BioavailabilityofPesticidesto BenthicInvertebrates TheRoleofAquaticBiofilmsandHumicSubstances FacultyofNaturalResourcesandAgriculturalSciences DepartmentofAquaticSciencesandAssessment Uppsala DoctoralThesis SwedishUniversityofAgriculturalSciences Uppsala2011 ʹͲͳͳǣͷͶ ǣ ȋǣ Ȍ ͳͷʹǦͺͺͲ ͻͺǦͻͳǦͷǦͷͻͺǦͻ ̹ʹͲͳͳǡ ǣ ȀǡʹͲͳͳ Bioavailability of Pesticides to Benthic Invertebrates: The Role of AquaticBiofilmsandHumicSubstances Abstract ǡ Ǥ ǡ ǡ Ǧ Ǥ Ǥǡ Ǥ ǡ Ǧ Ǥ Ǧ ǡ ǯ Ǥ ǡ Ǧ Ǥ ǡǦ Ǥ Ǥǡ ȋȌ ȋȌ Ǥ ǡ ǡ Ǧ ȋȌ ǡ Ǥǡ Ǧ Ǥ Ǧ ǡǡ Ǥ ǡ ǡ Ǥ ǡ ǡ ǡ ǡ Ǥ Keywordsǣ ǡ ǡ ǡ ȋȌǡ ȋȌǡ ȋȌǡ ǡǡ Author’saddress:ǡǡ ǡǤǤͲͷͲǡͷͲͲǡ EͲmail:Ǥ̷ǤǤ Contents ListofPublications 7 Abbreviations 9 1 1.1 1.2 1.3 Introduction OrganicContaminantsinAquaticEnvironments ContaminantUptakeinBenthicInvertebrates OrganicMatterandBioavailabilityinAquaticEnvironments 11 11 12 14 ObjectivesofthisThesis 16 MaterialsandMethods TestOrganismsandSubstances ExperimentalDesign(PapersIͲIV) 3.2.1BioavailabilityofChlorpyrifosinBottomSubstrateswith DifferentSourcesofOrganicMatter(PapersIͲII) 3.2.2FateandUptakeofInsecticidesalongDOMͲgradients(PaperIII) 3.2.3SorptionofInsecticidestoSizeͲFractionsofDifferentDOM (PaperIV) 17 17 19 2 3 3.1 3.2 19 21 23 4 4.1 4.2 4.3 5 6 25 ResultsandDiscussion BioavailabilityofChlorpyrifosinBottomSubstrateswithDifferent SourcesofOrganicMatter(PapersIͲII) 4.1.1SedimentMicrobesandBiofilmPositivelyAffectBioavailability (PaperI) 4.1.2EPSandHSNegativelyAffectBioavailability(PaperII) FateandUptakeofInsecticidesalongDOMͲgradients(PaperIII) SorptionofInsecticidestoSizeͲfractionsofDifferentDOM(PaperIV) 4.3.1InsecticidesSorptiontotheColumn 4.3.2AlternativeApproaches 25 27 