1. CHEMICAL-PHYSICO MONITORING SUPPORTING ECOLOGICAL STATUS FOR THE EU WATER FRAMEWORK DIRECTIVE BY MICHAEL JACKMAN CHEMISTRY EXPERT

2. EU Water Framework Directive (WFD) The overall objective of the WFD is to ensure all surface and ground waters achieve “good status”. The general definition of good ecological status is: “The values of the biological quality elements for the surface water body type show low levels of distortion resulting from human activity but deviate only slightly from those normally associated with the surface water body type under undisturbed conditions

3. Relative Roles of Biological, Hydro-morphological and Physico- chemical parameters in the Ecological Status Classification

4. Annex V – Chemical & Physico-Chemical Elements RIVERSLAKES Chemical and physico-chemical elements supporting the biological elements  Thermal conditions  Oxygenation conditions  Salinity  Acidification status  Nutrient conditions  Specific pollutants o pollution by Priority Substances discharged into the water body (*). o pollution by other substances discharged in significant quantities into the water body.  Transparency  Thermal conditions  Oxygenation conditions  Salinity  Acidification status  Nutrient conditions  Specific pollutants o pollution by Priority Substances discharged into the water body (*). o pollution by other substances in significant quantities into the water body.

5. Establishing the status of surface water bodies comprises actually of two assessments: ecological status & chemical status. In order for a surface water body to be classified as being of good status, the criteria for both good ecological status as well as good chemical status have to be met.

6. Establishing the status of surface water bodies comprises actually of two assessments: ecological status & chemical status. In order for a surface water body to be classified as being of good status, the criteria for both good ecological status as well as good chemical status have to be met

7. Ecological status The ecological status is assessed based on three groups of surface water quality elements: Biological Hydromorphological & Chemical & physico-chemical parameters:

8. Chemical & physico-chemical parameters supporting the biological elements are: General Physico Chemical elements (Annex V WFD) 2) Specific Non-priority Pollutants identified as being discharged (Annex VIII WFD) The Chemical Status - Specific priority pollutants as being discharged (Annex X WFD) should be assessed separately

9. Classification of the status of surface water bodies under the WFD

10. WFD Annex VIII: Indicative List of the 12 Main Pollutant types Organohalogen compounds and substances, which may form such compounds in the aquatic environment. Some have been addressed in WFD Annex X Priority Substances details in EU Directive on Environmental Quality Standards: Organo Chlorine Pesticides (OCP) Trichloroethylene Tetrachloroethylene Trichlorobenzene (all isomers), Pentachlorophenol, Hexachorobutadiene Carbon tetrachloride Dichloromethane 1,2-dichloroethane Chloropyriphos Chlorophenvynphos C10-13-chloroalkanes Pentabromodiphenylether

11. 2) Organophosphorous compounds. Two have been addressed in WFD Annex X Priority Substances details in EU Directive on Environmental Quality Standards: Chloropyriphos Chlorophenvynphos 3) Organotin compounds Tributyltin compounds has been addressed in WFD Annex X Priority Substances details in EU Directive on Environmental Quality Standards

12. 4) Substances and preparations, or the breakdown products of such, which have been proved to possess carcinogenic or mutagenic properties or properties which may affect steroidogenic, thyroid, reproduction or other endocrine-related functions in or via the aquatic environment. e.g.oestrogen 5) Persistent hydrocarbons and persistent and bio-accumulable organic toxic substances 6) Cyanides.

13. 7) Metals and their compounds Mercury Cadmium Lead Nickel Dissolved- filter the sample first before acidification They also have been addressed in WFD Annex X Priority Substances details in EU Directive on Environmental Quality Standards:

14. 8) Arsenic and its compounds. 9) Biocides and plant protection products – some pesticides have been addressed in WFD Annex X Priority Substances details in EU Directive on Environmental Quality Standards – Ideally needs a desk top study to identify likely compounds 10) Materials in suspension.

15. 11) Substances which contribute to eutrophication especially Nitrates & Phosphates - Also addressed in the WFD General Conditions 12) Substances, which have an unfavourable influence on the oxygen balance (and can be measured using parameters such as BOD, COD, etc. Also addressed in WFD General Conditions. In the case of annex VIII pollutants, good status means: Concentrations not in excess of the standards set in accordance with the procedure eco toxicological methods detailed in section 1.2.6 WFD

16. Common Implementation Strategy (CIS) for the WFD guidance document 13 “Overall Approach to the Classification of Ecological Status” Examples

17. The values of the physico-chemical elements must be taken into account when assigning high & good ecological status also from good to moderate. For lower status, hydro-biological results are regarded as preferable.

19. Procedure to check if General Physico- Element is too Stringent

20. Procedure to check if General Physico- Element is Insufficiently Stringent

21. Selection of Support Quality Elements Any priority list substances discharged into the river basin or sub-basins must be monitored. Other pollutants also need to be monitored if they are discharged in significant quantities in the river basin or sub-basin. The selection should also be derived from information on the ecological status where indications of toxic impacts are found or from ecotoxicological evidence.

