Describing the Behavior and Effects of Pesticides in Urban and Agricultural Settings 1168 ACS SYMPOSIUM SERIES Describing the Behavior and Effects of Pesticides in Urban and Agricultural Settings Russell L. Jones, Editor Bayer CropScience Research Triangle Park, North Carolina Mah Shamim, Editor U.S. Environmental Protection Agency Washington, DC Scott H. Jackson, Editor BASF Research Triangle Park, North Carolina Sponsored by the ACS Division of Agrochemicals AmericanChemicalSociety,Washington,DC DistributedinprintbyOxfordUniversityPress LibraryofCongressCataloging-in-PublicationData Describingthebehaviorandeffectsofpesticidesinurbanandagriculturalsettings/ RussellL.Jones,editor,BayerCropScience.ResearchTrianglePark,NorthCarolina, MahShamim,editor,U.S.EnvironmentalProtectionAgency,Washington,DC,ScottH. Jackson,editor,BASFResearchTrianglePark,NorthCarolina;sponsoredbytheACS DivisionofAgrochemicals. pagescm.-- (ACSsymposiumseries;1168) Includesbibliographicalreferencesandindex. ISBN978-0-8412-2974-7 1. Pesticides--Environmentalaspects. I.Jones,RussellL.(RussellLawrence),1951-II. AmericanChemicalSociety.DivisionofAgrochemicals. QH545.P4D472014 363.738′498--dc23 2014031546 ThepaperusedinthispublicationmeetstheminimumrequirementsofAmericanNational Standard for Information Sciences—Permanence of Paper for Printed Library Materials, ANSIZ39.48n1984. Copyright©2014AmericanChemicalSociety DistributedinprintbyOxfordUniversityPress AllRightsReserved. ReprographiccopyingbeyondthatpermittedbySections107or108 oftheU.S.CopyrightActisallowedforinternaluseonly,providedthataper-chapterfeeof $40.25plus$0.75perpageispaidtotheCopyrightClearanceCenter,Inc.,222Rosewood Drive,Danvers,MA01923,USA.Republicationorreproductionforsaleofpagesinthis bookispermittedonlyunderlicensefromACS.Directtheseandotherpermissionrequests toACSCopyrightOffice,PublicationsDivision,115516thStreet,N.W.,Washington,DC 20036. Thecitationoftradenamesand/ornamesofmanufacturersinthispublicationisnottobe construedasanendorsementorasapprovalbyACSofthecommercialproductsorservices referenced herein; nor should the mere reference herein to any drawing, specification, chemicalprocess, orotherdataberegardedasalicenseorasaconveyanceofanyright or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce,use,orsellanypatentedinventionorcopyrightedworkthatmayinanywaybe relatedthereto. Registerednames,trademarks,etc.,usedinthispublication,evenwithout specificindicationthereof,arenottobeconsideredunprotectedbylaw. PRINTEDINTHEUNITEDSTATESOFAMERICA Foreword The ACS Symposium Series was first published in 1974 to provide a mechanism for publishing symposia quickly in book form. The purpose of the series is to publish timely, comprehensive books developed from the ACS sponsoredsymposiabasedoncurrentscientificresearch. Occasionally,booksare developed from symposia sponsored by other organizations when the topic is of keeninteresttothechemistryaudience. Beforeagreeingtopublishabook,theproposedtableofcontentsisreviewed forappropriateandcomprehensivecoverageandforinteresttotheaudience. Some papersmaybeexcludedtobetterfocusthebook;othersmaybeaddedtoprovide comprehensiveness. When appropriate, overview or introductory chapters are added. Draftsofchaptersarepeer-reviewedpriortofinalacceptanceorrejection, andmanuscriptsarepreparedincamera-readyformat. As a rule, only original research papers and original review papers are included in the volumes. Verbatim reproductions of previous published papers arenotaccepted. ACSBooksDepartment Preface Studies of the behavior and effects of pesticides in the environment have been conducted for decades and have been the subject of numerous symposia at American Chemical Society meetings. Originally most of this work focused on agricultural settings, but in the past three decades there has been increasing interestalsoinnon-agriculturalusesofpesticides. Inthepastfewyears,increasing attentionhasbeenpaidtousesinresidentialsettings. This ACS Symposium Series volume consists of 13 book chapters from authorsmakingpresentationsattwosymposiaattheAmericanChemicalSociety 246th National Meeting and Exposition in September 2013 in Indianapolis, Indiana. All deal with agricultural and non-agricultural uses of pesticides. Ten of these book chapters are from authors making presentations