Atmospheric transport and deposition

of pesticides in Sweden

Jenny Kreuger, Martin Larsson & Therese Nanos Swedish University of Agricultural Sciences (SLU), Uppsala, Sweden

Pesticide Behaviour in Soils, Water and Air York, UK 2-4 September 2013

Background

• Long-term monitoring of environmental fate of pesticides in Sweden since 2002 (main focus on surface water and groundwater)

• However, one program also includes atmospheric deposition of pesticides (as well as other parameters such as particles, ozone, nitrogen, mercury etc)

• Overall aim of the pesticide monitoring program is to study the extent of deposition of pesticides via rainwater in rural background areas, incl. long-term trends

Sampling sites

Vavihill (Rainwater+air)

Aspvreten (Rainwater)

• Sampling sites located jointly with other international/national atmospheric monitoring programs (e.g. EMEP)

• Located in rural background areas, surrounded by forests, >1 km from treated fields

• Rain water collected • Event related sampling using a

bulk sampler (a stainless steel funnel, area 0.5 m2, above a fridge)

• Collected in 10 litre bottle • Ca 12-15 samples/season • Blank samples collected

regularly • Start in 2002 at Vavihill and in

2009 at Aspvreten • Main sampling season today

April-October (previously May-June + October)

Methods - rain

Analytical methods

• On-line LC-MS/MS for a broad range of pesticides • Method description Jansson & Kreuger, 2010, J. AOAC

Intern., vol 93, 1732-1747

• GC-MS for the most non-polar compounds

• Currently including ca 130 different pesticides in the monitoring program, incl. some degradation products, corresponds to ca 90 % of the applied amount of pesticides in Sweden, but also some obsolete

• LOD/LOQ levels are at the ng/l-level for most pesticides

Results rain 2002-2012

• 82 pesticides & 7 degradation products were detected in rainwater • 36 herbicides, 26 fungicides & 20 insecticides • 23 of these were banned in Sweden • Fewer pesticides and lower concentrations at

Aspvreten (northeast)

• Most detects at the low ng/l-level, though some were occasionally detected above 0.1 µg/l • prosulfocarb, MCPA, pendimethalin, isoproturon,

bentazone, terbutyhazine-desethyl, metazachlor and protioconazole-destio

• Max concentration - 3.6 µg/l (prosulfocarb)

0% 10%20%30%40%50%60%70%80%90%100%

lindane

endosulfan-alpha

propamocarb

prosulfocarb

chlorpyrifos

endosulfansulfate

MCPA

endosulfan-beta

terbuthylazine-desethyl

fluazinam

metazachlor

terbuthylazine

clomazone

isoproturon

metolachlor

prothioconazole-desthio

diflufenican

fenpropimorph

carbendazim

epoxiconazole

pendimethalin

spiroxamine

azoxystrobin

ethofumesate

cyprodinil

HCH-alpha

vinklozolin

mecoprop

2,4-D

dichlobenil

flu

r

oxypyr

pyraclostrobin

dicamba

Detec onfreq.Vavihill

Detection frequency in rainwater at Vavihill (south) 2002-2012 Of those pesticides detected in ≥ 20% of the samples 45% were not used in Sweden during the investigation period (lindane, endosulfan a+b, terbuthylazin, metolachlor, carbendazim, epoxiconazole, sprioxamin, vinclozolin, 2,4-D, dichlobenil)

Co

nce

ntr

atio

n (

µg

/l)

Apr-Jun Jul-Aug Sep-Oct Nov-Mar

Seasonal variation at Vavihill 2002-2012

0,1 1 10 100

prosulfocarb

MCPA

prothioconazole-desthio

pendimethalin

terbuthylazin-desethyl

isoproturon

terbuthylazin

fenpropimorph

ethofumesate

phenmedipham

metolachlor

propamocarb

metazachlor

epoxiconazole

cyprodinil

azoxystrobin

metamitron

2,4-D

propiconazole

fluroxypyr

diflufenican

spiroxamine

atrazine

aclonifen

Averagedeposi onMay-Jun+Oct2002-2011(µg/m2*year)

= not used in Sweden

Atmospheric deposition via rainwater at Vavihill in southern Sweden 2002-2011 • Herbicides

dominate, followed by fungicides

• Also pesticides not used in Sweden (red bars) contribute to the total load

0.0

0.5

1.0

1.5

2.0

Dep

osi

tio

n (

µg

/m2

) 2,4-D

0.0

0.5

1.0

1.5

2.0

20

02

20

03

20

04

20

05

20

06

20

07

20

08

20

09

20

10

20

11

Dep

osi

tio

n (

µg

/m2

)

atrazine

0.0

0.5

1.0

1.5

2.0

Dep

osi

tio

n (

µg

/m2

)

lindane

Yearly ∑ 3-month deposition (µg/m2) 2002-2011 for pesticides not used in Sweden

0.0

2.0

4.0

6.0

20

02

20

03

20

04

20

05

20

06

20

07

20

08

20

09

20

10

20

11

Dep

osi

tio

n (

µg

/m2

)

terbuthylazine

0

5

10

15

20

25

Dep

osi

tio

n (

µg

/m2

)

pendimetalin

0

50

100

150

200

250

20

02

20

03

20

04

20

05

20

06

20

07

20

08

20

09

20

10

20

11D

epo

siti

on

(µ

g/m

2)

prosulfokarb

0

5

10

15

20

25

Dep

osi

tio

n (

µg

/m2

)

MCPA 60

0

5

10

15

20

25

Dep

osi

tio

n (

µg

/m2

)

isoproturon

Yearly ∑ 3-month deposition (µg/m2) 2002-2011 for pesticides used in Sweden

Back-trajectory analysis

• Is there a correlation between composition of detected pesticides and origin of air-masses?

•In early May 2005 a major rainfall event occurred when air-masses came from the south-west

•Results showed that the deposition included 25 different pesticides, 10 of which were not registered for use in Sweden

•A week later (10 May) another major rain event took place when air-masses came from the north-west

•This time fewer pesticides were deposited, i.e. 15 pesticides, with 5 of these not registered for use in Sweden

Conclusions

• Currently used pesticides are regularly detected at ng/l-levels in rainwater, with occasional µg/l-level findings

• A larger number of pesticide detected during spring/early summer, however higher concentrations were detected during fall (mainly prosulfocarb)

• Deposited amount corresponds to ca 0.1-0.0001% of the applied dose in the field

• A significant contribution to atmospheric deposition in southern Sweden from pesticides not used within Sweden, i.e. a transboundary atmospheric transport of pesticides

• Lindane and atrazine, now banned within the EU, were detected at decreasing concentrations

Thank you! Questions?

Acknowledgement:

• The national pesticide monitoring programme is funded by the Swedish Environmental Protection Agency

• Information about the monitoring program for pesticides at www.slu.se/ckb (Centre for Chemical Pesticides)