1. Berlin, 20.-21. APRIL 2015 Groundwater Watch List Dr. Rüdiger Wolter Federal Environment Agency (Umweltbundesamt) ruediger.wolter@uba.de NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

2. Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances” Groundwater should be (kept) free from anthropogenic substances

3. Background of the activity is addressed in recital (4) of the groundwater directive: watch list should be set (4) The need to obtain and respond to new information on other substances posing a potential risk should be acknowledged. Therefore, a watch list for pollutants of groundwater should be established ……………. to increase the availability of monitoring data on substances posing a risk or potential risk to bodies of groundwater, and thereby facilitate the identification of substances, including emerging pollutants, for which groundwater quality standards or threshold values should be set.. This is a voluntary activity of the Member States Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

4. Groundwater Watch List: Agreement upon step by step approach Starting with pilot data collection (pharmaceuticals) Discussion about findings and elaboration of a procedure for the next steps at the next meeting (in Brussels – 15.04.2015) Revised paper on CIRCABC Comments to revised paper + template by 7 th Nov. 2014 to Rüdiger  Data provision at the latest mid Feb 2015  Group of volunteers Rob Ward, Ian Davy, Laurence Gourcy, Sarah Bonneville, Wilko Verwij, Ralph Eppinger, Robert Loos, Elisabetta Preziosi, Jonathan Smith, Dennis Lemke Results of the meeting in ROM and next steps: Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

5. (Example) Pharmaceuticals in Groundwater Contact person / Institution Name: Dr. Rüdiger Wolter In GERMANY Adress: Umweltbundesamt for the year 2013 Wörlitzer Platz 1 D-06844 Dessau the following data on the occurrence of Phone: ++49 340 2103 2212 Pharmaceuticals in groundwater are available Fax: e-mail: ruediger.wolter@uba.de Substance or metabolite LOQ Total number of sites Number of sites Type of water Year Member State Maximum concentration at sites below limit of quantific ation (LOQ) detection > LOQ to 0,05 µg/l detection > 0,05 to 0,1 µg/l detection > 0,1 bis 1,0 µg/l detection > 1,0 bis 3,0 µg/l detection > 3,0 bis 10,0 µg/l detection > 10,0 µg/l 17-alpha-Estradiol 125 000000 12013DE 4-Formylaminoantipyrin 129122430000 12013DE Acetbutolol 159 000000 12013DE Amidotrizoate 2419032000 12013DE Amidotrizoesaeure 3292972119100 12013DE Atenolol 393264000000 12013DE beta-Sitosterol 425 000000 12013DE Betaxolol 159 000000 12013DE Bezafibrat 635504110000 12013DE Bisoprolol 395265100000 12013DE Bromhexin 105 000000 12013DE Carazolol 158 000000 12013DE Carbamazepin 9624942797000 12013DE Chlortetracyclin 10 000000 12013DE Ciprofloxacin 129 000000 12013DE Clarithromycin 129 000000 12013DE Clenbuterol 266 000000 12013DE Clofibrinsäure 687501136000 12013DE

6. Second step: Check and summarize data Substance or metabolite CAS Total number of sites Number of sites Type of water Number of MS Maximum concentration at sites below (LOQ) > LOQ to 0,05 µg/l > 0,05 to 0,1 µg/l > 0,1 bis 1,0 µg/l > 1,0 bis 3,0 µg/l > 3,0 bis 10,0 µg/l > 10,0 µg/l Amidotrizoesaeure 329297211910011 Carbamazepin 962919279700011 Clofibrinsäure 68767713600011 Amidotrizoate 241903200011 4-Formylaminoantipyrin 12912243000011 Bezafibrat 63563311000011 Bisoprolol 39539410000011 List of substances most frequently found in European groundwater (2013) Is such a list sufficient to put substances into annex I or II? If not - What has to be done and why? Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

7. Data on pharmaceuticals in groundwater: Until the 10 th April 2015 we got an answer from eight countries. Six (five EU MS) delivered data on pharmaceuticals in groundwater. For 2 countries no data were available. It was announced that a monitoring campaign will start in 2015 in one of these countries. Comments to revised paper + template: From 8 organisations/stakeholders (16 persons) we received about 82 comments or remarks Thank you to all for your comments!! preselection Several comments indirectly referred to the “Surface Water Watch List”. To be clear, a preselection of substances by modelling is not planned for the “Groundwater Watch List”. As discussed and agreed in Rom the procedure to derive a “Ground Water Watch List” should not be mixed up with the procedure applied for the “Surface Water Watch List”. BUT: BUT: We should discuss what we can learn from the “Surface Water Watch List”. Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

