MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand

Miljøudvalget 2014-15 (1. samling)
MIU Alm.del Bilag 215
Offentligt

The Danish Pesticide

Leaching Assessment

Programme

Monitoring results May 1999–June 2013

Walter Brüsch, Annette E. Rosenbom, Nora Badawi, Lasse Gudmundsson, Frants von

Platten-Hallermund, Carsten B. Nielsen, Finn Plauborg, Troels Laier and Preben Olsen

Geological Survey of Denmark and Greenland

Danish Ministry of Climate, Energy and Building

Department of Agroecology

Aarhus University

Department of Bioscience

Aarhus University

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

Editor:

Walter Brüsch

Cover photo:

Jens Molbo

Cover:

Henrik Klinge Pedersen

Layout and graphic production:

Authors and Helle Winther

Printed:

March 2015

Price:

DKK 200

ISBN 978-87-7871-388-9

Available from:

Geological Survey of Denmark and Greenland

Øster Voldgade 10, DK-1350 Copenhagen K, Denmark

Phone: +45 3814 2000. Fax: +45 3814 2050

E-mail: [email protected]

Homepage: www.geus.dk

The report is also available as a pdf file at www.pesticidvarsling.dk

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

Table of contents

PREFACE

SUMMARY

DANSK SAMMENDRAG

INTRODUCTION .......................................................................................................................... 15

1.1

1.2

BJECTIVE

................................................................................................................................. 15

TRUCTURE OF THE

PLAP ......................................................................................................... 16

PESTICIDE LEACHING AT TYLSTRUP.................................................................................. 19

2.1

ATERIALS AND METHODS

........................................................................................................ 19

2.1.1

Site description and monitoring design ............................................................................

2.1.2

Agricultural management.................................................................................................

2.1.3

Model setup and calibration ............................................................................................

2.2

ESULTS AND DISCUSSION

......................................................................................................... 21

2.2.1

Soil water dynamics and water balances .........................................................................

2.2.2

Bromide leaching .............................................................................................................

2.2.3

Pesticide leaching ............................................................................................................

PESTICIDE LEACHING AT JYNDEVAD ................................................................................. 31

3.1

ATERIALS AND METHODS

........................................................................................................ 31

3.1.1

Site description and monitoring design ............................................................................

3.1.2

Agricultural management.................................................................................................

3.1.3

Model setup and calibration ............................................................................................

3.2

ESULTS AND DISCUSSION

......................................................................................................... 34

3.2.1

Soil water dynamics and water balances .........................................................................

3.2.2

Bromide leaching .............................................................................................................

3.2.3

Pesticide leaching ............................................................................................................

PESTICIDE LEACHING AT SILSTRUP ................................................................................... 43

4.1

ATERIALS AND METHODS

........................................................................................................ 43

4.1.1

Site description and monitoring design ............................................................................

4.1.2

Agricultural management................................................................................................. 43

4.1.3

Model setup and calibration ............................................................................................

4.2

ESULTS AND DISCUSSION

......................................................................................................... 45

4.2.1

Soil water dynamics and water balances .........................................................................

4.2.2

Bromide leaching .............................................................................................................

4.2.3

Pesticide leaching ............................................................................................................

PESTICIDE LEACHING AT ESTRUP ....................................................................................... 57

5.1

ATERIALS AND METHODS

........................................................................................................ 57

5.1.1

Site description and monitoring design ............................................................................

5.1.2

Agricultural management.................................................................................................

5.1.3

Model setup and calibration ............................................................................................

5.2

ESULTS AND DISCUSSION

......................................................................................................... 59

5.2.1

Soil water dynamics and water balances .........................................................................

5.2.2

Bromide leaching .............................................................................................................

5.2.3

Pesticide leaching ............................................................................................................

PESTICIDE LEACHING AT FAARDRUP ................................................................................. 71

6.1

ATERIALS AND METHODS

........................................................................................................ 71

6.1.1

Site description and monitoring design ............................................................................

6.1.2

Agricultural management.................................................................................................

6.1.3

Model setup and calibration ............................................................................................

6.2

ESULTS AND DISCUSSION

......................................................................................................... 74

6.2.1

Soil water dynamics and water balances .........................................................................

6.2.2

Bromide leaching .............................................................................................................

6.2.3

Pesticide leaching ............................................................................................................

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

PESTICIDE ANALYSIS QUALITY ASSURANCE ................................................................... 83

7.1

ATERIALS AND METHODS

........................................................................................................ 83

7.1.1

Internal QA.......................................................................................................................

7.1.2

External QA......................................................................................................................

7.2

ESULTS AND DISCUSSION

......................................................................................................... 85

7.2.1

Internal QA.......................................................................................................................

7.2.2

External QA......................................................................................................................

7.3

UMMARY AND CONCLUDING REMARKS

.................................................................................... 89

SUMMARY OF MONITORING RESULTS ............................................................................... 91

REFERENCES.............................................................................................................................. 105

APPENDIXES

PPENDIX

HEMICAL ABSTRACTS NOMENCLATURE FOR THE PESTICIDES ENCOMPASSED BY THE

PLAP............... 111

PPENDIX

ESTICIDE MONITORING PROGRAMME

– S

AMPLING PROCEDURE

.......................................................... 113

PPENDIX

GRICULTURAL MANAGEMENT

............................................................................................................ 117

PPENDIX

RECIPITATION DATA FOR THE

PLAP

SITES

.......................................................................................... 125

PPENDIX

ESTICIDE DETECTIONS IN SAMPLES FROM DRAINS

SUCTION CUPS AND

GROUNDWATER MONITORING WELLS

.................................................................................................... 127

PPENDIX

ABORATORY INTERNAL CONTROL CARDS

........................................................................................... 137

PPENDIX

ESTICIDES ANALYZED AT FIVE

PLAP

SITES IN THE PERIOD UP TO

2013 .............................................. 145

PPENDIX

EW HORIZONTAL WELLS

..................................................................................................................... 153

PPENDIX

ROUNDWATER AGE FROM RECHARGE MODELLING AND TRITIUM

HELIUM ANALYSIS

......................... 155

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

Preface

In 1998, the Danish Parliament initiated the Danish Pesticide Leaching Assessment

Programme (PLAP), an intensive monitoring programme aimed at evaluating the

leaching risk of pesticides under field conditions. The Danish Government funded the

first phase of the programme from 1998 to 2001. The programme has now been

prolonged twice, initially with funding from the Ministry of the Environment and the

Ministry of Food, Agriculture and Fisheries for the period 2002 to 2009, and presently

with funding from the Danish Environmental Protection Agency (EPA) for the period

2010 to 2015.

The work was conducted by the Geological Survey of Denmark and Greenland (GEUS),

the Department of Agroecology (AGRO) at Aarhus University and the Department of

Bioscience (BIOS) also at Aarhus University, under the direction of a management

group comprising Walter Brüsch (GEUS), Annette E. Rosenbom (GEUS), Lis Wollesen

de Jonge (AGRO), Preben Olsen (AGRO), Carsten B. Nielsen (BIOS), Steen Marcher

(Danish EPA) and Anne Louise Gimsing (Danish EPA).

Lea Frimann Hansen (Danish EPA) is chairman of the steering group, and the members

are Steen Marcher, Anne Louise Gimsing (Danish EPA), Flemming Larsen, Walter

Brüsch (GEUS), Erik Steen Kristensen (AGRO) and Christian Kjær (BIOS).

This report presents the results for the period May 1999–June 2013. Results including

part of the periode May 1999–June 2012 have been reported previously (Kjær

et al.,

2002, Kjær

et al.,

2003, Kjær

et al.,

2004, Kjær

et al.,

2005c, Kjær

et al.,

2006, Kjær

al.,

2007, Kjær

et al.,

2008, Kjær

et al.,

2009, Rosenbom

et al.,

2010b, Kjær

et al.,

2011, Brüsch

et al.,

2013a, and Brüsch

et al.,

2013b). The present report should

therefore be seen as a continuation of previous reports with the main focus on the

leaching risk of pesticides applied during the monitoring period 2011-2013.

The report was prepared jointly by Walter Brüsch (GEUS), Annette E. Rosenbom

(GEUS), Nora Badawi (GEUS), Frants von Platten-Hallermund (GEUS), Lasse

Gudmundsson (GEUS), Troels Laier (GEUS), Preben Olsen (AGRO), Finn Plauborg

(AGRO) and Carsten B. Nielsen (BIOS). While all authors contributed to the whole

report, authors were responsible for separate aspects as follows:

•

Pesticide and bromide leaching: Preben Olsen, Annette E. Rosenbom and Walter

Brüsch.

•

Soil water dynamics and water balances: Annette E. Rosenbom, Finn Plauborg and

Carsten B. Nielsen.

•

Pesticide analysis quality assurance: Nora Badawi.

•

Appendix 9: Troels Laier.

Walter Brüsch

February 2015

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

Summary

In 1998, the Danish Parliament initiated the Pesticide Leaching Assessment Programme

(PLAP), an intensive monitoring programme aimed at evaluating the leaching risk of

pesticides under field conditions. The objective of the PLAP is to improve the scientific

foundation for decision-making in the Danish regulation of pesticides. The specific aim

is to analyze whether pesticides applied in accordance with current regulations will

result in leaching of the pesticide and/or its degradation products to groundwater in

unacceptable concentrations.

Throughout the monitoring period (1999-2013) 101 pesticides and/or degradation

products have been analyzed in PLAP comprising five agricultural fields (1.2 to 2.4 ha)

grow with different crops. The 15 most frequently analyzed pesticides and/or

degradation products includes analyzes of 2.300–4.000 water samples collected from

groundwater, drainage, and suction cups, including quality analysis samples (Table 0.1).

Evaluation of pesticides is based upon detections in 1 meters depth (water collected via

drains and suction cups) and detections in groundwater monitoring screens (1.5-4.5

meter below ground surface, hereafter m b.g.s.).

This report presents the results of the monitoring period July 2011–June 2013

comprising 9.090 single analyzes conducted on water samples collected at the five

PLAP-fields: two sandy fields (Tylstrup and Jyndevad) and three clayey till fields

(Silstrup, Estrup and Faardrup). In this period, PLAP has evaluated the leaching risk of

19 pesticides and 22 degradation products (Table 0.2) after applying the maximum

allowed dose of the specific pesticide to the specific crop (Table 0.3).

Table 0.1.

The 15 most frequently analyzed pesticides and/or degradation product in the period 1999-June 2013. The

water samples being analyzed include quality analysis (QA) samples, samples from groundwater, and samples from

the vaiably-saturatede zone (drainage and suction cups).

Pesticide or

All samples Ground- Drainage +

degradation products

incl. QA

water

suction cups

Parent

Bentazone

3.926

2.433

983

AMPA

Glyphosat

3.571

2.108

1.044

Glyphosate

Glyphosat

3.568

2.106

1.043

Pirimicarb

3.432

2.120

887

Propiconazole

Propiconazol

3.421

2.084

899

Pirimicarb-desmethyl

Pirimicarb

3.078

1.911

780

Pendimethalin

2.881

1.811

694

CyPM

Azoxystrobin

2.854

1.801

691

Azoxystrobin

2.701

1.689

668

Pirimicarb-desmethyl-formamido

Pirimicarb

2.678

1.638

707

Desethyl-terbuthylazine

Terbuthylazin

2.619

1.664

612

Fenpropimorph

2.494

1.531

657

Triazinamin-methyl

Tribenuron-methyl

2.386

1.523

569

Fenpropimorph acid

Fenpropimorph

2.341

1.435

636

PPU

Rimsulfuron

2.311

1.519

502

PPU-desamino

Rimsulfuron

2.311

1.519

502

P: Parent pesticide. M: Degradation product.

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

Results covering the period May 1999–June 2011 have been reported previously (Kjær

et al.,

2002, Kjær

et al.,

2003, Kjær

et al.,

2004, Kjær

et al.,

2005c, Kjær

et al.,

2007,

Kjær

et al.,

2008, Kjær

et al.,

2009, Rosenbom

et al.,

2010b, Kjær

et al.,

2011, and

Brüsch

et al.,

2013a+b). The present report should therefore be seen as a continuation of

previous reports with the main focus on the leaching risk of pesticides applied during

June 2011- June 2013.

Table 0.2.

19 pesticides and 22 degradation products have been analyzed in PLAP in the period June 2011-June

2013. The number of water samples analyzed, detections, and detections ≥ 0.1µg/L in water samples from the

variably-saturated zone (drainage and suction cups) and groundwater (groundwater wells).

Analyte

Parent pesticide

Samples

Drain+suction cups

Groundwater wells

Max.

analyzed Detections ≥ 0.1µg/L Detections ≥ 0.1µg/L

conc.

Aclonifen

216

Aclonifen

Aminopyralid

216

Aminopyralid

Azoxystrobin

264

0.13

Azoxystrobin

CyPM

Azoxystrobin

264

0.4

Bentazone

289

1.9

Bentazone

Bifenox

485

0.38

Bifenox

Bifenox acid

Bifenox

490

4.8

Nitrofen

Bifenox

485

0.34

Boscalid

142

Boscalid

Bromoxynil

Clomazone

FMC 65317

Clomazone

Cyazofamid

170

Cyazofamid

Diflufenican

265

0.47

Diflufenican

AE-B107137

Diflufenican

273

0.13

AE-05422291

Diflufenican

265

TFMP

Fluazifop-P-buthyl

326

0.64

Fluazifop-P

Fluazifop-P-buthyl

Glyphosate

327

Glyphosat

AMPA

Glyphosat

327

0.58

Ioxynil

Mesotrione

113

Mesotrione

AMBA

Mesotrione

113

MNBA

Mesotrione

113

Metalaxyl-M

392

1.3

Metalaxyl-M

CGA 62826

Metalaxyl-M

403

0.68

CGA 108906

Metalaxyl-M

403

100

230

4.8

Metrafenone

258

0.072

Metrafenone

Propyzamide

Propyzamid

RH-24655

Propyzamid

RH-24644

Propyzamid

RH-24580

Propyzamid

Prosulfocarb

PPU

Rimsulfuron

264

0.23

PPU-desamino

Rimsulfuron

264

0.18

Tebuconazole

0.084

Tebuconazole

Thiacloprid

M34

Thiacloprid

Thiacloprid sulfonic

acid

Thiacloprid

Thiacloprid-amide

Thiacloprid

0.012

Triazinamin-methyl Tribenuron-methyl

ND - Pesticide not detected in monitoring period 2011-2013.Bold - parent pesticide analyzed.

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

Table 0.3.

Crops grown on the five PLAP-fields in 2011, 2012 and 2013.

Tylstrup

Jyndevad

Silstrup

Estrup

2011 Spring barley Spring barley Red fescue

2012 Spring barley Maize

2013 Winter rye

Peas

Red fescue and winter wheat

Winter wheat/spring barley*

Faardrup

Winter wheat Red fescue

Spring barley Spring barley and white clover

Peas

White clover

*Spring barley replacing frost affected winter wheat.

Highlights from the

monitoring period June 2011-June 2013:

•

Bentazone was applied to peas at Jyndevad and Estrup in 2013, white clower at

Faardrup in 2012 and 2013, and maize at Jyndevad in 2012. At the sandy field

Jyndevad bentazone was found to leaching through the variably-saturated zone

(suction cups) after application on peas in 2013. It was, however, only detected once

(0.01 µg/L) in a mixed groundwater sample from the horizontal well at 2.5 m b.g.s.

This confirmes the leaching pattern detected after the bentazon application on maize

in 2012, where it was frequently detected in the variably-saturated zone (suction

cups) in concentrations up to 1.9 µg/L, but not in the groundwater. After use on

clower, at the clayey till field Faardrup in 2012 and 2013, bentazone was detected in

one drainage sample (0.02 µg/L). Bentazone did not leach after use on peas at the

clayey till field Estrup in 2013. In total, bentazone has until 15 May 2013 been

applied 17 times to the five fields in PLAP and on different crops. In the period May

2001-June 2013 bentazone has been detected in 66 groundwater samples, where

eight groundwater samples had concentration above 0.1 µg/L. A total of 3.728

groundwater samples has been analyzed for bentazone.

Metalaxyl-M, and especially its two degradation products CGA 108906 and CGA

62826, have been detected in high frequency and concentrations both in the

variably-saturated zone and in the groundwater at the two sandy PLAP-fields, why

the compounds still will be under evaluation in PLAP. Metalaxyl-M was detected a

few times in low concentrations in watersamples from the variably-saturated zone

(suction cups). The degradation products CGA 108906 and CGA 62826, however,

leached to 1 m depth in concentrations often exceeding 0.1 µg/L up to 3 years after

application. The highest concentrations for both compounds were detected 1 m

depth in concentrations up to 3.7 µg/L (January 2012). In the period June 2011-

June 2013 both degradation products were found in 83-100% of the water samles

from the variably-saturated zone (suction cups) and especially CGA 108906 was

detected frequently in groundwater samples (75-83%) from Tylstrup and Jyndevad,

where 20-30% of the analyzed groundwater samples exceeded 0.1 µg/L.

Concentration measured in water samples from the variably-saturated zone and from

a horisontal well collecting groundwater just beneath the fluctuating groundwater

table at Jyndevad, clearly indicate leaching of the compounds after metalaxyl-M was

applied to potatoes in 2010 at the PLAP-fields. As a consequence of these

monitoring results, the Danish EPA has withdrawn the approval of metalaxyl-M per

August 1

, 2013.

Fluazifop-P-butyl was used in a new dose (50% lower than in past applications) in

the spring 2011 at the clayey till field Silstrup, and leaching of the degradation

product TFMP was negligible in 2011. Before the regulation, TFMP leached to both

drainage and groundwater in concentrations above 0.1 µg/L at Silstrup. Fluazifop-P-

butyl was also applied at Faardrup in May 2011, and TFMP did not leach. In April

•

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

2012 Fluazifop-P-butyl was applied on red fescue at Silstrup (50% reduced dose),

and TFMP-concentrations exceeding 0.1 µg/L was measured in drainage and

groundwater. In the monitoring year 2013, TFMP was found in both drainage and

groundwater, but in concentrations below 0.1 µ/L. Given these different TFMP-

leaching scenarios, the leaching risk of the compound will still be evaluated in

PLAP in the years to come. Fluazifop-P-butyl has been applied 10 times in PLAP at

four of the fields.

•

After application on red fescue at the clayey till field Silstrup September 2012,

glyphosate and AMPA were found in drainage in concentrations up to 0.66 µg/L.

The compounds were however not exceeding 0.1 µg/L in groundwater. Here

glyphosate was only detected in 10 groundwater samples from vertical wells and in

three groundwater samples from a horizontal well. At the clayey till field Estrup,

concentrations of glyphosate and AMPA in drainage both exceeded 0.1 µg/L

frequently after glyphosate application on winter wheat in October 2011. In the

groundwater AMPA was never detected, only glyphosate was occasionally detected

in two groundwater samples with concentrations ≥ 0.1 µg/L (0.21 and 0.13 µg/L).

At the clayey till field Faardrup, glyphosate was found in low concentrations (0.025

and 0.019 µg/L) in two samples from two levels in a vertical monitoring well after

application after harvest of spring barley and white clover in October 2011.

Monitoring at Faardrup stopped in August 2012.

Azoxystrobine was applied at the clayey till field Estrup in June 2012, and both

azoxystrobine and CyPM leached to drainage in concentrations above 0.1µg/L.

CyPM was detected in seven groundwater samples from both the new and old

horizontal wells, and one sample was exceeding 0.1 µg/L. There was no detections

in groundwater samples collected from the vertical monitoring wells.

The fungicide metrafenone was applied twice, 9 May and 7 June 2011, at the clayey

till field Estrup. 20 water samples of drainage and one of groundwater contained

metrafenone in concentrations <0.1 µg/L.

Diflufenican was applied in April 2012 and in November 2012 (red fescue and

winter wheat) at the clayey till field Silstrup. Diflufenican was detected in 9 water

samples of the drainage and in one groundwater sample. One drainage and one

groundwater sample exceeded 0.1 µg/L. The degradation product of diflufenican

AE-B107137 was detected in 5 water samples of the drainage, while the other

degradation product AE-05422291 was not detected (Table 0.2). Diflufenican and

the two degradation products were not detected in groundwater nor drainage after

application at spring barley in April 2011 at the sandy field Jyndevad.

Aclonifen, aminopyralid, boscalid, bromoxynil, clomazon, cyazofamid, ioxynil,

mesotrione, propyzamid, prosulfocarb, tribenuron-methyl and degradation products

were not detected in drainage and groundwater during the monitoring period. The

degradation product thiacloprid amid of thiacloprid was detected in one sample from

the drainage, while thiacloprid was not detected. Tebuconazole was detected in two

water samples collected in the drainage in August and September 2012 (Table 0.2).

•

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

The results of the

entire monitoring period 1999-2013

covering

pesticides and

degradation products show that:

•

Of the 50 pesticides applied, 16 pesticides and/or their degradation product(s)

(aclonifen, aminopyralid, boscalid, clopyralid, chlormequat, cyazofamid,

desmedipham, fenpropimorph, florasulam, iodosulfuron-methyl-natrium, linuron,

mesotrione, thiacloprid, thiamethoxam, tribenuron-methyl and triasulfuron) were not

detected in either drainage or groundwater during the entire monitoring period.

The monitoring data indicate pronounced leaching of 16 of the applied pesticides

and/or their degradation product(s). The following compounds leached through the

soil entering tile drains or suction cups (placed 1 m depth) in average concentrations

exceeding 0.1 µg/L:

azoxystrobin

and its degradation product

CyPM

bentazone

CL153815

(degradation product of picolinafen)

AE-B107103

(degradation product of diflufenican)

pirimicarb-desmethyl-formamido

(degradation product of pirimicarb)

propyzamide

tebuconazole

glyphosate

and its degradation product

AMPA

CGA 108906 and CGA 62826

(degradation products of metalaxyl-M)

PPU

(degradation products of rimsulfuron)

bifenox-acid

(degradation product of bifenox)

ethofumesate

TFMP

(degradation product of fluazifop-P-butyl)

metamitron

and its degradation product

desamino-metamitron

desamino-diketo-metribuzin

and

diketo-metribuzin

(degradation pro-

ducts of metribuzin)

terbuthylazine

and its degradation products

desethyl-terbuthylazine,

hydroxy-desethyl-terbuthylazine

and

hydroxy-terbuthylazine.

•

For pesticides and/or their degradation products

marked in italics,

pronounced

leaching is mainly confined to the depth of 1 m b.g.s., where pesticides were

frequently detected in water samples collected from tile drains and suction cups,

while a limited number of detections (fewer than five samples per field) exceeding

0.1 µg/L were detected in water samples collected from groundwater monitoring

wells.

For the pesticides and/or their degradation products

marked in bold,

pronounced

leaching below the depth of 1 m b.g.s. was observed. Apart from PPU, these were all

frequently detected in groundwater in concentrations exceeding 0.1µg/L more than

six months after application.

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

•

The monitoring data also indicate leaching of an additional 18 pesticides, but in

low

concentrations. Although concentrations exceeded 0.1 µg/L in several water

samples collected from suction cups and tile drains (1 m b.g.s.), average leaching

concentrations on a yearly basis did not exceed 0.1 µg/L. None of the compounds

were detected in water samples from the groundwater monitoring wells in

concentrations exceeding 0.1 µg/L.

In order to describe the water flow through the variably-saturated zone and into the

groundwater zone, a bromide tracer has been applied at least twice to each of the five

PLAP-fields. Bromide and pesticide concentrations are measured monthly in both the

variably-saturated zones and in the saturated zones, and weekly in the drainage.

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

Dansk sammendrag

I 1998 vedtog Folketinget at iværksætte projektet ”Varslingssystem for udvaskning af

Pesticider til grundvand” (VAP). VAP er et omfattende moniteringsprogram, der

undersøger udvaskning af pesticider anvendt i landbrug under reelle markforhold.

Programmet har til formål at undersøge, om godkendte pesticider eller deres

nedbrydningsprodukter – ved regelret brug og dosering – udvaskes til grundvandet i

koncentrationer over grænseværdien for herigennem at udvide det videnskabelige

grundlag for danske myndigheders (Miljøstyrelsen) procedurer for regulering af

godkendte sprøjtemidler.

Udvaskningsrisikoen for 101 pesticider og nedbrydningsprodukter er med udgangen af

juni 2013 (1999-2013) undersøgt på en til fem marker, og ofte på forskellige afgrøder

på samme mark. Disse fem marker har en størrelse på mellem 1,2 og 2,4 ha. De 15 mest

analyserede pesticider og nedbrydningsprodukter er analyseret i ca. 2.300 til 4.000

vandprøver fra sugeceller i den umættede zone (den variabelt mættede zone), dræn- og

grundvand fra marker med forskellige jordbundsforhold og på forskellige afgrøder, se

tabel 0.1. Undersøgelse af pesticider bygger på moniteringsresultater, som henholdsvis

repræsenterer fund i en meters dybde (indhentet via dræn og sugeceller) og fund i

grundvandsmoniteringsfiltre (1,5-4,5 meter under terræn, herefter m u.t.).

Denne rapport opsummerer analyser for 19 pesticider og 22 nedbrydningsprodukter, i

alt 41 stoffer, der har indgået i moniteringsprogrammet for de fem VAP marker i

perioden fra juli 2011 til juni 2013 (se tabel 0.2), efter anvendelse af pesticider på de

afgrøder, der er dyrket på de fem marker, (se tabel 0.3). I denne periode er der foretaget

9.090 enkeltstof analyser på vandprøver indsamlet på de fem VAP marker: to sandede

marker (Tylstrup og Jyndevad) og tre morænelers marker (Silstrup, Estrup og Fårdrup).

Analyseresultater fra foregående år (maj 1999 til juni 2011) er tidligere afrapporteret.

Resultater fra den seneste

moniteringsperiode juni 2011-juni 2013

viser følgende:

•

Bentazon blev anvendt på ærter i Jyndevad og Estrup i 2013, på hvidkløver i Fårdrup

i 2012 og 2013, samt på majs i Jyndevad i juni 2012. Bentazon blev fundet som

begyndende udvaskning i sugeceller i den umættede zone på den sandede mark i

Jyndevad, efter stoffet blev anvendt på ærter i 2013. Bentazon blev fundet i en enkelt

grundvandsprøve fra en horisontal boring (0,01µg/l). Bentazon blev fundet hyppigt i

vandprøver fra den umættede zone efter anvendelse på majs i 2012 i Jyndevad, hvor

den højeste koncentration var 1,9 µg/L, mens bentazon ikke blev fundet i

grundvandet. Efter anvendelse på hvidkløver på morænelersmarken i Fårdrup i 2012

og 2013, blev bentazon fundet i en enkelt drænprøve (0,02 µg/l) men ikke i

grundvand, og efter anvendelse på ærter på morænelersmarken i Estrup i 2013 blev

bentazon ikke fundet i hverken dræn eller grundvand. Bentazon har frem til den 15.

maj 2013 været anvendt 17 gange på de fem marker på forskellige afgrøder.

Bentazon er i hele moniteringsperioden fundet i 66 grundvandsprøver, og i otte af

disse i koncentrationer ≥ 0,1 µg/l (hhv. 2003 og 2005). 3.728 grundvandsprøver er i

alt analyseret for bentazon.

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•

Moniteringen af metalaxyl-M og nedbrydningsprodukter er fortsat i 2011-2013 på

grund af mange fund af nedbrydningsprodukterne i grundvand. Metalaxyl-M blev

fundet få gange i små koncentrationer i den umættede zone, hvorimod to af dets

nedbrydningsprodukter CGA62826 og CGA108906 blev fundet i høje

koncentrationer i grundvand, der ofte overskred grænseværdien for grundvand på de

to sandede marker Tylstrup og Jyndevad. Begge nedbrydningsprodukter blev fundet i

vand fra sugeceller placeret 1 m u.t. med stigende koncentration indtil januar 2012

(maksimum koncentration 3,7 µg/l). Metalaxyl-M blev fundet i grundvandet

opstrøms sandmarkerne før sprøjtningen med metalaxyl-M i 2010, og disse fund

stammer fra tidligere sprøjtninger på nabomarker beliggende opstrøms. I

moniteringsperioden fra juni 2011 til juni 2013 blev begge nedbrydningsprodukter

fundet i 83-100% af vandprøverne fra den umættede zone (sugeceller), mens særligt

CGA 108906 blev fundet hyppigt i vandprøver udtaget fra grundvand (75-83%) fra

de to sandede marker. Disse fund i vand fra den umættede zone og fra en horisontal

boring placeret under grundvandsspejlet i Jyndevad, viser at sprøjtningen på kartofler

med metalaxyl-M i 2010 medførte udvaskning af moderstof og

nedbrydningsprodukter fra markerne og at udvaskningen ikke stammer fra

anvendelse på marker opstrøms marken. Som følge af fund i grundvandet blev

anvendelsen af metalaxyl-M forbudt i 2013.

•

Fluazifop-P-butyl blev i 2008 pålagt restriktioner bl.a. i form af en nedsat dosering

for at beskytte grundvandet. Ved test af den nye lave dosering i foråret 2011 var

udvaskningen af nedbrydningsproduktet TFMP ubetydelig. Dette var ikke tilfældet i

2008, hvor TFMP blev fundet i høje koncentrationer i grundvandet efter anvendelse

af fluazifop-P-butyl. I 2012 blev fluazifop-P-butyl igen udbragt i den nye reducerede

dosis, hvilket resulterede i mange TFMP fund, også i 2013, i lave koncentrationer.

Dette indikerer, at TFMP ved anvendelse af moderstoffet i den nye dosering, i nogle

tilfælde kan overskride grænseværdien for grundvand. Udvaskningen af TFMP

følges stadigvæk i VAP. Fluazifop-P-butyl har frem til juli 2013 været anvendt ti

gange på fire VAP marker. Fluazifop-P-butyl er ikke længere godkendt i Danmark.

Såfremt der ansøges om godkendelse igen, vil resultaterne fra VAP blive inddraget i

Miljøstyrelsens vurdering af, hvorvidt der kan gives godkendelse til svampemidler

med dette aktivstof.

•

Efter udbringning på rødsvingel i september 2012 på den lerede mark i Silstrup blev

glyphosat og nedbrydningsproduktet AMPA fundet i koncentrationer op til 0,66 µg/l

i drænvand, men ikke i koncentrationer over grænseværdien i grundvand, hvor

glyphosat blev fundet i ti vandprøver fra moniteringsboringer og i tre vandprøver fra

en horisontal boring. Begge stoffer er fundet i koncentrationer over 0,1 µg/l i

drænvand fra morænelersmarken i Estrup efter anvendelse i oktober 2011, hvor der

var dyrket vinterhvede. Glyphosat blev fundet i to grundvandsprøver på samme

mark i koncentrationer over 0,1 µg/l (0,21 og 0,13 µg/l), mens AMPA ikke blev

detekteret. På den lerede mark i Fårdrup blev moderstoffet fundet i små

koncentrationer under grænseværdien i to vandprøver fra de øverste to indtag i en

vertikal grundvandsboring efter anvendelse i oktober 2011. Moniteringen i Fårdrup

stoppede i august 2012.

•

Azoxystrobin blev anvendt på Estrup i 2012 hvilket resulterende i, at både

azoxystrobin og nedbrydningsproduktet CyPM blev udvasket til dræn i

koncentrationer over 0,1 µg/l. CyPM blev fundet i syv ud af 37 grundvandsprøver fra

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horisontale boringer, hvoraf en prøve havde en koncentration over 0,1 µg/l. Der var

ikke fund i vertikale grundvandsboringer.

•

Metrafenone blev anvendt to gange i maj og juni 2011 på den lerede mark i Estrup,

og stoffet blev fundet i 20 drænvandsprøver og i en grundvandsprøve i

koncentrationer under 0,1 µg/l.

•

Diflufenican blev fundet i ni drænvandsprøver fra morænelersmarken i Silstrup efter

stoffet blev anvendt på rødsvingel og vinterhvede i april og november 2012.

Diflufenican blev fundet i koncentrationer større end 0,1 µg/l i en grundvandsprøve

og i en drænvandprøve. Nedbrydningsproduktet AE-B107137 blev fundet i fem

drænvandsprøver, mens det andet nedbrydningsprodukt AE-05422291 ikke blev

detekteret. Ingen af de tre stoffer blev fundet i vandprøver fra den sandede mark i

Jyndevad, efter diflufenican blev udsprøjtet på forårsbyg i april 2011.

•

Aclonifen, aminopyralid, boscalid, bromoxynil, clomazon, cyazofamid, ioxynil,

mesotrione,

propyzamid,

prosulfocarb,

tribenuron-methyl

deres

nedbrydningsprodukter blev ikke udvasket i moniteringsperioden fra juni 2011 til

juni 2013. Nedbrydningsproduktet thiacloprid-amid fra thiacloprid blev fundet i en

enkelt drænvandsprøve, mens moderstoffet og thiacloprid-sulfonsyre ikke blev

påvist. Tebuconazole blev fundet i to drænprøver (se tabel 0.2, der viser alle stoffer

analyseret i perioden).

Resultater for

hele moniteringsperioden 1999-2013,

som omfatter 50 pesticider viser

følgende:

•

Af de 50 pesticider, der er blevet udbragt, blev 16 pesticider eller nedbrydnings-

produkter heraf (aclonifen, aminopyralid, boscalid, clopyralid, chlormequat,

cyazofamid, desmedipham, fenpropimorph, florasulam, iodosulfuron-methyl-

natrium, linuron, mesotrion, thiacloprid, thiamethoxam, tribenuron-methyl og

triasulfuron) ikke fundet udvasket til hverken dræn-, jord- eller grundvand i løbet af

den samlede moniteringsperiode.

•

16 udbragte stoffer, eller nedbrydningsprodukter fra disse, gav anledning til en

udvaskning gennem rodzonen til dræn og til sugeceller i den umættede zone

beliggende i ca. 1 m u.t. i gennemsnitskoncentrationer over 0,1 µg/l:

azoxystrobin

og dets nedbrydningsprodukt

CyPM

bentazon

CL153815

(nedbrydningsprodukt af picolinafen)

diflufenican og AE-B107103

pirimicarb-desmethyl-formamido

(nedbrydningsprodukt af pirimicarb)

propyzamid

tebuconazol

glyphosat

og dets nedbrydningsprodukt

AMPA

CGA 108906 og CGA 62826

(nedbrydningsprodukt af metalaxyl-M)

PPU (nedbrydningsprodukt af rimsulfuron)

bifenox-syre

(nedbrydningsprodukt af bifenox)

ethofumesat

TFMP

(nedbrydningsprodukt af fluazifop-P-butyl)

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metamitron

og dets nedbrydningsprodukt desamino-metamitron

desamino-diketo-metribuzin

diketo-metribuzin

(nedbrydningsprodukter af metribuzin)

terbuthylazin

og dets nedbrydningsprodukter

desethyl-terbuthylazin,

2-hydroxy-desethyl-terbuthylazin og 2-hydroxy-terbuthylazin.

For de pesticider eller nedbrydningsprodukter der er

fremhævet med kursiv

var

udvaskningen primært begrænset til 1 m u.t., hvor de blev fundet i dræn og

sugeceller. Selvom hovedparten af stofferne blev fundet i koncentrationer over 0,1

µg/l i grundvandsfiltrene, var antallet af overskridelser få (mindre end fem pr.

mark), og der var ikke tale om, at udvaskningen som årsgennemsnit var højere end

0,1 µg/l.

Pesticider

markeret med fed

blev udvasket til grundvandsfiltrene i en grad, så

Miljøstyrelsen har foretaget nye vurderinger med forbud eller anden regulering af

anvendelsen til følge.

•

Andre 18 stoffer gav anledning til mindre udvaskning. Selv om flere af disse stoffer

i 1 m u.t. ofte blev fundet i koncentrationer over 0,1 µg/l, var der ikke tale om, at

udvaskningen som årsgennemsnit var højere end 0,1 µg/l i dræn eller sugeceller.

Stofferne blev heller ikke fundet i grundvandsfiltrene i koncentrationer over 0,1

µg/l.

Bromid er anvendt som sporstof for at beskrive den nedadrettede vandtransport gennem

den variabelt mættede zone mod grundvandet, og der er mindst to gange tilført bromid

til de fem VAP marker. Bromid- og pesticidkoncentrationer bliver analyseret månedligt

i vandprøver udtaget i den variabelt-mættede zone og i den mættede zone, samt

ugentligt i prøver af drænvand.

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1 Introduction

There is growing public concern in Denmark about pesticide contamination of our

surface waters and groundwater. Pesticides and their degradation products have

increasingly been detected in groundwater during the past decade and are now present

in much of the Danish groundwater. Under the Danish National Groundwater

Monitoring Programme (GRUMO), pesticides have so far been detected in 52% of all

screens monitored and in 62% of the screens placed in the upper shallow groundwater

(Thorling, L. (ed.), 2013).

The detection of pesticides in groundwater over the past 20 years has caused to the

desire to enhance the scientific foundation for the existing approval procedure for

pesticides and to improve the present risk assessment tools. A main issue in this respect

is that the EU assessment, and hence also the Danish assessment of the risk of pesticide

leaching to groundwater, is largely based on data from modelling, laboratory or

lysimeter studies. However, these types of data may not adequately describe the

leaching that may occur under actual field conditions. Although models are widely used

within the registration process, their validation requires further work, not least because

of the limited availability of field data (Boesten, 2000). Moreover, laboratory and

lysimeter studies do not include the spatial variability of the soil parameters (hydraulic,

chemical, physical and microbiological soil properties) affecting pesticide leaching.

This is of particular importance for silty and loamy soils, where preferential transport

may have a major impact on pesticide leaching. In fact, various field studies suggest that

considerable preferential transport of several pesticides occurs to a depth of 1 m under

conditions comparable to those pertaining in Denmark (Kördel, 1997, Jacobsen & Kjær,

2007).

The inclusion of field studies, i.e. test plots exceeding 1 ha, in risk assessment of

pesticide leaching to groundwater is considered an important improvement to the risk

assessment procedures. For example, the US Environmental Protection Agency (US-

EPA) has since 1987 included field-scale studies in its risk assessments. Pesticides that

may potentially leach to the groundwater are required to be included in field studies as

part of the registration procedure. The US-EPA has therefore conducted field studies on

more than 50 pesticides (US Environmental Protection Agency, 1998). A similar

concept has also been adopted within the European Union (EU), where Directive

91/414/EEC, Annexe VI (Council Directive 97/57/EC of 22 September 1997) enables

field leaching study results to be included in the risk assessments.

1.1 Objective

In 1998, the Danish Government initiated the Pesticide Leaching Assessment

Programme (PLAP), an intensive monitoring programme with the purpose of evaluating

the leaching risk of pesticides under field conditions. The PLAP is intended to serve as

an early warning system providing decision-makers with advance warning if approved

pesticides leach in unacceptable concentrations. The programme focuses on pesticides

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used in arable farming and PLAP monitors leaching at five agricultural test sites

representative of Danish conditions.

The objective of the PLAP is to improve the scientific foundation for decision-making

in the Danish registration and approval procedures for pesticides, enabling field studies

to be included in risk assessment of selected pesticides. The specific aim is to analyze

whether pesticides applied in accordance with current regulations leach at levels

exceeding the maximum allowable concentration of 0.1µg/L.

