching Assessment Program – a field based, early warning system

The Danish Pesticide Leaching Assessment Program

– a field based, early warning system.

Preben Olsen

- Danish Institute of Agricultural Sciences

Jeanne Kjær & Marlene Ullum

- Geological Survey of Denmark and Greenland

Ruth Grant

- The National Environmental Research Institute

The Danish Pesticide Leaching Assessment Program

– a field based, early warning system.

PLAP

Institutions involved

DIAS - Danish Institute of Agricultural Sciences

NERI - The National Environmental Research Institute

EPA - Environmental Protection AgencyEPA

GEUS - Geological Survey of Denmark and Greenland

• 98% of drinking water supplies in DK derives from ground water

• Pesticides and their degradation products have been detected in about 30% of all screens monitored and 10% are > 0.1 µg/l

Increasing concern about pesticide contamination of the Danish groundwater:

Is the existing approval procedure for pesticides sufficient?

Limitations comprises:

• Scale problems

• Spatial variability of the soil parameters

• Hydraulic boundary condition (e.g. tile drains)

Improving the current risk assessment of pesticide leaching

• Include field studies in the actual risk assessment

Background of the project

The bottom line

…is it point or difffuse sources that cause problems to our groundwater?

PLAP

• .. shall funtion as an early warning system

• ..is a monitoring programme for the evaluation of pesticide leaching risk under field conditions

• .. has the objective to analyse, whether approved pesticides – when applied in accordance with current regulations – leach to the groundwater in unacceptable concentrations

PLAP sites - precipitation

Average precipitation 1961-90 Source: DMI 1997

PLAP sites - soilsCoarse sandy soilFine sandy soilClayey sandy soilSandy clay soilClay soilHeavy clay soilOrganic soil Calcareous soil

Jyndevad

SilstrupTylstrup

Slæggerup

Fårdrup

Estrup

PLAP - sites

2 sandy soils

4 loamy soils

1-3 ha

26 pesticides

3. S ilstrup

4. Estrup

2. Jyndevad

1. Tylstrup

5. Fårdup

6. S læ ggerup

May 1999

Sep 1999

Sep 1999

Apr 2000

Apr 2000

Apr 2000

Leaching of pesticides from PLAP-fieldsTylstrup Jyndevad Silstrup Estrup Faardrup Slaeggerup

Metribuzin * * * (*) Glyphosate * * * * * * * * * Ethofumesate * * * Metamitron * * * Flamprop-M-isopropyl * * * * * Fluazifop-P * * * Bromoxynil * * * * * Fluroxypyr * * Ioxynil * * * * * Bentazone * * * Pendimethalin * * * * Tebuthylazin * * Pirimicarb * * * * * * * Propiconazole * * * * * * * * * * Fenpropimorph * * * * * * * * * * Dimethoat * * * * Metsulfuron-methyl * * * * Triazinamin-methyl (tribenuron methyl) * * * * * * * Triasulfuron * * Desmedipham * * * Phenmedipham * * * ETU (Mancozeb) * * Linuron * * Clomazon * Clopyralid * Pyridat *

Fine sandy soil

Tylstrup

Tylstrup

• 70 x 166 m• 1,1 ha• Loamy sand• 6 % clay• 2% TOC• 666 mm/y• Groundwater: 3-4

m.b.g.s.

N

0 50 m

M1

M2

M3

M4

M5

M6M7

Moniteringwells

P3

P6P4

P7

P8

P5

Piezometer

Rain GaugePt-100S1

S2Suction cups, TDR og

Monitoring design -crossection2 mMin. 3 m

1 m

2 m

2 m

1 m

Gwt

Bufferzone Treated area

Suction cups

Bufferzone

50 m

Agricultural management

Date Product Dosage Potatoes planted 4. May Var. Dianella 2200 kg/haHerbicide application 25. May Sencor WG Metribuzin 0,2 kg/ha

25. May Afalon Linuron 1 l/ha 7. Jun Sencor WG Metribuzin 0,15 kg/ha

Tracer application 27. May Potasium bromide 30 kg/ha

Fungicide application 22. Jun - 14 Sep Dithane DG Mancozeb (ETU) 10*2,0 kg/haIrrigation 12. Sep 33 mm

Harvest 28. Oct

Active ingedients

Agricultural management

Date Product Dosage Potatoes planted 4. May Var. Dianella 2200 kg/haHerbicide application 25. May Sencor WG Metribuzin 0,2 kg/ha

