The The ScorePP ApproachScorePP Approach to Predict Releases to Predict Releases of Priority Pollutants From Urban Sourcesof Priority Pollutants From Urban Sources

Hans-Christian Holten Lützhøft1, Erica Donner2, Veerle Gevaert3, Webbey De Keyser3, Tonie Wickman4, Matej Cerk5, Eva Eriksson1,

André Lecloux6, Primož Banovec5 and Anna Ledin1

1DTU Environment, Technical University of Denmark, Kgs. Lyngby, Denmark2Urban Pollution Research Centre, Middlesex University, London, UK

3BIOMATH, Ghent University, Gent, Belgium4Environmental Monitoring, Stockholm Stad, Stockholm, Sweden

5Faculty of civil and Geodetic Engineering, University of Ljubljana, Ljubljana, Slovenia6Envicat Consulting, Avenue Montesquieu 36, B-1300 Wavre, Belgium

EEA SeminarCopenhagen

Monday 6 December 2010

PresentationPresentationMSc in pharmacy (1991-1996)

― Medicinal chemistry, organic synthesis of AMPA-receptor ligands

PhD (1996-2000)― Environmental Risk Assessment of Antimicrobials; experimental work on ecotoxicity and

environmental fate; literature study of ecotoxicity and occurrence in relation to fish farming activities

PostDoc at KU-Life (2000-2001)― Environmental fate of antimicrobials in soil and porewater

PostDoc at Novo Nordisk (2001-2003)― Stability testing of tablets – development of super enhanced stability testing methods

AssProf at KU-Life (2003-2005)― Intestinal absorption of pharmaceuticals

Pharmacist (2005-2006)AssocProf at DTU Environment (2006- )

― Source characterisation of (organic) priority substances; inherent properties, source tracking, source dynamics, urban releases

― Sampling, extraction, purification and analysis or organic substances― Monitoring; Stakeholder interaction

BackgroundBackgroundEuropean Water Framework Directive (EU WFD) implemented in 2000 with Environmental Quality Standards implemented in 2008Aim of EU WFD is to improve water quality of European water coursesBoth pollution source inventories as well as monitoring programmes have to be establishedEU member states are obliged to improve water quality through more than one measure, for instance

LegislationImproved handling and treatment of waste streams (municipal/industrial wastewater or stormwater)Voluntary initiatives

The EU 6th framework programme financed the DTU Environment coordinated ScorePP (Source control options for reducing the emissions of Priority Pollutants) project9 partners with 30+ collaborators across Europe and 4 case citiesSEP2006-MAR2010, 3½ years

AimAimThe main aim of the ScorePP project was to develop Source Control Options for Reducing Emissions of Priority Pollutants from urban areas

The specific aim of this task was to identify potential sources and to quantify releases of priority pollutants

Aim Approach Substances Results Conclusions

ApproachApproach

Develop Source Classification Framework

Compile data on sources & releases

Classifying using the Emission String concept

Aim Approach Substances Results Conclusions

Establish releases based on the compiled data

Source Classification FrameworkSource Classification FrameworkRequirements

Content should be structured and organised in a harmonised wayEnsure that the different sources could be distinguished from each otherTo be dynamic and valid EU wide

InspirationUS EPA Source Classification Code (US EPA SCC)The Technical Guidance Document on Risk assessment (TGD)Harmonised codes likethe Common Nomenclature (CN), the National Classification of Economic Activities (NACE) and the NOmenclature for Sources Emissions (NOSE)EINECS, CAS#

Aim Approach Substances Results Conclusions

National Classification of Economic Activities National Classification of Economic Activities (NACE)(NACE)A Agriculture, hunting and forestry J Financial intermediation

B Fishing K Real estate, renting and business activities

C Mining and quarrying L Public administration and defence; compulsory social security

D Manufacturing M Education

E Electricity, gas and water supply N Health and social work

F Construction O Other community, social and personal service activities

G Wholesale and retail trade; repair of motor vehicles, motorcycles and personal and household goods

P Activities of households

H Hotels and restaurants Q Extra-territorial organizations and bodies

I Transport, storage and communication R Other

18 main classes and about 850 subclasses

Aim Approach Substances Results Conclusions

NOmenclature for Sources of Emissions (NOSE)NOmenclature for Sources of Emissions (NOSE)101. Combustion processes (production of heat and electricity)

104. Production processes in manufacturing industry, involving fuel combustion

105. Production processes in manufacturing industry and water supply, not involving fuel combustion and use of solvents and other products

106. Processes specific to the extraction and distribution of fossil fuels and geothermal energy

107. Processes involving use of solvents and other products

108. Processes specific to the nuclear power industry

109. Waste treatment and disposal operations

110. Processes specific to agriculture, forestry, hunting and fishing

111. Processes characteristic of service branches

112. Processes common to all branches

113. Households

201. Road transport

202. Other mobile sources

301. Processes in nature

14 main classes and about 750 subclasses

Aim Approach Substances Results Conclusions

ScorePP classification of the Urban Structure – ScorePP classification of the Urban Structure – the Urban Structure Descriptor (USD)the Urban Structure Descriptor (USD)

22 classes in use

Aim Approach Substances Results Conclusions

Source Classification Framework – Source Classification Framework – the the Emission StringEmission String concept concept

CAS #: unique identification of each substanceNOSE: unique identification of emission processes NACE: unique identification of economic activities related with the sourceThe ScorePP classifications

Urban Structure Descriptor (USD), comprising e.g.Construction sitesFacilities; e.g. factories, dentists, slaughter houses (i.e. legal entities)HouseholdsRiversRoadsWaste sites/landfills

Release Profile Descriptor (RPD)Temporal releases on a daily, weekly and yearly basis

Release Factor (RF)

All data are stored in a database

Aim Approach Substances Results Conclusions

Compiling dataCompiling dataOnline Risk Assessment Reports from EUHazardous Substance Data Bank and Household Product Database from US NLMHandbooks and electronic compilations, e.g. the Merck Index, Rippen, the e-Pesticide Manual, Kirk-Othmer’s Encyclopedia of Chemical TechnologyResearch articles

Aim Approach Substances Results Conclusions

Classifying sources using the ES conceptClassifying sources using the ES concept

Aim Approach Substances Results Conclusions

Classifying sources using the ES conceptClassifying sources using the ES concept

Aim Approach Substances Results Conclusions

Substances on the Water Framework Substances on the Water Framework DirectiveDirective

Aim Approach Substances Results Conclusions

ScorePP priority pollutants (PPs) grouped according to their main uses and classified according to whether they are priority substances (PSs), added due to the EQS-proposal (EQS), example chemicals (EX) or added as they belong to the group of “organometallics” (OM). Priority hazardous substances (PHSs) are printed in bold. Classa PS (33) EQS (11) EX (11) OM (13) Biocide (31) Trifluralin

Hexachlorocyclohexane Alachlor Pentachlorophenol Endosulfan Simazine Atrazine Chlorfenvinphos Isoproturon Diuron Chlorpyrifos Hexachlorobutadiene Tributyltin compounds

Aldrin Endrin Isodrin Dieldrin Para,para’-DDT Para,para’-DDEb Para,para’-DDDb Orto,para’-DDTc

Tributyltin-cation Alpha-endosulfan Gamma-isomer lindane 1,2,4-trichlorobenzene

Tetra-N-Butyltin Bis(tributyltin) oxide Phenylmercuric acetate Tributyltin methacrylate Tributyltinchlorostannane Methylmercury

Chlorinated solvent (6) Ethylene chloride Dichloromethane Chloroform

Trichloroethylene Tetrachloroethylene Carbontetrachlorid

Combustion (6) PAH Indeno(1,2,3-cd)pyrene Benzo(k)fluoranthene Benzo(g,h,i)perylene Benzo(a)pyrene Benzo(b)fluoranthene

a: Classified according to the WFD and the EQS-proposal. The numbers in brackets represent the number of chemicals in each class; b: Degradation product of para,para’-DDT; c: Impurity of para,para’-DDT; d: The term “various” covers a range of uses like alloys, catalysts, pigments, batteries, dentistry, measuring and control equipment, biocide, impurity, cables, stabilisers, intermediate; e: The individual metals represents the ionic form(s).