1.2 Structure of the PLAP

The pesticides included in the PLAP were selected by the Danish EPA on the basis of

expert judgement. At present, 50 pesticides and 51 degradation products have been

included in the PLAP. All the compounds analyzed since 1999 are listed in Appendix 1.

Figure 1.1.

Location of the PLAP field sites

Tylstrup, Jyndevad, Silstrup, Estrup,

and

Faardrup.

Monitoring at

Slaeggerup was terminated on 1 July 2003.

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Soil type and climatic conditions are considered to be some of the most important

parameters controlling pesticide leaching. The PLAP initially encompassed six test sites

representative of the dominant soil types and the climatic conditions in Denmark

(Figure 1.1).

Monitoring at the Slaeggerup site was terminated on 1 July 2003, and the monitoring

results are reported in Kjær

et al.

(2003). The groundwater table is shallow at all the

field sites, thereby enabling pesticide leaching to groundwater to be rapidly detected

(Table 1.1). Cultivation of the PLAP sites is in line with conventional agricultural

practice in the vicinity. The pesticides are applied at maximum permitted doses and in

the manner specified in the regulations. Hence any pesticides or degradation products

appearing in the groundwater downstream of the sites can be related to the current

approval conditions pertaining to the individual pesticides. The five test sites

encompassed by the present report were selected and established during 1999.

Monitoring was initiated at Tylstrup, Jyndevad and Faardrup in 1999 and at Silstrup and

Estrup in 2000 (Table 1.1).

Table 1.1.

Characteristics of the five PLAP sites (modified from Lindhardt

et al.,

2001).

Tylstrup

Jyndevad

Silstrup

Location

Precipitation

(mm/y)

Pot. evapotransp. (mm/y)

Estrup

Askov

862

543

105 x 120

1.3

Yes

Apr 2000

1.1

Faardrup

Slagelse

558

585

150 x 160

2.3

Yes

Sep 1999

Glacier

Clayey till

1.5

4.2

7.2·10

-6

JB5/6

Sandy loam

14–15

6.4–6.6

1.4

1.2

Brønderslev

668

552

70 x 166

1.1

May 1999

Saltwater

>12

–

2.0·10

-5

JB2

Loamy sand

4–4.5

2.0

Tinglev

858

555

135 x 184

2.4

Sep 1999

Meltwater

5–9

10–12

–

1.3·10

-4

JB1

Sand

5.6–6.2

1.8

Thisted

866

564

91 x 185

1.7

Yes

Apr 2000

Glacier

Clayey till

1.3

3.4·10

-6

JB7

Sandy clay loam/

sandy loam

18–26

6.7–7

2.2

1.1

Width (m) x Lenght (m)

Area (ha)

Tile drain

Depths to tile drain (m b.g.s.)

Monitoring initiated

Geological characteristics

– Deposited by

– Sediment type

– DGU symbol

– Depth to the calcareous matrix

(m b.g.s.)

– Depth to the reduced matrix (m b.g.s.)

– Max. fracture depth

(m)

– Fracture intensity 3–4 m depth

(fractures/m)

– Ks in C horizon (m/s)

Topsoil characteristics

– DK classification

– Classification

– Clay content (%)

– Silt content (%)

– Sand content (%)

– pH

– TOC (%)

Glacier/meltwater

Clayey till

1–4

>6.5

8.0·10

-8

JB5/6

Sandy loam

10–20

20–27

50–65

6.5–7.8

1.7–7.3

Fine sand Coarse sand

Yearly normal based on a time series for the period 1961–90. The data refer to precipitation measured 1.5 m above

ground surface.

Large variation within the field.

Maximum fracture depth refers to the maximum fracture depth found in excavations and wells.

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Site characterization and monitoring design are described in detail in Lindhardt

et al.

(2001). The present report presents the results of the monitoring period May 1999–June

2013, but the main focus of this report is on the leaching risk of pesticides applied

during 2011-2013. For a detailed description of the earlier part of the monitoring

periods (May 1999–June 2011), see previous publications on http://pesticidvarsling.dk/-

publ_result-/index.html. Under the PLAP the leaching risk of pesticides is evaluated on

the basis of at least two years of PLAP monitoring data.

For some pesticides the present report must be considered preliminary because they

have been monitored for an insufficient length of time.

Hydrological modelling of the variably-saturated zone at each PLAP site supports the

monitoring data. The MACRO model (version 5.2), see Larsbo

et al.

(2005), was used

to describe the soil water dynamics at each site during the entire monitoring period from

May 1999–June 2013. The five site models have been calibrated for the monitoring

period May 1999–June 2004 and validated for the monitoring period July 2004–June

2013.

Scientifically valid methods of analysis are essential to ensure the integrity of the PLAP.

The field monitoring work has therefore been supported by intensive quality assurance

entailing continuous evaluation of the analyzes employed. The quality assurance

methodology and results are presented in Section 7.

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2 Pesticide leaching at Tylstrup

2.1

Materials and methods

2.1.1 Site description and monitoring design

Tylstrup is located in northern Jutland (Figure 1.1). The test field covers a cultivated

area of 1.2 ha (70 m x 166 m) and is practically flat, with windbreaks bordering the

eastern and western sides. Based on two soil profiles dug in the buffer zone around the

test field the soil was classified as a Humic Psammentic Dystrudept (Soil Survey Staff,

1999). The topsoil is characterised as loamy sand with 6% clay and 2.0% total organic

carbon (Table 1.1). The aquifer material consists of an approx. 20 m deep layer of

marine sand sediment deposited in the Yoldia Sea. The southern part is rather

homogeneous, consisting entirely of fine-grained sand, whereas the northern part is

more heterogeneous due to the intrusion of several silt and clay lenses (Lindhardt

et al.,

2001). The overall direction of groundwater flow is towards the west (Figure 2.1).

During the monitoring period the groundwater table was 2.6–4.5 m b.g.s. (Figure 2.2).

A brief description of the sampling procedure is provided in Appendix 2 and the

analysis methods in Kjær

et al.

(2002). The monitoring design and test site are described

in detail in Lindhardt

et al.

(2001). In September 2011, the monitoring system was

extended with three horizontal screens (H1) 4.5 m b.g.s. in the South-Eastern corner of

the field (Figure 2.1). A brief description of the drilling and design of H1 is given in

Appendix 8.

Figure 2.1.

Overview of the

Tylstrup

site. The innermost white area indicates the cultivated land, while the grey area

indicates the surrounding buffer zone. The positions of the various installations are indicated, as is the direction of

groundwater flow (by an arrow). Pesticide monitoring is conducted monthly and half-yearly from suction cups and

selected both vertical and horizontal monitoring screens as described in Table A2.1 in Appendix 2.

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2.1.2 Agricultural management

Management practice during the 2012-2013 growing seasons is briefly summarized

below and detailed in Appendix 3 (Table A3.1). For information about management

practice during the previous monitoring periods, see previous monitoring reports

available on http://pesticidvarsling.dk/publ_result/index.html.

Ploughing of the field was done on 22 March 2012 and 2 days later the field was sown

with spring barley (cv. TamTam), which emerged on 10 April. Spraying of weeds was

done twice: Bifenox was used on 21 May whereafter aminopyralid, florasulam and 2,4-

D were applied on 25 May.

sAminopyralid was subsequently included in the

monitoring. Monitoring of bifenox and it’s degradation products ended in December

2012. Irrigation was done once using 24 mm on 31 May.

Spraying of fungi was done on 28 June 2012, using epoxiconazole and boscalid of

which only the later was monitored. Monitoring of boscalid ended on 11 December

2012. On 13 August 2012 the barley was sprayed with glyphosate due to problems with

couch-grass (Agropyrum repens, L.). The glyphosate was not monitored. At harvest on

27 August 2012, 62.0 hkg/ha of grain (85% dry matter) and 37.3 hkg/ha of straw (100%

dry matter) was removed from the field.

After ploughing on 20 September 2012 the field was sown with winter rye (cv.

Magnifico) on 23 September, which emerged on 5 October. The herbicides prosulfocarb

was applied on 12 October 2012 and fluroxypyr on 8 May 2013. Only prosulfocarb is

monitored.

2.1.3 Model setup and calibration

The numerical model MACRO (version 5.2 Larsbo

et al.,

2005) was applied to the

Tylstrup site covering the soil profile to a depth of 5 m b.g.s., always including the

groundwater table. The model was used to simulate water and bromide transport in the

variably-saturated zone during the full monitoring period May 1999–June 2013 and to

establish an annual water balance.

Compared to Brüsch

et al.

(2013b), one additional year of validation was added to the

MACRO-setup for the Tylstrup site. The setup was hereby calibrated for the monitoring

period May 1999-June 2004 and “validated” for the monitoring period July 2004-June

2013. Daily time series of groundwater table measured in the piezometers located in the

buffer zone, soil water content measured at three different depths (25, 60 and 110 cm

b.g.s.) from the two profiles S1 and S2 (Figure 2.1) and the bromide concentration

measured in the suction cups located 1 and 2 m b.g.s. were used in the calibration and

validation process. Data acquisition, model setup and results related to simulated

bromide transport are described in Barlebo

et al.

(2007).

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Table 2.1.

Annual water balance for

Tylstrup

(mm y

-1

). Precipitation is corrected to soil surface according to the

method of Allerup and Madsen (1979).

Normal

Actual

Groundwater

precipitation

Precipitation

Irrigation

evapotranspiration

recharge

1.5.99–30.6.99

120

269

112

156

1.7.99–30.6.00

773

1073

498

608

1.7.00–30.6.01

773

914

487

502

1.7.01–30.6.02

773

906

570

416

1.7.02–30.6.03

773

918

502

439

1.7.03–30.6.04

773

758

472

287

1.7.04–30.6.05

773

854

477

434

1.7.05–30.6.06

773

725

488

304

1.7.06–30.6.07

773

1147

591

615

1.7.07–30.6.08

773

913

126

572

467

1.7.08–30.6.09

773

1269

600

695

1.7.09–30.6.10

773

867

424

470

1.7.10–30.6.11

773

950

506

501

1.7.11–30.6.12

773

923

501

446

1.7.12–30.6.13

773

803

528

275

Accumulated for a two-month period.

Normal values based on time series for 1961–1990.

Groundwater recharge is calculated as precipitation + irrigation - actual evapotranspiration.

2.2

Results and discussion

2.2.1 Soil water dynamics and water balances

The model simulations were generally consistent with the observed data, thus indicating

a good model description of the overall soil water dynamics in the variably-saturated

zone (Figure 2.2). The overall trends in soil water saturation were modelled

successfully, with the model capturing soil water dynamics at all depths (Figure 2.2 C-

E). During the last six hydraulic years excluding the latest spring period, the level in

water saturation at 25 cm b.g.s. has been overestimated and the initial decrease in water

saturation observed during the summer periods at 25, 60 and 110 cm b.g.s. has been less

well captured.

The dynamics of the groundwater table were well captured whereas the amplitude of the

fluctuations was not (Figure 2.2B).

The resulting annual water balance is shown for each hydraulic year of the monitoring

period (July–June) in Table 2.1. In the recent hydraulic year, July 2012–June 2013,

precipitation were in the low end of the range observed since monitoring began at the

site and the actual evapotranspiration in the high end, leaving the groundwater

recharge/percolation being the lowest compared to the other hydraulic years (Figure

2.2B). The monthly precipitation pattern for this year was low to medium compared

with earlier years. March 2013 was the driest month ever monitored with only 3 mm of

precipitation (Appendix 4). No artificial irrigation was however needed on the winter

rye.

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Precipitation & irrigation

May-99

May-00

May-01

May-02

May-03

May-04

May-05

May-06

May-07

Simulated percolation

May-08

May-09

May-10

May-11

May-12

May-13

Percolation (mm/d)

Precipitation (mm/d)

-1

GWT (m)

Measured, Average

Measured, Automatic P6

Measured, P8

Measured, Logger in P61

-2

-3

-4

-5

100

SW sat. (%)

0.25 m b.g.s.

SW sat. (%)

0.6 m b.g.s.

SW sat. (%)

-0

1.1 m b.g.s.

May-99

May-00

May-01

May-02

May-03

May-04

May-05

May-06

May-07

May-08

May-09

May-10

May-11

May-12

May-13

Simulated

Measured - S1

Measured - S2

Figure 2.2.

Soil water dynamics at

Tylstrup:

Measured precipitation, irrigation and simulated percolation 1 m b.g.s.

(A), simulated and measured groundwater level GWT (B), and simulated and measured soil water saturation (SW

sat.) at three different soil depths (C, D, and E). The measured data in B derive from piezometers located in the buffer

zone. The measured data in C, D, and E derive from TDR probes installed at S1 and S2 (Figure 2.1). The broken

vertical line indicates the beginning of the validation period (July 2004-June 2013).

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Bromide (mg/l)

Suction cups - S1

1 m b.g.s.

2 m b.g.s.

Bromide (mg/l)

Suction cups - S2

1 m b.g.s.

2 m b.g.s.

Jan-03

Nov-08

Nov-09

Nov-10

Nov-11

Figure 2.3.

Measured bromide concentration in the variably-saturated zone at

Tylstrup.

The measured data derive

from suction cups installed 1 m b.g.s. and 2 m b.g.s. at locations S1 (A) and S2 (B) indicated in Figure 2.1. The green

vertical lines indicate the dates of bromide applications.

2.2.2 Bromide leaching

Bromide has now been applied three times (1999, 2003 and 2012) at Tylstrup. The

bromide concentrations measured until April 2003 (Figure 2.3, Figure 2.4 and Figure

2.5) relate to the bromide applied in May 1999, as described further in Kjær

et al.

(2003). Unsaturated transport of the bromide applied in March 2003 is evaluated in

Barlebo

et al.

(2007).

Nov-12

Dec-03

Dec-04

Dec-05

Dec-06

Dec-07

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Bromide (mg/l)

3-4 m

4-5 m

5-6 m

6-7 m

7-8 m

8-9 m

Bromide (mg/l)

Nov-08

Nov-09

Nov-10

Nov-11

Figure 2.4.

Bromide concentration in the groundwater at

Tylstrup.

The data derive from monitoring wells M1–M5.

Screen depth is indicated in m b.g.s. The green vertical lines indicate the dates of bromide applications.

Bromide (mg/l)

Horizontal well

Mar-13

Jan-12

Apr-12

Dec-12

Oct-12

Feb-12

Sep-12

Feb-13

May-12

Figure 2.5.

Bromide concentration in the groundwater at

Tylstrup.

The data derive from horizontal monitoring well

H1. The green vertical lines indicate the date of bromide application.

May-13

Jul-12

Nov-12

Dec-03

Dec-04

Dec-05

Dec-06

Dec-07

Jan-03

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2.2.3 Pesticide leaching

Monitoring at Tylstrup began in May 1999 and encompasses the pesticides and

degradation products shown in Appendix 7. Pesticide applications during the latest

growing seasons are listed in Table 2.2 and are shown together with precipitation and

simulated precipitation in Figure 2.6.

It should be noted that precipitation in Table 2.2 is corrected to soil surface according to

Allerup and Madsen (1979), whereas percolation (1 m b.g.s.) refers to accumulated

percolation as simulated with the MACRO model. Pesticides applied later than April

2013 are not evaluated in this report and hence are not included in Table 2.2 and Figure

2.6.

The current report focuses on the pesticide applied from 2011 and onwards, while

leaching risk of pesticides applied before 2011 has been evaluated in previous

monitoring reports (see http://pesticidvarsling.dk/publ_result/index.html).

May

Aug

Nov

Mar

Dec

Apr

Sep

Feb

Oct

Jun

Jan

Jul

Precipitation (mm/d)

2011/2012

Precipitation (mm/d)

Precip

2,4-D (2012)

Epoxiconazole (2012)

Bromoxynil (2011)

Aminopyralid (2012)

Glyphosate (2012)

Ioxynil (2011)

Percol

Prosulfocarb (2012)

2012/2013

Boscalid (2011)

Florasulam (2012)

Bifenox (2012)

Epoxiconazole (2011)

Boscalid (2012)

Figure 2.6.

Application of pesticides included in the monitoring programme, precipitation and irrigation (primary

axis) together with simulated percolation 1 m b.g.s. (secondary axis) at

Tylstrup

in 2011/2012 (upper) and

2012/2013 (lower). Boscalid 2011 included application boscalid and epoxyconazol.

Percolation (mm/d)

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Table 2.2.

Pesticides analyzed at

Tylstrup.

Precipitation (precip.) and percolation (percol.) are accumulated within

the first year (Precip 1

year, Percol 1

year) and first month (Precip 1

month, Percol 1

month) after the first

application. C

mean

refers to average leachate concentration at 1 m b.g.s. the first year after application. See Appendix

2 for calculation method and Appendix 8 (Table A8.1) for previous applications of pesticides. (End monito) end of

monitoring of pesticide (P) or degradation product (M). Bifenox (Fox 480 SC) was applied May 2012, and analyzed

from May to December 2012.

Crop

Applied

Analyzed

Applica. End

Y 1

M 1

mean

Product

pesticide

date

monito. precip. percol. precip. percol.

Amistar

Azoxystrobin(P) Jun 08

Jun 11 1316 662

141

0 <0.01

Winter wheat 2008

CyPM(M)

Folicur EC 250 Tebuconazole(P)

Stomp

Spring barley 2009

Amistar

Azoxystrobin(P)

CyPM(M)

Basagran M75 Bentazone(P)

Potatoes 2010

Fenix

Titus WSB

Aclonifen(P)

PPU(M)

Jun 08

Nov 07

Jun 09

May 09

May 10

Jun 11 1316

Mar 10 1133

Dec 09 1032

Jun 11

Jun 12

Dec 12

Dec.12

Jun 13

909

996

958

981

934

959

803

852

507

662

461

415

475

488

491

499

514

467

338

335

285

141

138

133

128

127

106

100

121

<0.01

0.01-

0.02

<0.01

0.03-

0.12

<0.01-

0.02

<0.01

<0.02

<0.05

<0.01

<0.02

<0.01

Pendimethalin(P) Oct 07

PPU-desamino(M) May 10

Ranman

Cyazofamid(P)

Jun 10

Ridomil Gold Metalaxyl-M(P) Jul 10

MZ Pepite

CGA 108906(M) Jul 10

CGA 62826(M)

Spring barley 2011

Spring barley 2012

Bell

Fox 480 SC

Boscalid (P)

Bifenox(P)

Jul 10

Jun 11

May 12

Oct 12

Bifenox acid(M)

Nitrofen(M)

Mustang forte Aminopyralid(P)

Winter rye 2013

Boxer

Prosulfocarb(P)

Systematic chemical nomenclature for the analyzed pesticides is given in Appendix 1.

monitoring continues the following year.

Bifenox (Fox 480 SC) was applied May 2012, and analyzed from May to December 2012.

Leaching of metalaxyl-M applied in potatoes in 2010 was minor at Tylstrup. The

compound was only detected in four samples collected from the variably-saturated zone,

concentration level ranging from 0.018 to 0.03 µg/L (Figure 2.7). However, two degra-

dation products of metalaxyl-M (CGA62826 and CGA108906) leached from the root

zone (1 m b.g.s.), the latter in average concentrations exceeding 0.1 µg/L (Table 2.2 and

Figure 2.7). Both compounds were found in suction cups 1 m b.g.s. in 2010, 2011, 2012

and 2013 and the leaching of CGA108906 has not yet ceased. In the second monitoring

year CGA108906 was found in even higher concentrations in the suction cups, with

maximum concentrations of 2.5 and 4.8 µg/L in S1 and S2, respectively, but in the

monitoring period 2012-2013 the concentrations have fallen below 0.1 µg/L, Figure 2.7.

In the saturated zone neither metalaxyl-M nor CGA62826 was found in any samples

collected from the wells situated downstream the field site before spraying, whereas

both compounds were found in samples collected from M1 situated upstream of the

field site (Figure 2.8). As the tracer test suggested that water sampled in M1 had not

infiltrated at the PLAP site, but originated from the upstream neighbouring fields,

detections in M1 show that these compound have leached from previous application

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occurring at these upstream neighbouring fields, where metalaxyl and metalaxyl-M

have been applied (Brüsch et al., 2013, Appendix 7).

In the period April 2010 to June 2013, CGA108906 was found in 90% of the analyzed

groundwater samples. In 21% of the analyzed samples concentrations exceed 0.1 µg/L.

Similar to the other compounds, CGA108906 was detected in samples from the

upstream well M1. Moreover, it was present in the groundwater before metalaxyl-M

was applied at the PLAP field in June 2010. The background concentration of CGA

108906 found in the monitoring wells makes it difficult to determine, whether the

elevated concentrations observed in the downstream monitoring wells are due to the

metalaxyl-M applied on the PLAP field site in 2010 or to previous applications on the

upstream fields. However, the background concentration suggests that leaching of CGA

108906 occurs both from the test field as well as from neighbouring upstream fields.

Further, with a background level of CGA108906 ranging between 0.02–0.3 µg/L,

additional input via root zone leaching is likely to increase the frequency of exceedance

of the 0.1 µg/L in samples collected from the groundwater monitoring wells. Findings

of CGA 108109 in suction cups and in the new horizontal well H 1, Figure 2.7 and 2.8,

clearly indicate that the findings originate from the test field.

Metalaxyl-M, CGA 62826 and CGA 108906 were found in up to 83% of the

groundwater samples, and one of the degradation products, CGA108906, was found in

100% of the water samles from the variably-saturated zone (Table 2.3).

CGA108906 was found in concentrations up to 1.5 µg/L in downstream monitoring

wells after the application in 2010, Figure 2.8D.

Metalaxyl was on the Danish market from 1980-1995, with reported maximum allowed

dosage from 1984-1995 being 375 g a.i./ha. It re-entered the Danish marked in 2007 as

metalaxyl-M with a maximum allowed dosage of 77.6 g a.i./ha.

Since 2006 metalaxyl-M has been applied upstream neighbouring fields. The reported

dosages of these fields did not exceed the maximum allowed dosage of 77.6 g a.i./ha.

Usage data from 1980-1995 are not available, but information from local farmers

suggest that metalaxyl during this period was applied on some of the upstream

neighbouring fields during this period.

Table 2.3.

Findings of metalaxyl–M, CGA 62826 and CGA 108906 in groundwater samples, and in water samples

from suction cups in the variably-saturated zone,

Tylstrup.

Data from June 2011 to June 2013.

June 2011- June 2013

Number of samples

in %

Groundwater Metalaxyl -M

CGA 62826

CGA 108906

Variably-

Metalaxyl -M

saturated

CGA 62826

zone

CGA 108906

Analyzed > D. L. ≥ 0.1 µg/L 0.01/0.02–0.1µg/L

146

4.8

146

9,6

146

121

67.1

21,9

89.1

≥ 0.1 µg/L Total

4.8

9.6

15.8

82.9

4,7

26.6

10.9

100

D.L. – detection limit: Metalaxyl-M - 0.01 µg/L, degradation products – 0.02 µg/l.

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Precipitation & irrigation

Simulated percolation

Mar/11

Mar/12

Precipitation (mm/d)

Mar/13

Apr/10

Sep/10

Sep/11

Sep/12

Percolation (mm/d)

10.0

Pesticide (µg/l)

1.0

0.1

0.0

Suction cups - S1

1 m b.g.s

10.0

Pesticide (µg/l)

1.0

0.1

0.0

10.0

Suction cups - S1

2 m b.g.s

Pesticide (µg/l)

1.0

0.1

0.0

10.0

Suction cups - S2

1 m b.g.s

Pesticide (µg/l)

1.0

0.1

0.0

Suction cups - S2

2 m b.g.s

Mar/11

Mar/12

Mar/13

Dec/10

Dec/11

Dec/12

Apr/10

Sep/10

Sep/11

Sep/12

Jun/11

Jun/12

Metalaxyl-M

CGA 62826

CGA 108906

Figure 2.7.

Precipitation, irrigation and simulated percolation 1 m b.g.s. (A) together with measured concentration of

metalaxyl-M, CGA62826

and

CGA108906

(µg/L) in suction cups installed at location S1 at 1 m b.g.s. (B) and 2 m

b.g.s. (C) and location S2 at 1 m b.g.s. (D) and 2 m b.g.s. (E) at

Tylstrup.

The green vertical line indicates the date of

pesticide application.

Jun/13

Jul/10

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Precipitation & irrigation

Simulated percolation

Mar/11

Mar/12

Mar/13

Apr/10

Sep/10

Sep/11

Sep/12

Precipitation (mm/d)

1.0

0.1

0.0

1.0

0.1

0.0

CGA 108906

CGA 62826

Pesticide (µg/l)

Metalaxyl-M

(

detections only

)

(

detections only

)

Pesticide (µg/l)

10.0

1.0

0.1

0.0

(

detections only

)

Mar/11

Mar/12

Mar/13

Dec/10

Dec/11

Dec/12

Apr/10

Sep/10

Sep/11

Sep/12

M1.3

M4.3

M5.2

M1.4

M4.4

M5.3

Jun/11

M3.3

M4.5

M5.4

M3.4

M4.6

Jun/12

M4.2

M4.7

Figure 2.8.

Precipitation, irrigation and simulated percolation 1 m b.g.s. (A) together with measured concentration of

metalaxyl-M

(B),

CGA62826

CGA108906

(D) (µg/L) in horizontal and monitoring wells at

Tylstrup.

The

green vertical line indicates the date of pesticide application.

Based on the available data it is concluded that residues detected in the groundwater are

most likely to derive from current usage of metalaxyl-M allowed since 2007 and not

previous usage of metalaxyl allowed from 1980–1995. With an average travel time to

all monitoring wells being less than four years (Appendix 9) it is unlikely that water

sampled from these screens have infiltrated the variably-saturated zone before 1995. A

possibility could, however, be that the residues originating from the initial usage of 375

g a.i./ha (allowed in 1980-1995) were left in the soil and continued to leach during a

long period of time. Should this be the case the persistency of these compounds would

be very high, allowing them to leach more than a decade after application. This

Jun/13

Jul/10

Percolation (mm/d)

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assumption does not correspond with the regulatory assessment, where final endpoints

for DT

were less than 18 days (Danish EPA, 2007).

Boscalid was applied to spring barley in June 2011 and 2012. There have been no

findings neither the saturated nor in the variably-saturated zone in Tylstrup between

April 2011 and until the monitoring stopped in December 2012.

Aminopyralid was applied on spring barley in May 2012. In the monitoring period there

have been no detections in the variably-saturated zone or in the groundwater.

Prosulfocarb was applied on winter rye October 2012, and there have been four findings

in groundwater, all below 0.1 µg/L. Prosulfocarb was not found in the variably-

saturated zone.

Bifenox was applied on spring barley in May 2012. The monitoring of bifenox and the

two degradation products stopped in December 2012 after bifenox was taken from the

market. Bifenox and the two degradation products were not found in concentrations

exceeding the detection limits.

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3 Pesticide leaching at Jyndevad

3.1

Materials and methods

3.1.1 Site description and monitoring design

Jyndevad is located in southern Jutland (Figure 1.1). The test site covers a cultivated

area of 2.4 ha (135 x 184 m) and is practically flat. A windbreak borders the eastern side

of the test site. The area has a shallow groundwater table ranging from 1 to 3 m b.g.s.

(Figure 3.2B) The overall direction of groundwater flow is towards the northwest

(Figure 3.1). The soil can be classified as Arenic Eutrudept and Humic Psammentic

Dystrudept (Soil Survey Staff, 1999) with coarse sand as the dominant texture class and

topsoil containing 5% clay and 1.8% total organic carbon (Table 1.1). The geological

description points to a rather homogeneous aquifer of meltwater sand, with local

occurrences of thin clay and silt beds. A brief description of the sampling procedure is

provided in Appendix 2 and the analysis methods in Kjær et al. (2002). The monitoring

design and test site are described in detail in Lindhardt et al. (2001). In September 2011,

the monitoring system was extended with three horizontal screens (H1) 2.5 m b.g.s. in

the South-Eastern corner of the field (Figure 3.1). A brief description of the drilling and

design of H1 is given in Appendix 8.

3.1.2 Agricultural management

Management practice during the 2012-2013 growing seasons is briefly summarized

below and detailed in Appendix 3 (Table A3.2). For information about management

practice during the previous monitoring periods, see previous monitoring reports

available on http://pesticidvarsling.dk/publ_result/index.html.

Ploughing of the field was done on 30 March 2012 followed by sowing of maize (cv.

Atrium) on 3 May. The maize emerged on 17 May. Spraying of weeds was done thrice

using bentazone on 26 May, mesotrione on 5 June, as well as fluroxypyr, florasulam,

and 2,4-D on 15 June. Mesotrione and two of its degradation products, as well as

bentazone were included in the monitoring. On 8 October 2012, 151.4 hkg/ha (100%

dry matter) of whole crop maize was harvested.

The field was ploughed 6 April 2013 and a crop of pea (cv. Alvesta), were sown on 14

April and emerged on 26 April. The herbicides, pendimethaline and bentazone were

applied twice; on 7 and 16 May 2013. Only the bentazone was included in the

monitoring programme. Irrigation of the pea was done twice, using 30 mm on both 6

June and 9 July.

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Figure 3.1.

Overview of the

Jyndevad

site. The innermost white area indicates the cultivated land, while the grey

area indicates the surrounding buffer zone. The positions of the various installations are indicated, as is the direction

of groundwater flow (by an arrow). Pesticide monitoring is conducted monthly and half-yearly from selected

horizontal and vertical monitoring screens and suctions cups as described in Table A2.1 in Appendix 2.

3.1.3 Model setup and calibration

The numerical model MACRO (version 5.2, Larsbo

et al.,

2005) was applied to the

Jyndevad site covering the soil profile to a depth of 5 m b.g.s., always including the

groundwater table. The model was used to simulate water flow and bromide transport in

the variably-saturated zone during the full monitoring period July 1999–June 2013 and

to establish an annual water balance.

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May-99

May-00

May-01

May-02

May-03

May-04

May-05

May-06

May-07

May-08

May-09

May-10

May-11

May-12

Precipitation (mm/d)

May-13

Percolation (mm/d)

-1

GWT (m)

-2

-3

-4

-5

0.25 m b.g.s.

Measured, Average

Measured, Automatic P11

Measured, P9

Logger P11.2

SW sat. (%)

0.6 m b.g.s.

SW sat. (%)

1.1 m b.g.s.

SW sat. (%)

May-99

May-00

May-01

May-02

May-03

May-04

May-05

May-06

May-07

May-08

May-09

May-10

May-11

May-12

Simulated

Measured - S1

Measured - S2

Figure 3.2.

Soil water dynamics at

Jyndevad:

Measured precipitation, irrigation and simulated percolation 1 m b.g.s.

(A), simulated and measured groundwater level (B), and simulated and measured soil water saturation (SW sat.) at

three different soil depths (C, D and E). The measured data in B derive from piezometers located in the buffer zone.

The measured data in C, D and E derive from TDR probes installed at S1 and S2 (Figure 3.1). The broken vertical

line indicates the beginning of the validation period (July 2004-June 2013).

May-13

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Compared with the setup in Brüsch

et al.

(2013b), a year of validation was added to the

MACRO-setup for the Jyndevad site. The setup was hereby calibrated for the

monitoring period May 1999-June 2004, and validated for the monitoring period July

2004-June 2013. For this purpose, the following time series have been used: the

groundwater table measured in the piezometers located in the buffer zone, soil water

content measured at three different depths (25, 60 and 110 cm b.g.s.) from the two

profiles S1 and S2 (location indicated at Figure 3.1), and the bromide concentration

measured in the suction cups located 1 and 2 m b.g.s. (Figure 3.3). Data acquisition,

model setup as well as results related to simulated bromide transport are described in

Barlebo

et al.

(2007).

3.2

Results and discussion

3.2.1 Soil water dynamics and water balances

The model simulations were generally consistent with the observed data, thus indicating

a good model description of the overall soil water dynamics in the variably-saturated

zone (Figure 3.2). The dynamics of the simulated groundwater table were well

described with MACRO 5.1 (Figure 3.2B). No measurements of the water saturation

were obtained during the following two periods: 1 June to 25 August 2009 (given

degradation in the TDR measuring system) and 7 February to 6 March 2010 (given a

sensor error). As noted earlier in Kjær

et al.

(2011), the model still had some difficulty

in capturing the degree of soil water saturation 1.1 m b.g.s. (Figure 3.2E) and also the

decrease in water saturation observed during summer periods at 25 and 60 cm b.g.s. A

similar decrease in water saturation is observed from December 2010 to February 2011

at 25 cm b.g.s., which is caused by precipitation falling as snow (air-temperature below

0°C). The water flow through the soil profile will hereby be delayed – a delay, which

cannot be captured by the MACRO-setup.

The resulting water balance for Jyndevad for all the monitoring periods is shown in

Table 3.1. Compared with the previous thirteen years, the latest hydraulic year, July

2012-June 2013, was characterised by having low precipitation, low simulated actual

evapotranspiration, low irrigation values and low groundwater recharge. Monthly

precipitation in the latest hydraulic year was characterised as being low to medium and

March was being the driest month monitored at this site with only 13 mm of

precipitation (Appendix 4). Artificial irrigation was however only needed twice during

summer with pea being sown in April. Continuous percolation 1 m b.g.s. was simulated

for this hydraulic year.

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Table 3.1.

Annual water balance for

Jyndevad

(mm yr

-1

). Precipitation is corrected to the soil surface according to

the method of Allerup and Madsen (1979).

Normal

Actual

Groundwater

Precipitation

Irrigation

Evapotranspiration

Recharge

1.7.99–30.6.00

995

1073

500

602

1.7.00–30.6.01

995

810

461

349

1.7.01–30.6.02

995

1204

545

740

1.7.02–30.6.03

995

991

415

627

1.7.03–30.6.04

995

937

432

531

1.7.04–30.6.05

995

1218

578

727

1.7.05–30.6.06

995

857

117

490

484

1.7.06–30.6.07

995

1304

114

571

847

1.7.07–30.6.08

995

1023

196

613

605

1.7.08–30.6.09

995

1078

551

610

1.7.09–30.6.10

995

1059

530

610

1.7.10–30.6.11

995

1070

554

607

1.7.11–30.6.12

995

1159

490

699

1.7.12–30.6.13

995

991

478

572

Normal values based on time series for 1961-1990.

Groundwater recharge is calculated as precipitation + irrigation - actual evapotranspiration

3.2.2 Bromide leaching

Bromide has now been applied three times at Jyndevad. The bromide concentrations

measured until April 2003 (Figure 3.3, Figure 3.4 and Figure 3.5) relate to the bromide

applied in autumn 1999, as described further in Kjær

et al.

(2003). Leaching of the

bromide applied in March 2003 is evaluated in Barlebo

et al.

(2007).

Bromide (mg/l)

Suction cups - S1

1 m b.g.s.

2 m b.g.s.

Bromide (mg/l)

Suction cups - S2

1 m b.g.s.

2 m b.g.s.

Jan-03

Nov-08

Nov-09

Nov-10

Nov-11

Figure 3.3.

Bromide concentration in the variably-saturated zone at

Jyndevad.

The measured data derive from

suction cups installed 1 m b.g.s. (upper) and 2 m b.g.s. (lower) at locations S1 and S2 (Figure 3.1). The green vertical

lines indicate the dates of bromide applications.

Nov-12

Dec-03

Dec-04

Dec-05

Dec-06

Dec-07

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Bromide (mg/l)

1-2 m

2-3 m b.g.s.

3-4 m b.g.s.

4-5 m b.g.s.

Bromide (mg/l)

Nov-08

Nov-09

Nov-10

Nov-11

Figure 3.4.

Bromide concentration in the groundwater at

Jyndevad.

The data derive from monitoring wells M1, M2,

M4, M5, and M7. Screen depth is indicated in m b.g.s. The green vertical lines indicate the dates of bromide

applications.

Bromide (mg/l)

Horizontal well

Mar-13

Jan-12

Apr-12

Dec-12

Oct-12

Feb-12

Sep-12

Feb-13

May-12

Figure 3.5

Bromide concentration in the groundwater at

Jyndevad.

The data derive from the horizontal monitoring

well H1. The green vertical line indicates the date of bromide application.

May-13

Jul-12

Nov-12

Dec-03

Dec-04

Dec-05

Dec-06

Dec-07

Jan-03

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May

Aug

Nov

Mar

Dec

Apr

Sep

Feb

Oct

Jun

Jan

Jul

Precipitation (mm/d)

2011/2012

Precipitation (mm/d)

Precipitation

Bentazone (2012)

Bromoxynil (2011)

Diflufenican (2011)

Ioxynil (2011)

2012/2013

2,4-D (2012)

Fluroxypyr (2012)

Simulated percolation Florasulam (2012)

Mesotrione (2012)

Figure 3.6.

Application of pesticides included in the monitoring programme, precipitation and irrigation (primary

axis) together with simulated percolation 1 m b.g.s. (secondary axis) at

Jyndevad

in 2011/2012 (upper) and

2012/2013 (lower).

3.2.3 Pesticide leaching

Monitoring at Jyndevad began in September 1999 and encompasses the pesticides and

degradation products, as indicated in Appendix 7. Pesticide application during the most

recent growing seasons is listed in Table 3.2 and shown together with precipitation and

simulated precipitation in Figure 3.6. It should be noted that precipitation is corrected to

the soil surface according to Allerup and Madsen (1979), whereas percolation (1 m

b.g.s.) refers to accumulated percolation as simulated with the MACRO model (Table

3.2). Pesticides applied later than May 2013 are not evaluated in this report and not

included in Table 3.2.

The current report focuses on the pesticides applied from 2011 and onwards, while

leaching risk of pesticides applied before 2011 has been evaluated in previous

monitoring reports (see http://pesticidvarsling.dk/publ_result/index.html).

Percolation (mm/d)

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Table 3.2.

Pesticides analyzed at

Jyndevad.

Precipitation (precip.) and percolation (percol.) are accumulated within

the first year (Precip 1

year, Percol 1

year) and first month (Precip 1

month, Percol 1

month) after the first

application. C

mean

refers to average leachate concentration at 1 m b.g.s. the first year after application. See Appendix

2 for calculation method and Appendix 8 (Table A8.2) for previous applications of pesticides. (End monito.) end of

monitoring of pesticide (P) or degradation product (M).

Crop

Applied

Analyzed

Applica. End Y 1

Y 1

M 1

mean

product

pesticide

date

monito. precip. percol. precip. percol.