25. May Afalon Linuron 1 l/ha 7. Jun Sencor WG Metribuzin 0,15 kg/ha

Tracer application 27. May Potasium bromide 30 kg/ha

Fungicide application 22. Jun - 14 Sep Dithane DG Mancozeb (ETU) 10*2,0 kg/haIrrigation 12. Sep 33 mm

Harvest 28. Oct

Active ingedients

Metribuzin - Desamino-metribuzin - Diketo-metribuzin - Desamino-diketo-metribuzin

Bromide concentration - unsaturated zone

0

3

6

9

12

Bro

mid

e (

mg

/l)

1 m b.g.s.2 m b.g.s

Suction cups S1

0

3

6

9

12

ma

j-9

9

jun

-99

jul-

99

au

g-9

9

sep

-99

okt

-99

no

v-9

9

de

c-9

9

jan

-00

feb

-00

ma

r-0

0

ap

r-0

0

ma

j-0

0

jun

-00

Bro

mid

e (m

g/l)

1 m b.g.s2 m b.g.s.

Suction cups S2

Bromide concentration - unsaturated zone

0

3

6

9

12

Bro

mid

e (

mg

/l)

1 m b.g.s.2 m b.g.s

Suction cups S1

0

3

6

9

12

ma

j-9

9

jun

-99

jul-

99

au

g-9

9

sep

-99

okt

-99

no

v-9

9

de

c-9

9

jan

-00

feb

-00

ma

r-0

0

ap

r-0

0

ma

j-0

0

jun

-00

Bro

mid

e (m

g/l)

1 m b.g.s2 m b.g.s.

Suction cups S2

Bromide concentration - saturated zone

3-4 m4-5 m5-6 m

M3

maj

-99

jun-

99

jul-9

9

aug-

99

sep-

99

okt-

99

nov-

99

dec-

99

jan-

00

feb-

00

mar

-00

apr-

00

maj

-00

jun-

00

M4

0

1

2

3

4

Bro

mid

e (m

g/l) 3-4 m

4-5 m5-6 m

M5

0

1

2

3

4

maj

-99

jun-

99

jul-9

9

aug-

99

sep-

99

okt-

99

nov-

99

dec-

99

jan-

00

feb-

00

mar

-00

apr-

00

maj

-00

jun-

00

Bro

mid

e (m

g/l) M6

Pesticide concentration - suction cup S1

0

3

6

9

12

Bro

mid

e (

mg

/l)

0,0

0,5

1,0

1,5

2,0

2,5

Pe

stic

ide

(µ

g/l)

Bromide

ETU

Metribuzin

Diketo-metribuzin

Desamino-diketo-metribuzin

1 m b.g.s.

0

3

6

9

12

ma

j-99

jun

-99

jul-9

9

au

g-9

9

sep

-99

okt

-99

no

v-9

9

de

c-9

9

jan

-00

feb

-00

ma

r-0

0

ap

r-0

0

ma

j-00

jun

-00

jul-0

0

Bro

mid

e (

mg

/l)

0,0

0,5

1,0

1,5

2,0

2,5

Pe

stic

ide

(µ

g/l)2 m b.g.s.


0

3

6

9

12

Bro

mid

e (

mg

/l)

0,0

0,5

1,0

1,5

2,0

2,5

Pe

stic

ide

(µ

g/l)

Bromide

ETU

Metribuzin

Diketo-metribuzin


1 m b.g.s.

0

3

6

9

12

ma

j-99

jun

-99

jul-9

9

au

g-9

9

sep

-99

okt

-99

no

v-9

9

de

c-9

9

jan

-00

feb

-00

ma

r-0

0

ap

r-0

0

ma

j-00

jun

-00

jul-0

0

Bro

mid

e (

mg

/l)

0,0

0,5

1,0

1,5

2,0

2,5

Pe

stic

ide

(µ

g/l)2 m b.g.s.


0

3

6

9

12

Bro

mid

e (

mg

/l)

0,0

0,5

1,0

1,5

2,0

2,5

Pe

stic

ide

(µ

g/l)

Bromide

ETU

Metribuzin

Diketo-metribuzin


1 m b.g.s.

0

3

6

9

12

ma

j-99

jun

-99

jul-9

9

au

g-9

9

sep

-99

okt

-99

no

v-9

9

de

c-9

9

jan

-00

feb

-00

ma

r-0

0

ap

r-0

0

ma

j-00

jun

-00

jul-0

0

Bro

mid

e (

mg

/l)

0,0

0,5

1,0

1,5

2,0

2,5

Pe

stic

ide

(µ

g/l)2 m b.g.s.


