9-paper-Determination of PCDDs, PCDFs, PCBs and HC

DeterminationofPCDDs,PCDFs,PCBsandHCBEmissionsfromtheMetallurgicalSectorinPolandGROCHOWALSKIAdam1,LASSENCarsten21.KrakowUniversityofTechnology,Kraków,[e-mail];2.COWIA/S,Havneparken1,DK-7100WejleDenmarkAbstract:TheaimoftheprojectwastomeasuretheactualemissionsofPCDD/F,PCBsandHCBfrom20selectedmetallurgicalinstallationsinPoland,inordertoupdatethenationalinventoryofdioxinemissionfrommetallurgicalindustryfordevelopingastrategyfordioxinsandfuransemissionabatementfromthesubjectfacilities(UNEP2005).SamplingmethodologyusedinthisworkwasdevelopedattheKrakowUniversityofTechnologybecauseofthecomplexityofsimultaneouslysamplinganddeterminingPCDFs,PCDDs,PCBandHCB.ForthedeterminationaGC-MS/MSsystemwasused.ResultsfromtheworkindicatethatthehighestdioxinsandPCBconcentrationswererecordedforironoresinteringplantsat1.10–1.32ngTEQ/Nm3followedbyaluminiumscrapmeltingat0.03–0.66ngTEQ/Nm3.ThehighestHCBconcentrationsat613–1491ng/Nm3werealsorecordedforironoresinteringplants,whereasataluminiumplantstheHCBconcentrationswereintherangeofonly10.1–22.7ng/Nm3.Theaboveinvestigationsindicatethatsecondaryaluminiumproductionisthemostsignificantdioxinssource,ifcalculatedasemissionfactorvalues.However,ironoresinteringplantsareoperatingatmuchhigherproductioncapacity,causingthisprocesstobecomethemajorsourceofdioxins,PCBandHCBpollutiontotheatmosphereinPoland.Keywords:Metalindustry;dioxin;PCB;HCB;emission;measurements;POPs;pollution0IntroductionEmissioninventorydataforthemetallurgicalsectorinPolanduntil2004wasestimatedonthebasisofdefaultemissionfactorstakengenerallyfromtheUNEPtoolkit[1].Becausetheformationofdioxins,furans,PCBandHCBisprocessspecific,inparticularforthermalprocessesinmetalindustry[2,3]theuseofdefaultemissionhastobeconsideredashighlyuncertain[4,5]Theaimofthestudyperformedin2004and2005wastomeasuretheactualdioxins,furans,PCBandHCBemissionsfromselectedmetallurgicalinstallationsinPolandinordertoupdatethenationalinventoryofunintentionallyPOPsemissionfromthemetallurgicalindustry,mainlydioxinsandfurans.Thegoaloftheprojectisalsotodevelopastrategyfordioxinsandfuransemissionabatementfromthesubjectfacilities.Forthispurposeinstallationsin20differentfacilitiesofthemetallurgicalsectorinPolandwereselected,chosenamongthose,whichrepliedpositivelytotheinvitationtoparticipate.Regardingtheselectionofplantsandinstallationsaneffortwasmadetoincludeintoinvestigationseachofthedifferentproductionprocessesconcernedandtoensurethattheemissionstandardofthetestedinstallationwastypicalforthegivenindustrialprocess.Atthetimeofmeasurementthetechnicalprocesshadtoberunundertypical,nominalloadandaccordingtoproductionstandards.ThemeasurementswereperformedbyCracowUniversityofTechnologywithinthePolish-Danish“ReductionofDioxinEmissionfromtheMetallurgicalSectorinPoland”project,financedbytheDanishEnvironmentProtectionAgency(fromDANCEEfunds).Projectactivitieswereco-ordinatedbyCOWIA/S,Denmark.MeasurementsweremadesinceMayuntilSeptember2004.1PlantSelectionandtheDescriptionofPlantProfileThemeasurementswereconductedin20metalindustryinstallationsinPolandastheyarepresentedinTable1,whichwereselectedandacceptedforthisworkbythePolishMinistryofEnvironment.(forconfidentialreasons,onlysectorandprofileoftheplantisgiven).EmissionofselectedchlorinatedPOPsfromtheseinstallationswasmeasured.Participationofallindustriesintheprojectwasvoluntary,theresultsobtained,thenamesofthefacilities,andtheiraddressesarekeptconfidential.Table1:Listofselectedandexaminedinstallationsanditsallocatedidentitynumber01Foundryofspheroidicalandcastiron11Aluminiumscrapmelting-naturalgasfurnace02Ironoresinteringplant12Aluminiumscrapandcansmelting-electricfurnace03Roastingofcopperore13Zincoreroasting(sphalerite)-H2SO4productionfromstackgases04Coppersmelting(productionofsulphuricacid)14Smeltingwastefromproductionofzinccathodes05Coppersmelting(de-copperingofslag)15Steelscrapmelting-steelproductioninanelectricarcfurnace**06Coppersmelting(productionofsulphuricacid)16Productionofprimaryironinablastfurnace07Foundryofcastiron*17Steelproductioninabasicoxygenfurnace08Foundryofcaststeel-electricarcfurnace18Greyandspheroidicalgraphiteironproduction-gasrotaryfurnace09Aluminiumscrapmelting-electricfurnace19Ironoresinteringplant10Aluminiumscrapmelting-rotaryfurnace20Steelscrapmelting-steelproductioninanelectricarcfurnace***-measurementswereperformedonrawgas.Thesamplingofcleanedgaswasnotpossibleforthisplantduetotechnicalreasons.**Fortheseplantsmeasurementswereperformedonlyonsecondaryoff-gas.However,thesecondaryoff-gasrepresentsonlyaverysmallpartofthetotalPCDD/PCDF/PCB/HCBemission,Duetotechnicalreasons,themeasurementofprimaryoff-gasfortheseplantswasnotpossible.Samplingportswereinstalledonthetopofthestackof6mdiameterand30mheight.1.1SteelandironmetallurgyTherearefourdifferentprocessesrepresentingthissector:Sinteringofironore.ThisprocessiscommonlyknownasgeneratinghighconcentrationsofdioxinsandPCB.Ascanbeseenintheliterature1–50goftheI-TEQ(onlyregardedtodioxins)arereleasedperplantannuallyintotheairbytheEuropeancountries.However,