Atlantis WG Mesosulfuron-

Oct 06 Dec 09 1346 809

<0.01

Triticale 2007

methyl(P)

Mesosulfuron(M) Oct 06 Dec 09 1346 809

<0.02

Cycocel 750

Opus

Pico 750 WG

Bell

Fox 480 SC

Potatoes 2010

Fenix

Ranman

Titus WSB

Ridomil Gold

MZ Pepite

Chlormequat(P)

Apr 07 Jun 08 1223

Dec 07 Mar 10 1396

Oct 07

Mar 10 1418

638

644

827

777

630

567

627

592

613

742

512

513

123

144

164

106

123

125

137

161

126

109

114

<0.01

<0.01-0.04

<0.01

<0.02

<0.05

<0.01

0.02

<0.01

0.02

0.37-0.6

0.16-0.19

<0.01

0.04-0.24

0.01-0.09

Epoxiconazole(P) May 07 Dec 09 1193

Picolinafen(P)

CL153815(M)

Winter wheat 2008

Folicur EC 250 Tebuconazole(P)

Spring barley 2009

Basagran M75 Bentazone(P)

Bifenox(P)

Bifenox acid(M)

Nitrofen(M)

Aclonifen(P)

Cyazofamid(P)

PPU(M)

Metalaxyl-M(P)

CGA108906(M)

CGA62826(M)

Spring barley 2011

DFF

Diflufenican(P)

AE-B107137(M)

Maize 2012

Callisto

Fighter 480

Peas 2013

May 09 Jun 12 1178

Apr 09 Jun 12 1206

May 10 Jun 12 1149

Jun 10

Jul 10

Jun 12 1188

Jun12

Jun13

1160

1073

1315

Epoxiconazole(P) May 09 Dec 09 1181

PPU-desamino(M) Jun 10

Apr 11 Jun13

AE-05422291(M) Apr 11 Jun13

Mesotrione (P)

AMBA(M)

MNBA(M)

Bentazone(P)

Apr 11 Jun 13 1315

Jun 12

Jun 13

993

Jun 13

993

Jun 13

993

Jun 13

994

Fighter 480

May 13 Jun 13 220

Systematic chemical nomenclature for the analyzed pesticides is given in Appendix.

mean

is only calculated from suction cups S1(see text).

Bentazone applied on 7May and 16 May.

monitoring continues the following year.

In Table 3.2 weighted average concentrations 1 m b.g.s. (C

mean

) is calculated from both

S1 and S2. When these values are reported as a range it indicates that C

mean

in S1 and S2

differs from each other. During the monitoring period 2011/2012 it was unfortunately

not possible to extract sufficient water from S2 to perform all pesticide analyzes. For

some of the compounds (metalaxyl-M, PPU, PPU-desamino) there was not sufficient

data to calculate weighted leachate concentration, why reported 2010 values in Table

3.2 refers to suction cups S1 only. For the same reason concentration of CGA62826 and

CGA108906 in S2 was not measured in S2 during the first months after applications.

The calculated concentration of CGA62826 and CGA108906 was 0.16-0.19 and 0.37-

0.6, respectively (Table 3.2) and refers to average leaching concentration from date of

first analysis on 4 November 2010 until 1 July 2011.

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Precipitation & irrigation

Simulated percolation

Mar/11

Mar/12

Precipitation (mm/d)

Mar/13

Apr/10

Sep/10

Sep/11

Sep/12

Percolation (mm/d)

2.0

monitoring wells

detections only

Metalaxyl-M

Pesticide (µg/l)

1.5

1.0

0.5

0.0

2.0

1.5

1.0

0.5

0.0

2.0

1.5

monitoring wells

detections only

CGA 62826

Pesticide (µg/l)

monitoring wells

detections only

CGA 108906

Pesticide (µg/l)

1.0

0.5

0.0

Mar/11

Mar/12

Mar/13

Dec/10

Dec/11

Dec/12

Apr/10

Sep/10

Sep/11

Sep/12

Jun/11

Jun/12

M1 (0.6-1.6)

M2 (1.9-2.9)

M4 (3.3-4.3)

M7 (1.6-2.6)

M1 (1.6-2.6)

M2 (2.9-3.9)

M5.1 (1.7-2.7)

M7 (2.6-3.6)

M1 (2.6-3.6)

M4 (1.4-2.4)

M5 (2.7-3.7)

M7 (3.6-4.6)

M2.1 (0.9-1.9)

M4 (2.4-3.4)

M5 (3.7-4.7)

Horizontal H1

Figure 3.7.

Precipitation, irrigation and simulated percolation 1 m b.g.s. in Jyndevad. (A) together with measured

concentrations (µg/L) in downstream (M1, M2, M4 and H1) and upstream horizontal and monitoring wells (M7) of

metalaxyl-M

(B), CGA 62826 (C) and CGA 108906 (D) at

Jyndevad.

The numbers in parentheses indicate the

depths of the analyzed screens. The green vertical line indicates the date of pesticide application.

Jun/13

Jul/10

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Both metalaxyl-M applied on potatoes in July 2010 as well as two of its degradation

product CGA62829 and CGA108909 leached from the root zone (1 m b.g.s.) - the two

latter in average concentrations exceeding 0.1 µg/L (Table 3.2, Figure 3.7 and Figure

3.8). Both degradation products were found in water from suction cups 1 m b.g.s. at the

end of the last monitoring period, indicating that leaching had not yet ceased.

Results from the saturated zone suggested that previous application occurring at up

stream neighbouring fields also have induced leaching to the groundwater of metalaxyl-

M, CGA62826 and CGA108906. All three compounds were present in the groundwater

before metalaxyl-M was applied to the field. They were also detected in water collected

from M7 situated upstream of the test field (Figure 3.7). CGA108906 was also found in

M5 located north of the field. The tracer test suggested that water sampled in M7 and

M5 (uppermost three filters) had not infiltrated at the PLAP site, but originated from the

upstream neighbouring fields, where metalaxyl-M have also been applied (Brüsch et al.,

2013).

CGA 62826 and CGA 108906 were detected in approximately 80% of the samples from

the variably-saturated zone and in up to 75% of the groundwater samples (Table 3.3).

Table 3.3.

Findings of metalaxyl–M, CGA 62826 and CGA 108906 in groundwater samples, and in water samples

from suction cups in the variably-saturated zone,

Jyndevad.

Data from June 2011 to June 2013.

June 2011- June 2013

Number of samples

in %

Groundwater Metalaxyl -M

CGA 62826

CGA 108906

Variably-

Metalaxyl -M

saturated

CGA 62826

zone

CGA 108906

Analyzed > D. L. ≥ 0.1 µg/L 0.01/0.02–0.1µg/L ≥ 0.1 µg/L

146

11.6

12.3

147

36.1

5.4

147

109

45.6

28.6

8.3

65.2

17.4

41.3

37.0

Total

41.5

74.1

8.3

82.6

78.3

D.L. – detection limit: Metalaxyl-M - 0.01 µg/L, degradation products – 0.02 µg/l.

The background concentration of CGA108906, found in water from all monitoring

wells, makes it difficult to determine, whether the elevated concentrations observed in

downstream monitoring wells during the two year monitoring period, are due to the

metalaxyl-M applied on the PLAP test site in 2010, or to previous application on the

upstream fields. However, with a background level of CGA 108906 ranging between

0.014–0.14 µg/L additional, input via root zone leaching is likely to increase

groundwater concentration and by this the frequency of exceedance of the 0.1 µg/L in

collected groundwater samples.

In the horizontal well, H1, CGA 108906 was found in 15 analyzed samples between

March 2012 and October 2013 in concentrations from 0.03-0.24 µg/L (Figure 3.7). The

average concentration was 0.11 µg/L. The findings in mixed samples from three screens

in the horizontal well indicate clearly that CGA 108906 originate from the test field.

Metalaxyl-M was detected in water from the upstream groundwater monitoring well M7

in high concentrations reaching 0.68 µg/L, but it was not detected in water from the

downstream groundwater monitoring wells. Metalaxyl-M was found in 12 water

samples, collected from the horizontal well H1, had concentrations reaching 1.3 µg/L in

June 2012. CGA62826 was only found in small concentrations in water from the

vertical groundwater wells, whereas it was found in increasing concentrations (between

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0.11µg/L and 0.68 µg/L) in water from H1 in the same period (March 2012 to June

2012). In the following period (July 2012 to June 2013) CGA62826 was found in all

eight analyzed water samples from H1, maximum being 0.24 µg/L in May 2013.

Metalaxyl was on the Danish market from 1980-1995, in a maximum allowed dosage

from 1984-1995 of 375 g a.i./ha. It was then banned, but re-entered the Danish marked

in 2007 as metalaxyl-M with a maximum allowed dosage of 77.6 g a.i./ha. Since 2006

metalaxyl-M was applied at upstream neighbouring fields, where reported dosage did

not exceed the maximum allowed dosage of 77.6 g a.i./ha, but evidence of higher

dosage used in the period 1988 to 1993 was also reported. For putting the results into a

regulatory context it would thus be important to assess, if the pesticide residues

measured in groundwater originate from the initial high usage of 375 g a.i/ha, allowed

in 1980-1995, or from the current usage of 77.6 g a.i/ha, allowed since 2007. With an

average travel time to all monitoring wells being less than 3 years (Appendix 9) it is

unlikely that water sampled from these screens have infiltrated from the variably-

saturated zone before 1995, 17 years ago. Based on available data, it is likely that the

residues detected in the groundwater originate from the current usage of metalaxyl-M

(allowed since 2007) and not the initial usage allowed from 1980–1995.

Precipitation & irrigation

Simulated percolation

Mar/11

Mar/12

Mar/13

Apr/10

Sep/10

Sep/11

Sep/12

Precipitation (mm/d)

10.0

Pesticide (µg/l)

1.0

0.1

Suction cups - S1

1 m b.g.s

0.0

10.0

Pesticide (µg/l)

1.0

0.1

0.0

Suction cups - S2

1 m b.g.s

Mar-11

Mar-12

Mar-13

Dec-10

Dec-11

Dec-12

Apr-10

Sep-10

Sep-11

Sep-12

Metalaxyl-M

Jun-11

CGA 62826

Jun-12

CGA 108906

Figure 3.8.

Precipitation, irrigation and simulated percolation 1 m b.g.s. (A) together with measured concentrations

Metalaxyl-M,

CGA 62826 and CGA 108906 at

Jyndevad.

The green vertical line indicates the date of pesticide

application

Jun-13

Jul-10

Percolation (mm/d)

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Precipitation & irrigation

Simulated percolation

Aug/12

Mar/12

Dec/12

Apr/12

Apr/13

Feb/13

Oct/12

Jun/12

Jun/13

Jan/12

Precipitation (mm/d)

10.0

Pesticide (µg/l)

Bentazone

1.0

0.1

0.0

Aug-12

Mar-12

Dec-12

Apr-12

Apr-13

Feb-13

Oct-12

Jun-12

Suction cups - S1 1 m.b.g.s.

Suction cups - S2 1 m.b.g.s.

Horizontal H1

Figure 3.9.

Precipitation, irrigation and simulated percolation 1 m b.g.s. (A) together with measured concentrations

of bentazone in suction cups S1 and S2 and horizontal well H1 at

Jyndevad.

The green vertical lines indicate the

dates of bentazone application.

A possibility could however be that the residues originating from the initial usage of

375 g a.i./ha (allowed in 1980-1995) were left in the soil and continued to leached

during a long period of time. Should this be the case, the persistency of these

compounds would be very high, allowing them to leach more than a decade after

application. An assumption not corresponding to the regulatory assessment, reporting

the final endpoints for DT

to be less than 18 days (Danish EPA, 2007).

Bentazone was not detected in any of the samples from the vertical monitoring wells,

whereas 0.01 µg/L was found in H1 on 14 February 2013, after the application on maize

in June 2012.

However, it was found frequently in samples from suction cups, reaching a maximum of

1.9 µg/L in September 2012 (Figure 3.9.b). The bentazone leached from the variably-

saturated zone in average concentrations between 0.04 and 0.24µg/L. Except for one

groundwater sample containing 0.01 µg/L collected September 2008, epoxiconazole did

not leach at Jyndevad.

Diflufenican, used in spring barley in 2011, and two of its degradation products AE-

05422291 and AE-B107137, were not detected in the variably-saturated zone or

saturated zone between April 2011 and June 2013.

Mesotrione was applied on maize in June 2012, and neither mestotrione nor two of its

degradation products AMBA and MNBA were detected in water samples from the

variably-saturated or saturated zone.

Jun-13

Jan-12

Percolation (mm/d)

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4 Pesticide leaching at Silstrup

4.1

Materials and methods

4.1.1 Site description and monitoring design

The test field at Silstrup is located south of the city Thisted in North-Western Jutland

(Figure 1.1). The cultivated area is 1.7 ha (91 x 185 m) and slopes gently 1–2° to the

north (Figure 4.1). Based on two profiles excavated in the buffer zone bordering the

field the soil was classified as Alfic Argiudoll and Typic Hapludoll (Soil Survey Staff,

1999). The topsoil content of clay in the two profiles was 18% and 26%, and the organic

carbon content was 3.4% and 2.8%, respectively (Table 1.1). The geological description

showed rather homogeneous clay till rich in chalk and chert, containing 20–35% clay,

20–40% silt and 20–40% sand. In some intervals the till was sandier, containing only

12–14% clay. Moreover, thin lenses of silt and sand were found in some of the wells.

The gravel content was approx. 5%, but could be as high as 20%. A brief description of

the sampling procedure is provided in Appendix 2 and the analysis methods in Kjær et

al. (2002). The monitoring design and test site are described in detail in Lindhardt et al.

(2001). In September 2011, the monitoring system was extended with three horizontal

screens (H3) 2 m b.g.s. in the North-Eastern corner of the field (Figure 4.1) - one of the

screens should be located just below the drain line (a lateral) 1.1 m b.g.s and two

screens between the laterals. A brief description of the drilling and design of H3 is given

in Appendix 8.

4.1.2 Agricultural management

Management practice during the 2012-2013 growing seasons is briefly summarized

below and detailed in Appendix 3 (Table A3.3). For information about management

practice during the previous monitoring periods, see previous reports available on

http://pesticidvarsling.dk/publ_result/index.html.

The crop of the field was a third year crop of red fescue (cv. Jasperina) that had been

under sown in spring barley on 11 April 2009. After trimming of the grass on 17 August

2011 the field was sprayed with the herbicide bifenox on 16 September. Pig slurry was

applied in the autumn, on 5 October 2011. Spraying against weeds was done twice using

diflufenican on 13 April and fluazifop-P-butyl on 19 April 2012, both compounds

included in the monitoring. The fungicide tebuconazole was applied on 18 May 2012,

and its degradation product 1,2,4-triazol, was planned included in the monitoring

programme, but problems in the analytical method development, meant that 1,2,4-

triazol was omitted from the program until next monitoring year.

An amount of 14.16 hkg/ha of grass seed (87% dry matter) was harvested and 48.3

hkg/ha of straw (100% dry matter) removed from the field on 25 July 2012. The grass

field was desiccated on 10 September 2012 using glyphosate. Ploughing was done 8

October 2012 and the following day the field was sown with winter wheat (cv.

Hereford), which emerged on 24 October. Spraying of weeds was done on 9 November

2012 using ioxynil, bromoxynil and diflufenican of which only the latter was included

in the monitoring.

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Due to a combination of late sowing as well as harsh winter conditions, very few winter

wheat plants survived, and the winter wheat was therefore replaced by a crop of spring

barley (cv. Quenc) sown on 3 May 2013 and emerging on 16 May.

Figure 4.1.

Overview of the

Silstrup

site. The innermost white area indicates the cultivated land, while the grey area

indicates the surrounding buffer zone. The positions of the various installations are indicated, as is the direction of

groundwater flow (by an arrow). Pesticide monitoring is conducted weekly from the drainage system (during period

of continuous drainage runoff) and monthly and half-yearly from selected vertical and horizontal monitoring screens

as described in Table A2.1 in Appendix 2

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4.1.3 Model setup and calibration

Compared with the setup in Brüsch

et al.

(2013b), a year of validation was added to the

MACRO setup for the Silstrup site. The setup was hereby calibrated for the monitoring

period May 1999-June 2004 and validated for the monitoring period July 2004-June

2013. For this purpose, the following time series have been used: the observed

groundwater table measured in the piezometers located in the buffer zone, soil water

content measured at three depths (25, 60 and 110 cm b.g.s.) from the two profiles S1

and S2 (Figure 4.1), and the measured drainage flow. Data acquisition, model setup and

results related to simulated bromide transport are described in Barlebo

et al.

(2007).

Given impounding of water in the drainage water monitoring well, estimates for the

measured drainage on 11 December 2006, 13-14 December 2006, 28 February 2007, 23

October 2011, 13 November 2011 and 11 December 2011 were based on expert

judgement. Additionally, TDR-measurements at 25 cm b.g.s. in the period from 15

December 2009 to 20 March 2010 were discarded given freezing soils (soil tempera-

tures at or below 0° C). The soil water content is measured with TDR based on Topp

calibration (Topp

et al.,

1980), which will underestimate the total soil water content at

the soil water freezing point as the permittivity of frozen water is much less than that of

liquid water (Flerchinger

et al.,

2006)

4.2

Results and discussion

4.2.1 Soil water dynamics and water balances

The model simulations were consistent with the observed data, thus indicating a

reasonable model description of the overall soil water dynamics in the variably-

saturated zone (Figure 4.2). As in Brüsch

et al.

(2013b), the simulated groundwater

table of this hydraulic year was validated against the much more fluctuating

groundwater table measured in piezometer P3, which yielded the best description of

measured drainage (Figure 4.2B and 4.2C). The drainage flow period of the past year

was well captured by the model (Figure 4.2C). As in the previous monitoring periods,

the overall trends in soil water content were described reasonably well (Figure 4.2D,

4.2E and 4.2F), although the model describe the topsoil as being more wet during the

summer period than actually measured by the upper TDR probes (Figure 4.2D).

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Precipitation

May-99

May-00

May-01

May-02

May-03

May-04

May-05

May-06

May-07

Simulated percolation

May-08

May-09

May-10

May-11

May-12

May-13

Precipitation (mm/d)

-1

GWT (m)

-2

-3

-4

-5

Measured, Automatic P1

Measured P4

Drainage

Measured, Automatic P3

Measured, Logger P3.2

Measured P3

Measured

(mm/d)

100

SW sat. (%)

0.25 m b.g.s.

120

100

SW sat. (%)

0.6 m b.g.s.

120

100

May-99

SW sat. (%)

May-00

May-01

May-02

May-03

May-04

May-05

May-06

May-07

May-08

May-09

May-10

May-11

May-12

Simulated

Measured - S2

Measured - S1

Figure 4.2.

Soil water dynamics at

Silstrup:

Measured precipitation and simulated percolation 1 m b.g.s. (A),

simulated and measured groundwater level GWT (B), simulated and measured drainage flow (C), and simulated and

measured soil water saturation (SW sat.) at three different soil depths (D, E and F). The measured data in B derive

from piezometers located in the buffer zone. The measured data in D, E and F derive from TDR probes installed at S1

and S2 (Figure 4.1). The dotted vertical line indicates the beginning of the validation period (July 2004-June 2013).

May-13

1.1 m b.g.s.

Percolation (mm/d)

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Table 4.1.

Annual water balance for

Silstrup

(mm/year). Precipitation is corrected to the soil surface according to the

method of Allerup and Madsen (1979).

Normal

Actual

Measured

Simulated Groundwater

precipitation

Precipitation evapotranspiration

drainage

recharge

1.7.99–30.6.00

976

1175

457

–

443

275

1.7.00–30.6.01

976

909

413

217

232

279

1.7.01–30.6.02

976

1034

470

227

279

338

1.7.02–30.6.03

976

879

537

261

1.7.03–30.6.04

976

760

517

148

1.7.04–30.6.05

976

913

491

155

158

267

1.7.05–30.6.06

976

808

506

101

201

1.7.06–30.6.07

976

1150

539

361

307

249

1.7.07–30.6.08

976

877

434

200

184

242

1.7.08–30.6.09

976

985

527

161

260

296

1.7.09–30.6.10

976

835

402

203

225

230

1.7.10–30.6.11

976

1063

399

172

569

492

1.7.11–30.6.12

976

1103

432

230

321

444

1.7.12–30.6.13

976

1020

466

249

333

306

The monitoring started in April 2000.

Normal values based on time series for 1961–1990 corrected to soil surface.

Groundwater recharge calculated as precipitation - actual evapotranspiration - measured drainage.

Where drainage flow measurements were lacking, simulated drainage flow was used to calculate groundwater recharge.

The resulting water balance for Silstrup for the entire monitoring period is shown in

Table 4.1. Compared with the previous 13 years, the recent hydraulic year July 2012-

June 2013 was characterised by having medium precipitation, medium simulated actual

evapotranspiration, and the second highest measured drainage. Precipitation of this year

was characterised by February-March being the driest since the monitoring started and a

very wet September-October (Appendix 4). Due to this precipitation pattern continuous

percolation was simulated for the whole hydrological year except for a few days in June

(Figure 4.2A). The climatic setting of this year gave rise to a continuous period with the

groundwater table just above the drainage level, causing the second largest measured

drainage compared to the other hydrological years (Figure 4.2B and 4.2C). Compared to

the hydrological year July 2011 – June 2012, less water was entering the soil media and

more water was entering the drainage system leaving less water to percolate to the

groundwater resulting in less groundwater recharge.

The simulated drainage (Figure 4.2C) matched the measured drainage flow quite well

except for a later initiation of drainage in autumn 2012. Drainage flow measured in

connection with the minor degree of snowmelt present, this hydrological year seems

also to be captured by MACRO.

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Bromide (mg/l)

Suction cups - S1

Suction cups - S2

1 m b.g.s.

2 m b.g.s.

Bromide (mg/l)

1 m b.g.s.

2 m b.g.s.

Bromide (mg/l)

Drains

Bromid, flow-proportional sampling

Drainage runoff (mm/d)

Bromide (mg/l)

Horizontal monitoring wells - 3.5 m b.g.s.

H1.2

H2.1

H1.1

H2.3

H1.3

H2.2

Jun-05

Jun-06

Jun-07

Jun-08

Jun-09

Jul-04

May-10

May-11

May-12

Figure 4.3.

Bromide concentration at

Silstrup.

A and B refer to suction cups located at S1 and S2 (see Figure 4.1).

The bromide concentration is also shown for drainage runoff (C) and the horizontal monitoring wells H1, H2 and H3

(D). From January 2009 to September 2012, bromide measurements in the suction cups were suspended. The green

vertical lines indicate the dates of bromide applications.

4.2.2 Bromide leaching

The bromide concentrations prior March, shown in Figure 4.3 and Figure 4.4, relate to

the bromide applied in May 2000, as described in previous reports (Kjær

et al.

2003 and

Kjær

et al.

2004) and further evaluated in Barlebo

et al.

(2007). In March 2009,

bromide measurements in the suction cups and monitoring wells M6 and M11 were

suspended. In September 2012 a third application of potasium bromide was done, 30.5

kg/ha.

May-13

Drainage runoff (mm/d)

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Bromide (mg/l)

1.5-2.5 m

3.5-4.5 m

4.5-5.5 m

Bromide (mg/l)

M10

Bromide (mg/l)

M12

Nov-08

Nov-09

Nov-10

Nov-11

Figure 4.4.

Bromide concentration at

Silstrup.

The data derive from the vertical monitoring wells (M5–M12). In

September 2008, monitoring wells M6 and M11 were suspended (Appendix 2). Screen depth is indicated in m b.g.s.

The green vertical lines indicate the dates of bromide applications.

4.2.3 Pesticide leaching

Monitoring at Silstrup began in May 2000 and the pesticides and degradation products

monitored are given in Appendix 7. Pesticide application from 2007 and during the

most recent growing seasons, 2011/2012 and 2012/2013 is listed in Table 4.2 and

shown together with precipitation and simulated percolation in Figure 4.5. It should be

noted that precipitation in Table 4.2 is corrected to soil surface according to Allerup and

Madsen (1979), whereas percolation (1 m b.g.s.) refers to accumulated percolation as

simulated with the MACRO model. Moreover, pesticides applied later than April 2013

are not evaluated in this report and hence not included in Table 4.2.

Nov-12

Dec-03

Dec-04

Dec-05

Dec-06

Dec-07

Jan-03

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Table 4.2.

Pesticides analyzed at

Silstrup.

Precipitation (precip.) and percolation (percol.) are accumulated within

the first year (Precip 1

year, Percol 1

year) and first month (Precip 1

month, Percol 1

month) after the first

application. C

mean

refers to average leachate concentration at 1 m b.g.s. the first year after application. See Appendix

2 for calculation method and Appendix 8, Table A8.3 for previous applications of pesticides. (End monito.) end of

monitoring of pesticide (P) or degradation product (M).

Applied

product

Winter wheat 2007

Cycocel 750

Hussar OD

Opus

Stomp Pentagon

Fodder beet 2008

Fusilade Max

Goliath

Safari

Crop

Analyzed

pesticide

Chlormequat(P)

Applica. End

Y 1

M 1

mean

date

Monito. precip. percol. precip. percol.

Apr 07 Jun 08 966

382

<0.01

Apr 07 Oct 10

Jun 07

Sep 06

Jul 08

Apr 09

Apr 08

Jun 12

Iodosulfuron-methyl(P)

Metsulfuron-methyl(P)

Epoxiconazole(P)

Pendimethalin(P)

Fluazifop-P(M)

TFMP(M)

Metamitron(P)

966

947

1166

985

969

979

835

876

888

1027

898

1024

1043

989

1067

1024

1073

836

463

382

407

508

494

498

497

390

391

390

520

390

520

550

493

584

532

581

514

270

173

111

105

101

112

127

207

121

<0.01

0.04

<0.01

0.24

0.01

0.02

<0.01

<0.02

<0.01

0.01

0.06

0.03

<0.02

2.26

<0.01

<0.02

<0.01

0.003

0.014

0.25

0.03

0.009

<0,01

0.007

0.003

0.074

0.15

0.067

<0.01

0.006

<0.01

0.001

May 08 Dec 10

Desamino-metamitron(M) May 08 Dec 10

Triflusulfuron-methyl(P) May 08 Jun 10

IN-D8526(M)

IN-E7710(M)

IN-M7222(M)

Tramat 500 SC

Spring barley 2009

Amistar

Fighter 480

Red fescue 2010

Fox 480 SC

Ethofumesate(P)

Azoxystrobin(P)

CyPM(M)

Bentazone(P)

Bifenox(P)

Bifenox acid(M)

Nitrofen(M)

Fusilade Max

Hussar OD

Fluazifop-P(M)

TFMP(M)

Iodosulfuron-methyl(P)

Metsulfuron-methyl(M)

Triazinamin(M)

Hussar OD

Red fescue 2011

Fusilade Max

Fox 480 SC

Iodosulfuron-methyl(P)

Metsulfuron-methyl(M)

TFMP(M)

Bifenox(P)

Bifenox acid(M)

Nitrofen(M)

Red fescue 2012

DFF

Diflufenican(P)

AE-05422291(M)

AE-B107137(M)

Folicur

Fusilade Max

Spring barley

May 08 Jun 10

May 08 Dec 10

Jun 09

Sep 09

Mar 12

Jun 12

May 09 Jun 11

Jun 12

May 10 Jun 12

Aug 09 Dec 10

May 10 Dec 10

May 11 Jun 12

Sep 11

Dec 12

Apr 12 Jun 13

1067’ 584

Apr 12 Jun 13

May 12 Dec 12

Apr 12 Jun 13

Sep 12

Jun 13

Tebuconazole(P)

TFMP(M)

AMPA(M)

Winter wheat 2013

Glyfonova 450 Plus Glyphosate(P)

Oxitril CM

DFF

Bromoxynil(P)

Ioxynil(P)

Diflufenican

AE-05422291(M)

AE-B107137(M)

Nov 12 Jun 13

Systematic chemical nomenclature for the analyzed pesticides is given in Appendix 1.

monitoring continues the following year.

On 3 May 2013: Sowing spring barley, replacing winter wheat injured by frost.

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May

Aug

Nov

Mar

Dec

Apr

Sep

Feb

Oct

Jun

Jan

Jul

Precipitation (mm/d)

2011/2012

Precipitation (mm/d)

Precipitation

Fluazifop-P-butyl (2011)

Tebuconazole (2012)

Diflufenican (2012)

Iodosulfuron-methyl-sodium (2011)

Fluazifop-P-butyl (2012)

Glyphosate (2012)

Ioxynil (2012)

2012/2013

Bifenox (2011)

Simulated percolation

Bromoxynil (2012)

Figure 4.5.

Pesticides included in the monitoring programme, precipitation and irrigation (primary axis) and

simulated percolation 1 m b.g.s. (secondary axis) at

Silstrup

in 2011/2012 (upper) and 2012/2013 (lower).

The current report focuses on the pesticides applied from 2011 and onwards, while the

leaching risk of pesticides applied in 2011 and before has been evaluated in previous

monitoring reports (see http://pesticidvarsling.dk/publ_result/index.html).

The herbicide fluazifop-P-butyl has been included in the PLAP at Silstrup in total five

times, and as fluazifop-P-butyl is rapidly degraded, main focus has been on its

degradation products, firstly fluazifop-P (free acid) and lately TFMP (Table 4.2). The

degradation product fluazifop-P (free acid) was only detected once in groundwater.

Since the 2008 application in fodder beet focus has been on the degradation product

TFMP. In Figure 4.6A, B and C it can be seen that an application of 375 g a.i./ha of

fluazifop-P-butyl (3.0 l/ha Fusilade Max) in 2008 lead to TFMP concentrations above

0.1 µg/L in both drainage and groundwater. Further, a concentration of 0.1 µg/L was

exceeded first in the groundwater and then later in the drainage water, which indicate a

preferential transport of TFMP. Subsequently, the Danish EPA has restricted the use of

fluazifop-P-butyl regarding dosage, crop types and frequency of applications.

When fluazifop-P-butyl was used for the third and fourth time, April 2010 and April

2011, the Danish EPA had restricted its use regarding applicable amounts, crop types

and frequency of applications, and as can be seen in Figure 4.6B, this seemed to have

reduced the environmental impact. However, a fifth application in April 2012, shows

that there still might be a problem, even when used in the low dosage and in a dense

grass crop. This may, very likely, relate to differences in the hydrological regimes at the

time of the third and fourth application, as compared to that of the fifth application in

2012.

Percolation (mm/d)

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As can be seen from Figure 4.6A, there was no instant leaching of TFMP to the

drainage system in neither 2010 nor in 2011. Thus, the concentrations in drainage never

exceeded 0.1 µg/L and TFMP was not detected in the groundwater. At the time of the

application in the spring of 2010 and 2011 sprayings and throughout most of following

summer there was virtually no percolation or drainage flow (Figure 4.6A). In 2010 it

took five months before 0.06 µg/L of TMP was detected in the drainage water and in

2011 four months before 0,05 µg/L was found. In 2012, the same amount of fluazifop-

P-butyl was applied on 19 April, again in a dense stand of red fescue grass, but this year

there was percolation and drainage flow. At the first sampling following the application,

TFMP could be found in both drainage and groundwater, Figure 4.6B and 4.6C in

concentrations exceeding the 0.1 µg/L in both drainage and groundwater. One month

after the spraying, on 23 May 2012, the maximal concentrations were reached in drain

and wells. Last exceedance of the limit for groundwater was 0.11µg/L on 3 October

2012. TFMP continued to leach to the groundwater until 15 May 2013 were 0.023 µg/L

was found.

Tebuconazole was applied on red fesque in May 2012. Tebuconazole was found in two

drainwater samples in August and September 2012 (0.013 and 0.084 µg/L). Analyze of

the degradation product, 1,2,4–triazole, was not possible in this monitoring period.

Since the most recent application (16 September 2011) of the herbicide bifenox in red

fescue, there have been numerous detections of bifenox acid in both drainage water and

groundwater (data not shown). The highest concentration in drainage water was 4.8

µg/L of bifenox acid sampled on 29 September 2011 and 1.2 µg/L of bifenox acid in

groundwater sampled November 2011 from the uppermost screen of monitoring well

M5. Bifenox itself has only been found a few times in the drainage water between 22

September and 19 October 2011, concentrations ranging from 0.023 to 0.38 µg/L.

Another degradation product nitrofen was solely found in drainage in the same period,

in concentrations ranging between 0.045 and 0.34 µg/L. The last measurement of

bifenox acid was done on 3 October 2012 showing 0.053 µg/L in groundwater, whereas

the last measurement in drainage showed 0.11 µg/L on 2 May 2012. Due to data from

the PLAP monitoring the Danish EPA has now banned all use of bifenox in Denmark.

Azoxystrobin has been applied at Silstrup three times since 2004 (Figure 4.7). The last

application (24 June 2009) still causes leaching of the degradation product CyPM to the

drainage (Figure 4.7C), whereas leaching of azoxystrobin itself seems to have ended,

the most recent detection was 0.011 µg/L on 24 March 2010 (Figure 4.7B). The

concentrations of CyPM were generally higher than the concentration of the parent

compound. Whereas there have been no detections of azoxystrobin in the groundwater,

CyPM was found in both horizontal and vertical wells, concentrations ranging from

0.013 to 0.086 µg/L and 0.011 to 0.1 µg/L, respectively. Latest detection of CyPM in

groundwater was 0.012 µg/L on 19 May 2010 (Figure 4.7D) and 0.01 µg/L in drainage

on 3 January 2013 (Figure 4.7C).

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May/08

Apr/09

Apr/10

Apr/11

Apr/12

Precipitation (mm/d)

Pesticide (µg/l)

0.1

TFMP

Drainage runoff (mm/d)

0.01

Pesticide (µg/l)

TFMP

Horisontal & monitoring wells (detections only)

0.1

May/08

Apr/09

Apr/10

Apr/11

Apr/12

M5 (1.5-2.5 m)

H1 (3.5 m b.g.s.)

M5 (2.5-3.5 m)

H2 (3.5 m b.g.s.)

M5 (3.5-4.5 m)

H3 (2 m b.g.s.)

Figure 4.6.

Precipitation and simulated percolation 1 m b.g.s. (A) together with the concentration of TFMP (B) in the

drainage runoff, and the concentration of TFMP (C) in the groundwater horizontal and monitoring screens at

Silstrup.

The green vertical lines indicate the dates of fluazifop-P-butyl applications. Values below the detection

limit of 0.01 µg/L are shown as 0.01 µg/L (all graphs) and further represented by open symbols in A, B and C.

Diflufenican was applied in April 2012 and in November 2012 (red fescue and winter

wheat). Diflufenican was detected in nine drainage water samples, and one drainage

water sample exceeded 0.1 µg/L (0.12 in April). Diflufenican was detected in one

groundwater sample in November (0.47 µg/L). The break down product AE-B107137

was detected in five drainage water samples where one sample exceeded 0.1 µg/L (0,13

µg/L). The other break down product AE-05422291 was not detected.

Apr/13

Oct/08

Oct/09

Oct/10

Oct/11

Oct/12

0.01

DR(mm/d)

TFMP

Drains

Percolation (mm/d)

Apr/13

Oct/08

Oct/09

Oct/10

Oct/11

Oct/12

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May/03

Apr/04

Apr/05

Apr/06

Apr/07

Apr/08

Apr/09

Apr/10

Apr/11

Apr/12

Precipitation (mm/d)

Azoxystrobin

Drains

Pesticide (µg/l)

0.1

CyPM

Drains

0.01

Pesticide (µg/l)

0.1

Pesticide concentration

Drainage runoff (mm/d)

0.01

Pesticide (µg/l)

CyPM

Horisontal & Monitoring wells detections only

0.1

May/03

Apr/04

Apr/05

Apr/06

Apr/07

Apr/08

Apr/09

Apr/10

Apr/11

Apr/12

M5 (1.5-2.5 m)

M9 (1.5-2.5 m)

H2 (3.5 m b.g.s.)

M5 (2.5-3.5 m)

M9 (1.5-2.5 m)

H3 (2 m b.g.s.)

M5 (3.5-4.5 m)

H1 (3.5 m b.g.s.)

Figure 4.7.

Precipitation and simulated percolation 1 m b.g.s. (A) together with the concentration of azoxystrobin (B)

and CyPM (C) in the drainage runoff, and the concentration of CyPM (D) in the groundwater monitoring screens at

Silstrup.

The green vertical lines indicate the dates of bentazone and azoxystrobin applications. Values below the

detection limit of 0.01 µg/L are shown as 0.01 µg/L (all graphs).

Glyphosate was applied on 10 September 2012, killing the red fescue, and both

glyphosate and AMPA were found in drainage nine days later. Glyphosate was found in

concentrations up to 0.66 µg/L (Figure 4.8) and AMPA in concentrations up to 0.13

µg/L. Glyphosate was found in ten groundwater samples from the monitoring wells, and

in three groundwater samles from the new horizontal well in small concentrations below

0.1 µg/L. AMPA was found in two water samples from groundwater and in three water

samples form the horizontal well, also in small concentrations ≤ 0.1 µg/L. After

February 2013 glyphosate and AMPA were found in monitoring wells, but not in the

drainage water (Figure 4.8). The average glyphosate concentration in the drainage water

was 0.15 µg/L, while the average AMPA concentration was 0.067 µg/L.

Apr/13

0.01

DR(mm/d)

Percolation (mm/d)

Apr/13

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May/13

Aug/12

Nov/12

Mar/13

Dec/12

Apr/13

Sep/12

Feb/13

Oct/12

Precipitation (mm/d)

Glyphosate

Drains

Pesticide (µg/l)

0.1

AMPA

Drains

0.01

Pesticide (µg/l)

0.1

Pesticide concentration

Drainage runoff (mm/d)

0.01

Pesticide (µg/l)

Glyphosate

Horisontal & Monitoring wells detections only

0.1

May/13

Aug/12

Nov/12

Mar/13

Dec/12

Apr/13

Sep/12

Feb/13

Oct/12

M5 (1.5-2.5 m)

M5 (2.5-3.5 m)

M9 (1.5-2.5 m)

H3 (2 m b.g.s.)

Pesticide (µg/l)

0.1

AMPA

Horisontal & Monitoring wells detections only

May/13

Aug/12

Nov/12

Mar/13

Dec/12

Apr/13

Sep/12

Feb/13

Oct/12

M5 (2.5-3.5 m)

H3 (2 m b.g.s.)

Figure 4.8.

Precipitation and simulated percolation 1 m b.g.s. (A) together with the concentration of glyphosate (B)

and AMPA (C) in the drainage runoff, and the concentration of glyphosate (D) and AMPA (E) in the groundwater

monitoring screens at

Silstrup.

The green vertical lines indicate the dates of glyphosate applications. Values below

the detection limit (not detected) of 0.01 µg/L, are shown as 0.01 µg/L.

Jun/13

Jan/13

Jul/12

0.01

Jun/13

Jan/13

Jul/12

0.01

DR(mm/d)

Percolation (mm/d)

Jun/13

Jan/13

Jul/12

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5 Pesticide leaching at Estrup

5.1

Materials and methods

5.1.1 Site description and monitoring design

Estrup is located in central Jutland (Figure 1.1) west of the Main Stationary Line on a

hill-island, i.e. a glacial till preserved from the Weichselian Glaciation. Estrup has thus

been exposed to weathering, erosion, leaching and other geomorphological processes

for a much longer period than the other sites. The test field covers a cultivated area of

1.3 ha (105 x 120 m) and is virtually flat (Figure 5.1). The site is highly heterogeneous

with considerable variation in both topsoil and aquifer characteristics (Lindhardt

et al.,

2001). Such heterogeneity is quite common for this geological formation, however.

