Improving monitoring campaigns : A case study Dissemination Workshop on Evaluating Source Control Options for Reducing Emissions of Priority Pollutants Lyngby, Denmark 2-3 February 2010

2 Source control option for Reducing Priority Pollutants 1.Role in the ScorePP project 2.Monitoring campaigns in an European case city 3.Priority pollutants in an European case city 4.Priority pollutants in an European case city: Conclusions and perspectives

3 Role in the ScorePP project Work package 2: Case city analysis 1.Baseline study of the case city, 2.Identification of PPs to monitor, 3.Monitoring campaign, 4.Identification of Emission Control Strategies, 5.Substance flow analysis, 6.Evaluation of Emission Control Strategies. PAH? Pesticide? Metals?

4 Source control option for Reducing Priority Pollutants 1.Role in the ScorePP project 2.Monitoring campaigns in an European case city 3.Priority pollutants in an European case city 4.Priority pollutants in an European case city: Conclusions and perspectives

5 Monitoring campaigns in an European case city Wastewater treatment plant:  Influent, effluent and sludge. Surface water:  Upstream, downstream of the city and sediments.

6 Monitoring campaigns in an European case city Monitored priority pollutants:  Screening campaign for all 33 priority pollutants. Global parameters (WWTP):  Chemical oxygen demand, suspended solids, Ph… Seasonal changes:  Wet and dry season, August 2008, December 2008, March 2009.

7 Monitoring campaigns in an European case city Use of different extraction techniques:  Traditional extraction techniques (TET): off site extraction and analysis,  Stir Bar Sorptive Extraction (SBSE): on site extraction and off site analysis.

8 Monitoring campaigns in an European case city Day long screening campaigns (TET):  Sampling 24 hours, Wastewater treatment plant, Surface water. Week long monitoring campaigns (TET and SBSE):  Sampling 24 hours, Wastewater treatment plant.  Sampling every 8 hours, Wastewater treatment plant

9 Source control option for Reducing Priority Pollutants 1.Role in the ScorePP project 2.Monitoring campaigns in an European case city 3.Priority pollutants in an European case city 4.Priority pollutants in an European case city: Conclusions and perspectives

10 Priority pollutants in an European city: One surface water and one sediments Surface water (upstream and downstream):  Three pollutants: Naphthalene, diuron and lead. Sediments:  Light PAH : fluoranthene and anthracene,  Heavy PAH: benzo(k)fluoranthene, benzo(a)pyrene, benzo (g,h,i)perylene indeno(1,2,3,-cd)pyrene and benzo(b)fluoranthene,  Metals : Mercury, nickel and lead.

11 Priority pollutants in an European city: Four wastewater samples (TET) Influent stream: Naphtalene, anthracene…(8 compounds), Alachlor, diuron and simazine (3 compounds), DEHP (in all samples), trichloromethane (2 compounds). Effluent stream Diuron (in 3 samples) (1 compound), DEHP (in all samples) and trichloromethane (2 compounds).

12 Priority pollutants in an European city: Twenty-eight wastewater samples (SBSE) wet event Influent stream: Naphtalene (in all samples), anthracene…(8 compounds), Diuron (in all samples), isoproturon, chlorpyrifos… (8 compounds), DEHP (in all samples), nonylphenol, nickel, lead…(8 compounds). Effluent stream: Naphtalene, anthracene…(8 compounds), Lindane, diuron, isoproturon…(7 compounds), DEHP (in all samples) and benzene (2 compounds).

13 Priority pollutants in an European city: Fourteen wastewater samples (SBSE) dry event Influent stream: Naphtalene (in all samples), anthracene…(8 compounds), Diuron (in all samples), isoproturon, chlorpyrifos … (5 compounds), DEHP (in all samples), benzene …(4 compounds). Effluent stream: Naphtalene, anthracene…(8 compounds), Chlorpyrifos, diuron, tributyltin…(4 compounds), DEHP (in all samples) and lead (2 compounds).

14 Priority pollutants in an European city: Extraction techniques similarities and differences Similarities:  Light and heavy PAH quantified,  Similar trends of PPs in wastewater streams. Priority pollutants quantified using traditional extraction technique found using SBSE. Differences between extraction techniques:  Cannot quantify metals with SBSE,  Difference in quantification limits,  Problems in recovery especially with poorly soluble priority pollutants, Improvement to be done for both extraction techniques.

15 Priority pollutants in a European city: Seasonal effects using SBSE Seasonal differences:  More priority pollutants present during rain events, Due to water run off on land.  Priority pollutants detected during rain and dry events found at lower concentrations during rain events, Possible dilution effects, Seasonal use of compounds (e.g. pesticides). Seasonal similarities:  Diuron and DEHP present in WWTP’s effluent, Above the European Environmental Quality Standards surface water (1.3 µg/l for DEHP and 0.20 µg/l for diuron).  PAH ubiquitous, Several sources within the city.

16 Priority pollutants in an European city: Four sludge samples PAH (fluoranthene, benzo(a)pyrene, …):  75% to 100% occurrence in sludge samples. Metals (cadmium, lead, mercury, nickel) :  75% to 100% occurrence in sludge samples. Pesticides (alachlor, pentachlorophenol…):  25% to 75% occurrence in sludge samples. DEHP:  100% occurrence in sludge samples.

17 Priority pollutants in an European city: Four sludge samples DEHP (29.3 mg/kg dm):  Used in several activities (hospital, construction, domestic...). PAH found often in sludge:  Partial combustion main source (heating, incineration...). Metals:  Metal sludge profile similar to literature, Hg =<Cd < Ni < Pb. Unexpected presence of priority pollutants:  Pentachlorophenol (found once),  Tributyltin (found 3 times).

18 Source control option for Reducing Priority Pollutants 1.Role in the ScorePP project 2.Monitoring campaigns in an European case city 3.Priority pollutants in an European case city 4.Priority pollutants in an European case city: Conclusions and perspectives

19 Priority pollutants in an European case city: Conclusions and perspectives The city has an impact on surface water quality:  Differences of concentrations of naphthalene and lead upstream and downstream of the river. Extraction techniques:  SBSE lower detection limits,  Complementary extraction techniques: SBSE practical for trace analysis (e.g. WWTP effluent). Seasonal effects:  Differences in wastewater streams’ composition, Understand seasonal uses of pollutants (or object containing pollutants).

20 Priority pollutants in an European case city: Conclusions and perspectives Presence of banned priority pollutants:  Pentachlorophenol, Found once (not alarming).  Tributyltin, Unaccounted uses of the compound. Priority pollutants of interest for the city (based on concentrations in different media):  Nickel, lead, cadmium, mercury, DEHP, diuron, pentachlorophenol and naphthalene.

21 Priority pollutants in an European case city: Conclusions and perspectives Substance Flow Analysis (SFA):  Based on results from monitoring campaigns. DEHP, cadmium, mercury, nickel, lead and naphthalene. Environmental Control Strategies (ECS):  Based on information collected during substance flow analysis propose ECS to reduce priority pollutants’ release within the city. DEHP found above EQS in surface water. Diuron despite regulation.

22 Thank you very much for your attention