22. Selection of Support Quality Elements

23. WFD Status CriteriaQuality ElementsIndicative parameters Ecological Status Physico – Chemical “ General Conditions ” Parameters Thermal conditionsTemperature Oxygenation conditionsDissolved oxygen, oxygen saturation Nutrient conditionsNitrate (NO3) Ammonium (NH3) Orthophosphates (PO4) SalinityElectrical Conductivity (EC) Chloride (Cl) Sulphate (SO4) Total dissolved solids (total mineralization) Acidification statuspH Ecological Status WFD Annex VIII Specific relevant pollutants MetalsDissolved Copper (Cu), Zinc (Zn) Total Copper (Cu), Zinc (Zn) MetalloidDissolved Arsenic (As) Total Arsenic (As), Substances affecting Oxygen Balance Chemical Oxygen Demand (COD) Biochemical Oxygen Demand (BOD5) Materials in SuspensionTotal suspended solids Turbidity Chemical Status WFD Annex X “ Priority Pollutants ” Organo Chlorine Pesticides Aldrin, Hexachlorobenzene, Endrin, pp DDT, Specific Heavy Metals:Dissolved Lead (Pb), Nickel (Ni), & Cadmium (Cd) Example of Recommended Parameters in Black Sea Project

24. Previous Studies There have been a number of studies previously undertaken within the project countries notably: 1) The Kura Projects, (USAid & EU) – Georgia, Armenia, & Azerbaijan 2) The OECD Governance Projects – Ukraine, & Moldova. It was noted within these studies that it was not possible for the Project countries to comply fully with the standards recommended by WFD owing to a lack of resources, expertise, and equipment. Especially in undertaking ecotoxicity testing. Therefore the values for the parameters have been assigned by other techniques.

25. ParametersAbbr.Units of Measure Class ІClass ІІClass ІІІClass ІVClass V General conditions Hydrophysical: TemperatureT ºСºСCold waters: 20 º С in summer 5 º С in winter Warm waters: 28 º С in summer 8 º С in winter Cold waters: 20 º С in summer 5 º С in winter Warm waters: 28 º С in summer 8 º С in winter Cold waters: 20 º С in summer 5 º С in winter Warm waters: 28 º С in summer 8 º С in winter Cold waters: 20 º С in summer 5 º С in winter Warm waters: 28 º С in summer 8 º С in winter Cold waters: 20 º С in summer 5 º С in winter Warm waters: 28 º С in summer 8 º С inwinter Colordegree< 3535120200> 200 Floating mattersVisu- ally VisuallyShould not be found Odor (at 20 and 60 º С)points< 2234> 4 OECD Standards for General Conditions

26. Hydrochemical: рН -6,5 – 8,5 Total nitrogen contentN total mgN/dm 3 1,54820> 20 AmmoniumNH4mgN/dm 3 0,20,40,83,1> 3,1 NitriteNO 2 mgN/dm 3 0,010,060,120,3> 0,3 NitrateNO 3 mgN/dm 3 135,611,3> 11,3 Total phosphorus content Р общ mg Р /dm 3 0,10,20,41> 1 Orthophosphates РО 4mg Р /dm 3 0,050,10,20,5> 0,5 Dissolved Oxygen О2О2 mg О 2 /dm 3 ≥7≥7 ≥7≥7 ≥5≥5 ≥4≥4<4 COD, permanganate oxidizability method CODmg О 2 /dm 3 <771520>20 Biochemical oxygen demand (5 days) BOD 5 mg О 2 /dm 3 <3357>7

27. OECD Standards for General Conditions Salt components: Mineralization (Total Dissolved Solids) М total mg/dm 3 < 1000100013001500> 1500 Electrical ConductivityEC µ S/cm500110038009000>9000 ChloridesClmg/dm 3 < 200200350500> 500 SulphatesSO4mg/dm 3 < 250250350500> 500

28. Special radioactive parameters: Strontium 90Sr 90 Bq/dm 3 < 0,030,030,51,2> 1,2 Cesium 137Cs 137 Bq/dm 3 < 0,040,041,02,5> 2,5 Priority substances Other special pollutants Total DDT contentmg/l0,0250,050,0650,075>0,075 para-para-DDTmg/l0,010,020,0260,03>0,03 Aldrinmg/l ∑ = 0,010 ∑ = 0,020 ∑ = 0,026 ∑ = 0,030 ∑ >0,030 Dieldrinmg/l Endrinmg/l Isodrinmg/l Carbon tetrachloridemg/l12243136>36 Tetrachloroethylenemg/l10202630>30 Trichloroethylenemg/l10202630>30

29. Armenian Standards

34. The application of chemical monitoring for supporting the classifications can be applied differently for each country. It should be customised to take into account their individual circumstances, environmental conditions and linked with the biological monitoring. This can take extensive research and monitoring to be finalised but it is worth doing well to apply the correct and most responsive parameters for the true classifications. Thank you for your attention