Based on three profiles excavated in the buffer zone bordering the field the soil was

classified as Abrupt Argiudoll, Aqua Argiudoll and Fragiaquic Glossudalf (Soil Survey

Staff, 1999). The topsoil is characterised as sandy loam with a clay content of 10–20%,

and an organic carbon content of 1.7–7.3%. A C-horizon of low permeability also c

haracterises the site. The saturated hydraulic conductivity in the C-horizon is 10

-8

m/s,

which is about two orders of magnitude lower than at the other loamy sites (Table 1.1).

The geological structure is complex comprising a clay till core with deposits of different

age and composition (Lindhardt

et al.,

2001). A brief description of the sampling

procedure is provided in Appendix 2 and the analysis methods in Kjær et al. (2002). The

monitoring design and test site are described in detail in Lindhardt et al. (2001). Please

note that the geological conditions only allowed one of the planned horizontal wells in

3.5 m b.g.s. to be installed. In September 2011, the monitoring system was extended

with three horizontal screens (H2) 2 m b.g.s. in the North-Eastern area of the field

(Figure 5.1), one of the screens should be located just below a tile drain 1.1 m b.g.s.,

whereas two are located between tile drains. A brief description of the drilling and

design of H2 is given in Appendix 8.

5.1.2 Agricultural management

Management practice during the 2012-2013 growing seasons is briefly summarized

below and detailed in Appendix 3 (Table A3.4). For information about management

practice during the previous monitoring periods, see previous monitoring reports

available on http://pesticidvarsling.dk/publ_result/index.html.

The field was ploughed on 9 November 2011, rotorharrowed on 29 March 2012 and on

30 March 2012 sown with spring barley (cv. Keops), emerging on 22 April. The field

was sprayed with the herbicides bifenox on 15 May and aminopyralid, florasulam and

2,4-D on 18 May. Aminopyralid and bifenox, including two degradation products of

each, were included in the monitoring. On 13 June the fungicide azoxystrobin was

sprayed and included. Harvest of spring barley was done on 13 August, yielding 62.9

hkg/ha of grain, whereas 41.0 hkg/ha of straw was shredded (85% and 100% dry matter,

respectively).

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Figure 5.1.

Overview of the

Estrup

site. The innermost white area indicates the cultivated land, while the grey area

indicates the surrounding buffer zone. The positions of the various installations are indicated, as is the direction of

groundwater flow (by an arrow). Pesticide monitoring is conducted weekly from the drainage system (during period

of continuous drainage runoff) and monthly and half-yearly from selected vertical and horizontal monitoring screens

as described in Table A2.1 in Appendix 2.

The field was ploughed on 8 March 2013 and sown with pea (cv. Alvesta) on 23 April,

emerging on 4 May 2013. The field was sprayed with the herbicides clomazone on 25

April and bentazone on 16 May. Bentazone as well as the degradation product of

clomazone FMC65317 were included in the monitoring. A spraying of aphids was done

on 16 May using cypermethrin, however the substance was not monitored.

5.1.3 Model setup and calibration

The numerical model MACRO (version 5.2, Larsbo

et al.,

2005) was applied to the

Estrup site covering the soil profile to a depth of 5 m b.g.s., always including the

groundwater table. The model is used to simulate the water flow in the variably-

saturated zone during the monitoring period from July 2000-June 2013 and to establish

an annual water balance.

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Compared to the setup in Brüsch

et al.

(2013b), a year of validation was added to the

MACRO setup for the Estrup site. The setup was subsequently calibrated for the

monitoring period May 1999-June 2004 and validated for the monitoring period July

2004-June 2013. For this purpose, the following time series have been used: the

observed groundwater table measured in the piezometers located in the buffer zone (a

new in situ logger allowing higher resolution has been installed instead of the diver),

measured drainage flow, and soil water content measured at two depths (25 and 40 cm

b.g.s.) from the soil profile S1 (Figure 5.1). The TDR probes installed at the other

depths yielded unreliable data with saturations far exceeding 100% and unreliable soil

water dynamics with increasing soil water content during the drier summer periods (data

not shown). No explanation can presently be given for the unreliable data, and they have

been excluded from the analysis. The data from the soil profile S2 have also been

excluded due to a problem with water ponding above the TDR probes installed at S2, as

mentioned in Kjær

et al.

(2003). Finally, TDR-measurements at 25 cm b.g.s. in

February 2010 were discarded given freezing soils (soil temperatures at or below 0° C).

The soil water content is measured with TDR based on Topp calibration (Topp

et al.,

1980), which will underestimate the total soil water content at the soil water freezing

point as the permittivity of frozen water is much less than that of liquid water

(Flerchinger

et al.,

2006)

Because of the erratic TDR data, calibration data are limited at this site. Data

acquisition, model setup as well as results related to simulated bromide transport are

described in Barlebo

et al.

(2007).

5.2

Results and discussion

5.2.1 Soil water dynamics and water balances

The model simulations were generally consistent with the observed data (which were

limited compared to other PLAP sites, as noted above), indicating a good model

description of the overall soil water dynamics in the variably-saturated zone (Figure

5.2). The model provided an acceptable simulation of the overall level of the

groundwater table. As in the previous hydrological year, a drop in the measured

groundwater table was seen after short periods of low precipitation (Figure 5.2B). Also

here the simulated groundwater table did not seem as sensitive to these short periods of

low precipitation and tended not to drop as much as the measured values. Since the

subsoil TDR data are limited, a more detailed study of soil water dynamics in these

layers is difficult. However, the overall soil water saturation at 25 and 40 cm b.g.s. was

captured (Figure 5.2D and 5.2E), except for the drop in water saturation at 25 cm b.g.s.

in April-June 2013. As in previous years (Brüsch

et al.,

2013b), the simulated

groundwater table often fluctuates slightly above the drain depth resulting in long

periods with drainage.

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Precipitation

May-99

May-00

May-01

May-02

May-03

May-04

May-05

May-06

Simulated percolation

May-07

May-08

May-09

May-10

May-11

May-12

May-13

Precipitation (mm/d)

-1

-2

-3

-4

-5

-6

120

Percolation (mm/d)

GWT (m)

Measured, Average

Measured, automatic P1.1

Drainage

Measured

Measured P3

Measured, Logger in P1.1 B

(mm/d)

SW sat. (%)

100

160

140

120

100

0.25 m b.g.s.

0.40 m b.g.s.

SW sat. (%)

May-99

May-00

May-01

May-02

May-03

May-04

May-05

May-06

May-07

May-08

May-09

May-10

May-11

May-12

May-13

Simulated

Measured - S1

Figure 5.2.

Soil water dynamics at

Estrup:

Measured precipitation and simulated percolation 0.6 m b.g.s. (A),

simulated and measured groundwater level (B), simulated and measured drainage flow (C), and simulated and

measured soil saturation (SW sat.) at two different soil depths (D and E). The measured data in B derive from

piezometers located in the buffer zone. The measured data in D and E derive from TDR probes installed at S1 (Figure

5.1). The dotted vertical line indicates the beginning of the validation period (July 2004-June 2013).

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Table 5.1.

Annual water balance for

Estrup

(mm/year). Precipitation is corrected to the soil surface according to the

method of Allerup and Madsen (1979).

Normal

Actual

Measured

Simulated Groundwater

precipitation

Precipitation evapotranspiration

drainage

recharge

1.7.99–30.6.00

968

1173

466

–

553

154

1.7.00–30.6.01

968

887

420

356

340

111

1.7.01–30.6.02

968

1290

516

505

555

270

1.7.02–30.6.03

968

939

466

329

346

144

1.7.03–30.6.04

968

928

499

298

312

131

1.7.04–30.6.05

968

1087

476

525

468

1.7.05–30.6.06

968

897

441

258

341

199

1.7.06–30.6.07

968

1365

515

547

618

303

1.7.07–30.6.08

968

1045

478

521

556

1.7.08–30.6.09

968

1065

480

523

362

1.7.09–30.6.10

968

1190

533

499

523

158

1.7.10–30.6.11

968

1158

486

210

341

462

1.7.11–30.6.12

968

1222

404

479

577

3397

1.7.12–30.6.13

968

1093

386

503

564

204

Monitoring started in April 2000.

Normal values based on time series for 1961–1990 corrected to the soil surface.

Groundwater recharge is calculated as precipitation minus actual evapotranspiration minus measured drainage.

Where drainage flow measurements are lacking, simulated drainage flow was used to calculate groundwater recharge.

The simulated drainage (Figure 5.2C) matches the measured drainage flow quite well

except for the drainage in July 2012 where it is overestimated. Drainage flow measured

in connection with the minor degree of snowmelt within this hydrological year seems

also to be captured by MACRO. Drainage was high during the whole monitoring period

compared to that of the other two till sites investigated in the PLAP. This was due to a

significantly lower permeability of the C-horizon than of the overlying A and B

horizons (see Kjær

et al.

(2005c) for details).

The resulting water balance for Estrup for the entire monitoring period is shown in

Table 5.1. Compared with the previous 13 years, the recent hydrological year July 2012-

June 2013, was characterized by having medium precipitation, the lowest simulated

actual evapotranspiration during the whole periode of PLAP monitoring, and medium

measured drainage. Having hardly any snowmelt, there is a good agreement between

simulated and observed drainage. The difference of 61 mm can primarily be ascribed by

the July 2012 drainage event being overestimated by MACRO. Precipitation in the

months of this year was characterized by medium precipitation compared to the other

PLAP-years except for March 2013, being the driest since PLAP-monitoring started

(Appendix 4). Due to this precipitation pattern, the simulated percolation pattern of the

year July 2012-June 2013 resulted in more or less continuously percolation at 1 m depth

(Figure 5.2A) with a medium input to the groundwater recharge (Table 5.1) as

compared to the other PLAP-years.

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-1

Bromide (mg/l)

Suction cups - S1

1 m b.g.s.

2 m b.g.s.

Bromide (mg/l)

Suction cups - S2

1 m b.g.s.

2 m b.g.s.

Bromide (mg/l)

Drains

Bromide, flow-proportional sampling

Drainage runoff (mm/d)

Bromide (mg/l)

Horizontal monitoring wells - 3.5 m b.g.s.

H1.1

H1.2

H1.3

H2 ( 2 m b.g.s.)

Jun-05

Jun-06

Jun-07

Jun-08

Jun-09

Jul-04

May-10

May-11

May-12

Figure 5.3.

Bromide concentration at

Estrup.

A and B refer to suction cups located at S1 and S2, respectively. The

bromide concentration is also shown for drainage runoff (C) and the horizontal monitoring well H1 and H3 (D). From

September 2008 to August 2012, bromide measurements in the suction cups were suspended. The green vertical lines

indicate the dates of bromide.

5.2.2 Bromide leaching

Bromide has now been applied four times at Estrup. The bromide concentrations

measured up to October 2005 (Figure 5.3 and Figure 5.4) relate to the bromide applied

in spring 2000, as described further in Kjær

et al.

(2003) and Barlebo

et al.

(2007). In

March 2009, bromide measurements in the suction cups and monitoring wells M3 and

M7 were suspended. Figure 5.3D show a very slow build up of the bromide

concentrations in the horizontal screens reflecting a slow transport due to the low

hydraulic conductivity.

May-13

Drainage runoff (mm/d)

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Bromide (mg/l)

2.5-3.5 m

3.5-4.5 m

4.5-5.5 m

5.5-6.5 m

Bromide (mg/l)

Nov-08

Nov-09

Nov-10

Nov-11

Figure 5.4.

Bromide concentration at

Estrup.

The data derive from the vertical monitoring wells (M1, M4, M5 and

M6). Screen depth is indicated in m b.g.s. In September 2008, monitoring wells M3 and M7 were suspended. The

green vertical lines indicate the dates of the three most recent bromide applications.

5.2.3 Pesticide leaching

Monitoring at Estrup began in May 2000. Pesticides and degradation products

monitored so far can be seen from Table 5.2 (2007-2013) and Table A7.4 in Appendix 7

(2000-2007). Pesticide application during the most recent growing seasons (2011/2012

and 2012/2013) is shown together with precipitation and simulated precipitation in

Figure 5.5. It should be noted that precipitation is corrected to the soil surface according

to Allerup and Madsen (1979), whereas percolation (0.6 m b.g.s.) refers to accumulated

percolation as simulated with the MACRO model (Section 5.2.1). Moreover, pesticides

applied later than April 2013 are not evaluated in this report and hence not included in

Table 5.2.

Nov-12

Dec-03

Dec-04

Dec-05

Dec-06

Dec-07

Jan-03

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Table 5.2.

Pesticides analyzed at

Estrup.

Precipitation (precip.) and percolation (percol.) are accumulated within the

first year (Precip 1

year, Percol 1

year) and first month (Precip 1

month, Percol 1

month) after the first

application C

mean

refers to average leachate concentration at 1 m b.g.s. the first year after application. See Appendix 2

for calculation method and Appendix 8 (Table A8.4) for previous applications of pesticides. End Monito.- end of

monitoring of pesticide(P) or degradation product(M).

Crop

Winter wheat 2007

Applied

product

Atlantis WG

Cycocel 750

Opus

Winter wheat 2008

Amistar

Folicur EC 250

Pico 750 WG

Roundup Max

Spring barley 2009

Amistar

Basagran M75

Fox 480 SC

Analyzed

pesticide

Mesosulfuron-methyl(P)

Mesosulfuron(M)

Chlormequat(P)

Epoxiconazole(P)

Azoxystrobin(P)

CyPM(M)

Tebuconazole(P)

Picolinafen(P)

CL153815(M)

Glyphosate(P)

AMPA(M)

Azoxystrobin(P)

CyPM(M)

Bentazone(P)

Bifenox(P)

Bifenox acid(M)

Nitrofen(M)

Winter rape 2010

Biscaya OD 240 Thiacloprid(P)

M34(M)

Thiacloprid sulfonic

acid(M)

Thiacloprid-amide(M)

Winter wheat 2011

Express ST

Fox 480 SC

Triazinamin-methyl(M)

Bifenox(P)

Bifenox acid(M)

Nitrofen

Flexity

Spring barley 2012

Amistar

Fox 480 SC

Metrafenone(P)

Azoxystrobin

CyPM

Bifenox

Bifenox acid

Nitrofen

Mustang forte

Roundup Max

Pea 2013

Fighter 480

Command CS

Applica.

Date

Oct 06

Apr 07

May 07

Jun 08

Nov 07

Oct 07

Sep 07

Jun 09

May 09

May 10

Sep 10

Apr 11

May 11

Jun 12

May 12

Oct 11

May 13

Apr 13

End

Monito.

Jul 08

Jun 12

Y 1

M 1

mean

precip percol precip percol

1420 305

0.01

1420

1261

1154

1093

1325

1253

1200

1215

1222

1243

1083

823

1217

1219

1083

1090

1098

1150

305

287

299

232

275

267

261

235

238

246

196

176

276

283

281

285

295

154

103

113

114

151

<0.02

<0.01

0.02

0.06

0.48

0.44

0.03

0.24

0.19

0.13

0.04

0.41

0.05

<0.02

0.16

<0.01

<0.02

<0.1

<0.01

0.01

<0.01

0.003

<0.01

0.02

0.04

0.24

< 0.02

0.011

< 0.02

< 0.01

0.88

0.26

Jun 12

Mar 10

Jun 12

Mar 12

Jun 12

Jun 13

Aminopyralid

Glyphosate(P)

AMPA(M)

Bentazone(P)

FMC-65317(M)

Jun 13

Systematic chemical nomenclature for the analyzed pesticides is given in Appendix 1.

Degradation product of tribenuron-methyl. The parent degrades rapidly to be detected by monitoring.

monitoring continues the following year.

Bentazone applied on 16 May 2013, and Command CS, clomazone, on 25 April 2013. Concentration will be calculated in

the next monitoring period.

The current report focuses on pesticides applied from 2011 and onwards, while leaching

risk of pesticides applied in 2010 and before has been evaluated in previous monitoring

reports (see http://pesticidvarsling.dk/publ_result/index.html).

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May

Aug

Nov

Mar

Dec

Apr

Sep

Feb

Oct

Jun

Jan

Jul

Precipitation (mm/d)

2011/2012

Precipitation (mm/d)

Precipitation

Bifenox (2012)

Florasulam (2012)

Bifenox (2011)

Simulated percolation

Azoxystrobin (2012)

Metrafenone (2011)

2,4-D (2012)

2012/2013

Glyphosate (2011)

Aminopyralid (2012)

Figure 5.5.

Application of pesticides included in the monitoring programme and precipitation (primary axis) together

with simulated percolation 0.6 m b.g.s. (secondary axis) at

Estrup

in 2011/2012 (upper) and 2012/2013 (lower).

Azoxystrobin has now been applied five times at Estrup: on 22 June 2004, 29 June

2006, 13 June 2008, 4 June 2009 and 13 June 2012 (Figure 5.6). The last application

before these five, was in June 1998 (Lindhardt

et al.,

2001). Following all five

applications azoxystrobin and its degradation product CyPM leached to the drainage at

the onset of the drainage period due to infiltration of excess rain. Concentrations in

drainage water of both parent and break down product are shown in Figure 5.6B and

5.6C. The maximum measured concentration of azoxystrobin was 1.4 µg/L on 24

August 2006 and 2.1 µg/L of CyPM on 11 September 2008. CyPM was for the first

time detected in groundwater above the limit, being 0.13 µg/L on 3 October 2012 in the

new horizontal well H3 2 m b.g.s. (Figure 5.6D). Within the year of application as well

as the following year, the average concentrations of CyPM in drainage were always

higher than that of the parent azoxystrobin (Figure 5.6B and 5.6C), indicating its higher

persistence. When drainage runoff commenced in the autumn of 2011, the third runoff

season following the 2009 spraying, CyPM could still be found in the drainage water in

concentrations above 0.1 µg/L, ranging between 0.022 and 0.29 µg/L. Differences in

persistence for the two substances are further underlined by the fact that only two out of

566 groundwater samples contained azoxystrobin (0.04 µg/L, data not shown) whereas

18 samples contained CyPM, maximum concentration being 0.13 µg/L (Figure 5.6D

and Table A5.4). The leaching pattern of azoxystrobin and CyPM is further described in

Jørgensen et al., 2012a and Jørgensen et al., 2013. Following the fifth application of

azoxystrobin on 13 June 2012, a similar pattern was seen in the drainage water, as that

following the first four applications i.e. both parent compound and degradation product

leached, the degradation product in the highest concentrations (Figure 5.6A and 5.6B).

Percolation (mm/d)

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Mar/08

Mar/09

Mar/10

Mar/11

Mar/12

Precipitation (mm/d)

Azoxystrobin

Drains

Pesticide (µg/l)

0.1

CyPM

Drains

0.01

Pesticide (µg/l)

0.1

Pesticide concentration

Drainage runoff (mm/d)

0.01

Pesticide (µg/l)

CyPM

Monitoring wells detections only

0.1

Mar/08

Mar/09

Mar/10

Mar/11

Mar/12

M4 (1.5-2.5 m)

M6 (1.5-2.5 m)

M5 (1.5-2.5 m)

H1 (3.5 m b.g.s.)

M5 (2.5-3.5 m)

H2 (2 m b.g.s.)

Figure 5.6.

Precipitation and simulated percolation 0.6 m b.g.s. (A) together with concentration of azoxystrobin (B)

and CyPM (C) in the drainage runoff (DR on the secondary axis) at

Estrup.

Detections of CyPM in groundwater

monitoring screen are indicated in D. Azoxystrobin was only detected twice in groundwater horizontal and

monitoring screens (see text). The green vertical lines indicate the dates of applications. Values below the detection

limit of 0.01µg/L are shown as 0.01 µg/L (all graphs).

The herbicide bifenox was used on 1 May and on 30 September 2009, 26 April 2011 as

well as 15 May 2012. Both applications in 2009 and May 2012 caused leaching of

bifenox to the drainage. A maximum concentration of 0.15 µg/L was reached less than

two weeks after the May 2009 application (data not shown, see Brüsch et al., 2013). The

degradation product bifenox acid was leached to the drainage water following all four

applications in concentrations larger than 0.1 µg/L (maximum concentration was 1.9

µg/L on 9 September 2009, data not shown). Only bifenox acid was found in a

groundwater monitoring screen, 0.11µg/L on 25 April 2012. This elevated content

probably must relate to one of the three applications done between 2009 and 2011. A

second degradation product nitrofen was not found in either drainage or groundwater.

Mar/13

Apr/04

Apr/05

Apr/06

Apr/07

0.01

DR(mm/d)

Percolation (mm/d)

Mar/13

Apr/04

Apr/05

Apr/06

Apr/07

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The Danish EPA has prohibited the use of bifenox in Denmark on the base of data from

the PLAP.

The herbicide glyphosate has now been applied at Estrup in 2000, 2002, 2005, 2007 and

2011 (Figure 5.7 and Figure 5.8). Following all applications, both glyphosate and

AMPA could be found in the drainage. Out of 480 drainage water samples analyzed for

glyphosate and AMPA in the period from 31 October 2000 to 6 February 2013, the

concentrations of glyphosate and AMPA exceeded 0.1 µg/L in 110 and 115 samples,

respectively (Figure 5.7B, 5.8B, 5.7C and 5.8C). During the period AMPA never

exceeded 0.1 µg/L in groundwater (Figure 5.7E, 5.8E and Table A5.4 in Appendix 5),

whereas glyphosate did so in five samples. In a sample taken from a horizontal well on

6 October 2011 the concentration was 0.21 µg/L (Figure 5.8D and Table A5.4 in

Appendix 5).

Following the glyphosate application of 3 October 2011, concentrations in drainage

water of particular glyphosate increaced, reaching 4.6 µg/L in a sample from 6 October

and 10 µg/L on 19 October. Concentrations of AMPA increaced less dramatically, but

maintained a higher level for a longer periode of time (Figure 5.8 B and 5.8 C.) In a

groundwater sample, taken from a depth of 3.5 m b.g.s., the concentration of glyphosate

amounted to 0.21 µg/L three days after the spraying (Figure 5.8C). Regarding AMPA it

is worth noticing that there were no detections following the 2011 application of

glyphosate (Figure 5.8 E).

The results from the external quality assurance reveal that in the period June 2007 to

July 2010 the concentration of glyphosate may have been underestimated by a factor of

up to approximately two as compared to previous periods. A modification of the

analytical procedure has been implemented in the analysis to address this problem (for

further details see section 7.2.2 in Rosenbom et al., 2010).

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Sep-04

Sep-05

Precipitation (mm/d)

Sep-06

Oct-00

Oct-01

Oct-02

Oct-03

A 5

100

Glyphosate (µg/l)

0.1

0.01

Glyphosate

AMPA (µg/l)

0.1

0.01

Sep-04

Sep-05

Time-proportional sampling

Flow-proportional sampling

Drainage runoff (DR)

Sep-06

Oct-00

Oct-01

Oct-02

Oct-03

Pesticide (µg/l)

Glyphosate

0.1

0.01

Pesticide (µg/l)

AMPA

0.1

Sep-04

Sep-05

M4 (1.5-2.5 m)

M5 (2.5-3.5 m)

M1 (3.5-4.5 m)

M6 (2.5-3.5 m)

M4 (2.5-3.5 m)

M5 (3.5-4.5 m)

M3 (1.5-2.5 m)

M6 (3.5-4.5 m)

M4 (3.5-4.5 m)

M5 (4.5-5.5 m)

M3 (2.5-3.5 m)

M4 (4.5-5.5 m)

H1 (3.5 m b.g.s.)

M3 (3.5-4.5 m)

Figure 5.7.

Precipitation and simulated percolation 0.6 m b.g.s. (A) together with the concentration of glyphosate (B)

and AMPA (C) in the drainage runoff (DR on the secondary axis) at

Estrup

from October 2000 until July 2007. Data

represent a seven-year period including four applications of glyphosate as indicated by the green vertical lines. Open

symbols indicate values below the detection limit of 0.01 µg/L. Detection of glyphosate and AMPA in groundwater

monitoring wells is shown in D and E.

Sep-06

Oct-00

Oct-01

Oct-02

Oct-03

0.01

M5 (1.5-2.5 m)

M1 (4.5-5.5 m)

M6 (1.5-2.5 m)

DR (mm/d)

AMPA

DR (mm/d)

Percolation (mm/d)

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Aug-07

Jul-08

Jul-09

Jul-10

Jul-11

Precipitation (mm/d)

Jul-12

100

Glyphosate (µg/l)

0.1

0.01

Glyphosate

AMPA (µg/l)

AMPA

0.1

0.01

Aug-07

Jul-08

Jul-09

Jul-10

Jul-11

Flow-proportional sampling

Drainage runoff (DR)

Pesticide (µg/l)

0.1

Glyphosate

0.01

Pesticide (µg/l)

Jul-12

AMPA

0.1

Aug-07

Jul-08

Jul-09

Jul-10

Jul-11

H1 (3.5 m b.g.s.)

M4 (1.5-2.5 m)

M5 (3.5-4.5 m)

H2 (2 m b.g.s.)

M4 (2.5-3.5 m)

M6 (1.5-2.5 m)

M3 (1.5-2.5 m)

M4 (3.5-4.5 m)

M6 (3.5-4.5 m)

M3 (2.5-3.5 m)

M5 (1.5-2.5 m)

Figure 5.8.

Precipitation and simulated percolation 0.6 m b.g.s. (A) together with the concentration of glyphosate (B)

and AMPA (C) in the drainage runoff (DR on the secondary axis) at

Estrup

from July 2007 until June 2013. Data

represent a six-year period including four applications of glyphosate as indicated by the green vertical lines. Open

symbols indicate values below the detection limit of 0.01 µg/L. Detection of glyphosate and AMPA in groundwater

monitoring wells is shown in D and E. In the period June 2007 until July 2010 analytical problems caused the

concentration of glyphosate to be underestimated (see text for details).

The fungicide metrafenone was applied twice on 9 May and 7 June 2011 (Fig 5.9).

Between 28 July 2011 and 27 February 2013, when there was drainage flow, a total of

55 water samples were taken. Thereof 20 samples contained metrafenone, but all in

concentrations below 0.1 µg/L. There was one finding of metrafenon in a total of 115

groundwater samples taken between 7 April 2011 and 12 June 2013 (data not shown).

The groundwater sample contained 0.04 µg/L (7 November 2012).

Jul-12

0.01

DR (mm/d)

Percolation (mm/d)

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May/12

Aug/12

Nov/12

Mar/13

Apr/11

Oct/11

Precipitation (mm/d)

0.1

Metrafenone

Drains

Pesticide (µg/l)

Aug-12

Nov-12

Mar-13

Apr-11

Oct-11

Pesticide concentration

May-12

Drainage runoff (mm/d)

Figure 5.9.

Precipitation and simulated percolation 1 m b.g.s. (A) together with the concentration of Metrafenone (B)

in the drainage runoff at

Estrup.

The green vertical lines indicate the dates of Metrafenone applications.

Jun-13

Jan-12

Jul-11

0.01

DR(mm/d)

Percolation (mm/d)

Jun/13

Jan/12

Jul/11

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6 Pesticide leaching at Faardrup

6.1

Materials and methods

6.1.1 Site description and monitoring design

Faardrup is located in southern Zealand (Figure 6.1). The test field covers a cultivated

area of 2.3 ha (150 x 160 m). The terrain slopes gently to the west by 1–3°. Based on

three profiles in the buffer zone bordering the field, the soil was classified as Haplic

Vermudoll, Oxyaquic Hapludoll and Oxyaquic Argiudoll (Soil Survey Staff, 1999). The

topsoil is characterised as sandy loam with 14–15% clay and 1.4% organic carbon.

Within the upper 1.5 m numerous desiccation cracks coated with clay are present. The

test field contains glacial deposits dominated by sandy till to a depth of about 1.5 m

overlying a clayey till. The geological description shows that small channels or basins

filled with melt water clay and sand occur both interbedded in the till and as a large

structure crossing the test field (Lindhardt

et al.,

2001). The calcareous matrix and the

reduced matrix begin at 1.5 m and 4.2 m b.g.s., respectively.

The dominant direction of groundwater flow is towards the west in the upper part of the

aquifer (Figure 6.1). During the monitoring period the groundwater table was located 1–

2 and 2–3 m b.g.s. in the lower and upper parts of the area, respectively. During

fieldwork within the 5 m deep test pit it was observed that most of the water entering

the pit came from an intensely horizontally-fractured zone in the till at a depth of 1.8–

2.5 m. The intensely fractured zone could very well be hydraulically connected to the

sand fill in the deep channel, which might facilitate parts of the percolation. The

bromide tracer study showed that the applied bromide reached the vertical monitoring

well (M6) located in the sand-filled basin (Figure 6.4), however, not in higher

concentrations compared to concentrations detected water from other vertical

monitoring wells. This indicate that the hydraulic contact with the surface in the “basin”

does not differ from that in other parts of the test field, and that the basin is a small pond

filled with sediments from local sources.

A brief description of the sampling procedure is provided in Appendix 2 and the

analysis methods in Kjær et al. (2002). The monitoring design and test site are described

in detail in Lindhardt et al. (2001). In September 2011, the monitoring system was

extended with three horizontal screens (H3) 2 m b.g.s. in the South-Western corner of

the field (Figure 6.1) - one of the screens should be located just below the drain 1.2 m

b.g.s. A brief description of the drilling and design of H3 is given in Appendix 8.

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Figure 6.1.

Overview of the

Faardrup

site. The innermost white area indicates the cultivated land, while the grey

area indicates the surrounding buffer zone. The positions of the various installations are indicated, as is the direction

of groundwater flow (by an arrow). Pesticide monitoring is conducted weekly from the drainage system (during

period of continuous drainage runoff) and monthly and half-yearly from selected vertical and horizontal monitoring

screens as described in Table A2.1 in Appendix 2.

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6.1.2 Agricultural management

Management practice during the 2012-2013 growing seasons is briefly summarized

below and detailed in Appendix 3 (Table A3.5). For information about management

practice during the previous monitoring periods, see previous monitoring reports

available on http://pesticidvarsling.dk/publ_result/index.html.

On 4 April 2012 the field was sown with a mixture of spring barley varieties under

sown with white clover (cv. Liflex) for clover seed production. The barley emerged on

19 April and the white clover on 24 April. Bentazone was used against weeds on 18

May and metrafenon against fungi on 6 June, and both substances included in the

monitoring. At harvest of the spring barley on 12 August 67.5 hkg/ha of grain (85% dry

matter) and 27.6 hkg/ha of straw (100% dry matter) was taken of the field. The

fungicide propyzamid was applied to the white clover on 26 January 2013 and the

herbicide bentazone on 14 May 2013. Bentazone and propyzamid as well as its three

degradation products RH-24580, RH-24644 and RH-24655 were included in the

monitoring. Pests were sprayed with lambda-cyhalothrin twice, on 31 May and 12 June,

but the compound was not monitored. Clover seed yield at harvest on 28 July was 1.56

hkg/ha.

6.1.3 Model setup and calibration

The numerical model MACRO (version 5.2) was applied to the Faardrup site covering

the soil profile to a depth of 5 m b.g.s., always including the groundwater table. The

model was used to simulate the water flow in the variably-saturated zone during the full

monitoring period September 1999-June 2013 and to establish an annual water balance.

Compared to the setup in Brüsch

et al.

(2013b), a year of validation was added to the

MACRO setup for the Faardrup site. The setup was accordingly calibrated for the

monitoring period May 1999-June 2004 and validated for the monitoring period July

2004-June 2013. For this purpose, the following time series were used: observed

groundwater table measured in the piezometers located in the buffer zone, water content

measured at three depths (25, 60 and 110 cm b.g.s.) from the two profiles S1 and S2

(Figure 6.1) and measured drainage flow. Data acquisition and model setup are

described in Barlebo

et al.

(2007).

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Table 6.1.

Annual water balance for

Faardrup

(mm/year). Precipitation is corrected to the soil surface according to

the method of Allerup and Madsen (1979).

Normal

Actual

Measured

Simulated Groundwater

precipitation

Precipitation

evapotranspiration

drainage

recharge

1.7.99–30.6.00

626

715

572

192

152

-50

1.7.00–30.6.01

626

639

383

206

1.7.01–30.6.02

626

810

514

197

201

1.7.02–30.6.03

626

636

480

107

1.7.03–30.6.04

626

685

505

144

1.7.04–30.6.05

626

671

469

131

1.7.05–30.6.06

626

557

372

158

1.7.06–30.6.07

626

796

518

202

212

1.7.07–30.6.08

626

645

522

111

1.7.08–30.6.09

626

713

463

204

1.7.09–30.6.10

626

624

415

155

1.7.10–30.6.11

626

694

471

133

184

1.7.11–30.6.12

626

746

400

106

247

1.7.12–30.6.13

626

569

453

Normal values based on time series for 1961–1990.

For July 1999-June 2002, July 2003-June 2004, in January and February of both 2005 and 2006, and July 2006-June

2007, measured at the DIAS Flakkebjerg meteorological station located 3 km from the test site (see detailed text above).

Groundwater recharge is calculated as precipitation minus actual evapotranspiration minus measured drainage.

Due to electronic problems, precipitation measured at Flakkebjerg located 3 km east of

Faardrup was used for the monitoring periods: July 1999-June 2002, July 2003-June

2004, January and February of both 2005 and 2006, and July 2006-June 2007.

Precipitation measured locally at Faardrup was used for the rest of the monitoring

period including the present reporting period.

6.2

Results and discussion

6.2.1 Soil water dynamics and water balances

The level and dynamics of the soil water saturation in all three horizons in the hydraulic

year July 2012-June 2013 were generally well described by the model (Figure 6.2D,

6.2E and 6.2F). However, for the summer period 2012 the model largely underestimated

the drop in measured water saturation at 25 cm b.g.s. (Figure 6.2D).

The resulting water balance of all monitoring periods is shown in Table 6.1. Compared

with the previous 13 years, the latest hydraulic year July 2012-June 2013 was

characterised by having the second lowest precipitation, a medium actual

evapotranspiration, and a medium measured and simulated drainage. This resulted in the

second lowest groundwater recharge estimated for this site within the PLAP-period.

Precipitation in this year was characterised by medium monthly precipitation compared

to the other PLAP-years, although March was the driest ever registered in PLAP

(Appendix 4). Due to this precipitation pattern, the duration of the simulated percolation

period of the year July 2012-June 2013 was represented by continuous percolation

throughout the period July-April (Figure 6.2A). Compared to the other years, the

climate this year gave rise to a short period, where the groundwater table was just below

drainage level, and causing medium contributions to the drains (Figure 6.2B and 6.2C).

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Precipitation & irrigation

Simulated percolation

May-99

jan-95

May-00

maj-95

sep-95

May-01

jan-96

May-02

May-03

May-04

May-05

May-06

May-07

May-08

May-09

sep-98

May-10

jan-99

maj-99

May-11

sep-99

May-12

maj-96

maj-97

maj-98

sep-96

sep-97

jan-97

jan-98

Precipitation (mm/d)

-1

GWT (m)

(m b.g.s.)

-2

-3

-4

-5

Measured, Average

Groundwater table

Measured, P1

Measured, Average

Measured, P1

(mm/d)

Drainage

Measured

100

SW sat.

(%)

SW sat.

(%)

0.25 b.g.s.

0.25 mm b.g.s.

SW sat. (%)

120

0.6 m b.g.s.

100

8080

6060

4040

0.6 m b.g.s.

1.1 m b.g.s.

120

SW sat. (%)

100

1.1 m b.g.s.

maj-04

May-13

May-10

maj-03

maj-01

May-05

sep-01

May-06

jan-02

May-07

maj-02

maj-00

May-02

sep-03

May-11

May-08

sep-02

sep-00

May-03

May-00

sep-99

jan-04

May-12

May-09

jan-03

jan-01

May-04

May-01

jan-00

May-99

maj-99

Simulated

Measured -

Measured - S1

Measured -

Measured - S2

Figure 6.2.

Soil water dynamics at

Faardrup:

Measured precipitation and simulated percolation 1 m b.g.s. (A),

simulated and measured groundwater level GWT (B), simulated and measured drainage flow (C), and simulated and

measured soil water saturation (SW sat.) at three different soil depths (D, E and F). The measured data in B derive

from piezometers located in the buffer zone. The measured data in D, E and F derive from TDR probes installed at S1

and S2 (Figure 6.1). The dotted vertical line indicates the beginning of the validation period (July 2004-June 2013).

Percolation (mm/d)

jan-00

May-13

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Suction cups - S1

Bromide (mg/l)

Suction cups - S2

1 m b.g.s.

2 m b.g.s.

Bromide (mg/l)

1 m b.g.s.

2 m b.g.s.

Bromide (mg/l)

Drains

Bromide, flow-proportional sampling

Drainage runoff (mm/d)

Bromide (mg/l)

Horizontal monitoring wells - 3.5 m b.g.s.

H1.1

H1.3

H2.1

H2.3

H2.5

H3 ( 2 m b.g.s.)

Jun-05

Jun-06

Jun-07

Jun-08

Jun-09

Jul-04

May-10

May-11

May-12

Figure 6.3.

Bromide concentrations at

Faardrup.

A and B refer to suction cups located at S1 and S2. The bromide

concentration is also shown for drainage runoff (C) and the horizontal monitoring wells. The horizontal wells H1 and

H2 are situated 3.5 m b.g.s., and H3 in 2.5 m b.g.s. (D). From December 2008 to March 2012, bromide measurements

in the suction cups were suspended. The green vertical lines indicate the dates of bromide applications.

The simulated drainage (Figure 6.2C) matched the measured drainage flow to some

degree. Drainage is initiated more or less correct; however the magnitude of drainage

was overestimated in the end of 2012 at the initiation of the drainage season. This

discrepancy could be caused by MACRO‘s lack of ability to capture snow melting. In

the periods of drainage temperature vent periodically below 0°C.

6.2.2 Bromide leaching

The bromide concentration shown in Figure 6.3 and Figure 6.4 relates to the bromide

applied in May 2000 and to August 2008, where 30 kg ha

-1

potassium bromide was

applied for the second time. In September 2008, bromide measurements in the suction

cups and monitoring wells M2 and M7 were suspended. A drastic increase in bromide

concentration in M4 and M5 was detected in May-June 2009 (Figure 6.4). On the 4

April 2012, 30 kg ha

-1

of potassium bromide was applied, the third application.

May-13

Drainage runoff (mm/d)

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Bromide (mg/l)

2.5-3.5 m

3.5-4.5 m

4.5-5.5 m

5.5-6.5 m

Bromide (mg/l)

Nov-08

Nov-09

Nov-10

Nov-11

Figure 6.4.

Bromide concentrations at

Faardrup.

The data derive from the vertical monitoring wells (M4, M5 and

M7). Screen depth is indicated in m b.g.s. The green vertical lines indicate the dates of the two most recent bromide

applications.

Nov-12

Dec-03

Dec-04

Dec-05

Dec-06

Dec-07

Jan-03

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May

Aug

Nov

Mar

Dec

Apr

Sep

Feb

Oct

Jun

Jan

Jul

Precipitation (mm/d)

2011/2012

Precipitation (mm/d)

Precipitation

Bentazone (2012)

Fluazifop-P-butyl (2011)

Simulated percolation

2012/2013

Glyphosate (2011)

Metrafenone (2012)

Figure 6.5.

Application of pesticides included in the monitoring programme and precipitation (primary axis) together

with simulated percolation (secondary axis) at

Faardrup

in 2011/2012 (upper), in 2012/2013 (lower).

