CHEMICAL-PHYSICO MONITORING SUPPORTING ECOLOGICAL STATUS FOR THE EU WATER FRAMEWORK DIRECTIVE

BY MICHAEL JACKMANCHEMISTRY EXPERT

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

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

Annex V – Chemical & Physico-Chemical Elements

RIVERS LAKES

Chemical and physico-chemical elements supporting the biological elements

Thermal conditionsOxygenation conditionsSalinityAcidification statusNutrient conditionsSpecific pollutantsopollution by Priority Substances discharged into the water body (*).opollution by other substances discharged in significant quantities into the water body.

TransparencyThermal conditionsOxygenation conditionsSalinityAcidification statusNutrient conditionsSpecific pollutantsopollution by Priority Substances discharged into the water body (*).opollution by other substances in significant quantities into the water body.

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.

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

Ecological statusThe ecological status is assessed based on three groups of surface water quality elements:BiologicalHydromorphological &Chemical & physico-chemical parameters:

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

Classification of the status of surface water bodies under the WFD

WFD Annex VIII: Indicative List of the 12 Main Pollutant typesOrganohalogen 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)TrichloroethyleneTetrachloroethylene Trichlorobenzene (all isomers),Pentachlorophenol,Hexachorobutadiene Carbon tetrachlorideDichloromethane1,2-dichloroethane Chloropyriphos Chlorophenvynphos C10-13-chloroalkanes Pentabromodiphenylether

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

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.oestrogen5) Persistent hydrocarbons and persistent and bio-accumulable organic toxic substances

6) Cyanides.

7) Metals and their compounds MercuryCadmiumLeadNickelDissolved- 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:

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 compounds10) Materials in suspension.

11) Substances which contribute to eutrophication especially Nitrates & Phosphates - Also addressed in the WFD General Conditions12) 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

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

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.

Procedure to check if General Physico- Element is too Stringent

Procedure to check if General Physico- Element is Insufficiently Stringent

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.

Selection of Support Quality Elements

WFD Status Criteria Quality Elements Indicative parameters

Ecological Status Physico – Chemical “General Conditions” Parameters

Thermal conditions Temperature

Oxygenation conditions Dissolved oxygen, oxygen saturation

Nutrient conditions Nitrate (NO3)Ammonium (NH3)Orthophosphates (PO4)

Salinity Electrical Conductivity (EC)Chloride (Cl)Sulphate (SO4) Total dissolved solids (total mineralization)

Acidification status pH

Ecological StatusWFD Annex VIII Specific relevant pollutants

Metals Dissolved Copper (Cu), Zinc (Zn)

Total Copper (Cu), Zinc (Zn)

Metalloid Dissolved Arsenic (As)

Total Arsenic (As),

Substances affecting Oxygen Balance

Chemical Oxygen Demand (COD)Biochemical Oxygen Demand (BOD5)

Materials in Suspension Total suspended solidsTurbidity

Chemical StatusWFD 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

Previous Studies There have been a number of studies previously undertaken within the project countries notably:1) The Kura Projects, (USAid & EU) – Georgia, Armenia, & Azerbaijan2) 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.

Parameters Abbr. Units of Measure

Class І Class ІІ Class ІІІ Class ІV Class V

General conditions

Hydrophysical:

Temperature T ºС Cold waters: 20 ºС in summer5 ºС in winterWarm

waters:28 ºС in summer8 ºС in winter

Cold waters: 20 ºС in summer5 ºС in winterWarm

waters:28 ºС in summer8 ºС in winter

Cold waters: 20 ºС in summer5 ºС in winterWarm

waters:28 ºС in summer8 ºС in winter

Cold waters: 20 ºС in summer5 ºС in winterWarm

waters:28 ºС in summer8 ºС in winter

Cold waters: 20 ºС in summer5 ºС in winterWarm

waters:28 ºС in summer

8 ºС inwinter

Color degree < 35 35 120 200 > 200

Floating matters Visu-ally

Visually Should not be found

Should not be found

Should not be found

Should not be found

Should not be found

Odor (at 20 and 60 ºС) points < 2 2 3 4 > 4

OECD Standards for General Conditions

OECD Standards for General ConditionsHydrochemical:

рН рН - 6,5 – 8,5

6,5 – 8,5

6,5 – 8,5

6,5 – 8,5

6,5 – 8,5

Total nitrogen content Ntotal mgN/dm3 1,5 4 8 20 > 20

Ammonium NH4 mgN/dm3 0,2 0,4 0,8 3,1 > 3,1

Nitrite NO2 mgN/dm3 0,01 0,06 0,12 0,3 > 0,3

Nitrate NO3 mgN/dm3 1 3 5,6 11,3 > 11,3

Total phosphorus content Робщ mgР/dm3 0,1 0,2 0,4 1 > 1

Orthophosphates РО4 mgР/dm3 0,05 0,1 0,2 0,5 > 0,5

Dissolved Oxygen О2 mgО2/dm3

≥7 ≥7 ≥5 ≥4 <4

COD, permanganate oxidizability method

COD mgО2/dm3

<7 7 15 20 >20

Biochemical oxygen demand (5 days)

BOD5 mgО2/dm3

<3 3 5 7 >7

OECD Standards for General ConditionsSalt components:

Mineralization (Total Dissolved Solids)

Мtotal mg/dm3 < 1000 1000 1300 1500 > 1500

Electrical Conductivity EC µS/cm 500 1100 3800 9000 >9000

Chlorides Cl mg/dm3 < 200 200 350 500 > 500

Sulphates SO4 mg/dm3 < 250 250 350 500 > 500

Special radioactive parameters:

Strontium 90 Sr90 Bq/dm3 < 0,03 0,03 0,5 1,2 > 1,2

Cesium 137 Cs137 Bq/dm3 < 0,04 0,04 1,0 2,5 > 2,5

Priority substances

Other special pollutants

Total DDT content mg/l 0,025 0,05 0,065 0,075 >0,075

para-para-DDT mg/l 0,01 0,02 0,026 0,03 >0,03

Aldrin mg/l ∑= 0,010

∑= 0,020

∑= 0,026

∑= 0,030

∑ >0,030

Dieldrin mg/l

Endrin mg/l

Isodrin mg/l

Carbon tetrachloride mg/l 12 24 31 36 >36

Tetrachloroethylene mg/l 10 20 26 30 >30

Trichloroethylene mg/l 10 20 26 30 >30

Armenian Standards

Armenian Standards

Armenian Standards

Armenian Standards

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