NoNewBAM. Christian Nyrop Albers, Ole Stig Jacobsen, Annette Elisabeth Rosenbom, GEUS, Department of Geochemistry

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AARHUS UNIVERSITY DEPARTMENT O ENVIRONMENTAL SCIENCE 22.

Bester, Pedro Carvalho, Sif Burlin Svendsen, Lars Kjerulf Petersen

Nyrop Albers, Ole Stig Jacobsen, Annette Elisabeth Rosenbom, GEUS,

1 AARHUS UNIVERSITY DEPARTMENT O ENVIRONMENTAL SCIENCE 22. juni 218 NoNewBAM Carsten Suhr Jacobsen, Lea Ellegaard-Jensen, Kai Bester, Pedro Carvalho, Sif Burlin Svendsen, Lars Kjerulf Petersen Aarhus University, Department of Environmental Sciences Christian Nyrop Albers, Ole Stig Jacobsen, Annette Elisabeth Rosenbom, GEUS, Department of Geochemistry Jes Vollertsen, Aalborg University, Department of Civil Engineering

AARHUS UNIVERSITY DEPARTMENT O ENVIRONMENTAL SCIENCE HYPOTESE I Urbane grusjorde er anderledes end landbrugsjorde: Svagere binding af moderforbindelsen diflufenican og sandsynligvis en lavere

2 AARHUS UNIVERSITY DEPARTMENT O ENVIRONMENTAL SCIENCE HYPOTESE I Urbane grusjorde er anderledes end landbrugsjorde: Svagere binding af moderforbindelsen diflufenican og sandsynligvis en lavere mineralisering pga. mindre co-metabolisk mikrobiel aktivitet i grus med lavt indhold af organisk materiale. Hurtigere nedbrydning af glyphosate i grus pga. højere biotilgængelighed men på same tid en svagere binding. Måske en større udvaskning af diflufenican og dets nedbrydningsprodukter til grundvandet fra urbane jorde og fortove sammenlignet med landbrugsjord. Ingeniør Andersen og medarbejdere præsentere stolt den innovative sprøjte togvogn

AARHUS UNIVERSITY DEPARTMENT O ENVIRONMENTAL SCIENCE HYPOTESE II På befæstede arealer forventer vi: Udvaskning gennem revner og samlinger i belægningen.

3 AARHUS UNIVERSITY DEPARTMENT O ENVIRONMENTAL SCIENCE HYPOTESE II På befæstede arealer forventer vi: Udvaskning gennem revner og samlinger i belægningen. Afhængig af moderstof og nedbrydningsprodukter vil stofferne tilbageholdes på overfladerne indtil evt. kraftig regn vil vaske forbindelserne væk. Hurtig afstrømning i tilfælde af kraftig regn. I landbrugsjorde med en intakt A-horisont forventer vi: Moderstofferne kan transporteres gennem jorden i høje koncentrationen, hvis der er tale om en lerjord med præferentielle flowkanaler. En eller flere polære nedbrydningsprodukter kan transporteres gennem sandede jord til grundvandet.

4 AARHUS UNIVERSITY DEPARTMENT O ENVIRONMENTAL SCIENCE Work Packages WP1: Degradation of diflufenican and glyphosate in soil and gravel WP2: Sorption and aging WP 3: Leaching and surface runoff of diflufenican and glyphosate from paved areas WP 4: Catchment

WP1: DEGRADATION O DILUENICAN AND GLYPHOSATE IN SOIL AND GRAVEL

JB1) rom bottom left: Stabilgrus (Stabilgrus /32mm, Øde Hastrup

the courtyard of Rørrendegård Silstrup Jyndevad Soils are sieved

5 WP1: DEGRADATION O DILUENICAN AND GLYPHOSATE IN SOIL AND GRAVEL rom top left: Silstrup (Loamy soil, JB6) Jyndevad (Sandy soil, JB1) rom bottom left: Stabilgrus (Stabilgrus /32mm, Øde Hastrup grusgrav) Slotsgrus (/11,2 mm, Stenrand Grusgrav) Soil/gravel from the courtyard of Rørrendegård Silstrup Jyndevad Soils are sieved at 2mm, Gravels sieved 4.75 mm Stored at 4 ºC Slotsgrus Stabilgrus Rørendegård

Degradation Draft asessment report from ESA based on cultivated soils: Proposed aerobic degradation pathway seen in figure Diflufenican: ield conditions: High to very high persistent Lab conditions:

