Dynamics of biocide emissions from buildings i n a suburban stormwater catchment

1. 30. Jan. 2014 Dynamics of biocide emissions from buildings in a suburban stormwater catchment Ulla E. Bollmann1, Jes Vollertsen2, Kai Bester1 1 Aarhus University, Roskilde, Denmark 2 Aalborg University, Aalborg, Denmark ueb@dmu.dk www.waterpurification.au.dk

2. Introduction • State-of-the-art in material protection • Preservatives for polymer based coatings: façade render and paint • Wood protection, Roof protection (flat roofs) • Content in exterior renders and paints • 2-4 different biocides, 0.1-1 g kg-1 each • Total: 0.2% in render, 0.2-0.4% in exterior paints • Different compounds with biocidal effects • Isothiazolinones, carbamates, phenylureas, triazines, triazoles used as algaecides, fungicides and bactericides • Hydrophilic molecules with toxic effects Biocides in buildingmaterial Burkhardt et al., WS&T 2007, 56, (12), 63-67 Schoknecht et al., ES&T 2009, 43, (24), 9321-9328 Burkhardt et al., WS&T 2011, 63, (9), 1974-1982 Principal construction of external thermal insulation composite system (ETICS)

3. Introduction • Laboratory experiments: • Constantly soaked test material and dipping experiments (wet and dry cycles) • Leaching dependent on: Substance & render properties, Immersion • Field study: • Concentrations in small Swiss catchment: 0.01-1 µg L-1 (Terbutryn, Carbendazim, Mecoprop) biocides Effects on aquaticorganisms Biocides in buildingmaterial Biocides in buildingmaterial ? Which compounds? Concentrations? Dynamics? First flush emissions? Which compounds? Concentrations? Dynamics? First flush emissions? Burkhardtet al. 2007, 2009 & 2012, Schoknecht et al. 2003 & 2009, Wangleret al. 2012, Wittmer et al. 2010

4. Catchment • Silkeborg (Denmark) • 21.5 ha, 7 ha connected to sewer, separated sewer system • Suburban, residential, 140 well-kept single family houses • 5 % equipped with renders/paints, 20 % (painted) wood, 75 % brick-facades

5. Sampling / Analysis • Flow proportional high resolution sampling with automatic water sampler • October 2011-June 2012 • Solid phase extraction • High performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS)

6. Concentrations • 191 samples, 11 biocides AA-EQS for fresh water DIRECTIVE 2013/39/EU Isoproturon: 300 ng L-1 Diuron: 200 ng L-1 Terbutryn: 65 ng L-1 Cybutryn: 2.5 ng L-1 IT: Isothiazolinone Bollmann et al., 2014, submitted

7. Mass loads IT: Isothiazolinone Bollmann et al., 2014, submitted

8. Biocides in buildings biocides Effects on aquaticorganisms Biocides in buildingmaterial ? Which compounds? Concentrations? Dynamics? First flush emissions? Which compounds? Concentrations? Dynamics? First flush emissions?

9. Load Particles, Heavy metals Water Time Emission dynamics • Howarethebiocidesemittedwithinthestormevent? • Particlemobilisation in roadrun-off withfirstflush

10. Emission dynamics • Common event TB: Terbutryn , CD: Carbendazim, IP: Isoproturon, TBU: Tebuconazole, MCPP: Mecoprop Bollmann et al., 2014, submitted

11. Emission dynamics • First flush: occurs irregularly First flush TB: Terbutryn , CD: Carbendazim, IP: Isoproturon, TBU: Tebuconazole, MCPP: Mecoprop Bollmann et al., 2014, submitted

12. Fast mobilization of biocides from the façade surface Constant emissions Partitioning from the facade Emission dynamics Common event Special event No first flush for biocides First flush for selected biocides No selected stormwater treatment possible Unnecessary loss of substance Fine tune application?

13. Emission dynamics • What is influencing the leaching? • Correlation of the concentration or acc. mass load per event with: • Rain amount / accumulated flow • Length of the event • Rain intensity • Length of the dry period prior to the event • Wind driven rain intensity

14. Emission dynamics Wind Driven Rain (WDR) WIND WDR R A I N Blocken& Carmeliet , J. Wind Eng. Ind. Aerodyn. 2004, 92, 1079 Burkhardtet al., Environ. Sci. Technol. 2012, 46, 5497 with CC= catchment specific factor Mass flow M during respective event with CS = substance specific constant

15. Emission dynamics CD: Carbendazim, TB: Terbutryn, PPZ: Propiconazole, TBU: Tebuconazole Bollmann et al., 2014, submitted

16. Biocides in buildings biocides Effects on aquaticorganisms Biocides in buildingmaterial Conclusions

17. Conclusions • Monitoring • Biocides also important pollutants in Danish urban areas • Different footprint than in other European countries Hard to set-up a sound monitoring strategy • Emission dynamics • Usually rather constant throughout an event • Irregular first flush phenomena • Indication for correlation between occurrence in storm water and wind driven rain • Treatment • Need to take the dynamics of the biocide emission into account

18. Acknowledgement • Scientific cooperation: • Jan Carmeliet and Timothy Wangler (ETH Zurich, Switzerland) • Michael Burkhardt (HSR, Rapperswil, Switzerland) • Diverse companies in the sector for the willingness to share materials and knowledge • Financial support: • Danish EPA through the project Methods for the improvement of scenarios concerning the emission of biocides from buildings(667-00065 & 667-00066) • AUFF grant: Advanced water purification using bio-inorganic nano catalysts and soil filters (www.waterpurification.au.dk) Thank you for your attention!

19. 30. Jan. 2014 Dynamics of biocide emissions from buildings in a suburban stormwater catchment Ulla E. Bollmann1, Jes Vollertsen2, Kai Bester1 1 Aarhus University, Roskilde, Denmark 2 Aalborg University, Aalborg, Denmark ueb@dmu.dk www.waterpurification.au.dk