NORMAN Working Group 1: Prioritisation Sub-Group 1 : Groundwater Approach suggested for exposure assessment Dr. Benjamin Lopez b.lopez@brgm.fr I will show you a short presentation on a proposal for prioritization of substances depending on different uses of groundwater resources. Groundwater Watch List Meeting at the 23rd/24th June 2016 in Vienna

NORMAN network History and Statutes Missions of the NORMAN network September 2005: financial support of the European Commission (NORMAN project - 6th Framework Programme – Priority 6.3 - Contract N° 018486). 2009: non-profit association (French law of 1901 on non-profit organisations) permanent self-sustaining network of reference laboratories, research centres and related organisations for the monitoring and biomonitoring of emerging substances. Missions of the NORMAN network Enhance the exchange of information and collection of data on emerging environmental substances; Encourage the validation and harmonisation of common measurement methods and monitoring tools so that the demands of risk assessors can be better met; Ensure that knowledge of emerging pollutants is maintained and developed by stimulating coordinated, interdisciplinary projects on problem-oriented research and knowledge transfer to address identified needs Working groups 6 Working Groups and two Cross-Working Group Activities, dealing with various issues related to emerging substances. WG-1: Prioritisation of emerging substances Sub-Group 1: Groundwater NORMAN network comes from an european project that started in 2005 under the financial support of the European Commision. The network became a non-profit association in 2009. The aim of the NORMAN network is to enhances Groundwater Watch List meeting June 2016 Vienna

General approach proposed for prioritisation of contaminants of emerging concern in GW Similar to the NORMAN prioritisation scheme for CECs in surface water (Dulio and von der Ohe, 2013)… …duly adapted to GW specificities (hydrogeological contexts and properties, actual or potential uses or functions of GW, GW pollution pathways, etc.) Decision tree universe of chemicals allocation of the substances to ‘action categories’ prioritisation within each category 4 main steps Step1: Universe of chemicals Step2: GW exposure Step3: Allocation in Cat. Step4: Prioritisation Groundwater Watch List meeting June 2016 Vienna

General approach proposed for prioritisation of contaminants of emerging concern in GW Groundwater Watch List meeting June 2016 Vienna

Universe of Chemicals Any list of compounds – emerging or not Substances withdrawn or no longer approved for use in the EU market (potentially long transfer-time and residence time of pollutants in soils, unsaturated zones and GW) Metadata needed Physico-chemical properties (DT50, Koc, Kow) Leaching potential Production volume and use pattern Proposal - already identified lists of substances: NORMAN List 2015 (967 CECs including pharmaceuticals, veterinary products, personal care products…) Candidate list of substances used by the JRC for the on-going modelling-based and monitoring-based prioritisation exercises for the review of the list of Priority Substances for surface water (2793 substances including 2033 industrial chemicals, 247 medecines, 73 biocides…) List of pesticides and associated metabolites FootPrint PPDB (1717 substances) and Inventory of pesticides carried out by AQUAREF in France (Baran et al., 2015) on the active substances for which analytical methods need to be improved Groundwater Watch List meeting June 2016 Vienna

Universe of Chemicals Questions: Do the inclusion of banned substances in the Universe of chemicals for GW relevant? Should the Universe of chemicals include all existing anthropogenic chemicals or emerging substances only? How to ensure an exhaustive and regularly updated Universe of chemicals? Which databases should be used: i) to estimate occurrence in GW; ii) to gather physico-chemical properties of the substances; iii) to evaluate use pattern and consumption levels of the substances? Is it possible to build and share a common EU database among all European groups dealing with chemicals’ prioritisation in GW? Groundwater Watch List meeting June 2016 Vienna

Potential for GW exposure Aims: Select chemicals that have already been observed in GW Select chemicals that have the potential to reach and to contaminate GW Proposed Criteria to evaluate the potential for GW exposure 1- Observation in groundwater 2- Persistence and mobility OR polarity 3- Use of the substances AND / OR Groundwater Watch List meeting June 2016 Vienna

Potential for GW exposure 1- Observation in groundwater At least one study showing evidence of occurrence of the substance in GW (i.e. data > LOQ) is sufficient to classify the substance as a substance with high potential for groundwater exposure. However, particular attention must be paid to non-diffuse point pollution sources and specific karstic systems that may be not representative of diffuse contamination => representativeness and reliability of data Evidence of occurrence in GW can be derived from monitoring data coming from: Member States GW databases EU GW databases Scientific literature Occurrence in GW Indicators Cut-off values Evidence in the scientific literature or from national / European monitoring studies At least 1 study showing data above LOQ in GW Groundwater Watch List meeting June 2016 Vienna

Potential for GW exposure Metabolism 2- Persistence AND Mobility OR Polarity Persistence expressed by half-life (t1/2) in water or in soil or by REACH classification Mobility expressed by its potential to be adsorbed to organic matter and (clay) minerals (expressed by the KOC) Polarity expressed by the ratio of a chemical's concentration in the octanol phase to its concentration in the aqueous phase (expressed by the Log Kow) or by its solubility? Cometabolism Are these indicators relevant to describe reactive transport through GW? Physico-chemical properties Indicator Cut-off values Persistence Half-life (t1/2) water OR Half-life (t1/2) sediment > 20d > 60d Classification P according to REACH classification Mobility Koc < 500 Mode of transport Particulate transport = Yes Polarity Log Kow < 5 Solubility ? Groundwater Watch List meeting June 2016 Vienna

Potential for GW exposure 2- Leaching potential (optional) Leaching potential indexes Leaching potential models Leaching potential Indicator Cut-off values Most conservative value among available indexes GUS leaching potential (for pesticides only) > 1.8 SCI-Grow groundwater index (estimate concentrations in vulnerable GW) > 0.001 µg/L Others…   Most conservative value (in defined conditions) among available transfer models PELMO : x STIC : y MACRO : z To be discussed Etc… To summary this second criteria… A substance will be considered to have a potential for GW exposure if: 1) one of the indicators of Persistence AND one of the indicators of Mobility are above the proposed cut-off values 2) the indicator of Polarity is below the proposed cut-off value (i.e. Log kow < 5) 3) one of the leaching potential indicators is above the proposed cut-off value. OR OR Groundwater Watch List meeting June 2016 Vienna

Potential for GW exposure 3- Use of the substance Use of substances Indicator Cut-off values Use pattern Used in the environment OR Wide dispersive use (i.e. substances present in diffuse sources and in urban wastewater) Yes   Volume Annual tonnage >100t / y (REACH) In conclusion the potential of a substance for GW exposure can be calculated using the following algorithm: High potential = IF [(Occurrence in GW = yes) OR (Properties = yes) OR (Use = yes) => Allocation into action categories Low potential = IF [(Occurrence in GW = no) AND (Properties = no) AND (Use = no) => Safety net Low potential for GW exposure chemicals are considered as low priority for the further actions in the prioritisation scheme. A specific safety net category should be created for these compounds Groundwater Watch List meeting June 2016 Vienna

Potential for GW exposure Questions: Can we estimate the mobility of molecules based on the assessment on the Koc only? How to estimate the reliability of Observation in GW data? Transfer models? Should we create a specific action category for chemicals for which no GW monitoring and no property data is available? Groundwater Watch List meeting June 2016 Vienna

Allocation of substances in Cat. 2: GW Watch List Candidate substances for EU Watch List are : Substances with high potential for GW exposure AND Insufficiently monitored substances for which monitoring data are needed (improvement of knowledge on CECs in EU GW) OR Sufficiently monitored substances but data are of insufficient quality (check GW occurrence with adequate analytical performance) Groundwater Watch List meeting June 2016 Vienna

Allocation of substances in Cat. 2: GW Watch List Groundwater Watch List meeting June 2016 Vienna

Allocation of substances in Cat. 2: GW Watch List Insufficiently monitored substances Substances monitored in less than 4 countries AND less than 100 sites in GW LOQ min < conservative TV. (0.01µg/L by default) Sufficiently monitored substances but data are of insufficient quality Substances monitored in more than 4 countries AND more than 100 sites in GW Less than 20 sites above LoQ LOQ max > conservative TV. (0.01µg/L by default) AND BUT AND AND Groundwater Watch List meeting June 2016 Vienna

Prioritisation of chemicals within the GW Watch List action category The substances allocated to the five action categories are ranked (from “high-” to “low priority” substances) using indicators specifically-designed for each category. Specific indicators are adopted for ranking of substances within each action category. Because the GW occurrence of the ‘GW Watch List’ substances is not well known, Potential of GW exposure is proposed to be a criteria for their ranking 3 main criteria: Potential for GW exposure Use of substances Hazardous properties (environment and human health) = risk assessment Groundwater Watch List meeting June 2016 Vienna

