1. WATER QUALITY LEGISLATION A.I. ZOUBOULIS Assoc. Professor, Dept. of Chemistry, Div. Of Chem. Technol. Main aspects: Introduction Dangerous substances in water bodies 1 rst list 2 nd list Red list Industrial wastewaters

2. Permissible concentration limits for pollutants “Standards” Maximum permissible concentrations of pollutants based upon the available technology Number of controlling parameters: depended upon the specific use/application of water bodies Water Quality Standards (WQS) Related with: Toxicity Bioaccumulation Chemical speciation Bioavailability (not dissolved) Persistence Example: Cu

3. Dangerous substances in water bodies Directive of E.U. - Aim: to eliminate pollution (1 rst list) to reduce pollution (2 nd list) Dangerous substances are controlled: Most countries - with Limit Values (LV) - in ww (based upon BAT) UK – with Environmental Quality Standards (EQS)-in receiving water body (based upon specific use) Similar to Water Quality Standards (USA) –WQS (based upon toxicological studies)

4. Comparison between LV and EQS for Hg/Cd (μg/l) Hg Cd LV EQS LVEQS Lakes-rivers 50 1 (total) 200 5 (total) Wetlands 50 0,3 (dissolved) 200 2,5 (dissolved) Coastal waters 50 0,3 (dissolved) 200 2,5 (dissolved)

5. Quality concentration limits for toxic metals in water bodies (μg/l) USA Toxic MetalLakes-RiversSeaWatersHumanHealt h CMCCCCCMCCCCW & OO As3601906936144300 Cd3.71.0429.30.0180.14 Cr (III)550180 Cr(VI)1510110050 Cu17112.4 Pb652.52108.1 Hg2.10.0121.80.0250.140.15 Ni1400160748.26104600 Se205.029071 Ag3.41.9 Zn1101009081 CMC: Contaminant Maximum Concentration Level (1h), CCC: Contaminant Continuous Concentration, W&O: swimming, drinking, consuming water organisms, O: consuming water organisms

6. Chemical substances included in the 1rst list E.g. metals: Hg, Cd, organic compounds: aldrin, DDT, CHCl 3, etc. For 109 substances need to be suggested LV or EQS (1995) Problem: which is the lowest concentration limit of these substances De minimis approach: the concentrations of these substances must be as low a possible In Greece, the LV can also be expressed as: a)Total quantity (kg/y) b)G of toxic substance /kg used material or /tn product Example: Lindane Both approaches must be followed: LV-EQS USA: National Pollutant Discharge Elimination System Permits, NPDES Problem: the set concentration limits could be in lower levels than the respective Method Detection Level (MDL) Practical Quantitation Level (PQL)

7. PollutantConcentration limits MDL Aldrin0.00010.004 Chlordane0.00010.01 Cyanide15 DDT0.00060.01 Dieldrin0.00010.002 Heptachlor0.00020.003 Heptachlor epoxide0.00010.08 Hexachloro benzene0.00070.05 Mercury0.030.2 PAHs (total)0.31 PCBs (total)0.00010.5 TCDD0.00000010.002 Toxaphene0.00070.24

8. AreaConcentration Dalmarnock (treated)44.0 8.0 26.2 10.6 Dalmuir (treated)311.0 32.0 41.7 43.4 Shieldhall (treated)28.7 18.5 72.3 39.6 Paisley (treated)20.8 <1.0 <5.0 5.0 Garnock Valley (non treated)50.0 <1.0 <42.2 <31.3 30.9 38.8 50.3 Irvine Valley (non treated)62.7 12.3 <10.0 34.0 16.3 38.7 Lindane concentrations (ng/l) in industrial wastewaters discharges EQS values for Lindane (ng/l) Lakes-Rivers100 Wetlands20 Coastal waters20

9. USA-Total Maximum Daily Load- TMDL Based upon the following parameters: number of polluted water bodies Watershed-geographical area covered Number of TMDL limits Number of different industrial activities monitoring data/ prediction models importance of environmental threat for the specific area Water Quality Based Effluent Limits, WQBEL Can be up to 280 times lower than the LV

10. Chemical (hazardous) substances of 2 nd list Included: several metals (less toxic): Cr, Pb, Zn, Cu, Ni, As pesticides: endosulfan, dichlorvos, attrazine EC Directive: estimation of EQS Methodology from WRc (UK) Literature review Evaluation of laboratory toxicity experiments Estimation of min possible concentration for which there are not expected negative effects in the receiving water bodies Security factor Background levels Other important parameters (hardness, temperature) Publication of EQS Re-evaluation of EQS according to the experience Example: Pb (biomonitoring by trout) Flexibility in limits setting (relative, not absolute limits), Pollution trading

11. Hardness mg/l CaCO 3 Rivers with salmoidsRivers with cyprinids 0-50450 50-15010125 >15020250 Suggested values for inorganic Pb in U.K (mean annual values, μg dissolved Pb/l) Mean concentration values of Pb in Glengonnar river (μg/l) Distance from the point source (km) Pb totalPb dissolvedHardness (mg CaCO 3 /l) 3.31486550 3.861.424.273 927.614.255

12. Chemical toxic substances of Red list: Priority Pollutants Most toxic substances: All of 1 rst list and some of the 2 nd Criteria: Toxicity, Persistence, Bioaccumulation, Production rate, Physicochemical properties Elimination plans (timely) for certain substances Problem: there are not enough data for loading of controlled substances due to flowrate variabilities and to different concentrations In order to reduce the disposal of these toxic substances e.g. in North Sea, the inland disposal of them must be systematically controlled: Application of PP/waster minimization Environmental management techniques Nevertheless, it could be possible that also after the implication of these measures, a visible improvement in North-Sea environment could not be noticed In Greece: another parameter controlling also the sum of all toxix substances in wastewaters (not onlyindividually): Y1/S1 +Y2/S2 + Y3/S3 +……….Yn/Sn < 3

13. Management of industrial wastewaters and its limitations USA: Determination of a) a general frame (EPA) b) Specified regional limits Substan ces All Industries- Maximum concentration (mg/l) Industries with mean daily discharge >20000 m 3 /d Mean daily concentration (mg/l) Industries with mean daily discharge <20000m 3 /d Mean daily concentration (mg/l) As4.01.04.0 Cd0.60.50.6 Cr5.02.755.0 Cu8.0 Pb4.02.04.0 Hg0.20.10.2 Ni5.02.55.0 Ag3.01.03.0 Zn10.05.010.0 CN-3.02.03.0

14. Permitted maximum concentrations of pollutants in wastewaters Pollution parameterConcentration (mg/l) BOD5300 TSS350 pH5-10 Oil250 Fe250 Cu3 Pb0.5 Hg0.0005