6.2.3 Pesticide leaching

Monitoring at Faardrup began in September 1999. Pesticides used as well as their

degradation products are shown in Table 6.2 and Table A7.5, in Appendix 7.

The application time of the pesticides included in the monitoring during the two most

recent growing seasons is shown together with precipitation and simulated precipitation

in Figure 6.5. It should be noted that precipitation is corrected to the soil surface

according to Allerup and Madsen (1979), whereas percolation (1 m b.g.s.) refers to

accumulated values as simulated with the MACRO model.

Percolation (mm/d)

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Table 6.2.

Pesticides analyzed at

Faardrup.

Precipitation (precip.) and percolation (percol.) are accumulated within

the first year (Y 1

precip., Y 1

percol.) and first month (M 1

precip., M 1

percol.) after the first application. C

mean

refers to average leachate concentration at 1 m b.g.s. the first year after application. See Appendix 2 for calculation

method and Appendix 8 (Table A8.5) for previous applications of pesticides. (End monito.) end of monitoring of the

pesticide (P) or their degradation products (M).

Crop

Spring barley 2006

Winter rape 2007

Applied

product

Opus

Analyzed

pesticide

Epoxiconazole(P)

Applica. End

Y 1

M 1

mean

Date

monito. precip. percol. precip. percol

Jun 06

Jun 08 790

306

<0.01

May 06

Aug 06

Feb 07

Jun 08

708

806

333

294

199

158

180

146

327

190

220

215

<0.02

<0.01

<0.02

0.01

<0.01

0.01

0.02

0.06

<0.01

<0.02

<0.01

0.02

2.54

0.01

<0.01

<0,01

<0.01

Starane 180 S Fluroxypyr(P)

CruiserRAPS Thiamethoxam(P)

CGA 322704(M)

Kerb 500 SC

Propyzamide(P)

RH-24580(M)

RH-24644(M)

RH-24655(M)

Winter wheat 2008

Sugar beet 2009

Folicur 250

Stomp SC

Ethosan

Goliath

Tebuconazole(P)

Pendimethalin(P)

Ethofumesate(P)

Metamitron(P)

Desamino-

metamitron(M)

Triflusulfuron-

methyl(P)

IN-D8526(M)

IN-E7710(M)

IN-M7222(M)

Spring barley and

red fescue 2010

Fighter 480

Fox 480 SC

Bentazone(P)

Bifenox(P)

Bifenox acid(M)

Nitrofen(M)

Red fescue 2011

Spring barley and

white clover 2012

Fusilade Max Fluazifop-P(M)

Fusilade Max TFMP(M)

Glyphogan

Fighter 480

Flexity

White clover 2013

Fighter 480

Kerb 400 SC

Glyphosate(P)

AMPA(M)

Bentazone(P)

Metrafenone(P)

Bentazone(P)

Propyzamid (P)

RH24560 (M)

RH24644 (M)

RH24655 (M)

Mar 09 735

Nov 07

Oct 07

Apr 09

Dec 09

Jun 11

693

673

609

351

Safari

Apr 09

Jun 11

Jun 10

Oct 10

Jun 12

693

Jun 12

May 11

Oct 11

May 12

Jun 12

May13

Jan 13

Mar 12 730

Jun 13

730

Aug 12 425

Jun 13

527

580

141

Jun 13

Systematic chemical nomenclature for the analyzed pesticides is given in Appendix 1.

monitoring continues the following year.

The current report focuses on the pesticides applied from 2011 and onwards, while the

leaching risk of pesticides applied before 2011 has been evaluated in previous

monitoring reports (see http://pesticidvarsling.dk/publ_result/index.html).

The following pesticides have been applied on the Faardrup field (Table 6.2) in

•

2011: Fluazifop-P-butyl and glyphosate

2012: Bentazone and metrafenone

2013: Propyzamid and bentazone.

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These pesticides, except fluazifop-P-butyl, and the degradation products of fluazifop-P-

butyl: fluazifop-P and TFMP, glyphosate: AMPA and propyzamid: RH24560, RH24644

and RH24655 have all been included in the PLAP-monitoring programme for Faardrup.

Bentazone, fluazifop-P, glyphosate and AMPA have been tested in PLAP at Faardrup

before 2011 (Table A7.5 in Appendix 7).

In the hydrological years 2010/2011, 2011/2012 and 2012/2013, bentazone was applied

to test its leaching potential in cereal (spring barley) with two different under sowings

(bentazone is not allowed to be used in cereal without under sowing) - red fescue in

2010 and white clover 2012 and 2013. The application onto spring barley and red fescue

on 1 June 2010 was followed by a very wet July-November 2010 resulting in bentazone

to be detected after 16 days in drainage water (0.11 µg/L) (Figure 6.7), and after 23 days

in water from 3.5 m depth (0.052 µg/L). Four and five months later bentazone was

found in water from 3.5 m depth (0.028 µg/L and 0.012 µg/L), and after five and six

and a half months in drainage water 1.2 m depth (0.012 µg/L and 0.013 µg/L).

The application onto spring barley and white clover on the 18 May 2012 was followed

by a dry period until the end of June (Appendix 5) and has not resulted in any detections

of bentazone during the remaining part of 2012. At the end of January one detection

(0.02 µg/L) in the drainage was obtained which could be the outcome of a sudden rise in

the groundwater table during this month caused by high percolation (Figure 6.7). From

the time of this detection until May 2013, where bentazone was applied a second time

on white clover, bentazone was not detected.

Fluazifop-P-butyl has earlier (21 June 2001) been applied at Faardrup, but it has only

been the degradation product fluazifop-P, which have been included in the PLAP-

monitoring. This compound was found in few samples with max concentrations of 3.8

µg/L in drain water and 0.17 µg/L in groundwater. The degradation product TFMP of

fluazifop-P-butyl has, however, not been included in the PLAP-monitoring at Faardrup

before May 2011.

Until 2011, glyphosate has only been applied at Faardrup as weed control both in

August 1999 and October 2001. On 3 October 2011 glyphosate was applied to desiccate

the red fescue. Compared to the earlier applications the dose was 1.000 g active

ingredient ha

-1

higher (from 800 to 1.800 g active ingredient ha

-1

) and plant cover larger.

After three days of no precipitation, a 7 mm day

-1

precipitation resulted in two

detections, 0.019 and 0.025 µg/L, of glyphosate in groundwater samples from the two

upper filters in the down gradient vertical well M4. No further detections were obtained

in the hydrological year 2011/2012 and monitoring was stopped in August 2012. There

has been no detections of AMPA during the samt period of time.

Metrafenone, which was applied on spring barley under sown with white clover in June

2012, has not been detected during the hydrological year 2012/2013.

At Faardrup, bifenox was detected in six water samples collected from drains from

November 2010 to January 2011. The concentrations were below 0.1 µg/L (0.021-0.085

µg/L). Its degradation product bifenox-acid was found in seven samples in 2010 from

the drain, but in high concentrations from 0.23-6.9 µg/L, and in one groundwater

sample from the horizontal well H2 in a concentration of 0.19 µg/L (Figure 6.6). From

January to August 2011 bifenox-acid was found in high, but decreasing concentrations

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in 11 water samples from the drain (8.6 to 0.074 µg/L). It should be noted that bifenox-

acid has a high detection limit 0.05 µg/L. Another degradation product, nitrofen, was

detected in five drain water samples in 2010, concentrations ranging from 0.014 to 0.16

µg/L, and in a drain water sample from 2011 (0.018 µg/L). Neither of the substances

were detected in the period from August 2011 to May 2012, why monitoring for these

compounds in PLAP was stopped.

Aug-10

Aug-11

Dec-10

Dec-11

Apr-11

Apr-12

Feb-11

Feb-12

Oct-10

Oct-11

Jun-11

Jun-12

Jul-10

Precipitation (mm/d)

Bifenox (black)

Nitrofen (red)

Drains

Pesticide (µg/l)

0.1

0.01

Pesticide (µg/l)

0.1

Bifenox-acid

Drainage runoff (DR)

0.01

Pesticide (µg/l)

Bifenox-acid

Monitoring wells

(detections only)

H2 (3.5 m b.g.s.)

0.1

Aug-11

Nov-11

Apr-11

Feb-12

Oct-10

Jan-11

Jul-10

Figure 6.6.

Precipitation and simulated percolation 0.6 m b.g.s. (A) together with concentration of bifenox and

nitrofen (B) and bifenox-acid (C) in the drainage runoff, and the detections of bifenox-acid (E) in the groundwater

monitoring screens at

Faardrup.

The green vertical line indicate the date of bifenox application. Open symbols in B

and C represent values below the detection limit of 0.01 µg/L (bifenox and nitrofen) and 0.05 µg/L (bifenox-acid).

May-12

0.01

DR (mm/d)

Bifenox-acid

Drains

DR (mm/d)

Percolation (mm/d)

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May-11

Mar-12

Aug-11

Dec-11

Apr-10

Precipitation (mm/d)

0.1

Bentazone

Drains

Pesticide (µg/l)

Aug-11

Mar-12

Dec-11

Apr-10

May-11

Bentazone

Drainage runoff (mm/d)

Figure 6.7.

Precipitation and simulated percolation 1 m b.g.s. (A) together with the concentration of bentazone (B) in

the drainage runoff at Faardrup. The green vertical lines indicate the dates of bentazone application.

Apr-13

Feb-11

Sep-12

Oct-10

Jun-12

Jan-10

Jan-13

Jul-10

0.01

DR(mm/d)

Percolation (mm/d)

Apr-13

Feb-11

Sep-12

Oct-10

Jun-12

Jan-10

Jan-13

Jul-10

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7 Pesticide analysis quality assurance

Reliable results and scientifically valid methods of analysis are essential for the integrity

of the present monitoring programme. Consequently, the field monitoring work has

been supported by intensive quality assurance entailing continuous evaluation of the

analyzes employed. Two types of sample are used in the quality control 1) samples with

known pesticide composition and concentration are used for

internal monitoring

of the

laboratory method (internal QA), and 2)

externally spiked samples

that are used to

incorporate additional procedures such as sample handling, transport and storage

(external QA). Pesticide analysis quality assurance (QA) data for the period July 2012

to June 2013 are presented below, while those for the preceding monitoring periods are

given

monitoring

reports

(available

http://pesticid-

varsling.dk/publ_result).

7.1 Materials and methods

All pesticide analyzes were carried out at a commercial laboratory selected on the basis

of a competitive tender. In order to assure the quality of the analyzes, the call for tenders

included requirements as to the laboratory’s quality assurance (QA) system comprising

both an internal and an external control procedure. In addition to specific quality control

under the PLAP, the laboratory takes part in the proficiency test scheme employed by

the Danish EPA when approving laboratories for the Nationwide Monitoring and

Assessment Programme for the Aquatic and Terrestrial Environments (NOVANA).

7.1.1 Internal QA

With each batch of samples the laboratory analyzed one or two control samples

prepared in-house at the laboratory as part of their standard method of analysis. The

pesticide concentration in the internal QA samples ranged between 0.03–0.10 µg/L.

Using these data it was possible to calculate and separate the analytical standard

deviation into within-day (S

), between-day (S

) and total standard deviation (S

). Total

standard deviation was calculated using the following formula (Wilson 1970, Danish

EPA 1997):

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7.1.2 External QA

Every four months, two external control samples per test field were analyzed at the

laboratories along with the various water samples from the five test sites. Two stock

solutions of different concentrations were prepared from standard mixtures in ampoules

prepared by Dr. Ehrenstorfer, Germany (Table 7.1). Fresh ampoules were used for each

set of standard solutions. The standard solutions were prepared two days before a

sampling day and stored in darkness and cold until use. For the preparation of stock

solutions 150 µl (low level) or 350 µl (high level) of the pesticide mixture was pipetted

into a preparation glass containing 10 ml of ultrapure water. The glass was sealed,

shaken thoroughly and shipped to the staff collecting samples on the field locations. The

staff finished the preparation of control samples in the field by quantitatively

transferring the standard solution to a 3.0 l measuring flask. The standard solution was

diluted and adjusted to the mark with groundwater from a defined groundwater well in

each field. After thorough mixing, the control sample was transferred to a sample bottle

similar to the monitoring sample bottles and transported to the laboratory together with

the regular samples.

In the present report period the final concentrations in the solutions shipped for analysis

in the laboratory were 0.050 µg/L for the spiked low level control sample, and 0.117

µg/L for the high level sample. The pesticide concentration in the solution is indicated

in Table 7.1.

Blank samples consisting only of HPLC water were also included as control for false

positive findings in the external QA procedure every month. All samples (both spiked

and blanks) included in the QA procedure were labelled with coded reference numbers,

so that the laboratory was unaware of which samples were controls, blanks or true

samples.

Table 7.1.

Pesticides included in the

external

control samples in the period 1.7.2012-30.6.2013. Concentrations in

both the original ampoules and in the resulting high-level and low-level external control samples used.

The

concentrations in ampule 2 from Ehrenstorfer were not correct.

Compound

Ampoule concentration

Ampoule

High-level control

Low-level control

(µg/L)

AMBA

1000

0.117

0.050

AMPA

1000

Aminopyralid

1000

0.117

0.050

Bentazone

1000

0.117

0.050

Bifenox acid

1000

0.117

0.050

Boscalid

1000

0.117

0.050

CGA 108906

1000

0.117

0.050

CyPM

1000

0.117

0.050

Diflufenican

1000

0.117

0.050

Glyphosate

1000

Metrafenone

1000

0.117

0.050

PPU

1000

0.117

0.050

RH-24644

1000

0.117

0.050

TFMP

1000

0.117

0.050

Tebuconazole

1000

0.117

0.050

Triazinamin-methyl

1000

0.117

0.050

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7.2

Results and discussion

7.2.1 Internal QA

Ideally, the analytical procedure provides precise and accurate results. However, in the

real world results from analysis are subject to a certain standard deviation. Such

standard deviation may be the combined result of several contributing factors. Overall,

the accuracy of an analytical result reflects two types of error: Random errors related to

precision and systematic errors relating to bias. In a programme like PLAP it is relevant

to consider possible changes in analytical “reliability over time”. As random and

systematic errors may both change over time it is relevant to distinguish between

standard deviations resulting from

within-day

variation as opposed to those associated

with

between-day

variation in the analytical result. To this end, control samples are

included in the analytical process as described above. Thus, by means of statistical

analysis of the internal QA data provided by the laboratory it is possible to separate and

estimate the different causes of the analytical variation in two categories:

day-to-day

variation and

within-day

variation (Miller

et al.,

2000; Funk

et al.,

1995). This kind of

analysis can provide an indication of the reliability of the analytical results used in the

PLAP. The statistical tool used is an analysis of variance (ANOVA) and encompasses

all duplicate QA pesticide analyzes, single analyzes being excluded. The analysis can be

divided into three stages:

Normality:

An initial test for normality is made as this is an underlying

assumption for the one-way ANOVA.

Between-day contribution:

In brief, this test will reveal any day-to-day

contribution to the variance in the measurements. If there is none, the total

standard deviation can be considered to be attributable to the within-day error of

the analysis. For this purpose an ANOVA-based test is used to determine if the

between-day standard deviation (S

) differs significantly from 0 (this test is

made as an F-test with the H

between-day mean square = within-day mean

square).

Calculating standard deviations:

If the F-test described above reveals a

contribution from the between-day standard deviation (S

), it is relevant to

calculate three values: The within-day standard deviation (S

), the between-day

standard deviation (S

), and the total standard deviation (S

As the error associated with the analytical result is likely to be highly dependent on the

compound analyzed, the QA applied is pesticide-specific. In the current reporting period

internal quality data was available for 32 compounds. The results of the internal QA

statistical analysis for each pesticide are presented in Table 7.2. For reference, estimated

values are listed for all pesticides, including those for which the between-day

variance is not significantly greater than the within-day variance. ANOVA details and

variance estimates are also included, even for pesticides where the requirement for

normality is not fulfilled. Obviously, such data should be interpreted with caution.

Considering all compounds the mean variation S

was 0.005, S

0.011 and S

was 0.013,

levels that are considered very suitable when relating to the residue limit for pesticides

(0.1 µg/L).

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As a rule of thumb, the between-day standard deviation should be no more than double

the within-day standard deviation. From Table 7.2 it can be seen that S

ratios

greater than two were observed for several compounds. For these compounds, the

results indicate that day-to-day variation makes a significant contribution. Among the

compounds meeting the normality requirement, three out of 16 compounds had ratios

above two, where the highest S

ratio in this group was 4.7 and observed for FMC

65317 (degradation product of clomazon). The two other compounds were boscalid with

a ratio of 2.4 and bifenox with a ratio of 2.3. These are rather low ratios compared to

ratios in the previous report. The cause differs for the three compounds.

FMC 65317 is a degradation product from clomazone and is recently included in the

program (it should be noted that only three sets of QA data were available for this

compound). The number of analyzed samples is not yet sufficient to do a thorough

statistical analysis and the statistical data should therefore be considered tentative.

For boscalid the ratio of 2.4 is still a little too high to meet the criteria but both S

and S

are small values. Compared to last years reporting period, where the ratio was 9.2 and it

did not meet the normality criteria, the analytical procedure now seems to have

improved and in good control. For bifenox it is apparent that the high S

ratio is

caused by the relatively high between-day deviation (S

), but both S

and S

are still

small values, actually indicating an analytical procedure in good control.

When all compounds are considered, high S

ratio is also apparent for clomazone

(6.8), propyzamide (4.9), RH-24580 (4.6), RH-24644 (4.2) and RH-24655 (4.5) (note

normality criteria were not met for these compounds). The high S

ratio is due to a

relatively high between-day deviation

(

)

indicating that it may be possible to improve

the analytical procedure for these compounds to bring down the this deviation. It

should, however, be noted that only three sets of QA data were available for clomazone

and the variation between days (S

) for all five compounds is within the range of S

values of all the other compounds analyzed.

In previous reports high S

ratio was observed for diflufenican (3.2) CGA 108906

(5.3), and aclonifen (7.0). In the current reporting period the S

ratio is still a little

too high for diflufenican (2.3) but has improved since last year. Both CGA 108906 and

aclonifen are now in good control with ratios of 1.0 and 0.6, respectively, and now

meets the criteria for normality.

In last years report MNBA both had the highest total standard deviation (S

) value and

the highest S

ratio of all included compounds. It was suggested that the high S

ratio of MNBA seemed to be caused by a rather high S

indicating that it may be

possible to improve the analytical procedure for this compound to bring down the

between-day deviation. In this reporting period all three standard deviations have been

lowered significantly and the MNBA analysis is now in good control and now meets all

the QA criteria.

The total standard deviation (S

) of the various analyzes of pesticides and degradation

products lie within the range 0.002-0.041 µg/L, the highest value being observed for

aminopyralid. In general, the data suggest that the analytical procedure used for the

quantification of the compounds with high S

ratio and/or high S

may benefit from a

critical review and possible optimisation of within-day variation.

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Table 7.2.

Internal QA of pesticide analyzes carried out in the period 1 July 2012-30 June 2013. Results of the test

for normality, one-way analysis of variance (ANOVA), the estimated values of standard deviations (w: within-day, b:

between-day, t: total – see text for details), pesticide concentration in internal QA sample (Conc.) and number of

duplicate samples (n) are given for each pesticide. For test the P value

α=0.05

was used.

Compound

Normal

Significant S

Ratio

N Conc.

distribution Between day

(µg/L) (µg/L) (µg/L) S

(µg/L)

contribution

α=0.05

ANOVA

α=0.05

Aclonifen

yes

0.003

0.002 0.003

0.6

0.05

AE-05422291*

yes

0.002

0.004 0.005

2.0 30

0.05

AE-B107137*

0.015

0.022 0.026

1.5 30

0.10

AMBA*

yes

0.009

0.009 0.013

1.0

0.10

Aminopyralid

0.015

0.038 0.041

2.6 30

0.10

AMPA*

yes

0.004

0.005 0.006

1.3 33

0.03

Azoxystrobin

0.003

0.011 0.012

3.9 32

0.05

Bentazone

0.004

0.009 0.010

2.1 38

0.05

Bifenox

yes

0.005

0.012 0.013

2.3 19

0.05

Bifenox acid*

0.006

0.029 0.029

4.8 19

0.10

Boscalid

yes

0.001

0.002 0.002

2.4

0.05

CGA108906*

yes

0.011

0.011 0.016

1.0

0.10

CGA62826*

yes

0.007

0.012 0.014

1.6

0.10

Clomazone

0.004

0.027 0.028

6.8

0.05

CyPM*

0.004

0.014 0.015

3.5 32

0.05

Diflufenican

0.001

0.003 0.003

2.3 30

0.05

FMC 65317*

yes

0.006

0.028 0.028

4.7

0.05

Glyphosate

yes

0.003

0.001 0.003

0.5 33

0.03

Mesotrione

yes

0.009

0.007 0.011

0.7

0.10

Metalaxyl-M

0.002

0.005 0.005

2.5 12

0.05

Metrafenone

0.003

0.009 0.009

2.8 35

0.05

MNBA*

yes

0.010

0.005 0.011

0.5

0.10

Nitrofen*

yes

0.004

0.007 0.008

2.0 21

0.05

Propyzamide

0.002

0.009 0.010

4.9 24

0.05

Prosulfocarb

yes

0.006

0.012 0.014

1.9

0.05

RH-24580*

0.002

0.009 0.009

4.6 24

0.05

RH-24644*

0.003

0.012 0.013

4.2 24

0.05

RH-24655*

0.002

0.011 0.011

4.5 24

0.05

Tebuconazole

yes

0.004

0.002 0.005

0.5 16

0.05

TFMP*

0.005

0.011 0.012

2.3 42

0.05

Triazinamin-methyl*

yes

0.003

0.002 0.004

0.9

0.05

*Degradation product.

7.2.2 External QA

As described above the external QA program was based on samples spiked at the field

sites. As part of the quality control a set of blanks made from HPLC water were also

analyzed to evaluate the possibility of false positive findings in the programme. From

these results it can be concluded that contamination of samples during collection,

storage and analysis is not likely to occur. A total of 32 blank samples made from

HPLC water were analyzed and no compounds were detected in any of these analyzed

blank samples. On the basis of this, samples analyzed in the monitoring program and

found to contain pesticides or degradation products are regarded as true positive

findings.

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Table 7.3.

Recovery of externally spiked samples carried out in the period 1.7.2012-30.6.2013. Average recovery

(%) of the nominal concentration at low/high concentration level is indicated for each site. For each compound n

low

and n

high

refer to the number of samples recovered with the spiked compound at low and high concentrations,

respectively. n

total analyzed

is the total number of spiked samples (including both low and high level samples). Bold font

is used for recoveries outside the range of 70-120%.

Tylstrup

Jyndevad

Silstrup

Estrup

Faardrup

Average n

low/

total

high analyzed

Low High Low High Low High Low High Low High

AMBA

64% 3/3

AMPA

18% 1/3

Aminopyralid

73% 4/4

Bentazone

102 101

102

99% 7/7

Bifenox acid

112

114

111

102

106% 2/3

Boscalid

88% 1/1

CGA108906

66% 6/6

CyPM

117

129% 5/5

124 134

137

Diflufenican

90% 6/6

Glyphosate

100

72% 6/6

Metrafenone

90% 6/6

RH-24644

102

99% 2/2

TFMP

66% 6/6

Tebuconazole

100

97% 1/1

The concentrations of glyphosate and AMPA in ampule 2 Dr. Ehrenstorfer A/S were not correct.

Table 7.3 provides an overview of the recovery of all externally spiked samples. Since

the results for each field site in Table 7.3 are based on only a few observations for each

concentration level (high/low), the data should not be interpreted too rigorously.

A total of 42 samples were spiked in this reporting period. In general, the recovery of

the spiked compounds in the samples is acceptable (i.e. in the range 70% to 120%), but

the broad range of average recoveries indicates that for some compounds there may be

reason for concern. Water used for making the spiked samples is taken on location from

up-stream wells. For this reason minor background content may be present in some of

the water used for spiking, and in particular for the low level QC samples, background

content can cause an elevated recovery percentage. For this reason, the QC data must be

considered as a whole, and used to keep track on possible changes in the quality of the

program from period to period. In the present reporting period, especially AMPA data

points to the need of keeping track on these particular compounds.

In previous reports the recoveries of AMPA at Estrup and Faardrup were good and

within the acceptable range. However, in this present reporting period very low

recoveries are observed both at low and high level at Silstrup and at Estrup AMPA was

not recovered in any of the low level external QC samples and only at low recoveries in

the high level samples. A total of 12 external QC samples were analyzed for the content

of AMPA. From these, AMPA was only recovered in 4 samples (and with very low

recoveries). Subsequent analysis of the initial ampoule 2 containing AMPA and

glyphosate showed that the low recoveries and false negative samples are due to a

failure in production of ampoule 2 (initial concentration of AMPA and glyphosate in the

ampoule was to low - especially the AMPA concentration was to low). This flawed

batch of ampoules was unfortuneately used in the external control program throughout

the reporting period. In regard to reliability of the AMPA monitoring sample results,

these data do not cause concern as the laboratory internal control samples show an

analytical method in good control (refer Table 7.2 and Appendix 6 – laboratory internal

control cards).

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Previous reports have discussed the QA for glyphosate and the initiatives that have been

taken to improve the analysis of this compound. In the previous reporting period the

externally spiked samples showed a good recovery (ranging from 73-107%) indicating

that a more robust analytical method has been implemented in the program. In the

present reporting period slightly lower recoveries (61-65%) were observed both at

Silstrup and Estrup, which is related to the incorrect concentrations in ampoule 2.

All the compounds included in the spiking procedure (Table 7.1) were detected in the

laboratory. Additionally, a number of compounds were measured at the threshold of

detection of the analytical procedure (i.e. close to 0.01 µg/L). The occurrence of a

number of false positives is expected when analysing environmental matrices and these

findings do not cause a general concern in relation to the reliability of the analytical

procedures used in the programme.

During the 2012/2013 monitoring period a total of eight pesticides (azoxystrobin,

bentazone, bifenox, diflufenican, glyphosate, metalaxyl-M, metrafenone and

tebuconazole) and nine degradation products (AE-B107137, AMPA, bifenox acid, CGA

108906, CGA 62826, CyPM, PPU, PPU-desamino and TFMP) were detected in

samples from the experimental fields. The external and internal QA data relating to

these particular pesticides/degradation products are of special interest. Control cards for

all presented QA data are illustrated in Appendix 6.

7.3 Summary and concluding remarks

The QA system showed that:

•

The internal QA indicates that the reproducibility of the pesticide analyzes was

good with total standard deviation (S

) in the range 0.002-0.041 µg/L.

•

As demonstrated by the external QA, recovery was generally good in externally

spiked samples. The low recoveries of AMPA and glyphosate are related to the

ampoules used for spiking in the external QA program in the reporting period.

Therefore, the reliability of the AMPA and glyphosate analyzes in the

monitoring program in general is not compromised.

•

Based on the results from analysis of blank ‘HPLC water samples’ shipped

together with the true monitoring samples it is concluded that contamination of

samples during collection, storage, and analysis is not likely to occur.

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8 Summary of monitoring results

This section summarizes the monitoring data from the entire monitoring period, i.e. both

data from the two most recent monitoring years (detailed in this report) and data from

the previous monitoring years (detailed in previous reports available on

http://pesticidvarsling.dk/publ_result/index.html). Pesticide detections in samples from

the drainage systems, suction cups and monitoring wells are detailed in Appendix 5.

The monitoring data in 1 m b.g.s. (collected in drains and suction cups) reveal that the

applied pesticides exhibit three different leaching patterns – no leaching, slight leaching

and pronounced leaching (Table 8.1). Pronounced leaching in 1 m b.g.s. is defined as

root zone leaching (1 m b.g.s.) exceeding an average concentration of 0.1 µg/L within

the first season after application. On sandy and loamy soils, leaching is determined as

the weighted average concentration in soil water and drainage water, respectively

(Appendix 2).

The monitoring data from the groundwater monitoring screens is divided into three

categories: no detection of the pesticide (or its degradation products), detections of the

pesticide (or its degradation products) not exceeding 0.1 µg/L and detections of the

pesticide (or its degradation products) exceeding 0.1 µg/L (Table 8.3). It should be

noted, though, that the present evaluation of the leaching risk of some of these

pesticides is still preliminary as their potential leaching period extends beyond the

current monitoring period. Up to 2013 16 of the applied pesticides (or their degradation

products) exhibited pronounced root zone leaching and 15 pesticides and degradation

products were also detected in the groundwater monitoring screens in concentrations

exceeding 0.1 µg/L.

•

Azoxystrobin, and in particular its degradation product CyPM, leached from the root

zone (1 m b.g.s.) in high average concentrations at the loamy sites Silstrup and

Estrup. CyPM leached into the drainage water in average concentrations exceeding

0.1 µg/L at both the Silstrup and Estrup sites, while azoxystrobin only leached in

concentrations exceeding 0.1 µg/L at Estrup (Table 8.1 and 8.2). At both sites,

leaching of azoxystrobin and CyPM has mostly been confined to the depth of the

drainage system, and they have rarely been detected in groundwater, (Table 8.3 and

8.4). However, detection of CyPM in groundwater monitoring wells has gradually

increased over time with highest numbers of detection found after the latest

applications (2009 at Silstrup, Figure 4.7 and 2008/2012 at Estrup, Figure 5.6). In

2010 and 2011 CyPM continued to enter the drain water especially in Silstrup in

high concentrations but in smaller concentrations in 2012. In this monitoring year

azoxystrobine was not detected, while CyPM was detected in one drain water

sample. Azoxystrobine was applied at Estrup in June 2012, and both azoxystrobine

and CyPM leached in high concentrations to drain water in concentrations ≥ 0.1

µg/L. The degradation product CyPM was found in 7 groundwater samples from the

two horizontal wells, and in one sample the concentration was ≥ 0.1 µg/L. There

were no findings in groundwater monitoring wells. At the loamy Faardrup site

azoxystrobin and CyPM were detected in four samples from the drainage water up

till 2007, and in no samples from the sandy Jyndevad site in the period 2005-2007

(Appendix 5).

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

Table 8.1.

Leaching 1 m b.g.s. of pesticides or their degradation products at the five PLAP sites. The colours indicate

the degree of leaching. Pesticides applied in spring 2013 are not included in the table.

Risk

Parent

Tylstrup

Jyndevad

Silstrup

Estrup

Faardrup

High

Azoxystrobin

Bentazone

Bifenox

Ethofumesate

Fluazifop-P-butyl

Fluroxypyr

Glyphosate

Metalaxyl-M

Metamitron

Metribuzin

Picolinafen

Pirimicarb

Propyzamide

Rimsulfuron

Tebuconazole

Terbuthylazine

Low

Amidosulfuron

Bromoxynil

Clomazone

Diflufenican

Dimethoate

Epoxiconazole

Flamprop-M-isopropyl

Ioxynil

MCPA

Mancozeb

Mesosulfuron-methyl

Metrafenone

Pendimethalin

Phenmedipham

Propiconazole

Prosulfocarb

Pyridate

Triflusulfuron-methyl

None Aclonifen

Aminopyralid

Boscalid

Chlormequat

Clopyralid

Cyazofamid

Desmedipham

Fenpropimorph

Florasulam

Iodosulfuron-methyl

Linuron

Mesotrione

Thiacloprid

Thiamethoxam

Triasulfuron

Tribenuron-methyl

Pesticide (or its degradation products) leached 1 m b.g.s. in average concentrations exceeding 0.1 µg/L

within the first season after application.

Pesticide (or its degradation products) was detected in more than three consecutive samples or in a single

sample in concentrations exceeding 0.1 µg/L; average concentration (1 m b.g.s.) below 0.1 µg/L within the

first season after application.

Pesticide either not detected or only detected in very few samples in concentrations below 0.1 µg/L.

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

Table 8.2.

Number of samples from

1 m b.g.s.

in which the various pesticides and their degradation products were

detected at each site with maximum concentration (µg/L) in parentheses. The table encompasses pesticides/-

degradation products detected in either several (more than three) consecutive samples or in a single sample in

concentrations exceeding 0.1

µg/l.

The pesticide and degradation products are mentioned if analyzed under

compound. Pesticides applied in spring 2013 are not included. N (number of samples with detections). M (maximum

concentration).

Silstrup

10 0.03

High Azoxystrobin

Azoxystrobin

79 0.34

CyPM

Bentazone

2-amino-N-isopropyl-benzamide

45 6.40

Bentazone

5 0.38

Bifenox

20 4.80

Bifenox acid

5 0.34

Nitrofen

20 0.23

Ethofumesate

Fluazifop-P-butyl

Fluazifop-P

51 0.64

TFMP

Fluroxypyr

1 0.01 138 0.35

Glyphosate

AMPA

83 4.70

Glyphosate

61 4.80 54 3.70

Metalaxyl-M

CGA 108906

24 0.12 55 1.20

CGA 62826

4 0.03 10 0.04

Metalaxyl-M

58 0.67

Metamitron

Desamino-metamitron

45 0.55

Metamitron

63 2.10 0

Metribuzin

Desamino-diketo-metribuzin

184 0.62 3 0.09

Diketo-metribuzin

Picolinafen

CL153815

1 0.02

Picolinafen

14 0.05

Pirimicarb

1 0.01 1 0.05

Pirimicarb-desmethyl

Pirimicarb-desmethyl-formamido

23 1.60

Propyzamide

2 0.02

RH-24580

15 0.05

RH-24644

RH-24655

PPU (IN70941)

153 0.09 194 0.29 0

Rimsulfuron

PPU-desamino (IN70942)

45 0.03 123 0.18 0

2 0.08

Tebuconazole

28 0.11

Terbuthylazine

2-hydroxy-desethyl-terbuthylazine 5 0.02

2 0.01 20 0.06 108 1.08

Desethyl-terbuthylazine

17 0.04

43 0.04

Desisopropylatrazine

1 0.04

26 0.04

Hydroxy-terbuthylazine

60 1.55

Terbuthylazine

3 0.11 0

Low Amidosulfuron

Amidosulfuron

Bromoxynil

Clomazone

FMC 65317

5 0.13

Diflufenican

AE-B107137

9 0.12

Diflufenican

1 1.42

Dimethoate

Epoxiconazole

7 0.10

Flamprop-M-isopropyl Flamprop

12 0.11

Flamprop-M-isopropyl

Ioxynil

MCPA

2-methyl-4-chlorophenol

MCPA

6 0.04

Mancozeb

ETU

Mesosulfuron-methyl Mesosulfuron-methyl

Metrafenone

14 0.06

Pendimethalin

Phenmedipham

MHPC

6 0.03

Propiconazole

5 0.18

Prosulfocarb

4 2.69

Pyridate

PHCP

5 0.01

Triflusulfuron-methyl IN-E7710

Risk

Parent

Analyte

Tylstrup

1 0.01

Jyndevad

2 0.03

54 1.90

2 0.04

1 0.10

Estrup

Faardrup

125 1.40 0

261 2.10 4 0.06

0.06 1 0.06

161 20.00 21 43.00

0.15 6 0.09

16 1.90 18 8.60

6 0.16

35 3.36 14 12.00

9 3.80

1.40 1 0.19

414 1.60 15 0.11

291 31.00 5 0.09

5.55 16

26.37 12

0.50

0.07

0.08

0.38

2.50

1.70

0.06

0.05

0.04

0.51

0.02

41 2.00

87 6.30

146 8.20

71 0.44

88 0.99

112 11.00

0.60

0.39

0.03

0.07

0.25

0.05

3.89

0.06

0.07

0.04

0.86

4 0.05

8 1.00

89 8.30

25 0.36

21 0.58

41 10.00

0.28

0.30

0.09

0.04

0.01

0.24

0.28

0.04

0.19

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Table 8.3.

Detections of pesticides and their degradation products in water samples from the

groundwater

monitoring screens

at the five PLAP sites (see Table 8.4 for details). Pesticides applied in spring 2013 are not

included in the table. The substances in Table 8.3 are sorted as in Table 8.1

Risk

Parent

Tylstrup

Jyndevad

Silstrup

Estrup

Faardrup

High

Azoxystrobin

Bentazone

Bifenox

Ethofumesate

Fluazifop-P-butyl

Fluroxypyr

Glyphosate

Metalaxyl-M

Metamitron

Metribuzin

Picolinafen

Pirimicarb

Propyzamide

Rimsulfuron

Tebuconazole

Terbuthylazine

Low

Amidosulfuron

Bromoxynil

Clomazone

Diflufenican

Dimethoate

Epoxiconazole

Flamprop-M-isopropyl

Ioxynil

MCPA

Mancozeb

Mesosulfuron-methyl

Metrafenone

Pendimethalin

Phenmedipham

Propiconazole

Prosulfocarb

Pyridate

Triflusulfuron-methyl

None

Aclonifen

Aminopyralid

Boscalid

Chlormequat

Clopyralid

Cyazofamid

Desmedipham

Fenpropimorph

Florasulam

Iodosulfuron-methyl

Linuron

Mesotrione

Thiacloprid

Metsulfuron-methyl

Thiamethoxam

Triasulfuron

Tribenuron-methyl

Pesticide (or its degradation products) detected in water samples from groundwater monitoring screens in

concentrations exceeding 0.1 µg/L.

Pesticide (or its degradation products) detected in water samples from groundwater monitoring screens in

concentrations not exceeding 0.1 µg/L.

Pesticide (or its degradation products) not detected in water samples from the groundwater monitoring

screens.

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

Table 8.4.

Number of samples from the

groundwater monitoring screens

in which the various pesticides and/or

their degradation products were detected at each site with the maximum concentration (µg/L) in parentheses (see

Appendix 5 for further details). Only high and low risk included. The parent pesticide and degradation products are

mentioned if analyzed under compound. Only pesticides/degradation products with more than two detections at one

site are included. Pesticides applied in spring 2013 are not included. N (number of samples with detections). M

(maximum concentration).