0

3

6

9

12

Bro

mid

e (

mg

/l)

0,0

0,5

1,0

1,5

2,0

2,5

Pe

stic

ide

(µ

g/l)

Bromide

ETU

Metribuzin

Diketo-metribuzin


1 m b.g.s.

0

3

6

9

12

ma

j-99

jun

-99

jul-9

9

au

g-9

9

sep

-99

okt

-99

no

v-9

9

de

c-9

9

jan

-00

feb

-00

ma

r-0

0

ap

r-0

0

ma

j-00

jun

-00

jul-0

0

Bro

mid

e (

mg

/l)

0,0

0,5

1,0

1,5

2,0

2,5

Pe

stic

ide

(µ

g/l)2 m b.g.s.

Average concentration - 1 m depth

Desamino-diketo-metribuzin Diketo-metribuzinS1 S2 S1 S2

1.7.99-1.7.00 0.87-0.98 0.14-0.27 0.25-0.32 0.05-0.111.7.00-1.7.01 0.30 0.26 0.12 0.10

Average concentration - 1 m depth

Desamino-diketo-metribuzin Diketo-metribuzin S1 S2 S1 S2

1.7.99-1.7.00 0.87-0.98 0.14-0.27 0.25-0.32 0.05-0.11 1.7.00-1.7.01 0.30 0.26 0.12 0.10

Pesticide concentration in groundwater - Tylstrup -

0

1

2

3

4(m

g/l)

3-4 m 4-5 m 5-6 mM4 Bromid

0.0

0.1

0.2

0.3

0.4

0.5

0.6

ma

j-9

9

jul-

99

ok

t-9

9

jan

-00

ap

r-0

0

jul-

00

ok

t-0

0

jan

-01

ap

r-0

1

jul-

01

(µg

/l)

M4 Metribuzin-desamino-diketo

0.0

0.1

0.2

0.3

0.4

0.5

0.6

(µg

/l)

M4 Metribuzin-diketo

Pesticide concentration in groundwater - Tylstrup -

0.0

0.1

0.2

0.3

0.4

0.5

0.6

ma

j-9

9

jul-

99

ok

t-9

9

jan

-00

ap

r-0

0

jul-

00

ok

t-0

0

jan

-01

ap

r-0

1

jul-

01

(µg

/l)

M6 Metribuzin-desamino-diketo

0.0

0.1

0.2

0.3

0.4

0.5

0.6

(µg

/l)

M6 Metribuzin-diketo

0

1

2

3

4(m

g/l)

3-4 m 4-5 m 5-6 mM6 Bromid

Concentrations are due to applications at least 4-6 years ago

Pesticide concentration in groundwater

M1 M3 M4 M5 M6Screendepths

(m b.g.s.) 3-4 4-5 5-6 3-4 4-5 5-6 3-4 4-5 5-6 3-4 4-5 5-6 3-4 4-5 5-6Apr-99 * * * * * * * *

09-sep-99 <0.2 <0.2 <0.2 <0.2 * *04-nov-99 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 * <0.208-dec-99 < 0.06 0.23 0.33 0.32 0.3304-jan-00 < < < 0.13 0.0603-feb-00 0.10 0.07 0.19 0.09 0.12 0.14 0.14 0.17 0.06 0.07 0.10 0.19 0.19 0.2002-mar-00 < 0.03 0.07 0.10 0.10 0.1606-apr-00 < 0.04 0.06 0.10 0.17 0.2010-maj-00 0.06 0.04 0.08 0.08 < < 0.11 0.08 0.12 < < 0.08 0.10 0.13 0.0907-jun-00 < < < 0.09 0.0605-jul-00 < 0.07 0.17 0.31

<) below the dectedtion limit of 0.02 µg/l. *) Degradation product was detected in the range of 0.05 – 0.5 µg/l;

Diketo-metribuzin (µg/l)

M1 M3 M4 M5 M6Screendepths

(m b.g.s.) 3-4 4-5 5-6 3-4 4-5 5-6 3-4 4-5 5-6 3-4 4-5 5-6 3-4 4-5 5-6Apr-99 * * * * * * * *

09-sep-99 <0.2 <0.2 <0.2 <0.2 * *04-nov-99 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 * <0.208-dec-99 < 0.06 0.23 0.33 0.32 0.3304-jan-00 < < < 0.13 0.0603-feb-00 0.10 0.07 0.19 0.09 0.12 0.14 0.14 0.17 0.06 0.07 0.10 0.19 0.19 0.2002-mar-00 < 0.03 0.07 0.10 0.10 0.1606-apr-00 < 0.04 0.06 0.10 0.17 0.2010-maj-00 0.06 0.04 0.08 0.08 < < 0.11 0.08 0.12 < < 0.08 0.10 0.13 0.0907-jun-00 < < < 0.09 0.0605-jul-00 < 0.07 0.17 0.31