at the symposium entitledAssessingPotentialEcologicalandHumanHealthEffectsfromFertilizer and Pesticide Use in Urban Environments, while the remaining three are from modeling papers from the symposium entitled Environmental Fate, Transport, andModelingofAgriculturallyRelatedChemicals. The book chapters cover a number of different topics related to non-agricultural uses of pesticides, including: transport mechanisms associated with residential applications and associated modeling of these processes; modelingofstormwaterdischargesfromresidentialsubdivisions;bioassessments performed on urban streams; monitoring of large rivers receiving water from urban areas; residues entering POTW (publicly owned treatment works, i.e., sewagetreatmentplants);analyticalmethods;andaspectsrelatedtotheregulation of non-agricultural uses of pesticides. The three papers dealing with modeling ofagriculturalusesofpesticidesconsiderscreeningassessmentsforconsidering potential movement to ground water, the sensitivity of model parameters used in assessing potential movement to surface water, and refined assessments for surfacewatercatchments We thank the AGRO Division of the American Chemical Society for includingthesetwosymposiaintheir2014fallmeeting. Wealsothanktheauthors for the careful preparation of the book chapters and their cooperation with the reviewprocess. Asaresult,webelievethatthisACSSymposiumprovidesuseful informationonrecentdevelopmentsinanumberofareasrelatedtodescribingthe behaviorandeffectsofpesticidesinurbanandagriculturalsettings. RussellL.Jones BayerCropScience 2T.W.AlexanderDrive ResearchTrianglePark,NorthCarolina27709,UnitedStates ix Mah Shamim OfficeofPesticidePrograms U.S.EnvironmentalProtectionAgency 1200PennsylvaniaAvenueNW,Washington,DC20460,UnitedStates ScottH.Jackson BASF 26DavisDrive ResearchTrianglePark,NorthCarolina27709,UnitedStates x Editors’ Biographies Russell L. Jones Russell L. Jones (Ph.D., University of California Berkeley) is currently a Fellow in Environmental Safety at Bayer CropScience in Research Triangle Park, NC, specializing in the behavior of crop protection products in soil and water. Research interests include the development of management practices for preventing movement of crop protection products to ground and surface water, designandconductoffieldresearchstudies,andtheapplicationofenvironmental modelingtoriskassessment. Hehasauthoredorco-authoredover100papersand 140presentationsatscientificmeetings. Mah Shamim Mah Shamim (Ph.D., Howard University) has been a Section Head and Branch Chief in Environmental Fate and Effects Division, Office of Pesticide Programs, United States Environmental Protection Agency since 1993. She managesmulti-disciplinaryteamsofscientistsinvolvedinperformingecological riskassessments,endangeredspeciesassessments,anddrinkingwaterassessments to be used in dietary human risk assessments. Prior to joining the EPA in 1991, she served as a Senior Staff Fellow at the National Heart, Lung and Blood Institute,theNationalInstitutesofHealth(1989–1991)andasaResearchFellow at the National Institute of Diabetes and Digestive and Kidney Diseases (1983 – 1989). Her research interests included development of oligonucleotide probes for site-specific cleavage of target DNA; design, development, and synthesis of potent and selective antagonists to adenosine receptors; and the study of insect pheromones as channels of communication for insects. She is the recipient of numerousAgencyawardsincludingtheEPAExcellenceinManagementAward. Scott H. Jackson Scott H. Jackson (Ph.D., Union University) is currently stewardship manager in the stewardship and sustainability group at BASF in Research Triangle Park, NC. He is responsible for managing risk assessments for human health, ecotoxicology, and spray drift as well as designing and supervising studies intended to monitor surface water, ground water and soil systems for environmental quality. He has authored or co-authored over 80 papers and 120 presentations at scientific meetings. He has organized or co-organized many symposiumsatnationalmeetings. ©2014AmericanChemicalSociety Chapter 1 Runoff of Phenylpyrazole Insecticide Fipronil from Concrete Surfaces WeiyingJiang,*,1,2JayGan,1andMichaelRust3 1DepartmentofEnvironmentalSciences,UniversityofCalifornia, Riverside,California92521,UnitedStates 