Substances on the Water Framework Substances on the Water Framework Directive – continuedDirective – continued

Aim Approach Substances Results Conclusions

ScorePP priority pollutants (PPs) grouped according to their main uses and classified according to whether they are priority substances (PSs), added due to the EQS-proposal (EQS), example chemicals (EX) or added as they belong to the group of “organometallics” (OM). Priority hazardous substances (PHSs) are printed in bold. Classa PS (33) EQS (11) EX (11) OM (13) Flame retardant (2) Pentabromobiphenylether

C10-13 chloroalkanes

Fuel additive (5) Tetramethyl lead Ethyltrimethyl lead Tetraethyl lead Methyltriethyl lead Diethyldimethyl lead

Intermediate (11) Naphthalene Anthracene Nonylphenol Fluoranthene Benzene Trichlorobenzenes Octylphenol Pentachlorobenzene

4-(para)nonylphenol Para-tert-octylphenol

Dimethylmercury

Plasticizer (1) DEHP Variousd (6) Hexachlorobenzene

Nickele Mercurye Leade Cadmiume

Diethylmercury

a: Classified according to the WFD and the EQS-proposal. The numbers in brackets represent the number of chemicals in each class; b: Degradation product of para,para’-DDT; c: Impurity of para,para’-DDT; d: The term “various” covers a range of uses like alloys, catalysts, pigments, batteries, dentistry, measuring and control equipment, biocide, impurity, cables, stabilisers, intermediate; e: The individual metals represents the ionic form(s).

SCF tested on a selection of WFD substancesSCF tested on a selection of WFD substances

Number of ESs for each PPNumber of ESs for each PP(ab 900 ESs in total)(ab 900 ESs in total)

Aim Approach Substances Results Conclusions

Which sources were identified for a Which sources were identified for a particular PP – DEHPparticular PP – DEHP

Handling of the pure substanceUndercoating of motor vehicles Production of electricityRelease from electrical cables – indoor and outdoorTreatment of waste; land fillsVarious manufacturing; sealants, paint, ink, ceramic, plastic, DEHP Release from floor and wall coveringVarious building materials; tubes, profiles, coated metal sheetsTextiles, clothing, footwear, shoes

Aim Approach Substances Results Conclusions

To which To which compartmentcompartment are the substances are the substances released to?released to?

Air

Groundwater

Generally to the urban surfaceTo an impervious urban surfaceTo a permeable urban surface

Generally to water (wastewater or receiving waters)Directly to water (receiving waters)Indirectly to water (wastewater going to WWTP)

Aim Approach Substances Results Conclusions

Substances are released to …Substances are released to …Aim Approach Substances Results Conclusions

Number of ESs in each urban structureNumber of ESs in each urban structure(ab 900 ESs in total)(ab 900 ESs in total)

Aim Approach Substances Results Conclusions

Archetype sourcesArchetype sourcesAgricultureConstruction sites and buildings

FacilitiesHouseholdsRoadsWaste disposal

Diffuse and other not immediately classifiable sources

Aim Approach Substances Results Conclusions

Number of ESs within Number of ESs within householdshouseholds(ab 85 ESs in total – 18 substances)(ab 85 ESs in total – 18 substances)

Aim Approach Substances Results Conclusions

Substances from Substances from householdshouseholds are released to … are released to …Aim Approach Substances Results Conclusions

Fertilizers and pest controlDiuron: 7,5-25 mg/applicationCd: from fertilizers

Building materialsNi: 0,3-0,8 mg/m2 stainless steel/yrCd: 0,01-10 kg/yr from Zn-materialsDEHP: 16 tonnes/yr

ClothesDEHP: 950 kg/yr

GreywaterHg: 17µg/PE/dCd: 5 kg/yrTCE: 8-100 µg/LNi: jewellery, coins, washing etc. Benzo(a)pyrene: 1,8 µg/PE/d

Painting and car washDEHP: 12 kg/yr

Environmental releases due to Environmental releases due to householdshouseholds Heating

Anthracene: 0,8-102 mg/kg woodBenzo(a)pyrene: 2,7 mg/kg coalBenzo(a)pyrene: 27 µg/kg wood

SmokingAnthracene: 34 ng/cigaretBenzene: 10-100 µg/cigaretBenzo(a)pyrene: 5-1600 ng/cigaret