Risk

Parent

Analyte

Tylstrup

Jyndevad

174

0.01

0.05

0.02

2.70

0.68

1.30

Silstrup

Estrup

N M

Faardrup

N M

High Azoxystrobin

Low

Azoxystrobin

CyPM

Bentazone

2-amino-N-isopropyl-benzamide

Bentazone

Bifenox

Bifenox acid

Ethofumesate

Fluazifop-P-butyl

Fluazifop-P

TFMP

Fluroxypyr

Glyphosate

AMPA

Glyphosate

Metalaxyl-M

CGA 108906

184

CGA 62826

Metalaxyl-M

Metamitron

Desamino-metamitron

Metamitron

Desamino-diketo-

Metribuzin

236

metribuzin

Diketo-metribuzin

453

Metribuzin

Pirimicarb

Pirimicarb-desmethyl

Pirimicarb-desmethyl-formamido

Propyzamide

RH-24644

PPU (IN70941)

Rimsulfuron

PPU-desamino (IN70942)

Tebuconazole

Terbuthylazine

2-hydroxy-desethyl-terbuthylazine 1

Desethyl-terbuthylazine

Desisopropylatrazine

Hydroxy-terbuthylazine

Terbuthylazine

Clomazone

FMC 65317

Diflufenican

Dimethoate

Epoxiconazole

Flamprop-M-isopropyl Flamprop-M-isopropyl

Ioxynil

MCPA

Mancozeb

ETU

Metrafenone

Phenmedipham

MHPC

Phenmedipham

Propiconazole

Prosulfocarb

Pyridate

PHCP

Triflusulfuron-methyl IN-M7222

2 0.04 0

0.1 18 0.13 0

1 0.03 0

0.44 16 0.02 13 0.60

0.10 0

3.10 1 0.11 1 0.19

0.04 0

31 1.40

0.07

6 0.17

0.29

1 0.06 1 0.07

0.08 8 0.07 2 0.03

0.04 47 0.67 5 0.03

1.50

0.04

0.08

0.20

0.55

0.01

0.05

0.03

0.01

0.03

0.01

1.83

1.37

0.19

0.17

48 1.30

24 0.63

0.01

0.14

0.03

0.02

0.04

0.08

0.03

374

0.23

0.09

0.01

0.02

0.02 161

0.01 0

5 0.12

0.02 0

0.14 7 0.05

0.05 27 0.03

0.12 1 0.02

0.47

0.09 0

0.02 0

1 0.02

0.04

0.01

0.09

0.94

0.04

0.07

1.90

0.01

0.05

0.03

0.04

0.03

0.31

0.05

0.02

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

•

Bentazone leached through the root zone (1 m b.g.s.) in average concentrations

exceeding 0.1 µg/L in the drainage system at the loamy sites of Silstrup, Estrup and

Faardrup. Moreover, bentazone was frequently detected in the monitoring screens

situated beneath the drainage system at Silstrup and Faardrup (Table 8.3 and 8.4). At

Estrup leaching was mostly confined to the depth of the drainage system and rarely

detected in deeper monitoring screens (Appendix 5). On the sandy soils, bentazone

leached at Jyndevad, but was only detected once 1 m b.g.s. at Tylstrup. At Jyndevad

high concentrations (exceeding 0.1 µg/L) were detected in the soil water samples

from suction cups 1 m b.g.s. four months after application. Thereafter, leaching

diminished, and bentazone was not subsequently detected in the monitoring wells.

Although leached in high average concentrations (>0.1 µg/L) at four sites,

bentazone was generally leached within a short period of time. Initial concentrations

of bentazone were usually very high, but then decreased rapidly. In general,

concentrations exceeding 0.1 µg/L were only found within a period of one to four

months following the application. The degradation product 2-amino-N-isopropyl-

benzamide was detected twice in the vadose zone at Jyndevad, once in drainage

water at Estrup and Faardrup (Table 8.2), and once in water from a horizontal well

at Estrup (Table 8.4). Bentazone has up till 15 May 2013 been applied 17 times to

the five tests fields. Bentazone has in the period 2001 to 2013 been found in eight

groundwater samples in concentration ≥ 0.1 µg/L, while bentazone has been found

in lower concentration in 58 groundwater samples. In total bentazone has been

analyzed in 3.728 groundwater samples.

Bifenox acid (degradation product of bifenox) leached through the root zone and

entered the drainage water system in average concentrations exceeding 0.1 µg/L at

the loamy sites of Silstrup, Estrup and Faardrup. While leaching at Estrup seems to

be confined to the depth of the drainage system, leaching to groundwater monitoring

wells situated beneath the drainage system was observed at Silstrup, where

concentrations exceeding 0.1 µg/L were observed up to six months after application.

As in Silstrup and Estrup the degradation product bifenox acid was found in very

high concentrations in drain water from Faardrup, in a yearly average concentrations

2.54 µg/L (Table 6.2). In 2011/2012 bifenox acid leached, but in small

concentrations, and bifenox was only found in few water samples. Another

degradation product from bifenox and nitrofen, was found in drain water from

Faardrup, often in low concentrations but 0.16 µg/L was found in one drainwater

sample in November 2010. In Silstrup, 0.34 and 0.22 µg/L was found in two

drainwater samples from October 2011. Similar evidence of pronounced leaching

was not observed on the coarse sandy soil as there was only a single detection of

bifenox acid in soil water, whereas bifenox was detected very sporadically in soil

and groundwater, concentrations always less than 0.1 µg/L. Monitoring of bifenox

stopped in December 2012.

In the loamy soil of Estrup, ethofumesate, metamitron, and its degradation product

desamino-metamitron leached through the root zone (1 m b.g.s.) into the drainage

water in average concentrations exceeding 0.1 µg/L (Table 8.1). The compounds

have not been detected in deeper monitoring screens. These compounds also leached

1 m b.g.s. at the Silstrup and Faardrup sites, reaching both the drainage system

(Table 8.1 and 8.2) and groundwater monitoring screens (Table 8.3 and 8.4).

Average concentrations in drainage water were not as high as at Estrup, although

concentrations exceeding 0.1 µg/L were observed in both drainage water and

•

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

groundwater monitoring screens during a 1–6 month period at both Silstrup and

Faardrup (see Kjær

et al.,

2002 and Kjær

et al.,

2004 for details). The above

leaching was observed following an application of 345 g/ha of ethofumesate and

2.100 g/ha of metamitron in 2000 and 2003. Since then, ethofumesate has been

regulated and the leaching risk related to the new admissible dose of 70 g/ha was

evaluated with the two recent applications (2008 at Silstrup and 2009 at Faardrup).

Although metamitron has not been regulated, a reduced dose of 1,400 g/ha was used

at one of the two recent applications, namely that at Silstrup in 2008. The leaching

following these recent applications (2008 at Silstrup and 2009 at Faardrup) was

minor. Apart from a few samples from the drainage system and groundwater

monitoring wells containing less than 0.1µg/L, neither ethofumesate nor metamitron

was found in the analyzed water samples. The monitoring of ethofumesate and

metamitrone stopped in June 2011.

•

Fluazifop-P-butyl has several times been included in the monitoring programme at

Jyndevad, Tylstrup, Silstrup and Faardrup. As fluazifop-P-butyl rapidly degrades,

until July 2008, monitoring has focused only on its degradation product fluazifop-P

(free acid). Except for one detection below 0.1 µg/L in groundwater at Silstrup and

17 detections with eight samples exceeding 0.1 µg/L (four drain water samples,

three soil water samples from the vadose zone and one groundwater sample), Table

8.2 and 8.4) at Faardrup, leaching was not evident. TFMP, the degradation product

of fluazifop-P-butyl, was included in the monitoring programme at Silstrup in July

2008 following an application of fluazifop-P-butyl. After approximately one month,

TFMP was detected in the groundwater monitoring wells, where concentrations at or

above 0.1 µg/L were detected, within a ten-month period, following application

(Figure 4.6, Table 8.3 and 8.4). At the onset of drainage flow in September, TFMP

was detected in all the drainage water samples at concentrations exceeding 0.1 µg/L

(Figure 4.6). The average TFMP concentration in drainwater was 0.24 µg/L in

2008/09. The leaching pattern of TFMP indicates pronounced preferential flow also

in periods with a relatively dry vadose zone. After use in low doses at Silstrup no

leaching was observed, but in 2012 after application in April 2012 TFMP was found

in increasing concentrations in drain water, where 0.64 µg/L was measured in June

2012. In Silstrup TFMP was found in groundwater at the end of April, and it is

possible that preferential flow caused the quick leaching. At Faardrup fluazifop-P-

butyl was applied May 2011 in the new dose, and TFMP was not found in drain or

groundwater. Up till now the pesticide has been applied ten times at four test fields.

Glyphosate and AMPA were found to leach through the root zone at high average

concentrations on loamy soils. At the loamy sites Silstrup and Estrup, glyphosate

has been applied seven times (in 2001, 2002, 2003, 2005, 2007, 2011 and 2012)

within the monitoring period. All seven autumn applications have resulted in

detectable leaching of glyphosate and AMPA from the upper meter into the drainage

water, often at concentrations exceeding 0.1 µg/L several months after application.

Higher leaching levels of glyphosate and AMPA have mainly been confined to the

depth of the drainage system and have rarely been detected in monitoring screens

located below the depth of the drainage systems, although it should be noted that

detections of particularly glyphosate in groundwater monitoring wells at Estrup

seem to increase over the years (Figure 5.7D). For the period June 2007 to July 2010

external quality assurance of the analytical methods indicates that the true

concentration of glyphosate may have been underestimated (see section 7.2.2). On

•

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

two occasions heavy rain events and snowmelt triggered leaching to the

groundwater monitoring wells in concentrations exceeding 0.1 µg/L more than two

years after the application (Figure 5.7D). Numbers of detections exceeding 0.1 µg/L

in groundwater monitoring wells is, however, very limited (only few samples).

Glyphosate and AMPA were also detected in drainage water at the loamy site of

Faardrup (as well as at the now discontinued Slaeggerup site), but in low

concentrations (Kjær

et al.,

2004). Evidence of glyphosate leaching was only seen

on loamy soils, whereas the leaching risk was negligible on the coarse sandy soil of

Jyndevad. Here, infiltrating water passed through a matrix rich in aluminium and

iron, thereby providing good conditions for sorption and degradation (see Kjær

al.,

2005a for details). After application in September 2012 glyphosate and its

degradation product AMPA have been found in concentrations up to 0,66 µg/L in

drainage water from Silstrup, but not in concentrations exceeding 0,1 µg/L in

groundwater. Glyphosate and its degradation product AMPA have been found

frequently in high concentrations ≥ 0.1 µg/L in drain water from Estrup after

application October 2011, and glyphosate was found in few groundwater samples in

concentrations ≥ 0.1 µg/L. Monitoring at Faardrup stopped en August 2012.

•

Two degradation products of metribuzin, diketo-metribuzin and desamino-diketo-

metribuzin, leached 1 m b.g.s. at average concentrations exceeding 0.1 µg/L in the

sandy soil at Tylstrup. Both degradation products appear to be relatively stable and

leached for a long period of time. Average concentrations reaching 0.1 µg/L were

seen as late as three years after application (Table 8.3). Evidence was also found that

their degradation products might be present in the groundwater several years after

application, meaning that metribuzin and its degradation products have long-term

sorption and dissipation characteristics (Rosenbom

et al.,

2009). At both sandy sites

(Tylstrup and Jyndevad), previous applications of metribuzin has caused marked

groundwater contamination with its degradation products (Kjær

et al.,

2005b).

Metribuzine has been removed from the market in Denmark. The monitoring of

metribuzine and degradation products stopped in February 2011.

Metalaxyl-M was applied in June 2010 and found in low concentrations in few

samples from the variably-saturated zone at Tylstrup. Two degradation products

(CGA 62829 and CGA108906) however, were leached from the root zone (1 m

b.g.s.), and CGA108906 in average concentrations exceeding 0.1 µg/L (Table 2.2,

Figure 2.6, Table 8.1-8.4). CGA108906 was found in 95% of the analyzed

groundwater samples and in 32% of the analyzed samples the concentration

exceeded 0.1 µg/L. Similar to the other compounds CGA108906 was detected in

samples from the upstream well of M1 and it was present in the groundwater before

metalaxyl-M was applied to the test field. The background concentration makes it

difficult to determine whether the elevated concentrations observed in downstream

monitoring wells are due to the metalaxyl-M applied in 2010 or to previous

applications “upstream”. Evaluating these results it should be noted that the

precipitation following the application amounted to 140 mm in July 2004 (97%

higher than normal) and 111 mm in June 2004 (50% higher than normal) (see

Appendix 4 and Table 2.2). During the second monitoring year CGA108906 was

found more frequently and in higher concentrations at Tylstrup and Jyndevad in

both the variably-saturated and the saturated zone. Both degradation products were

found at Jyndevad in concentrations exceeding 0.1 µg/L and in increasing

concentrations. In the third monitoring year the parent and degradation products

•

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were found in decreasing concentrations mostly < 0.1 µg/L. As a consequence of the

monitoring results, the Danish EPA has withdrawn the approval of metalaxyl-M in

August 2013. The monitoring of the parent and the two degradation products

continues.

•

At Estrup, CL153815 (degradation product of picolinafen) leached through the root

zone and into the drainage water in average concentrations exceeding 0.1 µg/L

(Appendix 5). CL153815 has not been detected in deeper monitoring screens (Table

8.3). Leaching of CL153815 has not been observed on the sandy soil at Jyndevad

after application in October 2007 (Table 8.1, Table 8.3 and Appendix 5). The

monitoring stopped in March 2010.

Pirimicarb together with its two degradation products pirimicarb-desmethyl and

pirimicarb-desmethyl-formamido has been included in the monitoring programme

for all five sites. All of the three compounds have been detected, but only

pirimicarb-desmethyl-formamido leached in average concentrations exceeding 0.1

µg/L through the root zone (1 m b.g.s.) entering the drainage system (Table 8.1) at

Estrup. Comparable high levels of leaching of pirimicarb-desmethyl-formamido

have not been observed with any of the previous applications of pirimicarb at the

other PLAP sites (Table 8.1 and Kjær

et al.,

2004). Both degradation products

(pirimicarb-desmethyl and pirimicarb-desmethyl-formamido) have been detected in

deeper monitoring screens at Faardrup (Table 8.3 and 8.4). The monitoring stopped

in June 2007.

•

Propyzamide leached through the root zone (1 m b.g.s.) at the loamy Silstrup and

Faardrup sites, entering the drainage system at average concentrations exceeding 0.1

µg/L (Table 8.1 and 8.2) in 2005, 2006 and 2007. Propyzamide was also detected in

the monitoring screens situated beneath the drainage system at Silstrup and

Faardrup. Apart from a few samples at Silstrup, the concentrations in the

groundwater from the screens were always less than 0.1 µg/L (Appendix 5, Table

8.3 and 8.4). Propyzamide was applied white clover in January 2013 at Faardrup,

and neither propyzamide nor the three degradation products (RH-24644, RH-24655,

RH-24580) were found in drain or groundwater. The monitoring is still ongoing.

•

One degradation product of rimsulfuron – PPU – leached from the root zone (1 m

b.g.s.) in average concentrations reaching 0.10–0.13 µg/L at the sandy soil site at

Jyndevad. Minor leaching of PPU was also seen at the sandy site Tylstrup, where

low concentrations (0.021-0.11 µg/L) were detected in the soil water sampled 1 and

2 m b.g.s. (Table 8.1 and 8.2). In groundwater PPU was occasionally detected and

three samples exceeded 0.1 µg/L at Jyndevad in 2011/12, whereas it was detected in

low concentration <0.1 µg/L at Tylstrup (Table 8.3 and 8.3). At both sites, PPU was

relatively stable and persisted in the soil water for several years, with relatively little

further degradation into PPU-desamino. Average leaching concentrations reaching

0.1 µg/L were seen as much as three years after application at Jyndevad. With an

overall transport time of about four years, PPU reached the downstream monitoring

screens. Thus, the concentration of PPU-desamino was much lower and apart from

six samples at Jyndevad, never exceeded 0.1 µg/L. It should be noted that the

concentration of PPU is underestimated by up to 22-47%. Results from the field-

spiked samples indicate that PPU is unstable and may have degraded to PPU-

desamino during analysis (Rosenbom

et al.,

2010a). As a consequence of the

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monitoring results, the Danish EPA has withdrawn the approval of rimsulfuron. The

monitoring stopped December 2012.

•

Terbuthylazine as well as its degradation products leached through the root zone (1

m b.g.s.) at high average concentrations on loamy soils. At the three loamy soil sites

Silstrup, Estrup and Faardrup, desethyl-terbuthylazine leached from the upper meter

entering the drainage water in average concentrations exceeding 0.1 µg/L (Table 8.1

and 8.2). Four years after application in 2005 at Estrup, both terbuthylazine and

desethyl-terbuthylazine were detected in drainage water, but not exceeding 0.1 µg/L.

At Silstrup (Kjær

et al.,

2007) and Faardrup (Kjær

et al.,

2009), desethyl-

terbuthylazine was frequently detected in the monitoring screens situated beneath

the drainage system (Table 8.3 and 8.4), at concentrations exceeding 0.1 µg/L

during a two and 24-month period, respectively. Leaching at Estrup (Kjær

et al.,

2007) was confined to the drainage depth, however. Minor leaching of desethyl-

terbuthylazine was also seen at the two sandy sites Jyndevad and Tylstrup, where

desethyl-terbuthylazine was detected in low concentrations (<0.1 µg/L) in the soil

water sampled 1 m b.g.s. While desethyl-terbuthylazine was not detected in the

groundwater monitoring screens at Tylstrup, it was frequently detected in low

concentration (< 0.1 µg/L) at Jyndevad (Table 8.4, Kjær

et al.,

2004). Marked

leaching of terbuthylazine was also seen at two of the three loamy sites (Estrup and

Faardrup), the leaching pattern being similar to that of desethyl-terbuthylazine. 2-

hydroxy-desethyl-terbuthylazine and hydroxy-terbuthylazine leached at both

Faardrup and Estrup and at the latter site, the average drainage concentration

exceeded 0.1 µg/L. Leaching of these two degradation products was at both sites

confined to the drainage system. None of the two degradation products were

detected in groundwater monitoring screen at Estrup, whereas at Faardrup both were

found, but at low frequencies of detection and concentrations. The monitoring of

terbuthylazine stopped June 2009.

Tebuconazole has been applied in autumn 2007 at Tylstrup, Jyndevad, Estrup and

Faardrup. Only on the loamy soil of Estrup it leached through the root zone (1 m

b.g.s.) and into the drainage water in average concentrations exceeding 0.1 µg/L in

an average yearly concentration of 0.44 µg/L (Table 8.1 and 8.2). Leaching was

mainly confined to the depth of the drainage system, although the snow melt

occurring in March 2011 (more than two years after application) induced leaching of

tebuconazole to the groundwater monitoring well in concentrations exceeding 0.1

µg/L (Table 8.3 and 8.4). None of the applications at the three other PLAP sites

caused tebuconazole to be detected in similarly high concentrations in the vadose

zone, though concentrations below 0.1 µg/L have been detected in a few samples

from the groundwater monitoring screens (Table 8.3 and 8.4). The monitoring

stopped in December 2012.

•

100

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CGA 108906

Diketo-metribuzin

PPU

Desamino-diketo-metribuzin

Desisopropylatrazine

PPU-desamino

CGA 62826

ETU

2-hydroxy-desethyl-…

metalaxyl-M

Prosulfocarb

Desethyl-terbuthylazine

Metribuzin

Clopyralid

Hydroxy-terbuthylazine

Bentazone

Tebuconazole

100

Tylstrup

Suction cup

100

Tylstrup

Groundwater

100

PPU

CGA 108906

CGA 62826

PPU-desamino

Diketo-metribuzin

Bentazone

metalaxyl-M

Desethyl-terbuthylazine

Amidosulfuron

2-amino-N-…

Bifenox

Picolinafen

Bifenox acid

Pirimicarb-desmethyl

AMPA

Fenpropimorph

Desamino-diketo-metribuzin

Tebuconazole

Epoxiconazole

Jyndevad

Groundwater

Jyndevad

Suction cups

>= 0,1

0,01 til 0,1

>= 0,1

0,01 til 0,1

Figure 8.1.

Frequency of detection in samples from the suction cups (left) and groundwater monitoring screens

located deeper than the suction cups (right) at

the sandy soil sites: Tylstrup

and

Jyndevad.

Frequency is estimated

for the entire monitoring period and the length of time that the different pesticides have been included in the

programme and the number of analyzed samples thus varies considerably among the different pesticides. The figure

only includes the fifteen most frequently detected pesticides. Pesticides monitored for less than one year are not

included.

The monitoring data also indicate leaching 1 m b.g.s. of a further 18 pesticides (or their

degradation products), but mostly in low concentrations. Although the concentrations

detected 1 m b.g.s. exceeded 0.1 µg/L in several samples, the average leaching

concentration (1 m b.g.s.) did not. This is summarized in Table 8.1.

Table 8.2 shows the number of samples in which the various pesticides were detected

on each site as well as the maximum concentration. Apart from slight leaching of ETU

(Kjær

et al.,

2002) and amidosulfuron, within this group of 18 pesticides (or their

degradation products) leaching from 1 meter was only observed at the loamy soil sites,

where it was associated with pronounced macropore transport, resulting in very rapid

movement of pesticides through the vadose zone. It should be noted that the findings

regarding amidosulfuron are of very limited use, since the degradation products – with

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which the leaching risk is probably mainly associated – are not included, as methods for

their analysis are not yet available.

16 of the 50 pesticides applied – about 32% – did not leach at all from 1 m b.g.s. during

the monitoring period (Table 8.1). The group of 16 includes the three different

sulfonylureas - metsulfuron-methyl, triasulfuron, iodosulfuron-methyl-sodium and

tribenuron-methyl - applied at several sites. For example, tribenuron-methyl was applied

at four different sites under different hydrological conditions, with percolation (1 m

b.g.s.) during the first month after application ranging from 0 to 114 mm. The

monitoring results give no indication of leaching for any of the compounds or their

degradation products.

The leaching patterns of the sandy and loamy sites are further illustrated in Figure 8.1

and 8.2, showing the frequency of detection in samples collected 1 m b.g.s. (suction

cups on sandy soils and drainage systems on loamy soils) and the deeper located

groundwater monitoring screens.

Desethyl-terbuthylazine

AMPA

Terbuthylazine

CyPM

Desisopropylatrazine

TFMP

Glyphosate

2-hydroxy-desethyl-…

Bentazone

Hydroxy-terbuthylazine

Bifenox acid

Propyzamide

Diflufenican

Desamino-metamitron

RH-24644

Metamitron

AE-B107137

IN-E7710

Flamprop-M-isopropyl

Pendimethalin

Ethofumesate

Azoxystrobin

Tebuconazole

Flamprop

Pirimicarb

Bifenox

Nitrofen

Propiconazole

Prosulfocarb

PHCP

Clopyralid

Chlormequat

RH-24580

Dimethoate

Fenpropimorph acid

Pirimicarb-desmethyl

100

Silstrup

Drain water

Silstrup

Ground water

Figure 8.2.

Frequency of detection in samples from the drainage system (left) and groundwater monitoring screens

located deeper than the drainage system (right)

at the loamy soil sites: Estrup, Silstrup

and

Faardrup.

Frequency is

estimated for the entire monitoring period and the time that the different pesticides have been included in the

programme and the number of analyzed samples thus varies considerably among the different pesticides. The figure

only includes the fifteen most frequently detected pesticides. Pesticides monitored for less than one year are not

included

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Desethyl-terbuthylazine

AMPA

Hydroxy-terbuthylazine

2-hydroxy-desethyl-…

Tebuconazole

Desisopropylatrazine

Azoxystrobin

CL153815

Pendimethalin

Ethofumesate

Picolinafen

Mesosulfuron-methyl

Bifenox acid

Propiconazole

MCPA

Bifenox

Fluroxypyr

Chlormequat

Fenpropimorph

2-amino-N-…

100

Estrup

drain

Estrup

Groundwater

Desethyl-terbuthylazine

Bifenox acid

Terbuthylazine

Desisopropylatrazine

Hydroxy-terbuthylazine

Desamino-metamitron

Metamitron

Bentazone

2-hydroxy-desethyl-terbuthylazine

Ethofumesate

Bifenox

Nitrofen

Tebuconazole

Fluazifop-P

AMPA

Pirimicarb

Pirimicarb-desmethyl

Propyzamide

RH-24644

CyPM

Pendimethalin

Clopyralid

MHPC

Pirimicarb-desmethyl-formamido

Glyphosate

2-amino-N-isopropylbenzamide

Flamprop-M-isopropyl

MCPA

Flamprop

Clomazone

FMC 65317

RH-24655

Phenmedipham

Ioxynil

2-methyl-4-chlorophenol

Fluroxypyr

Fenpropimorph

Propiconazole

100

Faardrup

Drain

>= 0,1

0,01 til 0,1

Faardrup

Groundwater

>= 0,1

0,01 til 0,1

Figure 8.2 (continued).

Frequency of detection in samples from the drainage system (left) and groundwater

monitoring screens located deeper than the drainage system (right)

at the loamy soil sites: Estrup, Silstrup

and

Faardrup.

Frequency is estimated for the entire monitoring period and the time that the different pesticides have

been included in the programme and the number of analyzsed samples thus varies considerably among the different

pesticides. The figure only includes the fifteen most frequently detected pesticides. Pesticides monitored for less than

one year are not included

On the sandy soils the number of leached pesticides as well as the frequency of

detection was lower than on loamy soils (Figure 8.1 and 8.2), the exceptions being the

mobile and persistent degradation products of metalaxyl-M, rimsulfuron and

metribuzin, frequently found in both suction cups and groundwater monitoring wells.

This difference was mainly due to the different flow patterns characterising the two

different soil types. On the sandy soils infiltrating water mainly passed through the

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matrix, which provides good conditions for sorption and degradation. Pesticides being

leached in the sandy soils were thus restricted to mobile as well as persistent pesticides.

On the loamy soils pronounced macropore transport resulted in the pesticides moving

very rapidly through the variably-saturated zone. Compared to the sandy soils residence

time was much lower on the structured, loamy soils. As a result of this, various types of

pesticides, even those being strongly sorbed, were prone to leaching on the loamy types

of soil.

At the loamy sites pronounced leaching was generally confined to the drainage system

(Figure 8.2), and several pesticides were often detected in the drainage system, whereas

the frequency of detection in the groundwater monitoring screens situated beneath the

drainage system was lower and varied considerably between the three sites (Figure 8.2).

These differences should be seen in relation to the different sampling procedures

applied. Integrated water samples are sampled from the drainage systems, and the

sample system continuously captures water infiltrating throughout the drainage runoff

season. However, although the monitoring screens situated beneath the drainage

systems were sampled less frequently (on a monthly basis from a limited number of the

monitoring screens (Appendix 2), pesticides were frequently found in selected screens

at Faardrup and Silstrup. Hitherto, at the Estrup site, leaching of pesticides has mainly

been confined to the depth of the drainage system. Apart from 99, 91, 58 and 87

samples containing glyphosate and AMPA, desisopropyl-atrazine, bentazone and TFMP

respectively, pesticides have only occasionally been detected in the screens beneath the

drainage system (Appendix 5 and Figure 8.2).

The differences are, however, largely attributable to the hydrological and geochemical

conditions. Compared to the Silstrup and Faardrup sites, the C horizon (situated beneath

the drainage depth) at the Estrup site is less permeable with less preferential flow

through macropores (see Kjær

et al.

2005c for details). The movement of water and

solute are therefore slower at Estrup, allowing dispersion, dilution, sorption and

degradation and thereby reducing the risk of transport to deeper soil layers. An

indication of this is the long periods with groundwater table over drainage depth in

which an increasing lateral transport to the drainage system will occur.

Comparing the loamy sites, the number of drainage water samples containing

pesticides/degradation products was higher at Silstrup and Estrup than at Faardrup,

which is largely attributable to the differences in the hydrological conditions.

The occurrence of precipitation and subsequent percolation within the first month after

application were, generally, higher at Silstrup and Estrup than at Faardrup where the

infiltration of water is smallest.

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Appendixes

Appendix 1

Chemical abstracts nomenclature for the pesticides encompassed by the PLAP

Appendix 2

Pesticide monitoring programme – Sampling procedure

Appendix 3

Agricultural management

Appendix 4

Precipitation data for the PLAP sites

Appendix 5

Pesticide detections in samples for drains, suction cups and groundwater

monitoring wells

Appendix 6

Laboratory internal control cards

Appendix 7

Pesticides analyzed at five PLAP sites in the period up to 2007

Appendix 8

New horizontal wells

Appendix 9

Groundwater age from recharge modelling and tritium-helium analysis

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Appendix 1

Chemical abstracts nomenclature for the pesticides encompassed by the PLAP

Table A1.1.

Systematic chemical nomenclature for the pesticides and degradation products encompassed by the

PLAP. P (parent). M (degradation product).

Parent pesticide

Aclonifen

Amidosulfuron

Aminopyralid

Azoxystrobin

Bentazone

Bifenox

Boscalid

Bromoxynil

Chlormequat

Clomazon

Clopyralid

Cyazofamid

Desmedipham

Diflufenican

Dimethoat

Epoxiconazole

Ethofumesat

Fenpropimorph

Flamprop-M-

isopropyl

Flamprop-M-

isopropyl

Florasulam

Fluazifop-P-buthyl

Fluroxypyr

Glyphosate

Iodosulfuron-

methyl-natrium

Iodosulfuron-

methyl-natrium

Ioxynil

Linuron

Mancozeb

MCPA

Mesosulfuron-

methyl

P/M Analyte

Systematic name

Aclonifen

Amidosulfuron

Desmethyl-

amidosulfuron

Aminopyralid

Azoxystrobin

CyPM

2-amino-N-

isopropylbenzamid

Bentazone

Bifenox

Bifenox acid

Nitrofen

Boscalid

Bromoxynil

Chlormequat

Clomazon

FMC65317

Clopyralid

Cyazofamid

Desmedipham

EHPC

AE-05422291

AE-B107137

Diflufenican

Dimethoat

Epoxiconazole

Ethofumesat

Fenpropimorph

Fenpropimorph-acid

Flamprop (free acid)

2-chloro-6-nitro-3-phenoxyaniline

N-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-amino]sulfonyl]-N-

methylmethanesulfonamide

3-(4-hydroxy-6-methoxypyrimidin-2-yl)-1-(N-methyl-N-methylsulfonyl-

aminosulfonyl)-urea

4-amino-3,6-dichloropyridine-2-carboxylic acid

Methyl (E)-2-{2-[(6-(2-cyanophenoxy)-4-pyrimidin-4-yloxy]phenyl}-3-

methoxyacrylate

E-2-(2-[6-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl) – 3-methoxyacrylic acid

2-amino-N-isopropylbenzamide

3-(1-methylethyl)-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2 dioxide

methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate

5-(2,4-dichlorophenoxy)-2-nitrobenzoic acid

2,4-dichlorophenyl 4'-nitrophenyl ether

2-chloro-N-(4'-chlorobiphenyl-2-yl)nicotinamide

3,5-dibromo-4-hydroxybenzonitrile

2-chloroethyltrimethylammonium chloride

2-[(2-chlorphenyl)methyl]-4,4-dimethyl-3-isoxazolidione

(N-[2- chlorophenol)methyl] -3-hydroxy-2,2- dimethyl propanamide

(Propanamide-clomazone)

3,6-Dichloropyridine-2-carboxylic acid

4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide

Ethyl 3-(phenylcarbamoyloxy)phenylcarbamate

Carbamic acid, (3-hydroxyphenyl)-ethyl ester

2-[3-(trifluoromethyl)phenoxy]pyridine-3-carboxamide

2-[3-(trifluoromethyl)phenoxy]pyridine-3-carboxylic acid

2',4'-difluoro-2-(a,a,a-trifluoro-m-tolyloxy)nicotinanilide

O,O-dimethyl S-methylcarbamoylmethyl-phosphorodithioate

(2RS, 3SR)-1-(2-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophenyl)propyl)-1H-

1,2,4-triazol

(±)-2-ethoxy-2,3-dihydro-3,3-dimethylbenzofuran-5-yl-methanesulfonate

Cis-4-[3-[4-(1,1-dimethylethyl)-phenyl]-2-methylpropyl]-2,6-

imethylmorpholine

Cis-4-[3-[4-(2-carboxypropyl)-phenyl]-2-methylpropyl]-2,6-

dimethylmorpholine

N-benzoyl-N-(3-chloro-4-flourophenyl)-D-alanine

Flamprop-M-isopropyl Isopropyl N-benzoyl-N-(3-chloro-4-flourophenyl)-D-alaninate

Florasulam

2’,6’,8-Trifluoro-5-methoxy-s-triazolo [1,5-c]pyrimidine-2-sulfonanilide

Florasulam-desmethyl N-(2,6-difluorophenyl)-8-fluro-5-hydroxy[1,2,4]triazolo[1,5-c]pyrimidine-2-

sulfonamide

Fluazifop-P (free acid) (R)-2-(4-((5-(trifluoromethyl)-2-pyridinyl)oxy)phenoxy-propanoic acid

Fluazifop-P-buthyl

butyl (R)-2-{4-[5-(trifluoromethyl)-2-pyridyloxy]phenoxy}propionate

TFMP

5-trifluoromethyl-pyridin-2-ol

Fluroxypyr

(4-amino-3,5-dichloro-6-fluro-2-pyridinyl)oxy]acetic acid

AMPA

Amino-methylphosphonic acid

Glyphosate

N-(phosphonomethyl)glycine

Iodosulfuron-methyl- sodium salt of methyl 4-iodo-2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-

natrium

yl)amino]carbonyl]amino]sulfonyl]benzoate

Metsulfuron methyl

methyl 2-(4-methoxy-6-methyl-1,3,5-triazin-2-ylcarbamoylsulfamoyl)benzoate

Ioxynil

Linuron

ETU

4-chlor-2-

methylphenol

MCPA

Mesosulfuron

4-hydroxy-3,5-diiodobenzonitrile

3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea

Ethylenethiourea

2-methyl-4-chlorophenol

(4-chloro-2-methylphenoxy)acetic acid

2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-4-

[[(methylsulfonyl)amino]methyl]benzoic acid

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Table A1.1 continued.

Systematic chemical nomenclature for the pesticides and degradation products encompassed

by the PLAP. P (parent). M (degradation product).

Parent pesticide

Mesosulfuron-

methyl

Mesotrione

Metalaxyl-M

Metamitron

Metrafenone

Metribuzin

Pendimethalin

Phenmedipham

Picolinafen

Pirimicarb

Propiconazol

Propyzamid

Prosulfocarb

Pyridat

Rimsulfuron

Tebuconazole

Terbuthylazin

Thiacloprid

Thiamethoxam

Triasulfuron

Tribenuron-methyl

Triflusulfuron-

methyl

Triflusulfuron-

methyl

Triflusulfuron-

methyl

Triflusulfuron-

methyl

P/M Analyte

Systematic name

Methyl 2-[3-(4,6-dimethoxypyrimidin-2-yl)ureidosulfonyl]-4-

methanesulfonamidomethylbenzoate

AMBA

2-amino-4-methylsulfonylbenzoic acid

Mesotrione

2-(4-mesyl-2-nitrobenzoyl)cyclohexane-1,3-dione

MNBA

methylsulfonyl-2-nitrobenzoic acid

CGA 108906

2-[(1-carboxyethyl)(methoxyacetyl)amino]-3-methylbenzoic acid

CGA 62826

2-[(2,6-dimethylphenyl)(methoxyacetyl)amino]propanoic acid

Metalaxyl-M

methyl N-(methoxyacetyl)-N-(2,6-xylyl)-D-alaninate

Metamitron

4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazin-5-one

Metamitron-desamino 4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazine-5-one

Metrafenone

3'-bromo-2,3,4,6'-tetramethoxy-2',6-dimethylbenzophenone

Metribuzin

4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazine-5-one

Metribuzin-desamino 6-(1,1-dimethylethyl)-3-(methylthio)- 1,2,4-triazin-5-(4H)-one

Metribuzin-desamino- 6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazine-3,5-dione

diketo

Metribuzin-diketo

4-amino-6-tert-butyl-4,5-dihydro-1,2,4-triazine-3,5-dione

Pendimethalin

N-(1-ethyl)-2,6-dinitro-3,4-xynile

3-aminophenol

1-amino-3-hydroxybenzene

MHPC

Methyl-N-(3-hydoxyphenyl)-carbamate

Phenmedipham

3-[(methoxycarbonyl)amino]phenyl (3-methylphenyl)carbamate

CL153815

6-(3-trifluoromethylphenoxy)-2-pyridine carboxylic acid

Picolinafen

4'-fluoro-6-(a,a,a-trifluoro-m-tolyloxy)pyridine-2-carboxanilide

Pirimicarb

2-(dimethylamino)-5,6-dimethyl-4-pyrimidinyldimethylcarbamate

Pirimicarb-desmethyl 2-(dimethylamino)-5,6-dimethyl-4-pyrimidinylmethylcarbamate

Pirimicarb-desmethyl- 2-methylformamido-5,6-dimethylpyrimidine-4-yl dimethylcarbamate

formamido

Propiconazol

1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-

triazole

Propyzamid

3,5-dichloro-N-(1,1-dimethylprop-2-ynyl)benzamide

RH24580

N-(1,1-dimethylacetonyl)-3,5-dichlorobenzamide

RH24644

2-(3,5-dichlorophenyl)-4,4-dimethyl-5-methylene-oxalzoline

RH24655

3,5-dichloro-N-(1,1-dimethylpropenyl)benzamide

Prosulfocarb

N-[[3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-3-[2-(3,3,3,-

trifluro=propyl)phenylsulfonyl]urea

PHCP

3-phenyl-4-hydroxy-6-chloropyridazine

Pyridat

O-6-chloro-3-phenylpyridazin-4-yl S-octyl thiocarbonate

IN70941 (PPU)

N-(4,6-dimethoxy-2-pyrimidinyl-N-((3-ethylsulfonyl)-2-pyridinyl)urea

(IN70941)

IN70942 (PPU-

N-((3-(ethylsulfonyl)-2-pyridyl)-4,6 dimethoxy-2 pyrimidinamine (IN70942)

desamino)

Rimsulfuron

N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-3-(ethylsulfonyl)-2-

pyridinesulfonamide

Tebuconazole

a-[2-(4-chlorophenyl)ethyl]-a-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol

2-hydroxy-desethyl-

6-hydroxy-N-(1,1-dimethylethyl)-1,3,5,triazine-2,4-diamine

terbuthylazine

2-hydroxy-

6-hydroxy-N-(1,1-dimethylethyl)-N´-ethyl-1,3,5,triazine-2,4-diamine

terbuthylazin

Desethylterbuthylazin 6-chloro-N-(1,1-dimethylethyl)-1,3,5,triazine-2,4-diamine

Desisopropylatrazin

6-chloro-N-ethyl-1,3,5-triazine-2,4-diamine

Terbuthylazin

6-chloro-N-(1,1-dimethylethyl)-N-ethyl-1,3,5,triazine-2,4-diamine

Thiacloprid-amide

(3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene) urea

Thiacloprid sulfonic

sodium 2-[[[(aminocarbonyl)amino]-carbonyl][(6-chloro-3-pyridinyl)-

acid

methyl]amino]ethanesulfonate

M34

2-{carbamoyl[(6-chloropyridin-3-yl)methyl]amino}etanesulfonic acid

Thiacloprid

(Z)-3-(6-chloro-3-pyridylmethyl)-1,3-thiazolidin-2-ylidenecyanamide

CGA 322704

[C(E)]-N-[(2-chloro-5-thiazolyl)methyl]-N'-methyl-N'-nitroguanidine

Thiamethoxam

3-(2-cholro-thiazol-5-ylmethyl)-5-methyl[1,3,5]oxadiazinan-4ylidene-N-

nitroamine

Triasulfuron

1-[2-(2-chloroethoxy)phenylsulfonyl]-2-(4-methoxy-6-methyl-1,3,5-triazine-2-

yl)-urea

Triazinamin

2-amino-4-methoxy-6-methyl-1,3,5-triazine

Triazinamin-methyl

4-methoxy-6-methyl-1,3,5-triazin-methylamine

Tribenuron-methyl

methyl 2-[4-methoxy-6-methyl-1,3,5-triazin-2-

yl(methyl)carbamoylsulfamoyl]benzoate

IN-D8526

N,N-dimethyl-6-(2,2,2-trifluoroethoxy)-1,3,5-triazine-2,4-diamine

IN-E7710

IN-M7222

Triflusulfuron-methyl

N-methyl-6-(2,2,2-trifluoroethoxy)-1,3,5-triazine-2,4-diamine

6-(2,2,2-trifluoroethoxy)-1,3,5-triazine-2,4-diamine

methyl 2-[4-dimethylamino-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-

ylcarbamoylsulfamoyl]-m-toluate

Mesosulfuron-methyl

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Appendix 2

Pesticide monitoring programme – Sampling procedure

From each of the PLAP sites, samples were collected of groundwater, drainage water

and soil water in the variably-saturated zone. A full description of the monitoring design

and sampling procedure is provided in Lindhardt

et al.