6 Degradation Draft asessment report from ESA based on cultivated soils: Proposed aerobic degradation pathway seen in figure Diflufenican: ield conditions: High to very high persistent Lab conditions: Moderate to high persistent Metabolites: Lab conditions: Moderate persistent Name [CAS number] Diflufenican Structure MW Water sol. (mg/l, 25 C) pka logkow [ ] NH O O N Expert data match (Episuite) 9.3±.7 (predicted Scifinder) 4.9 Expert data match (Episuite) 2-[3- (trifluoromethyl)phenoxy]pyridine- 3-carboxylic acid (Ref: AE-B17137) [ ] 2-[3- (trifluoromethyl)phenoxy]pyridine- 3-carboxamide (Ref: AE ) [ ] HO O O O N H 2 N O N 17.6 Episuite estimated 223 Episuite estimated 2.59±.36 (predicted Scifinder) 14.34±.5 (predicted Scifinder) 2.52 (Episuite estimated).99 (Episuite estimated) LOD (µg/l) LOQ (µg/l) D AE-B AE-O AE-C ,4-difluoroaniline (Ref: AE C522392) [ ] H 2 N Episuite estimated 3.26±.1 (predicted Scifinder) 1.54 Expert data match (Episuite)

Degradation 16 C Batch incubation experminent Diflufenican spiked to Jyndevad, Silstrup,

Incubated at 16 ºC for 15 days with sampling in triplicates at 2 timepoints for Jyndevad and

seperately to Jyndevad, Silstrup, Stabilgrus and Slotsgrus Incubated at 16 ºC for 112 days

for Silstrup and Stabilgrus Only Jyndevad and Slotsgrus extracted 1 g material in 6 ml brown

7 Degradation 16 C Batch incubation experminent Diflufenican spiked to Jyndevad, Silstrup, Stabilgrus and Slotsgrus. Incubated at 16 ºC for 15 days with sampling in triplicates at 2 timepoints for Jyndevad and Slotsgrus, and 7 timepoints for Silstrup and Stabilgrus Metabolite AE-B and AE- spiked seperately to Jyndevad, Silstrup, Stabilgrus and Slotsgrus Incubated at 16 ºC for 112 days with sampling in triplicates at 18 timepoints for Jyndevad and Slotsgrus, and 6 timepoints for Silstrup and Stabilgrus Only Jyndevad and Slotsgrus extracted 1 g material in 6 ml brown glasses covered with perforated alufoil. Applied dose: 33 ng/g. Calculated based on an application rate of 12 g/ha, a bulk density of 145 kg/m3 and a soil depth of 2.5 cm.

8 Percent of applied Percent of applied Percent of applied Percent of applied Diflufenican degradation 15 Jyndevad y = 18,45e -,5x R² =, Silstrup y = 93,4e -,3x R² =,959 5 Diflufenican AE-B 5 Diflufenican AE-B 5 15 Days Days 15 Slotsgrus y = 19,6e -,2x R² =, Stabilgrus y = 98,651e -6E-4x R² =,989 5 Diflufenican AE-B 5 Diflufenican AE-B Days Days AE-B detected in Jyndevad and Slotsgrus AE- not detected

=,942 5 Diflufenican AE-B 5 15 Days 15 Slotsgrus y

9 Percent of applied Percent of applied Diflufenican metabolite formation 15 Jyndevad y = 18,45e -,5x R² =,942 5 Diflufenican AE-B 5 15 Days 15 Slotsgrus y = 19,6e -,2x R² =, Days Diflufenican AE-B

10 Percent of applied Percent of applied Percent of applied Percent of applied The metabolites AE- spiked Slotsgrus AE- spiked Jyndevad 15 y = 114,72e -,2x R² =, y = 91,639e -,9x R² =, AE- AE-B 5 AE- AE-B 5 15 Days 5 15 Days AE-B spiked Slotsgrus AE-B spiked Jyndevad y = 12,4e -,12x R² =, y = 92,32e -,4x R² =, AE-B 5 AE-B 5 15 Days 5 15 Days

11 Degradation results

12 Mass balance In Jyndevad agricultural soil: Mineralization: (between 5 and 15%) Bound residues? Unknown metabolites? In Slotsgrus: Mineralization: around 2% Unknown metabolites?