8. First results of the pilot data collection: Substance or metabolite Total number of sites Member States Carbamazepine26626 Sulfamethoxazole13356 Bezafibrate9225 Diclofenac21255 Gemfibrozil2845 Ketoprofene3215 Trimethoprime6035 Clarithromycin4154 Erythromycin4464 Ibuprofen10394 Iopromide5224 Metoprolol9574 Naproxene5734 Paracetamol2274 Propranolol5364 Sulfadiazine5154 171 Six countries reported the monitoring results of 171 different pharmaceuticals (human, veterinary, degradation products, X-ray contrast agents). 76 76 substances were analysed in two or more countries. 16 16 substances were analysed in four or more countries. Tab. 1 gives a first overview of pharmaceuticals which are expected to be “of interest” for most of the countries. Tab. 1:Pharmaceuticals in groundwater - analyzed in four or more countries Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

9. Substance or metabolite Total number of sites Member State sites detection > LOQ in % Carbamazepine 26626 218 8,2 Amidotrizoic acid 6483 64 9,9 Sulfamethoxazole 13356 55 4,1 Diclofenac 21255 26 1,2 Iopamidol 7112 24 3,4 Primidon 4793 21 4,4 Clofibrinsäure 15702 21 1,3 Phenazon 7262 21 2,9 Tramadol 1832 10 5,5 Paracetamol 2274 9 4,0 Pentox(i)yfyllin 6052 9 1,5 Ibuprofen 10394 8 0,8 4-Formylaminoantipyrin 1372 7 5,1 Sulfadimidine 1913 6 3,1 Propyphenazon 8052 6 0,7 Epoxycarbamazepine 321 6 18,8 Amidotrizoate 241 5 20,8 N-Acetyl-4-aminoantipyrin 1291 5 3,9 Oxcarbazepin 4251 5 1,2 Sotalol 7283 4 0,5 Tab. 2: Pharmaceuticals most frequently found in groundwater We assume that countries have used the maximum concentration observed for the assignment if a site is analysed more than once a year. 48 from 171 substances analysed could be found at one or more sites in a concentration above the limit of quantification (LOQ). Tab 2. shows the pharmaceuticals most frequently found in groundwater Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

10. Substance or metabolite Total number of sites Member State sites detection > LOQ sites detection > 0.1 µg/l Carbamazepine 2662621849 Amidotrizoic acid 64836415 Diclofenac 212552611 Primidon 47932110 Clofibrinsäure 157022110 Pentox(i)yfyllin 605299 Sulfamethoxazole 13356554 Iopamidol 7112243 Phenazon 7262213 Metformin 190143 Gabapentin 151133 Ibuprofen 1039482 Propyphenazon 805262 Amidotrizoate 24152 N-Acetyl-4-aminoantipyrin 129151 Sulfadiazine 515421 Tab. 3: Pharmaceutical exceeding a concentration level of 0.1 µ g/l in groundwater. Several comments stated to refer findings to existing health, ecological or other quality criteria. For pharmaceuticals in the “Revised guideline on environmental impact assessment for veterinary medicine products” a limit concentration of 0.1 μg/l for groundwater is mentioned. 16 16 pharmaceuticals exceed this criterion at one or more groundwater monitoring sites. Is this already a watch list?? Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

11. The list is based on data from 6 countries only, additional results should be added to the summary to get a (more) representative overview and criteria for selection and identification of substances have to be discussed and agreed upon within WG GW. The discussion will refer to the comments, received so far. Different topics will have to be discussed, because in some cases there are different opinions or understandings or open questions. Topics for discussion will be: Structure of the template (referring to other substances than pharmaceuticals), Additional data on LOD/LOQ, Details on monitoring programs or sites, Quality of monitoring data, Criteria for an (additional) selection of substances ?? Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

12. Some comments and replies: Comment: Are the intervals (e.g. LOQ – 0.05 µg/l ……..) used in the questionnaire suitable for all substances? Reply: It could be better to adapt the classes with respect to different groups of substances. Which intervals should be chosen has to be discussed according to the group of substances requested. In some comments it was stressed to reduce the substances taken into account. E.g. only substances that pose a risk for receptors as defined in WFD and GWD should be looked at. Other comments did not agree and stated that there could be other reasons to identify a substance or group of substance as relevant for groundwater. Therefore we should collect and summarize all the monitoring data available in the first step of the process. Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

13. Comment: Classes/Classification of findings should not refer to concentration classes in the questionnaire but refer to LOQmax, percentage of quality criteria (1, 10, 100, 1000, 10.000%) or percentage of LOQmax. Reply: LOQs for the same substance may be different for different analytical methods, differ between different laboratories and may change over time. QS often not available. LOQ for Carbamazepin between 0.0004 and 0.02 µg/l Substance or metabolite Total number of sites below limit of quantification (LOQ) detection > LOQ to 0,05 µg/l detection > 0,05 to 0,1 µg/l detection > 0,1 bis 1,0 µg/l detection > 1,0 bis 3,0 µg/l detection > 3,0 bis 10,0 µg/l detection > 10,0 µg/l Carbamazepine2662244414722281344 Quality Standard = 0.1 µg/l Total number of sites up to 1 % of QS 1 to 10 % of QS 10 to100% of QS 100 to 1000 % 0f QS 1000 to 10000% of QS > 10000% of QS New classes in µg/l 2662 0 – 0.001 µg/l >0,001- 0,01 µg/l 0,01-0.1 µg/l 0.1-1.0 µg/l 1.0- 10µg/l >10 µg/l Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

14. Comment: Classification of individual sites should not refer to the maximum concentration at a site but to the median concentration over a large geographic area. Local point source impacts with high concentrations are pretty irrelevant if we are assessing the EU-wide impact on groundwater. Reply: “emerging contaminations” Local high concentrations are very important in groundwater. They are a first indication of “emerging contaminations” under comparable situations. Many groundwater monitoring sites are analyzed only once per year and thus the calculation of a mean value is not possible in these cases. Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

15. Comment: How frequently should data be collected? Once a year? Reply: The collection, summary and assessment of monitoring data as well as the revision of monitoring programs is a time consuming process. It has to be discussed how we can organize this process and who will do the work in the future? The interval of data collection could be every two or three years for specific groups of substances. Comments: Only data from representative monitoring programs or representative sites should be taken into account. Reply: What means representative? Many substances – in particular emerging substances – are analysed at only very few sites. All data available should be taken into account. Due to the long residence time in groundwater it has to be expected that emerging substances can be found in the beginning at only very view sites with specific conditions (e.g. short residence time, poorly protected aquifers, conditions in the catchment area). It is important to consider data from these “specific sites” as well. Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

16. Comment: What additional data are necessary (red/ox conditions at (each) site, depth of sampling, land use and thickness of the unsaturated zone)? At what step of the process do we need this information? Reply: At the very first step (collection an summary of monitoring data) there seems to be no need to collect additional data. In a later stage additional data are helpful/necessary. They might help to select specific substances or groups of substances for the final watch list. Comment: How can we integrate data on semi quantitative analysis (e.g. GC-MS and LC- MS analysis)?? Reply: ??? Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

17. Next steps: Organisation of a meeting of the group of Volunteers ? Discussion of findings of the pilot data collection and comments received Adaptation of data collection template, Issues to be discussed: 1.Feedback from MS (list of substances - monitoring campaign). 2.Development of criteria for assessing the relevance of substances concerning groundwater (e.g. concentration level, spatial extent of occurrence, temporal scale, ….) 3.How to classify substances that cannot be analysed (missing analytical methods) or substance specific data (e.g. ecotox, persistence …. ) are not available. 4.Selection criteria for groups of substances for data collection ? (which – PFOS?). 5.How to deal with substances which are not analysed in ground water up to now? 6.Additional results should be added to the summary list and presented at the next meeting. 7.…….. Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”

18. How can NORMAN support the activity ?? -Help to priories substances that are found already, -Find simple criteria to check the quality of monitoring data -Help to identify “important” substances that were not analysed up to now or that were analysed only at a very small number of sites, -Develop a methodology (model) to identify emerging pollutants in groundwater -Compare findings in GW with results of modelling (do we find substances that should occur in GW – if not, why? Berlin, 20.-21. APRIL 2015 NORMAN – Meeting of WG-1 “Prioritizations of emerging substances”