Diketo-metribuzin (µg/l)

The maximum allowed concentration of 0.1 µg/l was exeeded in 36% of the samples analysed

Pesticide concentration in groundwater

M1 M3 M4 M5 M6Screendepths(m.u.t.) 3-4 4-5 5-6 3-4 4-5 5-6 3-4 4-5 5-6 3-4 4-5 5-6 3-4 4-5 5-6Apr-99 * * * * * * * *

09-sep-99 <0.2 <0.2 <0.2 <0.2 <0.2 <0.204-nov-99 <0.2 <0.2 * <0.2 * <0.2 <0.2 <0.2 * <0.2 <0.2 <0.2 <0.2 <0.2 <0.208-dec-99 0.08 0.04 0.04 0.07 0.07 0.0504-jan-00 0.06 0.02 0.05 0.06 0.0603-feb-00 0.04 0.03 0.09 0.04 0.03 < 0.03 0.04 0.02 < < 0.02 0.02 0.0202-mar-00 < 0.02 0.02 0.04 0.05 0.0306-apr-00 < < < 0.03 0.02 0.0210-maj-00 0.05 0.02 0.08 < < < 0.04 0.04 0.03 < < < < 0.02 0.0307-jun-00 < < < < 0.05 <05-jul-00 < < < <

Pesticide concentration in groundwaterDesamino-diketo-metribuzin (µg/l)


Previous use of metribuzine at Tylstrup

Year Product Dose (kg /ha/y) PLAP field 1990 Sencor WG 0.70 1992 Sencor WG 0.50 1994 Sencor WG 0.30 1999 Sencor WG 0.35 Field south of PLAP

1989

Sencor WG

0.70

1992 1994

Sencor WG Sencor WG

0.50 0.30

Conclusion - Tylstrup

• ETU (degradation product of mancozeb) linuron or metribuzin did not leach from the root zone

• Diketo-metribuzin, desamino-diketo-metribuzin (degradation products of metribuzin) leached from the root zone in concentrations exceeding 0.1 µg/l.

• Previous application of metribuzin has caused a marked groundwater contamination with 2 degradation products

• The degradation products of metribuzin are quite stable.

Leaching of pesticides in PLAPTylstrup Jyndevad Silstrup Estrup Faardrup Slaeggerup




Uacceptabel UdvaskningUnacceptable leaching

Leaching of glyphosate - Estrup

0

10

20

30

ok

t-0

0

no

v-0

0

de

c-0

0

jan

-01

feb

-01

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r-0

1

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-01

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(mm

/d)

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Dræ

na

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(mm

/d)

0123 0102030

Drænafstrømning (mm/d) Drainage flow, mm/d

Dr a

i na

ge

flo

w,

mm

/ d

Pre

cip

. ,m

m/d


0

10

20

30

ok

t-0

0

no

v-0

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de

c-0

0

jan

-01

feb

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r-0

1

ma

j-0

1

jun

-01

Ne

db

ør

(mm

/d)

0

1

2

3

Gly

ph

os

at

(µg

/l)

0

10

20

30

Dræ

na

fs.

(mm

/d)

0

1

2

3

0

10

20

30

Pesticider (µg/l) Drænafstrømning (mm/d)Drainage flow, mm/dPesticide, µg/l

Dra

ina

ge

flo

w,

mm

/ d

Pre

cip

. ,m

m/d

Gly

ph

osa

te,

µg

/l


0

10

20

30

ok

t-0

0

no

v-0

0

de

c-0

0

jan

-01

feb

-01

ma

r-0

1

ap

r-0

1

ma

j-0

1

jun

-01

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db

ør

(mm

/d)

0

1

2

3

Gly

ph

os

at

(µg

/l)

0

10

20

30

Dræ

na

fs.