14 WP2: SORPTION AND AGING Sorption of diflufenican Stabilgrus Slotsgrus Cs (µg/kg) y = 6,72x,86 Pure comp. Cs (µg/kg) y = 9,28x 1,2 R² = 1, y = 1,83x 1,2 R² = 1, Pure comp. * + formul. 1,1 1 1 C w (µg/l) Silstrup-A + formul. 1,1 1 1 C w (µg/l) Jyndevad-A Cs (µg/kg) y = 13,91x,93 R² = 1, y = 138,72x,92 R² = 1, Pure comp. Cs (µg/kg) y = 95,62x,99 R² = 1, y = 9,71x,95 R² = 1, Pure comp. + formul. 1,1 1 1 C w (µg/l) + formul. 1,1 1 1 C w (µg/l) K d uden formulering (L/kg) K d med formulering (L/kg) Udgangskonc. (µg/l) K n K n Stabilgrus Slotsgrus Skærver Silstrup Jyndevad Literature: Soil: K =14-49 L/kg, n.9

Aging of D * Hypotheses: Aged sorption is mainly

diffusion in organic solids) => Aged sorption will be

the application: Incubation of fresh soil with 14

15 Aging of D * Hypotheses: Aged sorption is mainly determined by organic matter (hydrophobic nanopores + diffusion in organic solids) => Aged sorption will be relevant mainly in agricultural soil Method proposed in the application: Incubation of fresh soil with 14 C-labeled diflufenican Sequential extraction, e.g. Water; Water/AcN/AA; Acetone

16 WP 3: LEACHING AND SURACE RUNO O DILUENICAN AND GLYPHOSATE ROM PAVED AREAS Soil / Gravel material Quartssand 1 cm Steel frame Column shoe steel itting Steeltube 1meter 16

17 Pesticides added 31. October 1.8 ml sprayed with stretched glass pipette Same volume and concentration as recommended by the supplier New application planned May 218? 17

Br (mg/l) Br (mg/l) Br (mg/l) Br (mg/l) Br (mg/l) AARHUS UNIVERSITY DEPARTMENT O ENVIRONMENTAL SCIENCE Column experiments (4 replicates for each soil/gravel system) Tracer (Br-) study 7 7 8 6 5 4

2 1 Stabil + skærver 1 Stabil + skærver 2 Stabil + skærver 3 Stabil + skærver 4 2 4 6 8 Net precipitation (cumulative mm) 4 3 35 3 25 Largest variation in clay coulums from Silstrup 25 2 2 15 15

18 Br (mg/l) Br (mg/l) Br (mg/l) Br (mg/l) Br (mg/l) AARHUS UNIVERSITY DEPARTMENT O ENVIRONMENTAL SCIENCE Column experiments (4 replicates for each soil/gravel system) Tracer (Br-) study Stabil 1 Stabil 2 Stabil 3 Stabil Net precipitation (cumulative mm) Slotsgrus 1 Slotsgrus 2 Slotsgrus 3 Slotsgrus Net precipitation (cumulative mm) Stabil + skærver 1 Stabil + skærver 2 Stabil + skærver 3 Stabil + skærver Net precipitation (cumulative mm) Largest variation in clay coulums from Silstrup Silstrup 1 Silstrup 2 Silstrup 3 Silstrup Net precipitation (cumulative mm) Jyndevad 1 Jyndevad 2 Jyndevad 3 Jyndevad Net precipitation (cumulative mm) 8 Silstrup leachate

19 AARHUS UNIVERSITY DEPARTMENT O ENVIRONMENTAL SCIENCE Leaching - glyphosate and diflufenican

20 AARHUS UNIVERSITY DEPARTMENT O ENVIRONMENTAL SCIENCE Leaching AE-B and AE-O

21 Mass % Mass % AARHUS UNIVERSITY DEPARTMENT O ENVIRONMENTAL SCIENCE Leaching Mass balance as % of applied diflufenican mass Stabilgrus Stabil+skærve D AE-B AE-O AE-C D AE-B AE-O AE-C Net precipitation (cumulative mm) 2 3 Net precipitation (cumulative mm)

22 Runoff AARHUS UNIVERSITY from paved areas (to be sprayed in 218) DEPARTMENT O ENVIRONMENTAL SCIENCE 3 slope Sand caulking still missing between bricks Stabilgrus below bricks Application planned June 218? 22

diflufenican in stormwater Interview of garden

23 AARHUS UNIVERSITY DEPARTMENT O ENVIRONMENTAL SCIENCE WP 4: Catchment experiment in 218 Analyse diflufenican in stormwater Interview of garden owners to determine usage of Keeper and other pesticides 23

24 AARHUS UNIVERSITY DEPARTMENT O ENVIRONMENTAL SCIENCE Konklusioner på nuværende tidspunkt Mineralisering af glyphosate er på samme niveau i grus som i landbrugsjord Metaboliten AE-B danne både i landbrugsjorde og i grus men det ser ud til at den kun ophobes i grus Stadig for tidligt til at kvantificere udvaskninge men det ser ud til at de to metaboliter AE-O og AE-B ikke udvaskes fra søjlerne med landbrugsjord mens de samme metablitter udvaskes i koncentrationer mange gange grænseværdien (langt over,1 ug/l) 24

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