30 33 34 36 ConclusionsandFuturePerspectives 37 Svensksammanfattning 39 25 References 43 Tack! 49 ListofPublications ǡ ǣ ǡ Ǥǡ ǡ Ǥ Ƭ ǡ Ǥ ȋʹͲͲͺȌ Chironomus riparius ȋǡ ȌǤ Ecotoxicology and EnvironmentalSafetyͳǡͶͻͲǦͶͻ ǡ Ǥǡ ǡ Ǥ Ƭ ǡ Ǥ ȋʹͲͳͲȌ ChironomusripariusǤEcotoxicologyͳͻǡͳͶǦʹʹ ǤǡǡǤƬ ǡǤ Ǧ ȋ Ȍ ǡ Ǥ ǡ Ǥǡ ǡ Ǥǡ ǡ Ǥ Ƭ ǡ Ǥ ǡ ȋ Ȍ Ǥ ǣ ǡ Ǥ ǡ ǡǤ ǡǡ ǡ ǡ Ǥ ǡǡ ǡ ǡ Ǥ ǡ Ǥ ǡ Ǥ ͺ Abbreviations ͳͶ ȀȀ ǡȀ ȋͺȌ Ǧ Ǧ Ȃ Ú Ú ȋǦȌ ͻ ͳͲ 1 Introduction ǡ ǡ ǡ Ǥ 1.1 OrganicContaminantsinAquaticEnvironments ȋǤǤǡ ǡȌǡ ȋ Ǥ ʹͲͲͳǢ ʹͲͲȌǤ ȋȌ Ǥ ǡ Ǧ ȋƬͳͻͻȌǡ Ǥ ǡ Ǥ ȋƬͳͻͻʹȌǡ ȋ Ǥ ͳͻͻͻǢ Ƭ ʹͲͲȌ ȋ Ƭ ͳͻͻͳȌǡ ȋ Ǥ ͳͻͻȌǤ Ǧ ȋͳͻͺǢƬͳͻͻʹȌǤ ȋȌ ǡ ͳͳ Ǥ ǡ Ǧ Dz dz ȋ ȏȐ ʹͲͳͲȌǡ Ǥ ǡ ǡ ȋ ʹͲͲȌǤ Ǧ Ǧ ǡǦǡȋ ǤͳͻͻͻȌǤ ǡ Ǥ ǡ ǡ Ǥ ǡ Ǧ ǡ ǡ ȋ Ƭ ʹͲͲͷǢ Ǥ ʹͲͲͻȌǡ ǡ ǡǡȋÚǤͳͻͻͻǢ ǤʹͲͳͲȌǤ ǡ ȋȌ ȋ ǤͳͻͻͺǢʹͲͲȌǡ Ǥǡ ͳͻͷǡ ͳͷ ͳͲͲρȀ ȋȌ ȋ Ǥ ͳͻͻͻǤȌ ͳͻͲǯ ȋǤǤǡ Ǥ ͳͻͻͻȌǡ Ǥ 1.2 ContaminantUptakeinBenthicInvertebrates Ǥ ǡ Ǧ ȋ ͳͻͺǢͳͻͻȌǤ ͳʹ Figure1 Chironomusriparius ȋΪȌǡ ȋǡΪȌǡ ȋΪ ȌǤ ȋ Ȍ ȋȌǡ Ǥ ȋǤͳȌǤ ȋ ǤʹͲͲʹȌǡ ȋǤǤǡ Ǥ ͳͻͻͳǢ ͳͻͻȌǤ ǡ ǡ Ǧ ȋǡ ͳͻͺͳȌǡ ȋ Ƭ ͳͻͻȌǤ ǡ Ǧ ȋǤǤǡͳͻͻǢ Ǥ ͳͻͻͺǢ Ǥǡ ʹͲͲͲȌǤ ǡ Ǥ ǡ Ǧǡ ȋͳͻͻͺȌ ȋʹͲͲ͵ȌǦCapitellaǤ ȋƬͳͻͻͳǢ ǤͳͻͻͻǢǤͳͻͻͻǢ ƬʹͲͲȌǤ Ǧ Ǧ Ǥ ȋ Ǥ ͳͻͻͻȌǡ ȋ ͳ͵ ƬʹͲͲȌǤǡ ȋ Ǥ ͳͻͻȌǡ ȋ Ƭ ͳͻͻȌǤ ǡ Ǥ 1.3 OrganicMatterandBioavailabilityinAquaticEnvironments ǡ ǡ ǡ ǡ ȋ ͳͻͻȌǤ Ǧ ȋȌǡ ǡ ǡ ǡ ǡ ȋ ͳͻͻͲǢ Ǥ ʹͲͲȌǤ Ǧ ǡ ȋǤʹȌǡ ȋ ǡͳͻͻͲȌǤ ȋ ͳͻͻͲȌǡ ȋ Ǥ ͳͻͻͶȌ ȋ Ǥ ͳͻͻͺǢ Ǥ ͳͻͻͻȌǡ Ǥǡ ȋǤͳͻͻͺǢ Ǥ ʹͲͲͳǢ Ǥ ʹͲͲͶȌǤ ǡ ȋ Ƭ ͳͻͻ͵Ǣ Ƭ ʹͲͲͷȌǤ ǡ Ǧ Figure 2 Ǧ ȋȌ ǡ ǡ Ǧ ǡ ǡ ȋ ȋ ͳͻͻͲȌǤ Ƭͳͻͻ͵ȌǤ ͳͶ ǡ Ǧ Ǥ ǡ ǡ Ǥ ȋȌ ȋ Ƭ ͳͻͻͶȌǤ ȋǤǤǡ Ƭ ͳͻͻͶǢ Ǥ ͳͻͻͻȌǤ ǡ ǡ ǡ ǦǤ Ǧ ǡ ǡ ȋ ͳͻͺͷȌǤ ǡ ǡ ȋ ƬͳͻͻͺǢǤͳͻͻͻȌǤ Ǧ ǡ ȋ Ǥ ͳͻͻͶǢ Ǥ ͳͻͻͻǢ Ǥ ʹͲͲͶȌǤ ǡ ȋ Ǥ ͳͻͻͶǢ Ǥ ʹͲͲͲȌǤ ǡ Ǧ Ǧ ȋ Ƭ ͳͻͻͳǢ Ǥ ͳͻͻͻǢ Ƭ ʹͲͲͳȌǤ ǡ ǡ ȋ Ƭ ͳͻͺʹȌǡ ǡ Ǥ ǡ Ǧ ȋ Ǥ ʹͲͲǢ Ǥ ʹͲͳͲȌǡ ǡ ǡ Ǥ ͳͷ 2 ObjectivesofthisThesis Ǧ Ǥ ǡ Ǧ Ǥ ȋǦȌǣ ǡ ȋȌǡ ǡ ǡ Ǧ ChironomusripariusǤ C.riparius ǡ ȋȌǤ ȋ ǡ Ȍ ȋǡ Ȍ Ǥ ȋ ǡ Ȍ ȋ Ȍ ȋ Theodoxus fluviatilisȌ ȋǢ ǡ ȌǤ ȋ ǡ Ȍ ǡ Ǧ Ǥ ͳ 3 MaterialsandMethods Ǥ ǡ Ǥ 3.1 TestOrganismsandSubstances ȋȂȌ ǡ ǤǤǡ Ǧ Ǥ ȋ ͳͻͺǢ ͳͻͺȌǤ Ǥ ChironomusripariusȋǦȌǦǦ ȋǡ ȏȐǡ ȏȐȌǤ ǡ ǡ ǡ ȋ ͳͻͺȌǤ ǡ ȋ ͳͻͺǢ ͳͻͻͷȌǡ ȋ% Ƭ ʹͲͲ͵ȌǤ ǯ ǡ ǡ ȋ ǤͳȌǤ Chironomus ȋǤǤǡ Ǧ ȏȐ ʹͲͲͶȌǤ ǡ Ͷ Ǥ ͳ Theodoxus fluviatilis ȋȌ ǡ ȋʹͲͲȌǤǦ ȋ ͳͻͳȌ ǤChironomusǡT. fluviatilis ǡ ǤǤǡ ǡ Ǥ ǡ Ǥ ǡ ǡ ǡ Ǧ Ǥ ȋ ǡ Ȍ Ǥ ǡ Ǥ ͳͶǦǡ Ǥ Ǥ ǡ ȋǤͳȌǤ ȋ ͳͻͻ͵ȌǤ ǡ ȋ Ǥ ʹͲͳͲȌǤ Ǧ ǡ Table1 ǡ Ǧ ȋȌǦ ȋȌ Ǥ ʹͲͲͻ ͳͺ ͳǤͷ ʹʹͳǤ͵ ͵Ǥͷ ʹͻͲǤͺ ͶǤ ͵ͷͲǤ Ǥ ǡ Ǥ Ǥ ǡ ǡ Ǧ ǡ ǡ ǡ ȋ Ƭ ʹͲͲͷǢ ǤʹͲͲͻȌǤ 3.2 ExperimentalDesign(PapersI–IV) 3.2.1 BioavailabilityofChlorpyrifosinBottomSubstrateswithDifferentSources ofOrganicMatter(PapersIͲII) ǡ C. riparius ȋͶͲǦ͵ρǡ Chironomus Ǣ Ǥ ͳͻͻͻȌ ͷͲ ȋ Ȍ ǣ ͳǤ ǡ ʹǤ ǡ ͵Ǥ ǡ ͶǤ ǡ Ǥ Ǧ Ǥ Ǥ ǡ ǡ ǡ ǡ Ǧ Ǥ ȋ Ȍ Ǧ ǡ Ǥ ǡ ȋǦ Ǥ ʹͲͲͳȌǡ Ǥ ǡ ǡ Ǥ ȋ ǡ Ȃ Ȍ ȋͷͲȀȌ ǡ Ǥ ǡ ȋ Ȍ Ǥ ǡ ͳͻ Figure 3 Ǥ ȋȌ ȋȌ ǡ ȋǤǤǡ Ȍ ȋǡǡȌǤ ͳ͵ȋ ƬʹͲͲȌǤ ǡ Chironomus Ǥ ǡ ȋȌȋ Ȍ ǡ ȋǡȌȋǤ͵ȌǤ ǡ ȋͶͲǦ ͵ρȌǡ ȋǦǢ ʹͲͲͶȌǡ ǣ ͳǤ ȋ ǡȂ Ȍǡ ʹǤ ȋȌǡ ͵Ǥ ȋ ǡȂ Ȍǡ ͶǤ ȋȌ ȋǡ Ȍ Ǥ ǡ ȋ Ȍǡ Ǣ ȋͳǡͲͲugǡ ͳͷȌ ȋǡͳͲͲugǡ ͵ͲȌǤ ȋ Ǧ ǡ ǤǤǡ Ǧ ȌǦǤȋǤǤǡ Ȍ ȋ ÚȌ Ǧ Ǥ ȋͳͻͺ͵Ȍǡ Ƭ ȋͳͻͺͳȌǡǦǤ ʹͲ Figure4 ȋǦȌChironomusriparius ͳͶǦ ȋȌǤ ȋǦȌǡ ȋǢ ǤͶ ȏȐȌǡ ͳͶǦ ȋͲǤρȀȌ ǡ ͳͺȋȌʹͶȋȌǤǡ ȋȌȋȌͶ ʹͶǦʹ ȋǤͶȌǤ ǡ ǡ ȋȌǤ ȋȌ ȋȌ ȋǤͶȌǤ ȋʹͳǦʹͶȌ ǡ ȋ̺Ȍ ȋǤͶȌǤ ǡ ȋǤͶȌǤ ǡ Ǧ ʹͶ ȋǤͶȌǤ ǡ ȋǤͶȌǤ ͳͶǤ 3.2.2 FateandUptakeofInsecticidesalongDOMͲgradients(PaperIII) ǡ ǡ ǡ ȋTheodoxus fluviatilisȌ Ǥ Ǧ ȋʹͶǦͶͺȌǤ ǡ Ǧǣ ʹͳ Figure 5 ȋǢ ǡ ǡ Ȍ ȋDzdzȌ ȋDzǦdzȌǤ ͳǤ ǦȋͻǤͲάͳǤͳȀǡÚǦ¤ÚȌǡ ʹǤ ǦȋͳͻǤάͲǤ͵ͷȀǡÚȌǡ ͵Ǥ Ǧȋ͵ͷǤ͵άͳǤͷȀǡÚȌ ȋͳͲ u ͳͲ Ȍ ͵Ͳ ȋʹͲάʹιȌ ͳȀͺ Ȁ ȋǡ ͶͲͲǦͲͲ ȌǤ Ǧ ȋDz dzȌ ȋǤͷȌǤ ȋDzǦ dzȌ ǡ ǤǤ ȋǤͷȌǤǡǡ ǡ Ǧ Ǥ ͳͶǦ ȋ͵ǤͺάͲǤͲͷȀ ȏ Ȑǡ ͵ǤͲάͲǤͲ͵Ȁ ȏȐǡ ͷǤ͵άͲǤͲ͵Ȁȏ ȐȌʹͶǤ ʹͶ ǡ Ǥ Ǧ ǡ Ǥ Ǥ Ǧ Ǧ Ǥ ͷǡ ʹͶ Ͷͺ Ǥ ͳͶǤ ǡ ȋ α ȏȐ Ȁ ȏ Ȑǡ Ȍǡ Ǥ ʹʹ 3.2.3 SorptionofInsecticidestoSizeͲfractionsofDifferentDOM(PaperIV) ȋͳȌ ǡ ȋʹȌ Ǧ Ǥ ǡ Úǡ ǣ ͳǤ ȋȌǡ ʹǤ ȋȌǡ ͵Ǥ Ú ȋȌǡ ͶǤ Ú ȋȌ ǡ ǡ ǡȋ ǡ ȌǤ Ǥ Ǧ ǡ Úǡ ȋ ǢȌ Ǧ ȋȌǤ Ǧ Ǥ Ǧ ȋȌ Ǧ Ǧ ȋǤȌǤ Ǧ ̺Ǧ ȋ ʹͲͲͲǡ Ȍǡ ȋʹͶǡǤͺǡIαͲǤͲͷȀȌ ͲǤȀǤ ǡ ǡ ȋǢ͵ʹǡ ͳǡͺǤͲǡͶǤ͵ǡͳǤͲȌǤ Ǧ ͳͷ ͳȀͳǣȀ Ǧ ȋ ͵ͲȀȌǤ ͳͶǦ ǡ ͵ͲρȀǡ Ͷͺ ȋͳͲͲ ȏȐǡ ǡ ȌǤ ȋͳͲͲρȌ ̺Ǧ ǡ ȋǤȌ Ǧ ǣDzε͵ͲdzǡDz͵ͲǦ ʹͷdzǡ DzʹͷǦʹͲdzǡ DzʹͲǦͳͷdzǡ DzͳͷǦͳͲdzǡ DzͳͲǦͷdz ȋ Ȍǡ Dzͷ δʹͲdzǡ DzʹͲdzǡ Dz dzǤ Ǧ Ǥ Ǧ ͳͶǦ Ǥ ʹ͵ Figure6 Ǥ ǡǤǤǡǤ Ǧ ǡ ȋ Ȍ Ǥ ǡ ǡǤǤǡ ȋǤǤǡǦ ȌǤ ȋΨȌ ǡ Ǧ ȋȀȀȌ Ƭ ȋʹͲͳͲȌǤ ǡ Ǥ ȋ͵ͲρȀȌͳȀͳǣ Ȁ ȋ ͵ͲȀȌ ͳȀͳǣȀǤ ȋͳͲͲǡ ǡ ȌǤ ̺ Ǥ ǣ ȋͳȌ ǡǤǤǡǦ ǡ ȋʹǦ͵Ȍǡ ǡ ǡ ȋͶǦͷȌ ǡ Ǥ ȋͳǤͷȌ ǡ ͵Ͳρ ȀȀǤ ǡ Ǧ ȀȀ Ǥ ͷͲ Ǧ ǡ ͳͲͲΨ Ǥ ʹͶ 4 ResultsandDiscussion 4.1 BioavailabilityofChlorpyrifosinBottomSubstrateswith DifferentSourcesofOrganicMatter(PapersIͲII) Chironomus Ǥ ǡ ǡ Ǧ Ǥ 4.1.1 SedimentMicrobesandBiofilmsPositivelyAffectBioavailability(PaperI) ȋǤȌǤ ǡ ȋǤȌǤ Ǥ ǡǡ ǡǤǤǡ ǡ ǡ ȋǤȌǤ Ǧ ȋǤȌǤ C.ripariusǤ ȋǤǤǡ Ȍ Ǥ Chironomus ȋ Ǥ ͳͻͺͻȌǡ ȋ Ƭ ʹͷ Figure7 ȋρȀǡάͳȌ ȋȌȋ Ȍ Ǥ ȋȀȌǤ ͳͻͻͲȌǤ Ǧ Ǧ ȋ Ǥ ͳͻͻͶǢ Ǥ ͳͻͻͻǢ Ƭ ʹͲͲǢ Ǥ ʹͲͲͺȌǤ ǡ ǡ ǡ Ǥ Ǥ Ǧ ǡ ǤǤǡ ǡ Ǥ ǡ ǡ ǤC.riparius Ǧ ȋ%Ƭ ʹͲͲ͵Ȍǡ ȋ Ǥ ͳͻͺȌǤ Ǥǡ Chironomus Ǥ Ǥ ǡ ͶΨ ǡ Ǥ ʹ Ǣ ǡ Ǥ ǡ ǯ Ǥ ǡ ǡ Ǥ ǡ ȋ ͲǤͷάͲǤͲͻ ͲǤάͲǤͲͶρȀȌ ȋͲǤͶάͲǤͲʹρȀȌǡ ȋǤǤǡ Ȍ Ǥ ȋȌ ͵ʹͲά͵ ͲάͳʹͲȀǡ ǡ Ǥ ȋͶͺͲάȀȌͳǤͷ ǡ Ǥ ȋ Ƭ ͳͻͻͳǢ Ǥ ͳͻͻͻǢ Ƭ ʹͲͲͳȌǤ Ǥ ȋͷͺάͳǤͳȂͻάʹǤͲΨȌ Ǥ 4.1.2 EPSandHSNegativelyAffectBioavailability(PaperII) ȋǤͺȌǤ Ǧ ͻͲΨǤ Ǧ ͲΨǡ Ǥ Ǧ ǡ ȋǤǤǡ Ƭͳͻͻ͵Ȍ Ǧ ȋ Ƭ ͳͻͺͷǢ ǤͳͻͻͶǢ ǤͳͻͻͺǢ ǤͳͻͻͻȌǤ ʹ Figure8Ǧ ȋǡάͳǡȀȌ ȋ Ȍ ȋ Ȍ ȋȌ ȋȌǡ ǡ ȋǡ ȌǤ Ǥ ǡǡ Ǥ ǯ ȋ ͳͻͺͳǢ ƬʹͲͲȌǡǦ ǦǤ Ǥ ǡ ȀǦ Ǧ ǡ ǦǤ ȀǦ Ǧ Ǥ Ǧ Ǧ Ǧ ǡ ǦǤ Ǥ ȋǤȌǡ Ǧ ȋ ȌǤ ǡ ǡ ǡChironomus Ǥ ǡ ʹͺ ǡ Ǥ Chironomus ʹ ȋ Ǥ ʹͲͲʹȌǡ Ǥ ͶͲΨ ǡ Ǥ Ȁ Ǥ Ǧ ǦȀǦ Ȁǡ Ǥ ǡ Ǧ Ǥ ǡ Ǧ Ǧ ǡ Ǧ ǡ ȀǦ ǡ Ǥ ȋ Ǥ ʹͲͲʹȌǡǤ ǡ Ǥ Ǧ ǡǡ Ǥ ǡ ǡ Ǥ ȋȏͺȐȌ ȋǦ ǡ Ȍǡ ǡ ȋ ʹͲͲǡ Ǥ ǤȌǤ Ǧ ǡǡ ȋ Ƭͳͻͻ͵ȌǤ Ǥ ǡ Ǥ ͲΨ Ǥ ʹͻ Ǥ 4.2 FateandUptakeofInsecticidesalongDOMͲgradients (PaperIII) Ǧ Ǥ Ǧ ȋǤͻȌǤǡ Ǧ Ǧ Ǧ Ǧ ȋǤͻȌǤ ǡ Ǧ Ǧ Ǧ Ǧ Ǧ ȋǤͻȌǤ Ǧ ǡ Ǥ ȋȌ Ǧǡ Ǧ ǦȋǤͳͲȌǡ Ǧ Ǥ ǡ ͷͲ ͵ͲΨ Ǧ Ǧ ǡ ǡ Ǧ ȋǤͻȌǤ Figure9ȋȀǡάȌ ȋȌǡȋȌ ȋȌ Ǧ ȋȌǡ Ǧ ȋȌ Ǧ ȋȌ Ǥ Ǧ Ǥ Ǥ ͵Ͳ Figure10 ȋǡȀǡάȌȋȌǡ ȋȌ ȋȌǡȋȌǡ ȋȌǦȋȌǡ Ǧ ȋ Ȍ Ǧ ȋ Ȍ Ǥ Ǥ Ǥ Ǧ Ǧ ǯǤ Ǧ Ǥ ǡ Ǧ ȋǤͳͲȌǡ ȋȌ Ǧ Ǥ Ǧ Ǧǡ Ǧ ǡ Ǧ ǡ ǤǤǡ Ǧ ǡ ȋǤͳͻͻͶǢ Ǥ ʹͲͲ͵ȌǤ ǡ Ǥ ǡ ȋƬͳͻͻͳǢǤͳͻͻͶǢǤͳͻͻͻǢ Ǥ ʹͲͲͶȌǤ Ǧ Ǧ Ǧ ͻͲǡͳͻͲͲǡ ʹͲͲͲǡ ͻǤͺǡʹͻǡ͵ͳΨǦǡǦǡ ͵ͳ Ǧ ǡ Ǥ Ǧ Ǧ Ǥ ȋǤͳͲȌǤ ǡ ǡ ȋǤǤǡ Ǣ Ȍǡ Ǧ ͵Ǧ Ǥ ǡ ǤǤǡ ǤǡͳͶΨ Ǧǡ ȋǤǤǡ ǡ Ȍ Ǥ Ǧ ǡ ǤǦ ȋʹǤͻ͵άͲǤͲͶȀȌ ʹͶǦͳͲǦ Ǧ Ǧ ǡ Ǥ Ǧ ǡ ȋ Ǥ ʹͲͲʹȌǡ ȋ Ƭ ͳͻͺʹȌǡ ȋ Ǥ ͳͻͻͶȌǤ ǡ Ǧ Ǧ Ǥ ǡ Ǧǡ Ǧǡ Ǧ Ǥ ǡ Ǧ ǡ ǡ Ǥ ͳͲάͳǤͲΨ ǡ ǡǦ ǡ ͳάͲǤΨ ǦǤ Ǧǡ ǡ Ǧ ͵ʹ Ǥ ǡ Ȁ Ȁ ǡ ȋ ʹͲͲͻȌ ȋ ʹͲͳͳǡǤ ǤȌǤ ȋͳͳʹάͳǤǡͷάͳǤΨȌǡ ȋδͳΨȌǡ ȋȀȌ ǡ ǡ ǡ ͷǦǡ ͳ͵ͲǦ ͵ͺͲǦ ȋȀȌǤ ǡ Ǧ Ǥ ǡ ǦǤ 4.3 SorptionofInsecticidestoSizeͲfractionsofDifferentDOM (PaperIV) ȋǦȌǡ ǡǡǦ ǡ ȋǤǤ Ȍ Ǥǡ Ǥ Ǥ ǡ ǡ Ǧ Ǥ ǡ Ǧ Ǧ Ǧ Ǥ ǡ Ǧ Ǥ Ǥ ǡ ǡ Ǧ Ǥ Ǧ ȋ̺Ȍǡ ȋ ǡƬͳͻͻǢǤʹͲͲʹǢǤʹͲͲǢ ͵͵ Table2 ȋΨǡάͳȌ Ǧ Ǧȋ ȏȐ ȏ Ȑ Ú ȏ Ȑ Ú ȏȐȌǤ ͳͻάͳͳ ͳǤͻάͲǤͷ ͷǤͳάͲǤʹͲ ͵͵άͳ͵ ͷͲάͺǤ͵ ͺǤͻάʹǤ ͵ʹάͳͶ ͵άǤ ͷǤʹάͲǤͷ ͷͳάͳǤͷ ͵ͷάǤͷ ǤάͳǤͳ Ǥ ʹͲͲͻȌǤ ̺ ǡ Ǥ ͵ǤȂʹʹ ǡ ͵ǤȂͺͳǤǦÚǡ Ǥǡ Ǧ ǡ Ǥ Úȋ ƬͳͻͻͺȌǤ Ǧ ͳǤͻͷͳΨȋǤʹȌǤ ǡ ͳͲΨ ǦǤ ǡ ȋ Ȍǡ Ǥ ǡ Ǥ 4.3.1 InsecticideSorptiontotheColumn ȀȀ ǦǤ ǡ ȋǤͳͳȌǡ ǤǤǡ ͳͲͲΨǤͲǡ ǤǤǡ Ǧǡ ǡ ȋȌ ǡ ȋǤͳͳȌǤ ǡ ǡ ͲΨ ͺͲǡ ǤǤǡ ȋǤͳͳȌǡ Ǥ ǡ ǡ ͵Ͳ ȋǤͳͳȌǡ ǡ Ǥ ̺ ȋǡ ͵Ͷ Figure11 ȋΨȌ ȋ Ȍ ȋȌǡ ȋ Ȍ ȋ Ȍ ȋǤͳʹȌǤ ±ƬͳͻͻͲȌǤ ǡ Ǥ ǡ Ǥ ǡ Ǥ Ǧ Ǧ Ǥ ǡ Ǧ Ǥǡ ȋ ǡ ǡ Úǡ Ȍ ȋǡ ǡ ǡ Ȍǡ ȋ Ǧ Ȍ Ǥ Ǧ ǡ ǡ Ǥ ǡ Ǥǡ ǡ ǡ Ǧ Ǥ ͵ͷ 4.3.2 Alternativeapproaches Ǧ ǡ Ǥ ǡ̺ǡǦ ȋò Ǥ ʹͲͲͲǢ Ǥ ʹͲͲ͵ȌǤ ǡ ǡ ȋ Ǥ ʹͲͲ͵ȌǤ ǡ Ǥ ǡ ̺ ǡ Ǧ ǡǡ Ǥ ǡ ȋȌǤ ȋ Ǥ ͳͻͻͲȌǡ Ǧ ǦǦ ȋ ǦͳȌǤ ȋ Ǥ ʹͲͲͷȌǤ Ǧ Ǥǡ ǡ ǡ Ǥ ǡ Ǧ Ǧ ǦǤ ǡ ǡ Dz dz ǡ Ǥ ͵ 5 ConclusionsandFuturePerspectives ȋ ǤͳʹȌǤ Ǥ ǡ Ǥ Figure12 ǡ Ǥ ǣ x ȋȌ x ȋȌ x ǡ ǡ ȋȌ ͵ x Ǧ ȋǦȌ x ǡ Ǧ ȋǦȌ x ǦǦ ȋǦȌǤ x Ǧ ǡ ȋȌ x Ǧ ȋȌǤǡ Ǧ Ǥ ǡ ǡ ǯ Ǥ Ǧ ǡ Ǥ ǡ Ǥ ǡ Ǥ ǡ Ǥ ǡ Ǧ ǡ Ǥ Ǧ Ǥǡ Ǥ ͵ͺ 6 Svensksammanfattning Biotillgänglighetavbekämpningsmedeltillbottenlevandedjur: betydelsenavakvatiskabiofilmerochhumösaämnen ¡ǡ ¤ Ú ȋǤǤ Ȍǡ ¤ Ú ¡ ¡ Ú Ǥ ¡ ¡ ǤǤ ¤ ¤ Ú ¡ǡ ¡ ¤ Ǥ ǡ ǤǤ ¤ǡ¤¡Ú ¡ ¤Ǥ ¡ ¡ ¤ Ú ¡ǡ ¡ ¡¡Ǥ ¤ ǤǤǤ ¤ ¤ Ǧ ǡ ¤ ǡ ǤǤ Ǧ ǡ¤ Ǥ ¡¡¤Ú ¤ǤǤǤ Ú ¤ ǡ Ǥ ¡ ǡ ¤ ǤǤ ÚǤ ¡ ¡ǡǤǤǤǤ¡ ¡ ¤ ¤ Ú Ǥ ͵ͻ ÚÚ¤ ¤ǡǡÚ ǤÚ ¤ Úǡ ǤǤǤ ¡ Úǡ Ǧ ¡Ú Ú ¡ ¡ ¡ ǤÚÚ¤¡ǣȋͳȌ Ú Ú ǡ ȋʹȌ Ú ǡ ȋ͵Ȍ ȋ ͳȌǤ ¤ Ú Ú ǡ ÚǤ ¡ ¡ ¤ Ú ǣ ¡ Chironomus riparius Ú ¡¡ TheodoxusfluviatilisǤ¤¤ Ú¤Úǡ¤ÚÚǤ ¡¤Úǡ ¡ ¤ Ú ¡¡ ¡ ¤Ǥ ¡¡ ¤ǡ ¡ ¤ ¤ . dzdz Ǥ ¤ ¡ Ú Ǥ ¤ Ú Ú Ú ¡¡ǡ ¡ ¤ ¡ Ú ¡ Úǡ ÚǤ Ú¤ÚÚǤ ¤ ¡ÚǤ"¤Ú ǡ ¤ ǡ ¡ Ú ǡ ǤǤǤ ǤÚ¤ ¡ ÚÚǣ ȋͳȌ ǡ ¡ ¡ ¤ Ú ǡ ȋʹȌ ¡ǡ ¡ Ú ¡Ǥ¤¤¤ǡ ǤǤǤ ¡ǡ Ú ǡ ¤¡Ǥ ¤ ǡ ǤǤ ǡ ǡ ǡ ¤ Ǥ ͶͲ Ú ǤǤ ȋǤǡ Ǧ ǡʹȌÚÚÚǤ¤ Ú ǡ ǤǤǤ ¤ ǡ ¡¡ Ú Ú ÚǤ Ú ¡ Ú Ǥ ¡ Ú Ú Ú Úǡ ¡Ǧ ¡ǡ ¤ ¤ ¡ ¤ Ǥ ¡Ú¡Ú ǤǤǤ ¡ ¡ Ú Ǧ Ǥ ¡ǡ ¤ ǡ ¡ ¡ ¡ǡ¤ǡ ¡Ǥ ¡ Ú ¡Ú¤Ú ȋǤǡ ȌǤ ǡ Ú¤ ¡¡ÚǤ¡Ú¡ ¡ Ǥ Ú Ú ǡ ǡ ȀǦ Ǥ ȋǡ Ȍ Úǣ ¤ ÚÚǤÚÚ ȋʹͶȂͶͺȌÚ¤ǡǤǤǤ¤Ú ¡ Ú ǦÚ ȋ ¤ Ǧ ȌǤ ¤ ¤¡¡ ÚǤ Ú ȋ Ȍ ¡ ¤¡ǡ¡ÚǦ Ú Ǥ ¡ ¤Ú Ǥ ȋȌ¡ Ȃ Ú Ǥ¤ Ͷͳ Ȃ¤ȂÚ¡Ǧ Ǥ ȋȌ ¡¡ ¤ Ǥ ¤ ¡ ¤ ǡ ǤǤ Ǧ ÚǤ ¤ Ú ¡ǤǤǡ ¤¤¡ÚǤ Ú ¤ ¡ Ú ǡ Ú ȋǦȌǤ ¤ ¤ Ǧ ȋ ǦȌǡ ȋ Ȍ ¤ ¡ Ǧ ȋ ȌǤ ¡ ǡ ǤǤǤ Ǥ ¡ ¤ ¤ÚÚǤ Ú¡¡ ¡ ¤ Ǥ Ú ¤ ¡Ú¡Ǥ Ú ¤ Úǡ ¡ Ú ¡Ǥ ¤ǡ Ǧ Ú ǤǤǤ Ú¡ǡ ¡ Ú ¡ ¡ ǡ ¡ ¤Ǥ Ͷʹ References ǡǤƬǡǤȋʹͲͲͳȌ ǤEnvironmentalToxicology andChemistryʹͲǡʹ͵Ͳ͵Ǧʹ͵Ͳͺ ǡǤǡǡǤƬǡǤȋʹͲͲͶȌ ǤAquaticSciencesǡͳͳǦͳ ǡǤǡǡǤǡǡǤƬǡǤȋʹͲͲͶȌ ǣ ǤPestManagementScienceͲǡͶͳǦͶ͵͵ ǡǤǡ ǡǤƬǡǤȋʹͲͲʹȌ ȋȌ ȋȌǤ OrganicGeochemistry͵͵ǡͺͳǦͺʹͺ ǡǤǡǡǤǡ ǡǤǡǡǤǡǡǤƬǤ ȋʹͲͲͳȌ LymnaeastagnalisǤCanadian JournalofFisheriesandAquaticSciencesͷͺǡͳͲͺǦͳͳͷ ǡǤǡǡǤǡǡǤǡǡǤǡǡǤǡǡǤƬǡǤȋʹͲͲȌ ǣ ǤNatureReviewsMicrobiologyͷǡ Ǧͺͳ ±ǡǤƬǡǤȋͳͻͻͲȌ Ǧ Ǥ JournalofSoilSciencesͶͳǡͳǦʹ ǡǤȋͳͻͻͷȌǤInǣǡǤǡǤƬ ǡǤȋȌTheChironomidae–thebiologyandecologyofnonǦbitingmidgesǤ ǣƬǤǤͳ͵Ǧͳͺ ÚǡǤǡǡǤƬǡǤȋͳͻͻͻȌ ǣ ǤEcologicalEconomicsʹͻǡʹͻǦʹͻͳ Ͷ͵ ǡǤǡǡǤƬǤȋʹͲͲʹȌ ȏ͵ȐȏͳͶȐ ǤCanadian 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ǤBulletinof EnvironmentalContaminationandToxicologyʹǡͷͷǦʹ ǡǤƬǡǤȋͳͻͻͳȌ ǤWaterresearchʹͷǡͶͷͷǦͶ͵ ǡǤƬǡǤȋͳͻͻȌ Ǧ ǤChemosphere͵ʹǡ ͳͲ͵ǦͳͲ ǡǤǡǡ ǤǡǡǤƬǡǤȋʹͲͲͳȌ ǤCanadianJournalofMicrobiology Ͷǡ͵ͶǦͶͳǤ ǡǤƬǡǤǦǤȋʹͲͲȌǤ TheodoxusfluviatilisǤ FreshwaterBiologyͷʹǡͳͻͻȂʹͲͲͺ ǡǤƬǡǤȋʹͲͲͷȌ ǤEnvironmentalToxicologyandChemistryʹͶǡͻͷͶǦͻͷ ǡǤƬǡ ǤȋͳͻͻͺȌ ǤInǣǡ ȋȌAquatichumicsubstances–Ecologyandbiogeochemistryǡǡ ǤǤͻǦ͵ͻ ǡǤȋʹͲͳͳȌǦǡͺǡδ Ǥ ̷ǤǤεǤ ǦǡǤǡǡ ǤǡǡǤƬ±ǡǤȋʹͲͲͳȌǤ ǤInternationalReviewofHydrobiologyͺǡ͵ͶͻǦ͵Ͳ ǡǤǡ ǡǤƬǡǤȋͳͻͺ͵Ȍ ǤAnalyticalChemistryͷͷǡͶͳͲǦͶͳͳ ǡǤǡǡǤǡǡǤǡǡǤǡǡǤǡÞ¤ǡǤǡǡ Ǥǡ¤ǡǤǡǡǤǡǡǤǡǡǤǡ ǡǤƬǡǤ ȋʹͲͲȌ ǤNatureͶͷͲǡͷ͵ǦͷͶͲ òǡǤǡ ǡǤƬǡǤȋʹͲͲͲȌ Ȃ Ǥ EnvironmentalScienceandTechnology͵ͶǡͶͺǦͶͺʹ ǡǤȋͳͻͳȌ¡ Ǥ Hydrobiologiaͳǡͳ͵͵Ǧͳͷͳȋ Ȍ Ͷ ǦǡȋʹͲͲͶȌ ȂǦ ǤǦǤʹͳͻ ǡǤƬǡǤȋʹͲͲͷȌ Ǧ ǤNematologyǡʹǦ ʹͺͲ ǡǤƬǡǤȋͳͻͻȌ ǤAnalyticaChimicaActa,͵͵ǡͳ͵͵ǦͳͶͻ ǡǤȋͳͻͺȌǤAnnualReviewofEntomology ͵ͳǡͳǦʹ͵ ǡǤƬǡǤȋͳͻͻʹȌǤInǣǡ ǤȋȌ SedimentToxicityAssessmentǤ ǡǡ ǤǤͳǦͳͺ ǡǤȋͳͻͺȌ ǤHydrobiologiaͳͶͻǡͷ͵Ǧ ǡǤǡ ǡǤƬǡ ǤȋͳͻͻͺȌ Ǥ EnvironmentalToxicologyandChemistryͳǡͳͺǦͳͺͶ ǡǤǡ ǡǤƬǡ ǤȋͳͻͻͻȌ Leptocheirusplumulosusǣ ǤMarineEcology– ProgressSeriesͳͺ͵ǡʹͲͷǦʹͳ ǡǤǡǡǤƬǡǤȋͳͻͻͺȌ CapitellaǤǣ ǤMarienEcologyProgressSeriesͳͶǡͳǦͳͺ ǡǤǡ ǡǤƬǡǤȋͳͻͻͻȌ Ǧ Capitella ǤEnvironmentalToxicologyand ChemistryͳͺǡͳʹͺͻǦͳʹͻ ǡǤǡǡǤƬǡǤȋʹͲͲ͵Ȍǡǡ Ǧ CapitellaǤǤ EnvironmentalToxicologyand.Chemistryʹʹǡʹ͵ͷͶǦʹ͵͵ ǡ ǤȋͳͻͺȌ LymneaperegraTheodoxusfluviatilisȋ ȌǤ Oikos͵ͳǡ͵ͶͲǦ͵Ͷͺ ǡǤȋͳͻͻȌ Ǥ ǣǡǤǡǡǤƬȋȌ Ǧ Ǥ ǡǡ͵Ǧ͵Ͳ ǡ ǤǡǡǤƬǡǤȋͳͻͺȌ ǣ ǤLimnologyandOceanographyʹ͵ǡͷʹǦͷͻ ǡ ǤȋͳͻͺͳȌ ǣ ǤAmericanNaturalistͳͳͺǡʹͲʹǦʹͳͶ ǡǤǡòǡǤǡǡǤǡǡǤǡÚǡǤƬǡǤȋʹͲͲͻȌ ǤHydrologyandEarthSystemSciencesͳ͵ǡͳͷǦͳͷͺʹ Ͷ ǡǤǡǡǤǡǡǤǡ ǡǤƬ ǡǤȋʹͲͲͺȌ Ǧͻͻ ǤMarineEnvironmentalResearchͷǡʹͶǦʹͺͳ ǡǤƬ ǡǤȋͳͻͺͳȌ ǤEnvironmentalScienceandTechnologyͳͷǡͶ͵ǦͶ ǡǤȋͳͻͺͷȌ ǤȀǤ ǡ ǡǤȋʹͲͲͻȌ Ǥͳͷǡǣ ǡǤǡǡǤǦǤǡǡ ǤƬ ǡǤȋͳͻͻͻȌ ǣ ǤEnvironmentalScienceandTechnology͵͵ǡʹͳͷǦʹͳͺ ǡǤǡǡǤǡ ǡǤǡǡǤǡǡ ǤƬ ǡǤ ȋʹͲͲͻȌ Ǧ ǣ ǤEnvironmentalPollutionͳͷǡʹ͵ǦʹͶͻ ǡ Ǥȋͳͻͻ͵Ȍ ǡͶǡ ǡ ǡǤǡǡ Ǥǡ ǡǤǡǡǤǡǡǤƬǡǤȋʹͲͲ͵Ȍ ǤEnvironmentalScienceand Technology͵ǡͶͲʹǦͶͲͺ ǡǤǡǡǤƬ ǡǤȋʹͲͲͲȌǤ Ǧ ǤArchivesof EnvironmentalContaminationandToxicology͵ͺǡͶͶǦͶͷͶ Ǥǡ ǡǤǡǡǤǡǡǤƬǡǤȋͳͻͻͶȌ Ǥ MicrobialEcologyʹǡʹͻǦʹͻͳ ǡȋʹͲͳͲȌʹͲͳͲȂǡ ǤǤͻͺǦʹǦͻͶͲͶͶ͵ǦͲͺǦ ǡǤǡǡǤǡǡǤƬǡǤȋʹͲͲȌ ǤAppliedGeochemistryʹʹǡͳͷͻͺǦͳͲͷ %ǡǤƬ ǡǤȋʹͲͲ͵Ȍ Chironomusriparius Ǥ EnvironmentalToxicologyandChemistryʹʹǡͳͶ͵ǦͳͶͺͲ Ͷͺ Tack! ǡ Ǧ Ǩ Ú ǡ ÚǤ Willemǡ Ú Ǩ Ú ¡ Ȃ ¡¡Ǥ ¤±ǡǤ Ú ¤ Ǩ ¤ ¤ ¡ǡ Ǥ¡ Ú¤ ǡ ¡Ǩ Stefanǡ Ú¡ǡ¡ ¤ Ǥ Ú ¤ ǡ Ú¡ÚǤ ¡Ǩ Henrikǡ Ú ǡ Ú¤ ¤Ǩ Ú ¤ ǡ¤Ǥ Ú ¤ Ǩ Anneliǡ Ú Ǥ ¡ ¡ ¡Ǩ Kristinaǡ Ú Ú ¡Ǩ Ǩ Ͷͻ ¡ Lina Ú ¡ ¤ ǡ ¡CissiÚ¡ ¤¡Ú¤Ú ¡Ú¡Ǩ ¤ ¤ ¡¤Ǥ OMK ȋ¡ǡ ǡ %ǡ ¤Ȍǡ Ú ¡ ¡ǡ Ǧǡ ¤ ¡ǡÚ Ú ¡¤Ǩ Hasse,Herman,Annika Brittaǡ ¡ÚǨ ¤¡ ¤Ǥ ¡ Tommy AndersÚ¡Ǥ IVM ¤ Ǥ ¡ Ǧ ÚǤ Nina Staffanǡ Ú ¡ ¡ Ǩ Marcus Jennyǡ ǡ ¤ ¤ Ǩ Ú ¤ǡ Ú Ǩ ¡ doktorander/PhDǦstudents Ú personal/staff Ú ǡ ¡Ǩ Ǩ ¡ǡ ¡ ¤ Ǩ ¡ ¤ ǡ Sofia Jennyǡ ¡ ¡ Ǣ Maja Ú ¡ ǢKarinǡNinaǡSaraǡJoelǡKaroǡLinaǡZandra AnnaǡÚ ¤ ¡ ǡ ¤ Úǡ ǡ¡¤ǡ ǡ ¡ ¤ ¤¤ǡ ǡ ǡ ǡ Ú Ǣ Aoisha Danielleǡ ǡ ǢCissiBǡÚ¡ ¡¡ ¡ǢNina PeterǡÚ ¡ ¡Ǥ%¤ ͷͲ ǡ ¡ǡ ¡ ¡ ÚǤ ÚÚ Ǩ Mamma pappaǡ¡¡Ǩ¡ Ǧ Ǥ Ú ¤ ǡ ǡ Úǡ¤¤¡Ú¤ ¤ǤÚǨMaxǡ Ú ¡ Ú Ǩ ¡ ¤ ¡ ǡ ÚÚǤ ¡ ǡ Karinǡ Janneǡ Micke Cissi Ú¤¡ǡ Ú ¤ Ú Ǥ ¡¡Ǩ Ú ¡ǡFredrikǡ EdithǡRut DorisǨ¡ǡ ¡¤ Ú Ǥ ǡ 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