(mm

/d)

0

1

2

3

AM

PA

(µ

g/l)

0

10

20

30

Dræ

na

fs. (

mm

/d)

Pesticider (µg/l) Drænafstrømning (mm/d)

0,54 µg/l

0,17 µg/l

Pre

cip

. ,m

m/d

Gly

ph

osa

te,

µg

/l

Dr a

i na

ge

flo

w,

mm

/ dD

r ai n

ag

e f

low

, m

m/ d

Drainage flow, mm/dPesticide, µg/l

AM

PA

, µ

g/l



Ingen Udvaskning Uacceptabel Udvaskning UdvaskningNo leaching Unacceptable leaching Leaching



Ingen Udvaskning Uacceptabel Udvaskning UdvaskningUnacceptable leaching LeachingNo leaching



Ingen Udvaskning Uacceptabel Udvaskning UdvaskningUnacceptable leaching LeachingNo leaching

11

13

2

Status after 3 years of monitoring

• Leaching from fields can significantly pollute groundwater with pesticides

• Some approved pesticides can cause significant groundwater pollution

• When the damage is done, pesticides can be around for several years within the groundwater

Conclusion

• It provides a realistic description of the leaching behaviour of pesticides under field conditions

• It provides essential data for the calibration/validation of the models used in the current risk assessment of pesticides leaching

The PLAP monitoring programme gives an important contribution towards an improved risk assessment of pesticides leaching:

Further information is available on

www.pesticidvarsling.dk

Estrup- loamy soil

#

%

%

%

%

$Z$Z

0 5 0 m

P 2S 2

S 1

P 3

P 4

P 1

##

#

#

#

#

#

M 2

M 3

M 4

M 5

M 6

M 7

M 1

H 1

NO u tle t

S u c tio n cu p s , T D R an dP t-1 0 0

% P iezo m e te r

# M o n ito rin g w e ll

S h ed

$Z R ain G au g e

T ile -d ra in , in s id e fie ld

T ile -d ra in , o u ts id e fie ld

C o llec to r p ip e

S am p le p o in t fo r h o rizo n ta lsc reenB u ffe r Z o n e

H o rizo n ta l sc reen

Sampling of drainage water

Campbell logger

ISCO samplers

30o V notch InletOutletPresure transducer

Geological profile -Tylstrup

P6 P7 M 1 M 2 M 3 M 4 M 5P5 P8 M 7 M 6

P lø je lag

2

4

6

8

10

12

N ord

M arint sand

M arint s ilt og ler

F iltre

Kote (m )

Syd

Precipication

• 1047 mm • 35% more than the yearly normal

0

20

40

60

80

100

120

140

160M

aj

Jun Jul

Aug

Sep

Oct

Nov

Dec Jan

Feb

Mar Apr

Maj

Jun

(mm

/mån

ed)

Moniteringsperiode

Normal (1960-1991)

N

N

N

N

SO

M etribuzin

N

N

N

N

OO

D iketo-m etribuzin

N

N

N

SO

Desam ino-m etribuzin

N

N

N

OO

Diketo-desam ino-m etribuzin

Leaching of glyphosate - Silstrup

3716537437

0

10

20

30

ok

t-0

1

no

v-0

1

de

c-0

1

jan

-02

feb

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ma

r-0

2

ap

r-0

2

ma

j-0

2

jun

-02

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db

ør

(mm

/d)

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10

20

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na

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(mm

/d)

0,0

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3716537437

0

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ok

t-0

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-02

feb

-02

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r-0

2

ap

r-0

2

ma

j-0

2

jun

-02

Ne

db

ør

(mm

/d)

0,0

1,5

3,0

4,5

Gly

ph

os

at

(µg

/l)

0

10

20

30

Dræ

na

fs.

(mm

/d)

0,0

0,2

0,3

0,5

0

10

20

30



3716537437

0

10

20

30

ok

t-0

1

no

v-0

1

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c-0

1

jan

-02

feb

-02

ma

r-0

2

ap

r-0

2

ma

j-0

2

jun

-02

Ne

db

ør

(mm

/d)

0,0

1,5

3,0

4,5

Gly

ph

os

at

(µg

/l)

0

10

20

30

Dræ

na

fs.

(mm

/d)

0,0

0,2

0,3

0,5

AM

PA

(µ

g/l)

0

10

20

30

Dræ

na

fs. (

mm

/d)


0,12 µg/l

0,06 µg/l

Required by locations included in the PLAP (examples)

• Be fields in crop rotations with a size of 1-3 ha

• Past cultivation known for at least 10 years

• Undisturbed soil - no previous excavations

• Irrigation system (sandy soils)

• Room for a bufferzone

• Tracers could be applied (bromide)

• Inside an infiltration area -downward gradient

• A thin, unsaturated zone (shallow groundwater)

• A well defined groundwater table

• Old drainage system (loamy soils)

• Homogenius soil

• And several more……

Documents

The Danish Pesticide Leaching Assessment Program – a field based, early warning system