(2001) and Kjær

et al.

(2003),

respectively.

Until March 2002, pesticide analysis was performed monthly on water samples from the

suction cups located both 1 m b.g.s. and 2 m b.g.s., from two screens of the horizontal

monitoring wells and from two of the downstream vertical monitoring wells. In

addition, more intensive monitoring encompassing all four groups of suction cups, six

screens of the horizontal monitoring wells and five monitoring wells was performed

every four months (Kjær

et al.,

2002). At the loamy sites, the pesticide analysis was also

performed on drainage water samples.

The monitoring programme was revised in March 2002 and the number of pesticide

analyzes was reduced. At the loamy sites, pesticide analysis of water sampled from the

suction cups was ceased, and the monthly monitoring was restricted to just one

monitoring well. At Jyndevad, pesticide analysis of the suction cups located 2 m b.g.s.

was ceased and the interval for the intensive monitoring encompassing the larger

number of monitoring screens was extended to six months, except for the suction cups 2

m b.g.s. at Tylstrup, where the four-month interval was retained (Kjær

et al.,

2003).

On the sandy soils, the analysis of a number of pesticides in water from the monitoring

wells had to be further reduced, due to economical constraints imposed by the high

prices on pesticide analysis. This reduction was based on results from the suction cups

implying that leaching risk of certain pesticides was negligible, why analysis of a

limited number of groundwater samples would be reasonable (see Table A5.1 and Table

A5.2 in Appendix 5).

Table A2.1.

Pesticide monitoring programme in suction cups (S), horizontal monitoring wells (H) and vertical

monitoring wells (M) 2012-13. Water sampling places (S, H and M) from where sampling stopped in 2008 and 2009

are given in bold. Well M10 at Silstrup was included in the programme on 5 February 2009.

Site

Monthly monitoring

Half-yearly monitoring

Not monitored

(Intensive)

(Extensive)

Tylstrup

M4, M5, S1a, S2a, H1

M1, M3, M4, M5, S1a,

M2,

M6,

S2a, S1b , S2b

Jyndevad

M1, M4, S1a, S2a, H1

M2, M5, M7

M3,

M6,

S1b, S2b

Silstrup

Estrup

Faardrup

M5, H1.2, H2

M4, H1.2, H2

M4, M5, H2.3, H2

M9, M10. M12, H1.1, H1.3

M1, M5, M6, H1.1 H1.3

M6, H2.1, H2.5

M1, M2, M4,

M6,

M8, M7,

M11,

M13, H2.1, H2.2, H2.3

M2,

M3, M7

M1,

M2, M3, M7, H1.1,

H1.2,

H1.3

S1a and S1b refer to suction cups installed 1 and 2 m b.g.s., respectively, at location S1, whereas S2a and S2b refer to

suction cups installed 1 and 2 m b.g.s., respectively, at location S2.

- Mixed water samples from three screens.

At Tylstrup suctions cups installed 2 m b.g.s.are monitored four times a year (see text).

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In March 2008, a new revision of the monitoring programme was completed resulting in

an optimization of the programme including an additional reduction in the sampling

programme (Table A2.1). On the loamy sites, sampling from the suction cups for

inorganic analysis, from one-two monitoring wells per site, and one horizontal well at

Silstrup (H2) and Faardrup (H1) was suspended. On the sandy sites, only sampling from

the monitoring well M6 at Tylstrup has been suspended (see Rosenbom

et al.,

2010b for

details).

From 2012 five new horizontal monitoring wells at the five PLAP sites were sampeled

monthly. Each horizontal well contain three screens and water sampels form the screens

are mixed to one sample.

Until July 2004, pesticide analyzes were performed weekly on water sampled time-

proportionally from the drainage system. Moreover, during storm events additional

samples (sampled flow-proportionally over 1–2 days) were also analyzed for pesticides.

In June 2004 the drainage monitoring programme was revised. From July 2004 and

onwards pesticide analyzes were done weekly on water sampled flow- proportionally

from the drainage water system. See Kjær

et al.

2003 for further details on the methods

of flow-proportional sampling. The weighted average concentration of pesticides in the

drainage water was calculated according to the following equation:

∑

where:

n = Number of weeks within the period of continuous drainage runoff

= Weekly accumulated drainage runoff (mm/week)

= Pesticide concentration collected by means of the flow-proportional sampler

(µg/L). ND are included as 0 µg/L calculating average concentrations.

Until July 2004 where both time and flow-proportional sampling was applied the

numbers were:

If no flow event occurs within the i

th week

If a flow event occurs within the i

th week and if Cf

·Vf

> Ct

·V

where:

n = Number of weeks within the period of continuous drainage runoff

= Weekly accumulated drainage runoff (mm/week)

= Drainage runoff accumulated during a “flow event” (mm/storm event)

= Pesticide concentration in the “event samples” collected by means of the flow-

proportional sampler (µg/L)

= Pesticide concentration in the weekly samples collected by means of the time-

proportional sampler (µg/L)

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Table 2.2, 3.2, 4.2, 5.2 and 6.2 report the weighted average leachate concentration in the

drainage water within the first drainage season after application. In these tables this

calculation period is defined as the period from application until 1 July the following

year, as pesticides are usually present in the first drainage runoff occurring after

application of pesticide.

On the sandy soils the weighted average concentration of pesticides leached to the

suction cups situated 1 m b.g.s. was estimated using the measured pesticide

concentration and estimated percolation on a monthly basis. Pesticide concentrations

measured in suction cups S1 and S2 were assumed to be representative for each sample

period. Moreover, accumulated percolation rates deriving from the MACRO model

were assumed to be representative for both suction cups S1 and S2. For each of the

measured concentrations, the corresponding percolation (Perc.) was estimated according

to the equation:

∑

where:

t = sampling date; t

= 0.5(t

i-1

) ; t

=0.5(t

i+1

)

= daily percolation at 1 m b.g.s. as estimated by the MACRO model (mm)

The average concentration was estimated according to the equation:

∑

where:

= measured pesticide concentration in the suction cups located 1 m b.g.s.

Table 2.2 and 3.2 report the weighted average leachate concentration. In these tables

this calculation period is defined as the period from the date of first detection until 1

July the following year. On sandy soils the transport of pesticides down to the suction

cups situated at 1 m depth may take some time. In most cases the first detection of

pesticides occurs around 1 July, why the reported concentration represents the yearly

average concentration. In a few cases the first detection of pesticides occurs later, but

this later occurrence does not affect the weighted average calculation. E.g. the reported

average concentration using a calculation period from the first detection until 1 July the

following year is equal to that using a calculation period of a year (1 July–30 June) the

following year). Unless noted the concentrations listed in Table 2.2 and 3.2 can

therefore be considered as yearly average concentrations. In the few cases where

reported concentrations are either not representative for an annual average concentration

or not representative for the given leaching pattern (leaching increases the second or

third year after application) a note is inserted in the table.

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Appendix 3

Agricultural management

Table A3.1.

Management practice at

Tylstrup

during the 2009 to 2013 growing seasons. The active

ingredients of the various pesticides are indicated in parentheses.

Date

08-07-2009

20-08-2009

28-08-2009

04-04-2010

26-04-2010

04-05-2010

06-05-2010

17-05-2010

26-05-2010

08-06-2010

15-06-2010

24-06-2010

01-07-2010

06-07-2010

09-07-2010

16-07-2010

23-07-2010

27-07-2010

02-08-2010

09-08-2010

17-08-2010

23-08-2010

20-10-2010

17-04-2011

18-04-2011

19-04-2011

10-05-2011

16-08-2011

18-08-2011

22-03-2012

24-03-2012

29-04-2012

21-05-2012

25-05-2012

31-05-2012

28-06-2012

13-08-2012

27-08-2012

31-08-2012

20-09-2012

23-09-2012

12-10-2012

04-04-2013

02-05-2013

08-05-2013

Management practice

Irrigation 27 mm. Started 08/07 23.00 Ended 09/07 07.00

Mavrik 2F (tau-fluvalinate) - pests - 0.1 l/ha (not analyzed)

Harvest of spring barley. Stubleheight 16 cm, grainyield 53.4 hkg/ha 85% DM

Straw remowed, yield 17.4 hkg/ha 100% DM

Ploughed - depth 24 cm

Rolled with concrete roller

Seed bed preparation, 10.0 cm depth (across)

Planting of potatoes. cv. Kuras rowdistance 75 cm, plantdistance 25 cm, depth 17 cm, final

plantnumber 4,0/m

Ridging

Fenix (aclonifen) - weeds - 1.0 l/ha + Titus WSB (rimsulfuron) - weeds - 10 g/ha

Titus WSB (rimsulfuron) - weeds - 20 g/ha

Ranman (cyazofamid) - fungi - 0.2 l/ha

Irrigation 29 mm. Started 06/07 22:00 Ended 07/07 07:00

Ridomil Gold MZ Pepite (mancozeb - metalaxyl) - fungi - 2.0 kg/ha

Ranman (cyazofamid) - fungi - 0.2 l/ha

Irrigation 28 mm. Started 27/07 22:00 Ended 28/07 07:00

Ranman (cyazofamid) - fungi - 0.2 l/ha

Dithane NT (mancozeb) - fungi - 2.0 kg/ha

Harvest of potatoes. Tuber yield 128,02 hkg/ha - 100% DM

Ploughed - depth 24 cm.

Rolled with concrete roller

Spring barley sown, cv.TamTam, seeding rate 180 kg/ha, sowing depth 3.3 cm, row distance 12.5

cm. Final plantnumber 365/m

Seed bed preparation, 8 cm depth

Oxitril CM (ioxynil + bromoxynil) - weeds - 0.4 l/ha (not analyzed)

Harvest of spring barley. Stubble height 14 cm, grain yield 75.7 hkg/ha - 85% DM

Straw remowed, yield 34.6 hkg/ha - 100% DM

Ploughed - depth 24 cm.

Spring barley

Spring barley sown, cv. TamTam, seeding rate 185 kg/ha, sowing depth 2.75 cm, row distance 12.5

cm. Using combine driller with a tubular packer roller, Final plant number 344 /m2 Sown with rotor

harrow combine sowing machine

Fertilisation - 123.9 N, 17.7 P, 59 K, kg/ha

Fox 480 SC (bifenox) - weeds - 1.2 l/ha

Mustang forte (aminopyralid/florasulam/2,4-D) - weeds - 0.75 l/ha

Irrigation 24 mm. Started 31/5 ended

31/5

Bell (boscalid + epoxiconazol) - fungi - 1.5 l/ha (epoxiconazol not analyzed)

Glyfonova 450 Plus (glyphosate) - weeds - 2.4 l/ha (not analyzed)

Harvest of spring barley. Tubbleheight 15 cm, grain yield 62.0 hkg/ha - 85% DM. Straw remowed,

yield 37.3 hkg/ha - 100% DM

Tracer (potasium bromide), 30 kg/ha

Ploughed - depth 22 cm

Winter rye sown, cv. Magnifico, seeding rate 64.0 kg/ha, sowing depth 3.5 cm, row distance 13.0

cm. Finalplant number 125/m2 Sown with rotorharrow combine sowing machine

Boxer (prosulfocarb) - weeds - 4.0 l/ha

Fertilisation - 56.7 N, 8.1 P, 27 K, kg/ha

Fertilisation - 71.4 N, 10.2 P, 34 K, kg/ha

Starane XL (fluroxypyr) - weeds - 1.2 l/ha

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Date

20-08-2013

Management practice

Harvest of winter rye. Stubleheight 15 cm, grainyield 77.4 hkg/ha - 85% DM, Straw remowed, yield

33.8 hkg/ha - 100% DM

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Table A3.2.

Management practice at

Jyndevad

during the 2009 to 2013 growing seasons. The active ingredients of

the various pesticides are indicated in parentheses.

Date

Management practice

07-08-2009 Harvest of spring barley. Seed yield 63.96 hkg/ha 85% DM, strawyield 19.5 hkg/ha 100% DM,

stubbleheight 15 cm

14-04-2010 Ploughed. Depth 24 cm

15-04-2010 Rolled with concrete roller

22-04-2010 Seed bed preparation. 9.0 cm depth

Planting of potatoes. cv. Kuras rowdistance 75 cm, plantdistance 33 cm, depth 8 cm, final plantnumber

04-05-2010

4,0/m

04-05-2010 Ridging

27-05-2010 Fenix (aclonifen) - weeds - 1.0 l/ha + Titus WSB (rimsulfuron) - weeds - 10 g/ha

08-06-2010 Titus WSB (rimsulfuron) - weeds - 20 g/ha

24-06-2010 Irrigation - 25 mm/ha started on 24/6 ended on 25/6

28-06-2010 Ranman (cyazofamid) - fungi - 0.2 l/ha

30-06-2010 Irrigation - 25 mm/ha started on 30/6 ended on 1/7

06-07-2010 Amistar (azoxystrobin) - fungi - 0.5 l/ha

07-07-2010 Ranman (cyazofamid) - fungi - 0.2 l/ha

08-07-2010 Irrigation - 30 mm/ha started on 8/7 ended on 9/7

14-07-2010 Ranman (cyazofamid) - fungi - 0.2 l/ha

16-07-2010 Karate 2,5 WG (Lambda-cyhalothrin) - 0.3 kg/ha (not analyzed)

25-07-2010 Ridomil Gold MZ Pepite (mancozeb - metalaxyl-M) - fungi - 2.0 kg/ha

01-08-2010 Ranman (cyazofamid) - fungi - 0.2 l/ha

09-08-2010 Ranman (cyazofamid) - fungi - 0.2 l/ha

16-08-2010 Ranman (cyazofamid) - fungi - 0.2 l/ha

23-08-2010 Tyfon (propamocarb+fenamidone) - fungi - 2 l/ha (not analyzed)

31-08-2010 Dithane NT (mancozeb) - fungi - 2.0 kg/ha (not analyzed)

10-09-2010 Dithane NT (mancozeb) - fungi - 2.0 kg/ha (not analyzed)

23-09-2010 Shirlan (fluazinam) - fungi - 0.4 l/ha (not analyzed)

19-10-2010 Harvest of potatoes Yield in tubers 120.6 hkg/ha, 100% DM

22-03-2011 Ploughed. Depth 24 cm

Sowing spring barley cv. Quench, depth 4.0 cm, rowdistance 12 cm, seed rate 164 kg/ha, final

23-03-2011

plantnumber 301 m

- using a combine drill

24-03-2011 Rolled with concrete roller

26-04-2011 Oxitril CM (bromoxynil + ioxynil) - 0.5 l/ha (not analyzed) + DFF (diflufenican) - 0.25 l/ha- weeds

02-05-2011 Irrigation - 30 mm/ha started on 02/05 ended on 03/05

23-05-2011 Irrigation - 32 mm/ha started on 23/05 ended on 24/05

04-07-2011 Irrigation - 30 mm/ha started on 4/7 ended on 5/7

23-08-2011 Harvest of spring barley. Seed yield 72.4 hkg/ha 85% DM, stubble height 15 cm

25-08-2011 Remowal of straw, straw yield 30.2 hkg/ha 100% DM,

30-03-2012 Ploughed. Depth 22 cm

30-03-2012 Maize

02-04-2012 Rolled with a concrete roller

30-04-2012 Fertilization 140 N, 17.7 P, 65.3 K, kg/ha

30-04-2012 Fertilization 120 K, kg/ha

03-05-2012 Fertilization 29.4 N, 14.7 P, kg/ha

Sowing maize - cv. Atrium - seed distance 12 cm, row distance 75 cm, depth 6 cm - Seed rate 111.000

03-05-2012 seeds/ha, final plant number 12.8/m

07-05-2012 Tracer (potasium bromide), 30,54 kg/ha

26-05-2012 Fighter 480 (bentazone) - weeds - 1.0 l/ha

05-06-2012 Callisto (mesotrion) - weeds - 1.5 l/ha

15-06-2012 Catch (florasulam + 2,4 D) - 0.06 l/ha - weeds - (not analyzed)

15-06-2012 Tomahawk 180 EC (fluroxypyr) - 1.5 l/ha weeds - (not analyzed)

08-10-2012 Harvest of maize.Whole crop yield 151.41 hkg/ha 100% DM. Stubble height 25 cm

06-04-2013 Ploughing - 22 cm depth

06-04-2013 Pea

12-04-2013 Rolled with concrete roller

Sowing pea cultivare Alvestra, depth 5 cm, rowdistance 12 cm, seed rate 235 kg/ha,using a combine

14-04-2013 drill, final plant number 92/m

Fighter 480 (bentazon) + Stomp (pendimethalin) 0.4 l/ha + 0.6 l/ha - weeds (pendimethalin not

07-05-2013 analyzed)

Bentazon 480 (bentazon) + Stomp (pendimethalin) 0.5 l/ha + 0.6 l/ha - weeds (pendimethalin not

16-05-2013 analyzed)

17-05-2013 Fertilization 16.0 P, 83.2 K, kg/ha

06-06-2013 Irrigation - 30 mm/ha started on eastside 06/06 ended on westside 07/06

09-07-2013 Irrigation - 30 mm/ha started on eastside 09/07 ended on westside10/07

16-07-2013 Pirimor G (pirimicarb) - pests - 0.25 kg/ha (not analyzed)

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Date

07-08-2013

14-08-2013

20-08-2013

22-08-2013

Management practice

Harvest of pea - western half of the field - interrupted by rain. Seed yield 38.8 hkg/ha 86%

DM.Strawyield 30.1 hkg/ha 100% DM, stubble height 10 cm. Straw shreddet at harvest

Harvest of the eastern half of the field - straw shreddet at harvest

Stuble cultivation - 8,0 cm depth

Rotor harrowed - 7 cm depth

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Table A3.3.

Management practice at

Silstrup

during the 2009 to 2013 growing seasons. The active ingredients of the

various pesticides are indicated in parentheses.

Date

Management practice

30-03-2009

Harrowed 2 times across - depth 5 cm

02-04-2009

Tracer (potasium bromide). 31.5 kg/ha

11-04-2009

Sowing spring barley cv. Keops depth 3.5 cm, row distance 15 cm, seeding rate 120 kg/ha, final

plantnumber 263/m

. Undersown red fescue cv. Jasperina, broadcast, seeding rate 8.8 kg/ha

11-04-2009

Rolled with Cambridge roller

19-05-2009

Fighter 480 (bentazone) - weeds - 1.25 l/ha

24-06-2009

Amistar (azoxystrobin) - fungi - 1.0 l/ha

16-07-2009

Whole crop harvest, 94.6 hkg/ha 100% DM stubble height 15 cm

24-08-2009

Hussar OD (iodosulfuron-methyl) - weeds - 0.020 l/ha

09-09-2009

Fox 480 SC (bifenox) - weeds - 1.5 l/ha

02-05-2010

Fusilade Max (fluazifop-P-butyl) - weeds - 1.5 l/ha

05-05-2010

Hussar OD (iodosulfuron) + SweDane MCPA 750 - weeds - 0.1 l/ha + 0.7 l/ha

20-07-2010

Harvest of grass seed. Yield 16.5 hkg/ha 87% DM, stubble height 12 cm,

21-07-2010

Straw burned, 69.3 hkg/ha 100% DM

21-07-2010

Harvest of grass seed. Yield 15.2 hkg/ha 87% DM, stubble height 5 cm.

15-04-2011

Hussar OD (iodosulfuron) - weeds - 0.05 l/ha (not analyzed)

26-04-2011

Fusilade Max (fluazifop-P-butyl) - weeds - 1.5 l/ha

21-07-2011

Harvest of grass seed. Yield 15.2 hkg/ha 87% DM.

30-07-2011

Straw removed - straw yield 45.8 hkg/ha 100% DM, stubble height 12 cm

31-07-2011

Red fescue

16-09-2011

Fox 480 SC (bifenox) - weeds - 1.5 l/ha

05-10-2011

Pig slurry application -surface applied - 29.0 t/ha - 122,1 Total-N, 72.8 NH4-N,30.2 P, 52.2 K, 14,9

Mg, kg/ha, 908 g/ha CU, (VAP nr 36552)

15-03-2012

Fertilization 60 N, 32 S kg/ha

13-04-2012

DFF (diflufenican) - weeds - 0.15 l/ha

19-04-2012

Fusilade Max (fluazifop-P-butyl) - weeds - 1.5 l/ha

18-05-2012

Folicur (tebuconazol) - fungi - 1.0 l/ha

25-07-2012

Straw removed - straw yield 48.3 hkg/ha 100% DM, stubble height 12 cm

25-07-2012

Harvest of grass seed. Yield 14.16 hkg/ha 87% DM.

10-09-2012

Tracer (potasium bromide) 30.0 kg/ha

10-09-2012

Glyfonova 450 Plus (glyphosate) - weeds (killing the red fescue) - 4.8 l/ha

10-09-2012

Winter wheat

08-10-2012

Ploughed - depth 24 cm -packed

09-10-2012

Sowing winter wheat cv. Hereford. Depth 2.4 cm, seeding rate 200 kg/ha, row distance 15.0 cm

using a Horch Pronto 6 DC

09-11-2012

DFF (diflufenican) + Oxitril CM (ioxynil+bromoxynil - not analyzed) - weeds - 0.12 g/ha + 0.2 l/ha

22-02-2013

Fertilization 52.5 N, 7.5 P, 25.0 K kg/ha

03-05-2013

Sowing spring barlye cv. Quenc, replacing winter wheat injured by frost. Depth 3.8 cm, seeding rate

175 kg/ha, row distance 15 cm, Horch Pronto 6 DC, final plant number 303 m

03-05-2013

Spring barley

04-05-2013

Fertilization 67.2 N, 9.6 P, 32.0 K kg/ha

30-05-2013

Duotril 400 EC (ioxynil+bromoxynil - not analyzed) - weeds - 0.6 l/ha

25-06-2013

Amistar (azoxystrobin) - fungi - 1.0 l/ha

01-07-2013

Folicur 250 EC (tebuconazol) - fungi - 1.0 l/ha

20-08-2013

Glyfonova 450 Plus (glyphosate) - weeds (killing the grass) - 2.4 l/ha

06-09-2013

Harvest of spring barley. Grain yield 59.8 hkg/ha 85% DM, straw yield 46.0 hkg/ha 100% DM,

stubbleheight 14 cm. Straw shredded at harvest.

20-09-2013

Liming 3.2 t/ha

24-09-2013

Ploughed - depth 24 cm - packed

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Table A3.4.

Management practice at

Estrup

during the 2009 to 2013 growing seasons. The active ingredients of the

various pesticides are indicated in parentheses.

Date

Management practice

12-03-2009

Ploughed - depth 18 cm - packed with a ring roller

02-04-2009

Seed bed preparation depth 5 cm

06-04-2009

Tracer (potasium bromide) 30 kg/ha

08-04-2009

Spring barley sown, cv. Keops, seeding rate 182 kg/ha, sowing depth 4.0 cm, row distance 12 cm.

Final plantnumber 350/m

08-04-2009

Rolled with a cam roller

01-05-2009

Fox 480 SC (bifenox) - weeds - 1.2 l/ha

14-05-2009

Basagran M75 (bentazone+MCPA) - weeds - 1.5 l/ha

04-06-2009

Amistar (azoxystrobin) - fungi - 1.0 l/ha

07-08-2009

Harvest of spring barley. Stuble height 12 cm, grainyield 71.4 hkg/ha 85% DM,

07-08-2009

Straw shredded. Amount 39.9 hkg/ha 100% DM

24-08-2009

Sowing winter rape. Cv. Cabernet, sowing depth 3.0 cm, seeding rate 4 kg/ha, row distance 12.5 cm

final plantnumber 86/m

24-08-2009

Ploughed - depth 20 cm - packed with a ring roller

24-08-2009

Rotor harrowed - depth 4 cm

25-08-2009

Command CS ( Clomazone) - weeds - 0.33 l/ha

30-09-2009

Fox 480 SC (bifenox) - weeds - 0.75 l/ha

09-10-2009

Cyperb (cypermethrin) - pests - 0.15 l/ha

20-04-2010

Due to outwintering field partially sown withspring rape. Cv. Pluto, sowing depth 3.0 cm and 0.5

cm, seeding rate 5,0 kg/ha, row distance 12.0 cm

10-05-2010

Biscaya OD 240 (thiacloprid) - pests- 0.3 l/ha

20-08-2010

Harwest of winter rape. Seed yield 38.3 hkg/ha 91% DM. Straw shredded 41.8 hkg/ha 100% DM.

Stubble height 30 cm

23-08-2010

Spring rape shredded 11.64 hkg/ha 100% DM. Stubble height 8 cm

06-09-2010

Rotor harrowed - depth 5 cm

14-09-2010

Winter wheat sown cv. Frument. depth 4.0 cm rowdistance 12 cm seeding rate 210 kg/ha, final

plantnumber 370/m

14-09-2010

Ploughed - depth 20 cm - packed with a ring roller

14-09-2010

Seedbed preparation - depth 5 cm

30-09-2010

Express ST (tribenuron-methyl) - weeds - 1 tablet/ha

26-04-2011

Fox 480 SC (bifenox) - weeds - 1.2 L/ha

09-05-2011

Flexity (metrafenon) - fungi - 0.5 L/ha

07-06-2011

Flexity (metrafenon) - fungi - 0.5 L/ha

22-08-2011

Straw shredded at harvest - 53.8 hkg/ha 100% DM

22-08-2011

Harvest of winter wheat. Stubble height 12 cm, grain yield 66.3 hkg/ha 85% DM

03-10-2011

Roundup Max (glyphosate) - weeds - 2.0 kg/ha

03-10-2011

spring barley

22-03-2012

Fertilization 117 N, 15 P, 55 K, kg/ha

29-03-2012

Rotor harrowed - depth 4 cm

30-03-2012

Spring barley sown, cv. Keops, seeding rate 159 kg/ha, sowing depth 4.3 cm, row distance 12 cm.

Final plant number 330/m

03-04-2012

Rolled with a Cambridge roller

15-05-2012

Fox 480 SC (bifenox) - weeds - 1.2 l/ha

18-05-2012

Mustang forte (aminopyralid/florasulam/2,4-D) - weeds - 0.75 l/ha

21-05-2012

Fertilization manganes nitrate (23,5%) - 2.0 l/ha

29-05-2012

Fertilization manganes nitrate (23,5%) - 2.0 l/ha

13-06-2012

Amistar (azoxystrobin) - fungi - 1.0 l/ha

13-08-2012

Harvest of spring barley. stubble height 12 cm, grain yield 62,9 hkg/ha 85% DM.

13-08-2012

Straw shredded at harvest - 41.0 hkg/ha 100% DM

26-09-2012

Tracer (potasium bromide) - 30 kg/ha

09-11-2012

Ploughed - depth 20 cm - packed with a Dalbo ring roller

08-03-2013

Ploughed - depth 20 cm - packed with a Dalbo ring roller

08-03-2013

Peas

05-04-2013

Fertilization 16 P, 84 K, kg/ha

23-04-2013

Rolled with a Cambridge roller

23-04-2013

Sowing peas - cultivare Alvesta - depth 5 cm rowdistance 12 cm seeding rate 230 kg/ha. Final

plantnumber 82/m

23-04-2013

Seedbed preparation - depth 5 cm

25-04-2013

Command CS ( Clomazone) - weeds - 0.25 l/ha

16-05-2013

Cyperb (cypermethrin) - pests - 0.3 l/ha (not analyzed)

16-05-2013

Fighter 480 (bentazone) - weeds - 1.0 l/ha

13-07-2013

Pirimor G (pirimicarb) - pests - 0.25 kg/ha

21-08-2013

Glyphonova 450 Plus (glyphosate) - weeds - 2.4 l/ha

06-09-2013

Straw shedded at harvest - 24.38 hkg/ha 100% DM

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Table A3.5.

Management practice at

Faardrup

during the 2009 to 2013 growing seasons. The active ingredients of

the various pesticides are indicated in parentheses.

Date

Management practice

05-04-2009 Sowing sugar beet cv. Palace. depth 3.0 cm row distance 50.0 cm plant distance 20 cm seeding rate

100000 seeds/ha. Final plantnumber 8.5/m

05-04-2009 Seed bed preparation - depth 6 cm

24-04-2009 1.5 l/ha Betanal (phenmedipham) + 1.0 l/ha Goliath (metamitron) - weeds

30-04-2009 10 g/ha Safari (triflusulfuron-methyl) + 1.5 l/ha Betanal (phenmedipham) + 1.0 l/ha Goliath

(metamitron) + 0.07 l/ha Ethosan (ethofumesate) - weeds

11-05-2009 10 g/ha Safari (triflusulfuron-methyl) + 1.5 l/ha Betanal (phenmedipham) + 1.0 l/ha Goliath

(metamitron) + 0.07 l/ha Ethosan (ethofumesate) - weeds

14-05-2009 Focus Ultra (cycloxydim) - weeds -1.0 l/ha

17-06-2009 Focus Ultra (cycloxydim) - weeds -1.0 l/ha

06-10-2009 Harvest of sugar beet. 147.9 hkg/ha 100% root dry matter and 40.1 hkg/ha 100% top dry matter

01-11-2009 Ploughing - depth 20 cm

07-04-2010 Seed bed preparation - depth 6 cm

22-04-2010 Sowing spring barley using a mixture of varieties. Depth 4.5 cm, row distance 12 cm seeding rate 150

kg/ha. Undersown red fescue cv. Maximum, seeding rate 7,0 kg/ha. Depth 2.0 cm row distance 13 cm

01-06-2010 Fighter 480 (bentazone) - weeds - 1.25 l/ha

02-07-2010 Amistar (azoxystrobin) - fungi - 1.0 l/ha (not analyzed)

21-08-2010 Harvest of spring barley. Grain yield 58.5 hkg 85% DM.

21-08-2010 Straw removed. Straw yield 27.5 hkg/ha 100% DM. Stubbleheight 10 cm

25-10-2010 Fox 480 SC (bifenox) - weeds - 1.5 l/ha

21-05-2011 Fusilade Max (fluazifop-P-butyl) - weeds - 1.5 l/ha

05-07-2011 Windrowing. Stubble hight 5 cm

20-07-2011 Threshing of grass seed. Yield 7.2 hkg/ha 87% DM, stubble height 5 cm.

20-07-2011 Straw removed. Straw yield 21.1 hkg/ha

03-10-2011 Spring barley and white clover

03-10-2011 Glyphogan (glyphosate) - weeds - 5.0 l/ha

08-11-2011 Ploughing - depth 20 cm

26-03-2012 Fertilization 112 N, 9 P, 30 K, kg/ha

04-04-2012 Seed bed preparation - depth 7 cm

04-04-2012 Sowing spring barley using a mixture of varieties. Depth 3-4 cm, row distance 13 cm seeding rate 98

kg/ha. Final plant number 200/m

. Under-sown white clover cv. Liflex, seeding rate 2.0 kg/ha, depth

2-3 cm, row distance 13 cm

04-04-2012 Tracer (potasium bromide), 30 kg/ha

18-05-2012 Fighter 480 (bentazone) - weeds - 1.25 l/ha

06-06-2012 Flexity (metrafenon) - fungi - 0.5 l/ha

12-08-2012 Harvest of spring barley stubble height 15 cm. Grain yield 67.51 hkg/ha, 85% DM

12-08-2012 Straw removed. Straw yield 27.62 hkg/ha, 100% DM

27-08-2012 White clover

26-01-2013 Kerb 400 SC (propyzamid) - fungi - 1.0 l/ha

14-05-2013 Fighter 480 (bentazone) - weeds - 3.0 l/ha

22-05-2013 Rolled with a concrete roller

31-05-2013 Karate (Lambda-cyhalothrin) - pest - 0.3 l/ha (not analyzed)

12-06-2013 Karate (Lambda-cyhalothrin) - pest - 0.3 l/ha (not analyzed)

28-07-2013 Threshing of white clover. Seed yield fresh 1.560 hkg/ha, Straw yield fresh 0.96 hkg/ha

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Appendix 4

Precipitation data for the PLAP sites

350

300

Precipitation

(mm/month)

Tylstrup

250

200

150

100

350

300

Jyndevad

250

200

150

100

350

300

Silstrup

250

200

150

100

350

300

Estrup

250

200

150

100

350

300

Faardrup

250

200

150

100

Sept

Mar

May

Feb

Jul

Aug

Nov

Dec

Apr

Oct

Jun

Jan

Precipitation

(mm/month)

Precipitation

(mm/month)

Precipitation

(mm/month)

Precipitation

(mm/month)

Normal (1961-1991)

July 2002 - June 2003

July 2006 - June 2007

July 2010 - June 2011

May 1999 - June 2000

July 2003 - June 2004

July 2007 - June 2008

July 2011 - June 2012

July 2000 - June 2001

July 2004 - June 2005

July 2008 - June 2009

July 2012 - June 2013

July 2001 - June 2002

July 2005 - June 2006

July 2009 - June 2010

Figure A4.1.

Monthly precipitation at all localities for the monitoring period July 2000–June 2013. Normal values

(1961–1990) are included for comparison.

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Appendix 5

Pesticide detections in samples for drains, suction cups and

groundwater monitoring wells

Table A5.1.

Number of samples where pesticides were not detected (nd), detected in concentrations below 0.1 µg/L

(≤0.1 µg/L) or detected in concentrations above 0.1 µg/L (> 0.1 µg/L) at

Tylstrup.

Numbers are accumulated for the

entire monitoring period, and pesticides monitored for less than one year are not included. All samples included.

Horizontal

Vertical

Suction cups

Parent

Compound

nd <0.1 ≥0.1

Aclonifen

123

Aminopyralid

Azoxystrobin

216

CyPM

216

Bentazone

2-amino-N-isopropyl-

191

benzamide

Bentazone

330

- 136

Bifenox

Bifenox acid

Nitrofen

Boscalid

102

Bromoxynil

192

Clomazone

230

FMC 65317

208

Clopyralid

Cyazofamid

123

Dimethoate

176

Epoxiconazole

199

Fenpropimorph

313

Fenpropimorph acid

276

Flamprop-M-

Flamprop

176

isopropyl

Flamprop-M-isopropyl

176

Fluazifop-P-butyl

Fluazifop-P

178

TFMP

Fluroxypyr

194

Ioxynil

198

Linuron

271

Mancozeb

ETU

198

Metalaxyl-M

CGA 108906

130

CGA 62826

182

Metalaxyl-M

184

Metribuzin

Desamino-diketo-metribuzin

289

231

5 168

Desamino-metribuzin

366

Diketo-metribuzin

138 315

81 192

Metribuzin

387

Pendimethalin

436

- 144

Pirimicarb

301

Pirimicarb-desmethyl

301

Pirimicarb-desmethyl-

173

formamido

Propiconazole

313

Propyzamide

221

RH-24580

221

127

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Horizontal

Parent

Compound

RH-24644

RH-24655

Prosulfocarb

PPU

PPU-desamino

Rimsulfuron

Tebuconazole

2-hydroxy-desethyl-

terbuthylazine

Desethyl-terbuthylazine

Desisopropylatrazine

Hydroxy-terbuthylazine

Terbuthylazine

CGA 322704

Thiamethoxam

Triasulfuron

Triazinamin

Triazinamin-methyl

<0.1

≥0.1

221

157

589

638

178

195

190

191

190

191

179

175

301

291

446

Vertical

<0.1

≥0.1

Suction cups

205

138

<0.1

191

≥0.1

Prosulfocarb

Rimsulfuron

Tebuconazole

Terbuthylazine

Thiamethoxam

Triasulfuron

Tribenuron-methyl

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Table A5.2.

Number of samples where pesticides were either not detected (nd), detected in concentrations below 0.1

µg/L (<=0.1 µg/L) or detected in concentrations above 0.1 µg/L (>0.1 µg/L) at

Jyndevad.

Numbers are accumulated

for the entire monitoring period, and pesticides monitored for less than one year are not included. All samples

included.

Horizontal

Vertical

Suction cups

Compound

Aclonifen

Amidosulfuron

Desmethyl-amidosulfuron

Azoxystrobin

CyPM

2-amino-N-isopropyl-

Bentazone

benzamide

Bentazone

Bifenox

Bifenox acid

Nitrofen

Bromoxynil

Chlormequat

Clomazone

FMC 65317

Cyazofamid

Diflufenican

AE-05422291

AE-B107137

Diflufenican

Dimethoate

Epoxiconazole

Fenpropimorph

Fenpropimorph acid

Florasulam

Florasulam-desmethyl

Fluazifop-P-butyl

Fluazifop-P

TFMP

Fluroxypyr

Glyphosate

AMPA

Glyphosate

Ioxynil

MCPA

2-methyl-4-chlorophenol

MCPA

Mesosulfuron-methyl Mesosulfuron

Mesosulfuron-methyl

Mesotrione

AMBA

MNBA

Mesotrione

Metalaxyl-M

CGA 108906

CGA 62826

Metalaxyl-M

Metribuzin

Desamino-diketo-metribuzin

Desamino-metribuzin

Diketo-metribuzin

Metribuzin

Pendimethalin

Picolinafen

CL153815

Picolinafen

Pirimicarb

Parent

Aclonifen

Amidosulfuron

<0.1

≥0.1

162

233

178

510

216

166

218

131

140

190

323

257

264

191

190

193

221

223

218

210

285

137

175

257

251

<0.1

≥0.1

<0.1

≥0.1

101

129

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

Horizontal

Parent

Compound

Pirimicarb-desmethyl

Pirimicarb-desmethyl-

formamido

Propiconazole

PHCP

Pyridate

PPU

PPU-desamino

Rimsulfuron

Tebuconazole

Desethyl-terbuthylazine

Terbuthylazine

Triazinamin-methyl

<0.1

≥0.1

251

291

184

116

489

765

189

213

490

260

252

Vertical

<0.1

361

≥0.1

Suction cups

110

130

<0.1

130

117

≥0.1

Propiconazole

Pyridate

Rimsulfuron

Tebuconazole

Terbuthylazine

Tribenuron-methyl

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MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

Table A5.3.

Number of samples where pesticides were either not detected (nd), detected in concentrations below 0.1

µg/L (<0.1) or detected in concentrations above 0.1 µg/L (>=0.1) at

Silstrup.

Numbers are accumulated for the entire

monitoring period, and pesticides monitored for less than one year are not included. All samples included.