Prioritisation of chemicals within the GW Watch List action category Potential for GW exposure Criteria Indicators Cut off values Rank and associated score Persistence Half-life (t1/2) in water > 20d High = 10 5-20d Moderate = 7.5 1-5d Weak = 5 < 1d No = 0 Classification P according to REACH classification Not classified P Mobility Koc < 100 100 - 500 500 - 1000 > 1000 Mode of transport Particulate transport Yes = 5 Polarity logKow < 5 10 5-10 5 > 10 Leaching potential Most conservative value among available indexes GUS leaching potential (for pesticides only) > 2.8 = High = 10 1.8-2.8 = Moderate = 5 < 1.8 = No = 0 SCI-Grow groundwater index (estimate concentrations in vulnerable GW) > 0.1 µg/L = High = 10 0.01-0.1 µg/L = Moderate = 7.5 0.001-0.01 µg/L = Weak = 5 < 0.001 µg/L = No = 0 Most conservative value (in defined conditions) among available transfer models PELMO : x STIC : y MACRO : z Etc… To be discussed Groundwater Watch List meeting June 2016 Vienna

Prioritisation of chemicals within the GW Watch List action category Use of substances Indicators Cut off values Rank and associated score Use pattern Used in the environment High = 10 Wide dispersive use (diffuse sources and substances in urban wastewater) Moderate = 7.5 Non-dispersive use (industrial, controlled point sources) Weak = 5 Controlled systems No = 0 Production volume (REACH) Annual tonnage >1000t 10 100-1000t 7.5 10-100t 5 0.1 – 10t 2.5 < 0.1t Groundwater Watch List meeting June 2016 Vienna

Prioritisation of chemicals within the GW Watch List action category Hazardous properties (environment and human health) Indicators Cut off values Rank and associated score CMR (Cf. Dulio and von der Ohe, 2013 Annex II. 2.) CMR, category 1 10 CMR, category 2 7.5 CMR, category 3 5 Under examination 2.5 Examined and info not suff. Not examined Examined and not classified ED (endocrine disruption potential) Proven ED Suspect ED Not proven ED Threshold of Toxicological Concern (Cramer Class) Tox-tree open source application Class III Class II Class I Score “CMR” = Max (“Carcinogenicity”, “Mutagenicity”, “Reprotoxicity”) individual scores Score “ED” = (Endocrine disrupting effects) score Groundwater Watch List meeting June 2016 Vienna

Prioritisation of chemicals within the GW Watch List action category The final score is calculated for each substance by applying a prioritisation algorithm. The 3 intermediate scores (Potential for GW exposure; Use; Hazardous properties) are calculated on a scale of 10 based on the following equations: Score “Potential for GW exposure” = (Max “persistence” score) + (Max “mobility” score) + (“polarity” score) + (Max “leaching potential” score)] / number of filled “indicators” Score “Use” = [(“use pattern” score) + (“volume” score)] / number of filled “indicators” Score “Hazard” = (“CMR” score*) + (“ED” score**)] / number of filled “indicators” The final score is calculated on a scale of 30 as the sum of the three intermediate scores as follow: Score “Potential for GW exposure” + Score “Use” + Score “Hazard” Groundwater Watch List meeting June 2016 Vienna

NORMAN WG-1 Sub-Group GW agenda 27-28 June 2016: Meeting in Paris of WG-1on “Prioritisation of emerging substances” and Sub-Group Groundwater (28/06) Agreement on objectives and methodology Data that must be used to allocate substances in the GW actions’ categories End of June 2016: First run test to allocate substances in Cat. 2: Watch List Groundwater July 2016: Finalisation of a Background paper - Prioritisation methodology for contaminants in GW – taking into account the conclusions of the NORMAN meeting September/October 2016: NORMAN GW Watch List proposal Groundwater Watch List meeting June 2016 Vienna

Watch List GW First Run Test Identification of substances with high potential for GW exposure First run test without occurrence data Work carried out for each selected list for the universe of chemical: 1- NORMAN Database 2- JRC Database 3- Footprint PPDB Database Groundwater Watch List meeting June 2016 Vienna