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Kombinationswirkung Der Beiden Pflanzenschutzmittel Karate Zeon Kombinationswirkung der beiden Pflanzenschutzmittel Karate® Zeon und Callisto® in aquatischen Modellökosystemen Inauguraldissertation zur Erlangung des Doktorgrades der Naturwissenschaften im Fachbereich Geowissenschaften der Westfälischen Wilhelms-Universität Münster vorgelegt von Rabea Christmann Dekan: Prof. Dr. Hans Kerp Erster Gutachter: Prof. Dr. Klaus Peter Ebke Zweiter Gutachter Prof. Dr. Dr. Wilfried Huber Dritter Gutachter Prof. Dr. Hermann Mattes Tag der mündlichen Prüfung: 05. Februar 2014 Tag der Promotion: ____________________________ INHALTSVERZEICHNIS Zusammenfassung .................................................................................................................. III Abstract .................................................................................................................................... V 1 Einleitung .......................................................................................................................... 1 1.1 Pflanzenschutzmittel-Zulassung .................................................................................. 2 1.2 Problematik Mischungstoxizität .................................................................................. 4 1.3 Testsubstanzen ............................................................................................................. 7 1.3.1 Insektizid – Karate® Zeon .................................................................................... 7 1.3.2 Herbizid – Callisto® ........................................................................................... 10 1.4 Zielsetzung ................................................................................................................. 12 2 Material und Methoden ................................................................................................. 14 2.1 Versuchsdesign .......................................................................................................... 14 2.1.1 Testsysteme ........................................................................................................ 14 2.1.2 Applikation der Testsubstanzen ......................................................................... 17 2.2 Analytik ..................................................................................................................... 20 2.3 Erhebung der ökologischen Daten ............................................................................. 21 2.3.1 Probennahme ...................................................................................................... 21 2.3.2 Entnahme der Wassersäulen ............................................................................... 23 2.3.3 Physikalische Parameter ..................................................................................... 24 2.3.4 Chemische Parameter ......................................................................................... 24 2.3.5 Biologische Parameter ........................................................................................ 25 2.4 Aufbereitung der Daten ............................................................................................. 28 2.5 Statistische Auswertung ............................................................................................ 28 2.5.1 Mittelwerte ......................................................................................................... 28 2.5.2 Datentransformation ........................................................................................... 28 2.5.3 Univariate Statistik ............................................................................................. 29 2.5.4 Multivariate Statistik .......................................................................................... 32 2.5.5 Effektbeurteilung ................................................................................................ 35 2.5.6 Ableitung einer Regulatory Acceptable Concentration (RAC) .......................... 36 3 Ergebnisse ....................................................................................................................... 38 3.1 Mesokosmos I – Einzelbelastung Karate® Zeon ....................................................... 38 3.1.1 Wasserqualität (physikalische und chemische Parameter) (I) ............................ 38 3.1.2 Makroinvertebraten (I) ....................................................................................... 38 3.1.3 Zooplankton (I) .................................................................................................. 53 I 3.2 Mesokosmos II – Kombinationsbelastung bei zeitgleicher Applikation ................... 69 3.2.1 Analytik (II) ........................................................................................................ 69 3.2.2 Physikalische Parameter (II) .............................................................................. 70 3.2.3 Chemische Parameter (II) ................................................................................... 77 3.2.4 Makroinvertebraten (II) ...................................................................................... 80 3.2.5 Zooplankton (II) ................................................................................................. 97 3.2.6 Makrophyten (II) .............................................................................................. 110 3.2.7 Phytoplankton (II) ............................................................................................ 111 3.3 Mesokosmos III – Kombinationsbelastung bei versetzter Applikation ................... 122 3.3.1 Physikalische Parameter (III) ........................................................................... 122 3.3.2 Chemische Parameter (III) ............................................................................... 130 3.3.3 Makroinvertebraten (III) .................................................................................. 135 3.3.4 Zooplankton (III) .............................................................................................. 150 3.4 Tabellarische Zusammenfassung der Ergebnisse .................................................... 171 4 Diskussion ..................................................................................................................... 174 4.1 Mesokosmos I – Einzelbelastung Karate® Zeon ..................................................... 174 4.1.1 Bewertung der Ergebnisse (I) ........................................................................... 174 4.1.2 Risikomanagement (I) ........................................................................................... 180 4.2 Mesokosmos II – Kombinationsbelastung bei zeitgleicher Applikation ................. 181 4.2.1 Bewertung der Ergebnisse (II) ......................................................................... 181 4.2.2 Risikomanagement (II) ..................................................................................... 189 4.3 Mesokosmos III – Kombinationsbelastung bei versetzter Applikation ................... 190 4.3.1 Bewertung der Ergebnisse (III) ........................................................................ 190 4.3.2 Risikomanagement (III) ................................................................................... 194 4.4 Extrapolation der Effekte der Einzelsubstanzen auf Kombinationseffekte ................. 196 4.5 zeitgleiche vs. versetzte Kombinationsbelastung ......................................................... 198 5 Fazit ............................................................................................................................... 200 Danksagung ............................................................................................................................ 202 Quellen ................................................................................................................................... 203 II ZUSAMMENFASSUNG ZUSAMMENFASSUNG Bis heute liegt das Augenmerk der aquatischen Risikobewertung von Pflanzenschutzmitteln (PSM) auf der Evaluierung und Regulierung einzelner aktiver Substanzen (VAN DEN BRINK ET AL. 2009, KUNZ ET AL. 2011, BACKHAUS & FAUST 2012). Verbindliche Richtlinien für die Regulatorik von PSM fehlen bislang, obgleich Organismen betroffener aquatischer Ökosysteme gegenüber einer Vielzahl unterschiedlicher, potentiell toxischer Stoffe exponiert sind. Dieser Diskrepanz widmet sich die vorliegende Studie. Insbesondere soll die experimentelle Arbeit klären, inwieweit sich aus der Kenntnis der Toxizität einzelner PSM Aussagen über die Kombinationswirkung der Substanzen einer PSM-Mischung treffen lassen. Ein weiterer Aspekt der Arbeit zur Kombinationswirkung von PSM liegt im Vergleich einer zeitgleichen gegenüber einer zeitlich versetzten Applikation einer binären PSM-Mischung. Im Fokus der Studie stehen das Pyrethroidinsektizid Karate® Zeon (Wirkstoff Lambda- Cyhalothrin) und das Bleichherbizid Callisto® (Wirkstoff Mesotrione). Beide Produkte finden ihre Anwendung unter anderem im Bereich des Maisanbaus, so dass sie sowohl zeitgleich auf benachbarten Feldern als auch zeitversetzt auf gleichen Ackerflächen in der Umwelt ausgebracht werden. Um das Risikopotential der Mischung dieser PSM auf ein aquatisches Ökosystem abschätzen zu können, wurden drei Freilandmesokosmenstudien durchgeführt: Die Einzeltoxizität des Insektizids wurde zunächst zwischen 1 ng active ingredient (a.i.)/L – 1000 ng a.i./L Karate® Zeon getestet (Mesokosmos I). Die Kombinationswirkung
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