Drainage

Horizontal

Vertical

Suction cups

Parent

Amidosulfuron

Azoxystrobin

Bentazone

Bifenox

Compound

Amidosulfuron

Desmethyl-

amidosulfuron

Azoxystrobin

CyPM

2-amino-N-isopropyl-

benzamide

Bentazone

Bifenox

Bifenox acid

Nitrofen

Bromoxynil

Chlormequat

Clopyralid

Clomazone

FMC 65317

Desmedipham

EHPC

AE-05422291

AE-B107137

Diflufenican

Dimethoate

Epoxiconazole

Ethofumesate

Fenpropimorph

Fenpropimorph acid

Flamprop

nd <0.1 ≥0.1

101

127

116

111

101

160

173

141

121

nd <0.1 ≥0.1

133

162

133

107

169

140

145

165

161

122

108

210

160

253

308

131

244

116

103

121

124

240

139

148

117

355

148

301

141

142

257

255

165

124

123

334

339

222

173

240

433

436

308

148

Bromoxynil

Chlormequat

Clopyralid

Clomazone

Desmedipham

Diflufenican

Dimethoate

Epoxiconazole

Ethofumesate

Fenpropimorph

Flamprop-M-

isopropyl

Flamprop-M-isopropyl

Fluazifop-P-butyl Fluazifop-P

TFMP

Fluroxypyr

Glyphosate

AMPA

Glyphosate

Iodosulfuron-

Iodosulfuron-methyl

methyl

Metsulfuron-methyl

Ioxynil

MCPA

2-methyl-4-

chlorophenol

MCPA

Metamitron

Desamino-metamitron

Metamitron

Pendimethalin

Phenmedipham 3-aminophenol

MHPC

Phenmedipham

Pirimicarb

Pirimicarb-desmethyl

Pirimicarb-desmethyl-

formamido

Propiconazole

131

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Drainage

Parent

Propyzamide

Compound

Propyzamide

RH-24580

RH-24644

RH-24655

Prosulfocarb

PHCP

PPU

PPU-desamino

Tebuconazole

2-hydroxy-desethyl-

terbuthylazine

Desethyl-terbuthylazine

Desisopropylatrazine

Hydroxy-terbuthylazine

Terbuthylazine

Triazinamin

Triazinamin-methyl

IN-D8526

IN-E7710

IN-M7222

Triflusulfuron-methyl

nd <0.1 ≥0.1

Horizontal

nd <0.1 ≥0.1

Vertical

nd <0.1 ≥0.1

143

149

148

149

147

109

Suction cups

nd <0.1 ≥0.1

Prosulfocarb

Pyridate

Rimsulfuron

Tebuconazole

Terbuthylazine

101

107

151

113

148

152

173

146

148

102

127

Triasulfuron

Tribenuron-

methyl

Triflusulfuron-

methyl

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Table A5.4.

Number of samples where pesticides were either not detected (nd), detected in concentrations below 0.1

µg/L (<0.1 µg/L) or detected in concentrations above 0.1 µg/L (>=0.1 µg/L) at

Estrup.

Numbers are accumulated for

the entire monitoring period, and pesticides monitored for less than one year are not included. All samples included.

Drainage

Horizontal

Vertical

Suction cups

Compound

Amidosulfuron

Aminopyralid

Azoxystrobin

CyPM

Bentazone

2-amino-N-isopropyl-

benzamide

Bentazone

Bifenox

Bifenox acid

Nitrofen

Bromoxynil

Chlormequat

Clomazone

FMC 65317

Clopyralid

Dimethoate

Epoxiconazole

Ethofumesate

Fenpropimorph

Fenpropimorph acid

Flamprop-M-isopropyl Flamprop

Flamprop-M-

isopropyl

Florasulam

Florasulam-desmethyl

Fluroxypyr

Glyphosate

AMPA

Glyphosate

Iodosulfuron-methyl Metsulfuron-methyl

Ioxynil

MCPA

2-methyl-4-

chlorophenol

MCPA

Mesosulfuron-methyl Mesosulfuron

Mesosulfuron-methyl

Metamitron

Desamino-metamitron

Metamitron

Metrafenone

Pendimethalin

Picolinafen

CL153815

Picolinafen

Pirimicarb

Pirimicarb-desmethyl

Pirimicarb-desmethyl-

formamido

Propiconazole

Tebuconazole

Terbuthylazine

2-hydroxy-desethyl-

terbuthylazine

Desethyl-

terbuthylazine

Desisopropylatrazine

Parent

Amidosulfuron

Aminopyralid

Azoxystrobin

nd <0.1 ≥0.1 nd <0.1 ≥0.1 nd <0.1 ≥ 0.1 nd <0.1 ≥0.1

100

- 34

- 109

- 23

- 37

172 110 15 148

- 418

36 138 123 136 12

1 414

237

- 79

- 271

- 5

177 145

136

35 12

91 27

119 13

112 20

12 127

1 61

10 63

- 61

2 41

- 18

- 42

2 19

8 46

- 39

- 34

- 55

445

132

133

132

125

158

150

124

208

125

100

120

642

606

208

125

112

111

157

158

147

118

225

223

261

- 35

- 30

2 34

66 307 107 216

189 191 100 211

131

- 55

119 15

5 41

102

- 34

119

159

192

199

192

- 309

- 118

- 180

- 232

- 197

18 111

133

MIU, Alm.del - 2014-15 (1. samling) - Bilag 215: Rapport fra Varslingssystem for udvaskning af pesticider til grundvand - 2014, fra miljøministeren

Drainage

Parent

Compound

Hydroxy-

terbuthylazine

Terbuthylazine

M34

Thiacloprid

Thiacloprid sulfonic

acid

Thiacloprid-amide

Triazinamin

Triazinamin-methyl

nd <0.1 ≥0.1

43 72 16

131

Horizontal

Vertical

Suction cups

nd <0.1 ≥0.1 nd <0.1 ≥ 0.1 nd <0.1 ≥0.1

- 180

- 222

- 66

- 203

- 70

Thiacloprid

Triasulfuron

Tribenuron-methyl

No samples from drainage.

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Table A5.5.

Number of samples where pesticides were either not detected (nd), detected in concentrations below 0.1

µg/L (<0.1 µg/L) or detected in concentrations above 0.1 µg/L (>=0.1µg/L) at

Faardrup.

Numbers are accumulated

for the entire monitoring period, and pesticides monitored for less than one year are not included. All samples

included.

Drainage

Horizontal

Vertical

Suction cups

Parent

Azoxystrobin

Bentazone

Bifenox

Compound

Azoxystrobin

CyPM

2-amino-N-isopropyl-

benzamide

Bentazone

Bifenox

Bifenox acid

Nitrofen

Bromoxynil

Clomazone

FMC 65317

Desmedipham

EHPC

Dimethoate

Epoxiconazole

Ethofumesate

Fenpropimorph

Fenpropimorph acid

Flamprop

106

102

144

101

150

101

123

182

163

169

142

141

147

151

148

178

<0.1 ≥ 0.1

nd <0.1 ≥ 0.1

110

104

146

128

127

109

104

116

138

Nd <0.1 ≥ 0.1

194

132

252

225

166

124

149

143

227

225

149

143

206

166

368

321

319

224

256

210

234

125

165

164

319

163

164

372

178

126

120

126

149

nd <0.1 ≥ 0.1

Bromoxynil

Clomazone

Desmedipham

Dimethoate

Epoxiconazole

Ethofumesate

Fenpropimorph

Flamprop-M-

isopropyl

Flamprop-M-isopropyl

Fluazifop-P-butyl Fluazifop-P

Fluazifop-P-butyl

TFMP

Fluroxypyr

Glyphosate

AMPA

Glyphosate

Ioxynil

MCPA

2-methyl-4-

chlorophenol

MCPA

Metamitron

Desamino-metamitron

Metamitron

Metrafenone

Pendimethalin

Phenmedipham MHPC

Phenmedipham

Pirimicarb

Pirimicarb-desmethyl

Pirimicarb-desmethyl-

formamido

Propiconazole

Propyzamide

RH-24580

RH-24644

RH-24655

Prosulfocarb

Tebuconazole

Terbuthylazine

2-hydroxy-desethyl-

terbuthylazine

Desethyl-terbuthylazine

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Drainage

Parent

Compound

Desisopropylatrazine

Hydroxy-terbuthylazine

Terbuthylazine

CGA 322704

Thiamethoxam

Triazinamin-methyl

IN-D8526

IN-E7710

IN-M7222

Triflusulfuron-methyl

<0.1 ≥ 0.1

30 11

Horizontal

nd <0.1 ≥ 0.1

57 32

Vertical

Nd <0.1 ≥ 0.1

166 28

164 30

149 25 20

126

148

Suction cups

nd <0.1 ≥ 0.1

Thiamethoxam

Tribenuron-

methyl

Triflusulfuron-

methyl

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Appendix 6

Laboratory internal control cards

Aclonifen

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

AE-05422291

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

AE-B107137

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

AMBA

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Figure A6.1.

Quality control data for pesticide analysis by laboratory 1. Internal laboratory control (IQ) samples are

indicated by square symbols and the nominal level is indicated by the solid grey line (□ IQ measured, ― IQ nominal

concentration). External control (EQ) samples are indicated by circles. Open circles indicate the nominal level (



nominal low,



EQ nominal high), and closed circles the measured concentration ( EQ measured low,



measured high).

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Aminopyralid

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

AMPA

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Azoxystrobin

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Bentazone

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Bifenox

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Figure A6.1 continued.

Quality control data for pesticide analysis by laboratory 1. Internal laboratory control (IQ)

samples are indicated by square symbols and the nominal level is indicated by the solid grey line (□ IQ measured, ―

IQ nominal concentration). External control (EQ) samples are indicated by circles. Open circles indicate the nominal

level (



EQ nominal low,



EQ nominal high), and closed circles the measured concentration ( EQ measured low,



EQ measured high).

138

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Bifenoxacid

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Boscalid

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

CGA108906

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

CGA62826

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Clomazone

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Figure A6.1 continued.

Quality control data for pesticide analysis by laboratory 1. Internal laboratory control (IQ)

samples are indicated by square symbols and the nominal level is indicated by the solid grey line (□ IQ measured, ―

IQ nominal concentration). External control (EQ) samples are indicated by circles. Open circles indicate the nominal

level (



EQ nominal low,



EQ nominal high), and closed circles the measured concentration ( EQ measured low,



EQ measured high).

139

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CyPM

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Diflufenican

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

FMC65317

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Glyphosate

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Mesotrione

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Figure A6.1 continued.

Quality control data for pesticide analysis by laboratory 1. Internal laboratory control (IQ)

samples are indicated by square symbols and the nominal level is indicated by the solid grey line (□ IQ measured, ―

IQ nominal concentration). External control (EQ) samples are indicated by circles. Open circles indicate the nominal

level (



EQ nominal low,



EQ nominal high), and closed circles the measured concentration ( EQ measured low,



EQ measured high).

140

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Metalaxyl-M

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Metrafenone

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

MNBA

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Nitrofen

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

PPU

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Figure A6.1 continued.

Quality control data for pesticide analysis by laboratory 1. Internal laboratory control (IQ)

samples are indicated by square symbols and the nominal level is indicated by the solid grey line (□ IQ measured, ―

IQ nominal concentration). External control (EQ) samples are indicated by circles. Open circles indicate the nominal

level (



EQ nominal low,



EQ nominal high), and closed circles the measured concentration ( EQ measured low,



EQ measured high).

141

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PPU-desamino

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Propyzamide

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Prosulfocarb

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

RH-24580

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

RH-24644

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Figure A6.1 continued.

Quality control data for pesticide analysis by laboratory 1. Internal laboratory control (IQ)

samples are indicated by square symbols and the nominal level is indicated by the solid grey line (□ IQ measured, ―

IQ nominal concentration). External control (EQ) samples are indicated by circles. Open circles indicate the nominal

level (



EQ nominal low,



EQ nominal high), and closed circles the measured concentration ( EQ measured low,



EQ measured high).

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RH-24655

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Tebuconazole

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

TFMP

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Triazinamin-methyl

Conc(µg/l)

0.15

0.10

0.05

0.00

2012/07

2012/08

2012/09

2012/10

2012/11

2012/12

2013/01

2013/02

2013/03

2013/04

2013/05

2013/06

date

Figure A6.1 continued.

Quality control data for pesticide analysis by laboratory 1. Internal laboratory control (IQ)

samples are indicated by square symbols and the nominal level is indicated by the solid grey line (□ IQ measured, ―

IQ nominal concentration). External control (EQ) samples are indicated by circles. Open circles indicate the nominal

level (



EQ nominal low,



EQ nominal high), and closed circles the measured concentration ( EQ measured low,



EQ measured high).

143

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Appendix 7

Pesticides analyzed at five PLAP sites in the period up to 2007

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Table A7.1.

Pesticides analyzed at

Tylstrup

with the products used shown in parentheses. Degradation products are

in italics. Precipitation (prec.) and percolation (perc.) are accumulated from the date of first application until the end

of monitoring. 1

month perc. refers to accumulated percolation within the first month after the application. C

mean

refers to average leachate concentration at 1 m b.g.s. the first year after application. (See Appendix 2 for calculation

method).

Crop and analyzed pesticides

Application End of

date

monitoring

May 99

Jun 99

Jul 01

Oct 01

Jul 03

Jul 10

†

Jul 03

Apr 08

Apr 03

Jul 03

Apr 03

Prec.

(mm)

Perc.

(mm)

1253

1169

2097

5387

2097

4192

1283

1341

1263

month

perc. (mm)

mean

(µg/L)

Potatoes 1999

Linuron (Afalon)

- ETU

(Dithane DG)

Metribuzine (Sencor WG)

- metribuzine-diketo

- metribuzine-desamino

- metribuzine-desamino-diketo

Spring barley 2000

Triasulfuron (Logran 20 WG)

- triazinamin

Propiconazole (Tilt Top)

Fenpropimorph (Tilt Top)

- fenpropimorphic acid

Pirimicarb (Pirimor G)

- pirimicarb-desmethyl

- pirimicarb-desmethyl-formamido

Winter rye 2001

Pendimethalin (Stomp SC)

Triazinamin-methyl

(Express)

Propiconazole (Tilt Top)

Fenpropimorph (Tilt Top)

- fenpropimorphic acid

Winter rape 2002

Clomazone (Command CS)

- FMC65317 (propanamide-clomazone)

Winter wheat 2003

Bromoxynil (Oxitril CM)

Ioxynil (Oxitril CM)

Fluroxypyr (Starane 180)

Flamprop-M-isopropyl (Barnon Plus 3)

- Flamprop-M (free acid)

Dimethoate (Perfekthion 500 S)

2550

2381

4223

11142

4223

8689

2740

2948

2622

<0.01

0.05–0.36

<0.02

0.14–0.97

<0.02

<0.01

<0.02

<0.01

<0.02

<0.01

<0.02

<0.01

<0.02

<0.01

<0.02

<0.01

May 00

Jun 00

Nov 00

May 01

Apr 03

Jul 03

2271

2948

1219

1341

109

Sep 01

Jul 04

2534

1194

Oct 02

May 03

Jul 03

Apr 05

Jul 05

Jul 06

Jul 10

†

Jul 10

†

Jul 07

2082

1867

2635

1629

1754

6211

2145

995

787

1031

722

704

3008

933

Potatoes 2004

-Fluazifop-P (free acid)

(Fusilade X-tra) May 04

- PPU

(Titus)

Jun 04

- PPU-desamino

(Titus)

Jun 04

Maize 2005

Terbuthylazine (Inter-Terbutylazine)

-desethyl-terbuthylazine

-2-hydroxy-terbuthylazine

-desisopropyl-atrazine

-2-hydroxy-desethyl-terbuthylazine

Bentazone (Laddok TE)

-AIBA

May 05

Jun 05

Jul 07

2061

927

Spring barley 2006

-triazinamin-methyl

(Express ST)

Jun 06

Jul 08

2349

1184

<0.02

Epoxiconazole (Opus)

Jul 06

Jul 08

2233

1148

<0.01

Systematic chemical nomenclature for the analyzed pesticides is given in Appendix 1.

Degradation product of mancozeb. The parent compound degrades too rapidly to be detected by monitoring.

Degradation product of tribenuron-methyl. The parent compound degrades too rapidly to be detected by monitoring.

Degradation product of fluazifop-P-butyl. The parent compound degrades too rapidly to be detected by monitoring.

Degradation product of rimsulfuron. The parent compound degrades too rapidly to be detected by monitoring.

Leaching increased the second and third year after application.

Leaching increased during the second year after application but measured concentrations did not exceed 0.042 µg/L (see Kjær et

al., 2008).

Degradation product of tribenuron-methyl. The parent compound degrades too rapidly to be detected by monitoring.

† Monitoring will continue during the following year. The values for prec. and perc. are accumulated up to July 2009.

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Table A7.2.

Pesticides analyzed at

Jyndevad

with the product used shown in parentheses. Degradation products are

in italics. Precipitation (prec.) and percolation (perc.) are accumulated from date of first application until end of

monitoring. 1

month perc. refers to accumulated percolation within the first month after application. C

mean

refers to

average leachate concentration 1 m b.g.s.the first year after application. (See Appendix 2 for calculation method).

Crop and analyzed pesticides

Application End of

Prec.

Perc.

month

mean

date

monitoring

(mm)

perc. (mm)

(µg/L)

Winter rye 2000

Glyphosate (Roundup 2000)

AMPA

Triazinamin-methyl

(Express)

Propiconazole (Tilt Top)

Fenpropimorph (Tilt Top)

fenpropimorphic acid

Maize 2001

Terbuthylazine (Lido 410 SC)

desethyl-terbuthylazine

PHCP

(Lido 410 SC)

Potatoes 2002

PPU

(Titus)

- PPU-desamino

(Titus)

Spring barley 2003

MCPA (Metaxon)

- 4-chlor,2-methylphenol

Dimethoate (Perfekthion 500 S)

Pea 2004

Bentazone (Basagran 480)

- AIBA

Pendimethalin (Stomp SC)

Pirimicarb (Pirimor G)

Pirimicarb-desmethyl

-Pirimicarb-desmethyl-

- fluazifop-P(free acid)

(Fusilade X-tra)

Winter wheat 2005

Ioxynil (Oxitril CM)

Bromoxynil (Oxitril CM)

Amidosulfuron (Gratil 75 WG)

Fluroxypyr (Starane 180 S)

Azoxystrobin (Amistar)

- CyPM

Spring barley 2006

Florasulam (Primus)

- florasulam-desmethyl

Epoxiconazole (Opus)

Sep 99

Nov 99

Apr 00

May 01

May 02

Jun 03

May 04

Jun 04

Oct 04

Apr 05

May 05

May 06

Jun 06

Apr 02

Jul 02

Apr 02

Apr 04

Apr 07

Jul 03

Jul 10

†

Jul 10

†

Jul 05

Jul 07

Apr 07

Jul 06

Apr 07

Jul 07

Apr 07

Jul 08

Dec 09

2759

2534

2301

2015

3118

6742

2413

9389

2340

2278

3888

3557

3493

2395

2955

1070

2683

2274

2779

4698

1607

1451

1061

1029

1809

3826

1366

5126

1233

1232

2044

1996

1993

1233

1791

515

1360

1283

1487

2592

139

<0.01

<0.02

<0.01

<0.01-0.02

<0.02

0.06

-0.13

0.01-0.03

<0.01

0.02-0.13

<0.01

<0.02

<0.01

<0.02

<0.01

<0.02

<0.01

<0.03

<0.01

Systematic chemical nomenclature for the analyzed pesticides is given in Appendix 1.

Degradation product of tribenuron-methyl. The parent compound degrades too rapidly to be detected by monitoring.

Degradation product of pyridate. The parent compound degrades too rapidly to be detected by monitoring.

Degradation product of rimsulfuron. The parent compound degrades too rapidly to be detected by monitoring.

Leaching increased the second year after application.

Degradation product of fluazifop-P-butyl. The parent compound degrades too rapidly to be detected by monitoring.

† Monitoring will continue during the following year. The values for prec. and perc. are accumulated up to July 2009.

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Table A7.3.

Pesticides analyzed at

Silstrup

with the product used shown in parentheses. Degradation products are in

italics. Precipitation (prec.) and percolation (perc.) are accumulated from date of first application until end of

monitoring. 1

month perc. refers to accumulated percolation within the first month after application. C

mean

refers to

average leachate concentration in the drainage water within the first drainage season after application. (See Appendix

2 for calculation methods).

Crop and analyzed pesticides

Application End of

Prec.

Perc.

month

mean

date

monitoring

(mm)

(mm) perc. (mm)

(µg/L)

Fodder beet 2000

Metamitron (Goltix WG)

metamitron-desamino

Ethofumesate (Betanal Optima)

Desmedipham (Betanal Optima)

EHPC

Phenmedipham (Betanal Optima)

MHPC

- 3-aminophenol

Fluazifop-P-butyl (Fusilade X-tra)

- fluazifop (free acid)

Pirimicarb (Pirimor G)

- pirimicarb-desmethyl

- pirimicarb-desmethyl-formamido

Spring barley 2001

Triazinamin-methyl

(Express)

Flamprop-M-isopropyl (Barnon Plus 3)

- flamprop (free acid)

Propiconazole (Tilt Top)

Fenpropimorph (Tilt Top)

- fenpropimorphic acid

Dimethoate (Perfekthion 500 S)

Maize 2002

Glyphosate (Roundup Bio)

- AMPA

PHCP

(Lido 410 SC)

Terbuthylazine (Lido 410 SC)

- desethyl-terbuthylazine

- 2- hydroxy-terbuthylazine

- 2-hydroxy-desethyl-terbuthylazine

- desisopropyl-atrazine

Peas 2003

Bentazone (Basagran 480)

AIBA

Pendimethalin (Storm SC)

Glyphosate (Roundup Bio)

AMBA

Winter wheat 2004

Prosulfocarb (Boxer EC)

MCPA (Metaxon)

- 4-chlor,2-methylphenol

Azoxystrobin (Amistar)

- CyPM

Pirimicarb (Pirimor G)

- Pirimicarb-desmethyl

- Pirimicarb-desmethyl-formamido

Spring barley 2005

Fluroxypyr (Starane 180 S)

Azoxystrobin (Amistar)

- CyPM

Pirimicarb (Pirimor G)

- Pirimicarb-desmethyl

- Pirimicarb-desmethyl-formamido

May 00

Jun 00

Jul 00

Apr 03

Jul 02

Jul 07

2634

1953

6452

1328

1019

2825

0.05

0.06

0.03

<0.01

<0.02

<0.01

<0.02

<0.01

<0.02

<0.01

<0.02

<0.01

0.02

0.13

0.06

0.07

0.15

May 01

Jun 01

Jul 01

Oct 01

May 02

Jul 03

Apr 06

Jul 04

Apr 06

Apr 05

Jul 06

Apr 06

Jul 06

Jul 07

1941

1928

1882

3802

1764

3320

951

944

937

1694

738

1327

May 03

Sep 03

Oct 03

May 04

Jun 04

Jul 04

2634

2207

2125

1797

1781

2931

2818

1055

971

974

710

706

1202

1205

0.26

<0.01

0.02

0.01

<0.01

0.01

0.09

<0.01

<0.02

0.01

0.02

<0.01

May 05

Jun 05

Jul 05

Jul 07

Jul 06

Jul 07

2012

862

2012

1933

830

332

828

818

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Table A7.3 continued.

Pesticides analyzed at

Silstrup

with the product used shown in parentheses. Degradation

products are in italics. Precipitation (prec.) and percolation (perc.) are accumulated from date of first application until

end of monitoring. 1

month perc. refers to accumulated percolation within the first month after application. C

mean

refers to average leachate concentration in the drainage water within the first drainage season after application. (See

Appendix 2 for calculation methods).

Crop and analyzed pesticides

Application End of

Prec.

Perc. 1

month

mean

date

monitoring

(mm)

(mm) perc. (mm)

(µg/L)

Winter rape 2006

Propyzamide (Kerb 500 SC)

- RH-24644

- RH-24580

- RH-24655

Clopyralid (Matrigon)

Nov 05

Apr 08

2345

1115

Apr 06

Apr 08

2009

859

0.22

0.01

<0.01

Degradation product of tribenuron-methyl. The parent compound degrades too rapidly to be detected by monitoring.

Degradation product of pyridate. The parent compound degrades too rapidly to be detected by monitoring.

Average leachate concentration within the first drainage season after application could not be calculated, as monitoring

started January 2003 (7 months after application). See Kjær et al.(2007) for further information.

Drainage runoff commenced two weeks prior to the application of propyzamide, and the weighted concentrations refer to

the period from the date of application until 1 July 2007.

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Table A7.4.

Pesticides analyzed at

Estrup

with the product used shown in parentheses. Degradation products are in

italics. Precipitation (prec.) and percolation (perc.) are accumulated from the date of first application until the end of

monitoring. 1st month perc. refers to accumulated percolation within the first month after application. C

mean

refers to

average leachate concentration in the drainage water within the first drainage season after application. (See Appendix

2 for calculation methods).

Crop and analyzed pesticides

Application

date

May 00

Jun 00

Oct 00

May 01

Jun 01

End of

monitoring

Apr 03

Apr 05

Jul 02

Jul 10

†

Jul 08

Jul 03

Jul 05

Prec.

(mm)

2990

2914

4938

2211

10484

7629

2208

4251

Perc.

(mm)

1456

1434

2294

1048

4977

3621

1096

1995

month

perc. (mm)

123

mean

(µg/L)

<0.01

<0.02

0.02

0.01

<0.01

<0.02

<0.01

0.54

0.17

0.03

<0.01

0.01

<0.02

0.04

0.01

<0.01

0.02

0.01

<0.02

0.43

0.19

0.11

1.1

0.21

<0.01

0.12

<0.02

0.12

0.23

0.48

0.31

0.11

0.02

0.24

0.18

<0.01

4.04

0.42

<0.01

<0.03

0.03

0.13

Spring barley 2000

Metsulfuron-methyl (Ally)

- triazinamin

Flamprop-M-isopropyl (Barnon Plus 3)

- flamprop (free acid)

Propiconazole (Tilt Top)

Fenpropimorph (Tilt Top)

- fenpropimorphic acid

Dimethoate (Perfekthion 500 S)

Pea 2001

Glyphosate (Roundup Bio)

- AMPA

Bentazone (Basagran 480)

- AIBA

Pendimethalin (Stomp SC)

Pirimicarb (Pirimor G)

- pirimicarb-desmethyl

- pirimicarb-desmethyl-formamido

Winter wheat 2002

Ioxynil (Oxitril CM)

Bromoxynil (Oxitril CM)

Amidosulfuron (Gratil 75 WG)

MCPA (Metaxon)

- 4-chlor,2-methylphenol

Propiconazole (Tilt 250 EC)

Pirimicarb (Pirimor G)

- pirimicarb-desmethyl

- pirimicarb-desmethyl-formamido

Fodder beet 2003

Glyphosate (Roundup Bio)

- AMPA

Ethofumesate (Betanal Optima)

Metamitron (Goltix WG)

- metamitron-desamino

Pirimicarb (Pirimor G)

- pirimicarb-desmethyl

- pirimicarb-desmethyl-formamido

Spring barley 2004

Fluroxypyr (Starane 180)

Azoxystrobin (Amistar)

- CyPM

Maize 2005

Terbuthylazine (Inter-Terbuthylazin)

- desethyl-terbuthylazine

- 2-hydroxy-terbuthylazine

- desisopropyl-atrazine

- 2-hydroxy-desethyl-terbuthylazine

Bentazone (Laddok TE)

- AIBA

Glyphosate (Roundup Bio)

- AMPA

Spring barley 2006

Florasulam (Primus)

- florasulam-desmethyl

Azoxystrobin (Amistar)

- CyPM

Nov 01

Apr 02

May 02

Jun 02

Jul 03

Jul 04

Apr 05

Jul 05

Apr 06

1580

2148

2091

2920

2982

860

928

1336

1403

Sep 02

May 03

Jul 03

Jul 10

†

Apr 06

Jul 05

Apr 06

Jul 06

Jul 08

Apr 09

Jul 09

Jul 08

Apr 09

Jul 08

Jul 10

†

Jul 08

8289

2901

2071

3900

1371

939

May 04

Jun 04

May 05

2073

4452

4247

4406

3338

4247

3338

5191

2442

2414

1030

2209

2042

2051

1628

2042

1628

2460

1163

1170

Jun 05

Nov 05

Jun 06

Systematic chemical nomenclature for the analyzed pesticides is given in Appendix 1.

† Monitoring will continue during the following year. The values for prec. and perc. are accumulated up to July 2006.

Drainage runoff commenced about two and a half months prior to the application of ioxynil and bromoxynil, and the

weighted concentrations refer to the period from the date of application until 1 July 2002.

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Table A7.5.

Pesticides analyzed at

Faardrup

with the product used shown in parentheses. Degradation products are

in italics. Precipitation (prec.) and percolation (perc.) are accumulated from the date of first application (app. date)

until the end of monitoring. 1

month perc. refers to accumulated percolation within the first month after application.

mean

refers to average leachate concentration in the drainage water the first drainage season after application. (See

Appendix 2 for calculation methods).

Crop and analyzed pesticides

Application

date

Aug 99

Oct 99

Apr 00

May 00

Jun 00

End of

monitoring

Apr 03

Apr 02

Jul 03

Jul 02

Jul 03

Prec.

(mm)

2526

1738

1408

2151

1518

2066

Perc.

(mm)

947

751

494

669

491

684

month

perc. (mm)

mean

(µg/L)

<0.01

<0.02

<0.01

0.01

0.06

<0.01

<0.02

<0.01

<0.02

<0.01

0.02

<0.01

<0.02

<0.01

<0.02

<0.01

<0.02

<0.01

0.67

0.59

0.04

0.03

0.07

2.82

<0.01

Winter wheat 1999

Glyphosate (Roundup 2000)

- AMPA

Bromoxynil (Briotril)

Ioxynil (Briotril)

Fluroxypyr (Starane 180)

Propiconazole (Tilt Top)

Fenpropimorph (Tilt Top)

- fenpropimorphic acid

Pirimicarb (Pirimor G)

- pirimicarb-desmethyl

- pirimicarb-desmethyl-formamido

Sugar beet 2001

Glyphosate (Roundup 2000)

- AMPA

Metamitron (Goltix WG)

- metamitron-desamino

Ethofumesate (Betanal Optima)

Desmedipham (Betanal Optima)

- EHPC

Phenmedipham (Betanal Optima)

- MHPC

Fluazifop-P-butyl (Fusilade X-tra)

- fluazifop-P (free acid)

Pirimicarb (Pirimor G)

- pirimicarb-desmethyl

- pirimicarb-desmethyl-formamido

Spring barley 2002

Flamprop-M-isopropyl (Barnon Plus 3)

- flamprop-M (free acid)

MCPA (Metaxon)

- 4-chlor-2-methylphenol

- triazinamin-methyl

(Express)

Dimethoate (Perfekthion 500 S)

Propiconazole (Tilt 250 EC)

Oct 00

May 01

Jun 01

Jul 01

Jul 03

1747

1512

1460

709

507

503

May 02

Jun 02

Jul 04

Apr 05

1337

1358

1328

1761

333

337

333

509

Winter rape 2003

Clomazone (Command CS)

Aug 02

- FMC65317 (propanamide-clomazon)

Winter wheat 2004

Prosulfocarb (Boxer EC)

MCPA (Metaxon)

- 4-chlor,2-methylphenol

Azoxystrobin (Amistar)

- CyPM

Maize 2005

Terbuthylazine (Inter-Terbutylazin)

- desethyl-terbuthylazine

- 2-hydroxy-terbuthylazine

- desisopropyl-atrazine

- 2- hydroxy-desethyl-terbuthylazine

Bentazone (Laddok TE)

- AIBA

Oct 03

Jun 04

Apr 06

Jul 06

Jul 07

1542

1307

2098

454

331

636

May 05

Jul 08

Jul 07

2078

1428

1408

666

465

464

Spring barley 2006

Fluroxypyr (Starane 180 S)

May 06

Jul 08

1496

524

<0.02

Epoxiconazole (Opus)

Jun 06

Jul 08

1441

507

<0.01

Systematic chemical nomenclature for the analyzed pesticides is given in Appendix 1.

Degradation product of tribenuron-methyl. The parent compound degrades too rapidly to be detected by monitoring.

† Monitoring will continue during the following year. The values for prec. and perc. are accumulated up to July 2009.

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Appendix 8

New horizontal wells

New horizontal wells at each PLAP-site, with three new horizontal screens were

established at each PLAP-site in 2011.

A horizontal well with three PE-screens (3 m long, separated by 1 m packer-section

attached 0.8 m bentonite, slits of 0.1 mm, Figure A8.1) was installed September 2011 at

all five PLAP-sites to optimize monitoring of the sites both in time and space.

The aim of the optimization was:

•

at the sandy sites (Tylstrup and Jyndevad) to improve the early warning regarding

pesticides and/or their degradation products leaching to the upper fluctuating

groundwater by sampling a spatially representative sample of the porewater,

which has just reaching the groundwater zone. The well was hence installed at 4.5

m depth at Tylstrup and 2.5 m depth at Jyndevad,

•

at the loamy sites (Silstrup, Estrup and Faardrup) to improve spatial

representativity of the water sampled in the variably-saturated zone below drain-

depth. To ensure this, the wells are (i) installated at 2 m depth, (ii) oriented such

as it is as orthogonal to the orientation of the dominating fracture system as

possible and at the same time crossing underneath a drain-line with one of its

three filtersections/screens, and (iii) not affected by or affecting sampling from the

vertical monitoring wells.

The location of the wells on the PLAP-fields is illustrated in Figure 2.1, 3.1, 4.1, 5.1 and

6.1. The wells/screens/filtersections are installed in boreholes of 9 cm in diameter.

These boreholes are drilled by applying the directional drilling system RotamoleTM,

which uses a dry percussion-hammer air pressure technique causing minimal

disturbances of the soil medium.

Figure A8.1.

Design of horizontal well with three filter sections of 3 m (inner diameter 25 mm; outer diameter 32

mm) each separated by 1m packer-section attached 0.8 m bentonite (thickness at installation 1 cm; expand to a

thickness of 3.5 cm). Water can be sampled through two PE-tubes (inner diameter 4 mm; outer diameter 6 mm)

ending 1 and 2 meters into each section, repectively.

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Water sampling for pesticide analysis from these new horizontal screens started April

2012 (half a year after installation) and is only conducted when the soil media

surrounding the screens is saturated. Water samples are, hence, collected at the:

•

Sandy sites

monthly. 3 liters are sampled from each filter via applying suction

onto the two tubes. A half liter of the 3 liters, is passed through cells in a flow

box measuring pH, temperature, and conductivity. The remaining 2�½ liters is

pooled with the equal volumes from the two other filters. Subsamples for

analysis are then taken from the 7�½ liter pooled sample.

Loamy sites

monthly if the groundwater table in the nearest vertical monitoring

well is situated more than 20 cm above the screens. Having saturated

conditions, one liter of water sample is collected from each screen via the two

tubes during approximately 10 minutes. The liter sample is passed through cells

in a flow box measuring pH, temperature, and conductivity. The samples from

each screens are then pooled and send for analysis.

•

The design of the wells facilitates the possibility of collecting water from six points

along the 12 m long well. This option is not utilised yet.

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Appendix 9

Groundwater age from recharge modelling and tritium-helium analysis

The site investigations carried out at the various PLAP sites offer good opportunity to

model the groundwater age from soil porosity and netprecipitation assuming simple

piston flow for groundwater.

For obvious reasons it would be advantageous to be able to compare groundwater age

obtained by recharge modelling and soil porosities with groundwater age obtained by

other methods.

Other methods for agedating of young groundwater are based on natural or

anthropogenic tracers include tritium-helium (

He), chlorofluorocarbons (CFCs) and

sulphurhexafluoride (SF

). Preliminary studies using the latter two methods were,

however, unable to produce sufficiently accurate results to permit direct comparison,

due to:

•

Decline in atmospheric CFCs over the last two decades and

Difficulties in determining the amount of excess air entering groundwater due to

dynamic change in groundwater table.

The tritium-helium method was tested in 2010 at Jyndevad and Tylstrup.

The other sites were discounted becauce of:

•

Low pumping rate excluded sampling for dissolved gases in clamped copper

tubes and

the piston flow model cannot be expected to be valid for the glacial till sites,

making direct comparison of the two methods impossible.

Age from recharge modelling

Recharge data obtained by the MACRO model for the 2000-2009 (Rosenbom et al.,

2010) were used to estimate water velocity and groundwater age from the deepest

screens at the Jyndevad and Tylstrup sites, Table 9.1. The deeper wells are normally

only used for water level monitoring, and the wells were included to be able to extend

the age interval. Porosity obtained from bulk density of 10 cm cores indicates a soil

porosity of 0.43 at 0.5 m and deeper (Lindhardt et al., 2001).

The average water velocities during the last 2-3 years (prior to age-dating in 2010),

which are probably more realistic for estimating groundwater age for the shallower

filters were 1.42–1.60 m/yr for Jyndevad and 1.35–1.38 m/yr for Tylstrup. A water

velocity of 1.4 m/yr appears reasonable for estimating groundwater age at both sites

based on recharge data. Groundwater age estimates using a water velocity of 1.4 m/yr

for all filters, except for the deep one at Tylstrup (1.1 m/yr) are compared with

groundwater age estimated by the tritium-helium method, Figure A9.1.

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Table A9.1.

Average recharge 2000-2009, water velocity and groundwater age. Yr- year.

Location

Recharge

Porosity

Velocity

Water Table

mm/yr

m/yr

m b.s.

Jyndevad

613

0.43

1.43

2.5

Tylstrup

477

0.43

1.11

4.5

Fiter depth

m b.s.

11.5

Age

6.3

Age from tritium-helium analysis

Samples for tritium and helium collected in one liter plastic bottles and clamped copper

tubes respectively were shipped to the University of Bremen and analyzed according to

Sültenfuß et al. (2009). The age of water was determined from the ratio between tritium

(

H), half-life 12.5 yr., and its daughter product helium-3 (

He) in the water.

The tritium-helium age and the recharge model age differ less than one year for most

wells over the entire depth interval and no systematic difference in age can be observed

(Figure A9.1). Wells including both sites are shown with increasing depth from left to

right in Figure A9.1. The depths are meters below water table to the mid-screen. The

length of each screen is 1 m, meaning that the water table was 10 cm below top-screen

for the shallowest depth indicated in the figure. Depth of water table checked during

pumping did not indicate problems with intake of air, and no bubbles were observed

during sampling.

Age in years

model age

3H/3He

0,4 0,5 0,8 0,8 0,9 1,1 1,7 1,8 1,8 2,5 2,5 2,5 2,7 2,8 3,8 3,8 7,0 9,1

Average dept below water table (m), J - Jyndevad, T- Tylstrup

Figure A9.1.

Groundwater age at Jyndevad and Tylstrup. Recharge model age assumes water velocity of 1.4 m/yr,

except for the Tylstrup deep filter (1.1 m/yr).

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Minor difference in groundwater age determined by recharge modelling and tritium-

helium analyzes is expected due to the analytical uncertainty regarding tritium and

helium. Furthermore, groundwater velocity may vary due to local variations in porosity

and permeability affecting the depth of iso-age lines below water table. Given these

uncertainties it is concluded that the model age and the tritium-helium age are

consistens.

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