Clothes and building materialsDEHP:250 kg DCM: 10-80 µg/m2/hTCE: 3,6 µg/m2/h

FertilizersCd: 500 g/yr

Building materialsDEHP:600 kg/yr

Plus releases of HCB, HCH, PeCB, TBTs, chlorpyrifos, endrin, Pb, trifluralin and NPs

Aim Approach Substances Results Conclusions

Environmental releases due to Environmental releases due to vehicular transport on vehicular transport on roadsroads

AnthraceneCombustion: 5,2-28 µg/kg fuel burned, depending on vehicle and fuel type

BenzeneCombustion: 4-10 mg/km driven, depending on vehicle type

Benzo(a)pyreneCombustion: 1-8 µg/km driven, without and with catalyst

Cadmium (from both break linings, tyres, fuel and asphalt)7 kg/year is released in Stockholm with 780.000 inhabitants

DEHP (from undercoating)200 kg/year is released in Stockholm with 780.000 inhabitants

MercuryTyres: 4-240 µg/km depending on vehicle typeRoads: 3-17 µg/km depending on vehicle type

NickelCombustion: 21-107 and 3,2-2310 ng/km driven, for gasoline and diesel, respectivelyBrake-linings, tyres and asphalt: 91-182 ng/km

Aim Approach Substances Results Conclusions

Statistics for Denmark year 2007Statistics for Denmark year 2007

Aim Approach Substances Results Conclusions

Environmental releases due to Environmental releases due to vehicular transport on vehicular transport on roadsroads

Depending on fuel and vehicle type:

Anthracene: 12-67 kg Nickel: 4,4-117 kg

Benzene frombusses, lorries etc: 105 tonnes

Cadmium: 49 kg

Mercury: 0,3-12 tonnes

Plus releases of anthracene from wear & tear of tyres and asphalt and release of anthracene, benzene, benzo(a)pyrene due to leakage & spillage

Benzene from cars: 154 tonnes

Benzo(a)pyrene: 360 kg

DEHP: 1,41 tonnes

Release of nickel from Danish highways: 108 kg

Thomas Ruby Bentzen, PhD thesis (2008)

Aim Approach Substances Results Conclusions

ConclusionsConclusionsSCF established – based on literature knowledge about sourcesAbout 900 ESs established for the 25 WFD substances

Ranging from 5 ESs for atrazine and 133 ESs for nickelOverall 16% with concrete knowledge about release quantitiesOverall 65% without any quantitative data on release into the technosphere

WFD substances occur in a wide variety of sources and activities in urban settings and are released to all studied compartments

Most sources are related to production activitiesOther large categories are households, waste disposal, agriculture, construction and transportSubstances from households are mainly released to air, wastewater and to the urban surfaceSubstances released to air (both from household and transport) are mainly bi-products from combustion

Aim Approach Substances Results Conclusions

Conclusions – continuedConclusions – continuedClassifying the sources according to the Urban Structure descriptor enables

Sources to be linked to GIS, thus enhancing visualisationDefinition of archetype sources and thus a better targeting of mitigation options and Emission Control Strategies

Aim Approach Substances Results Conclusions

OutlookOutlookSCF has been used on national scale to calculate releases from a particular archetype source, i.e. roads (Holten Lützhøft et al., 2009)SCF has been used to identify pollution sources in catchments of Copenhagen (Holten Lützhøft et al., submitted)

SCF can be used to establish a pollution inventory for a given catchment in the process of either identifying pollution sources or identifying the most appropriate emission control strategy (Eriksson et al., 2010)Implemented European wide it will help in the process of prioritising finances and work power

It would be interesting to perform a comparison of pollution inventories with human health statistics, i.e. the spatial incidents of cancer compared with for instance the expected releases of benzo[a]pyrene

Aim Approach Substances Results Conclusions

AcknowledgementAcknowledgementThe presented results have been obtained within the framework of the project ScorePP - “Source Control Options for Reducing Emissions of Priority Pollutants”, contract no. 037036, a project coordinated by Department of Environmental Engineering, Technical University of Denmark within the Energy, Environment and Sustainable Development section of the European Community’s Sixth Framework Programme for Research, Technological Development and Demonstration.