2DepartmentofPesticideRegulation,CaliforniaEnvironmentalProtection Agency,Sacramento,California95812,UnitedStates 3DepartmentofEntomology,UniversityofCalifornia, Riverside,California92521,UnitedStates *Tel.: (916)445-4244. Fax: (951)445-4280. E-mail: [email protected] Fipronil is a phenylpyrazole insecticide first registered in U.S. in 1996 and in California, is exclusively used for urban structural pest control and landscape maintenance. Although commonly found in urban waterways, runoff potential of fipronil from urban surfaces was seldom assessed, and with different physicochemical properties, conclusions obtained from pyrethroid runoff may not be applicable to fipronil. We conducted a field study by placing concrete blocks in real environment, treating the surfaces with fipronil, and analyzingsurfacerunoffaftersimulatedornaturalprecipitation. Isopropanol-wettedspongesweresimultaneouslyusedtowipe concrete surfaces for runoff prediction. The results showed during repeated precipitations fipronil residue could remain on the concrete for up to 3 months, and fipronil could still be detected in natural rainfall-induced runoff even 7 months after fipronil treatment. Compared to pyrethroids, fipronil has better water transferability. The wash-off in Day 1 was 2.1 ± 0.7 % of applied amount, higher than 0.8 ± 0.5 % for bifenthrin and 0.7 ± 0.5 % for permethrin. However, fipronil is less persistent, and the runoff half-life was 17.2 d. Unlike pyrethroids, 81.1-96.7 % of runoff fipronil was dissolved in ©2014AmericanChemicalSociety the aqueous phase, implying the potential for long-distance transportandbetterbioavailability. Thesurfacewipingmethod successfullymeasuredfipronilonconcrete,andthesamelinear modeldevelopedforpyrethroidscouldbealsousedonfipronil, even for different precipitation schemes and after different periodsofpost-treatmentexposure. Introduction Fipronil was introduced into U.S. in 1996 and in California is almost exclusivelyusedforstructuralpestcontrol(1, 2). Withmodeofactiondifferent from other common insecticides such as pyrethroids, organophosphates and carbamates, fipronil showed low insect resistance, and its use rapidly increased especially in urban and residential areas (1). In 2011, licensed California applicatorsused28,785kgfipronil, comparedto300kgin2000(2). Thisrapid increase has caused fipronil contamination in urban waterways and aquatic toxicity(3–5). Forinstance,fipronilcouldbedetectedinalmostallurbanrunoff samples from southern California (3). The 90th percentile concentrations at the foursamplingsiteswere176-472ng/L,whichwereaboveEC50(0.14μg/L)for mysidshrimp(6). Urbanareasfeatureimpervioussurfacessuchasconcretewhichareusedto drain surface runoff fast. However not until recently studies have found these surfacescanaffectpesticidepersistenceandrunoffbehaviorsinurbanareas(7–11). Forinstance,permethrinonconcretecouldcontinuouslydesorbintowaterforover 300 h, and the runoff persistence extended longer as permethrin residence time on concrete increased (8). Jorgenson and Young treated commercial formulated pyrethroids on concrete slabs and during a 60 min rainfall, and depending on differentpesticideformulations,0.8-60%ofappliedpyrethroidswerewashed-off (9). While most of these studies addressed pyrethroids, little is known about fipronil (11). In a different pesticide class, fipronil is treated at rates different frompyrethroids,andmayalsodisplaydifferentpersistenceandrunoffpotential. In a preliminary bench-top study we treated small concrete disks with different pesticides and washed the surfaces immediately after treatments, more fipronil was recovered in the wash-off water than pyrethroids (7). However, if the concreteleftinoutdoorfor56days,lessfipronilwasleftonconcretethanmany pyrethroidssuchasbifenthrin,permethrinandcyfluthrin. The objective of this study is to measure fipronil levels in concrete runoff after extended outdoor exposure and during different precipitation schemes. By comparing with pyrethroids, the results will improve the understanding of current-usepesticiderunoff,whichisessentialforacomprehensivecontamination mitigation plan. We also used a wiping method that successfully predicted pyrethroidrunoffinpreviousstudies,andtesteditsapplicabilityforfipronil. 2