Long-term monitoring of pesticides in air and atmospheric deposition - PowerPoint PPT Presentation

Long-term monitoring of pesticides in air and atmospheric deposition in Sweden Jenny Kreuger & Bodil Lindström Swedish University of Agricultural Sciences (SLU), Uppsala, Sweden IUPAC Ghent, Belgium 20 May 2019

Background • Long-term monitoring of environmental fate of pesticides in Sweden since 2002 • Main focus on surface water* • To a lesser extent, also monitoring of pesticides in atmospheric deposition and in air * Boye et al (2019) Journal of Environmental Quality – in press DOI:10.2134/jeq2019.02.0056

Sampling sites • Sampling sites located Norunda - from 2017 jointly with other international/national atmospheric monitoring programs Aspvreten - 2009-2016 (e.g. EMEP & ICOS) Located in rural • background areas, Vavihill – 2002-2016 surrounded by forests, Hallahus – from 2017 >1 km from treated fields

Methods - precipitation • Event related sampling using a bulk sampler (a stainless steel funnel, area 0.5 m 2 , above a fridge) • Ca 12-15 samples/season • Ca 140 pesticides analysed today • Sampling during main growing season • From 2009 April-October • Previously May-June + October • Started in 2002 at Vavihill & in 2009 at Aspvreten (further north)

Methods - air Air samples collected • At fixed, weekly, intervals using a high- volume pump (ca 400 m 3 /day) • Using pre-cleaned cartridges with quartz fiber filter and PUF/XAD/PUF • Ca 10-12 samples/season • Ca 100 pesticides analysed today • Started in 2009 at Vavihill PUF-2 / XAD / PUF-1 Airflow

Vavihill (south) - Total concentration in precipitation/ sample 2002 - 2015 10 Total concentration (µg/l) 1 0,1 0,01 0,001 0,0001 2001 2003 2005 2007 2009 2011 2013 2015 Max total concentration 3.9 µ g/l in a sample from October 2015, with prosulfocarb constituting the major part (3.8 µ g/l)

Vavihill (south) - Total concentration per sample 10 2002 - 2015 Total concentration (µg/l) 1 • During later years (2012-2015) 65 a.i. & 6 TP:s were detected 0,1 • Most detects at the low ng/l-level, though some were occasionally detected above 0,01 0.1 µg/l, mainly • prosulfocarb, protioconazole-destio, 0,001 MCPA, pendimethalin, and terbutyhazine-desethyl 0,0001 2001 2003 2005 2007 2009 2011 2013 2015 Max total concentration 3.9 µ g/l in a sample from October 2015, with prosulfocarb constituting the major part (3.8 µ g/l)

0% 25% 50% 75% 100% Detection frequency in lindane prosulfocarb rainwater at Vavihill propamocarb endosulfan-alpha (south) during recent years chlorpyrifos terbuthylazine-desethyl 2012-2015 MCPA metazachlor terbuthylazine Of those pesticides boscalid endosulfan-sulfate detected in ≥ 20 % of the prothiochonazole-desthio clomazone samples – ca 50 % were not Approved endosulfan-beta isoproturon used in Sweden during the metolachlor fluazinam investigation period (e.g. epoxiconazole diflufenican lindane, endosulfan, azoxystrobin fenpropimorph chlorpyrifos, ethofumesate flufenacet terbuthylazine, HCH-alpha carbendazim metolachlor, pendimethalin cyprodinil epoxiconazole, flufenacet) dicamba vinclozolin pyraclostrobin 2,4-D

Average deposi-on 2012-2015 (µg/m2*year) Atmospheric 0,1 1 10 100 deposition at Vavihill prosulfokarb in southern Sweden prothioconazole-desthio terbuthylazine-desethyl 2012-2015 (April- metazachlor propamocarb October) = not used in terbuthylazine MCPA Sweden • Herbicides boscalid bentazone dominate, followed Non-registred pes.cides isoproturon metamitron 0,001 0,01 0,1 1 10 100 by fungicides terbuthylazine-desethyl flufenacet terbuthylazine metolachlor • Also pesticides not flufenacet trinexapac-acid metolachlor epoxiconazole registered for use 2,4-D pendimethalin epoxiconazole tri-allate in Sweden (red chlomazon lindane chlorpyrifos clopyralid diuron bars) contribute to propiconazole quinoxyfen linuron diflufenican the total load BAM ethofumesat methabenzthiazuron pendimethalin atrazine HCH-alfa fenpropimorph dimethoate endosulfan-alfa endosulfansulfat endosulfan-beta dichlobenil HCB

Long-term trends - deposition Now registered in Sweden, with sale starting in 2015 Yearly ∑ 3-month deposition (µg/m 2 ) 2002-2017 for pesticides not used in Sweden Banned within the EU (left) and approved within EU (right)

Long-term trends - deposition 66 15 Yearly ∑ 3-month deposition (µg/m 2 ) 2002-2017 Pesticides used in Sweden (left) and for pesticides banned during the period (right)

Air samples - distribution between filter, PUF and XAD for 26 pesticides detected in >20% of the air samples (n = 34) • PUF breakthrough (> 30%) for dichlobenil, HCH-a, HCB and trifluralin. • However, only 4% of total pesticide concentration found in XAD and PUF-2 * Substances not approved for use within EU at the time of sampling

Pesticides in air April 2017 – March 2018 • Some were primarily detected on filter • Seasonal occurrence

Pesticides in air April 2017 – March 2018 • Others were detected on PUF • Year round

Detection frequency in air (adsorbent, PUF-1) 2012-2015 • A total of 31 a.i. and 5 TP:s 0% 20% 40% 60% 80% 100% • Majority of pesticides endosulfan-alpha HCH-alpha detected in the gas phase chlorpyrifos are not approved for use lindane HCB within Sweden, many not prosulfocarb even within the EU DDE-p,p DDT-p,p • Most concentrations at low chlordane-gamma levels (< 0.1 µg/m 3 air), chlordane-alfa mainly prosulfocarb endosulfan-beta endosulfan-sulfat detected above this level terbutylazine (max. 30 µg/m 3 air) pendimethalin Not approved terbuthylazine-desethyl Approved etofumesate tolchlofos-methyl

Detection frequency in air (filter) 2012-2015 0% 20% 40% 60% 80% 100% diflufenican • Majority of pesticides lambda-cyhalotrin detected in the esfenvalerate particulate phase are fenpropimorph approved for use within propiconazole chlorpyrifos Sweden azoxystrobin • Most concentrations at tau-fluvalinate Not approved low levels (< 0.1 µg/m 3 aclonifen terbuthylazine-… Approved air), mainly cypermethrin fenpropimorph detected pendimethalin above this level (max. terbuthylazine 0.8 µg/m 3 air) cyprodinil prosulfocarb alfa-cypermethrin isoproturon

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

Thank you! Questions? Acknowledgement: The national pesticide monitoring programme is funded by the Swedish • Environmental Protection Agency Information about the pesticide monitoring program at • • Department of Aquatic Sciences and Assessment or • Centre for Chemical Pesticides