EMERGING ORGANIC MOLECULES (EDCs) IN URBAN WATERSHED AND RUNOFF

1. EMERGING ORGANIC MOLECULES (EDCs) IN URBAN WATERSHED AND RUNOFF Dr. A. K. Mittal Department of Civil Engineering Indian Institute of Technology Delhi New Delhi 110016

2. CONTENTS • Introduction • Sources of these compounds • Global and Indian scenario • Delhi: a metro city • Need of study • Scope of the study • Methodology

3. Conventional Water Pollutants Water Pollution COD Carbon Industrial Activities BOD TSS pH Solids TS Heavy Metals Proteins TKN Emerging Organic Compounds Salts EC

4. HC Emerging Organic Compounds PAHs PCBs THMs EDCs Surfactants Pesticides PPCPs/PhACs

5. WHATS ARE THE EDCs? • The chemicals that interfere with the synthesis, transport, and/or action of natural hormones responsible for the reproduction, development, and/or behavior of an organism . • Soya products • Detergents • Pesticides • Plasticizers • Polyaromatic-hydrocarbons • Pharmaceutical residues • Oral contraceptives • Personal care products • Hormone-replacement treatments

6. Selected EDCs Categories Pesticide Residues Include Organochlorine Pesticides Organophosphorous Pesticides Pharmaceutical and Personal Care Products (PPCPs) include NSAIDs Antibiotics Antiepileptic drugs Other Compounds

7. Introduction • Sources of these compounds • Literature review • Global and Indian scenario • Delhi: a metro city • Need of study • Scope of the study • Methodology • Work done

8. Sources of EDCs in Water and Wastewater • Modern Agricultural Practices • Household Pest Control Programme • Personal hygiene • Human urine and excreta • Disposal of discarded medicines Contd.

9. Sources…………………… • Emission from Medical Care Units • Industrial effluents from Pharmaceutical Industry • Leaching and run off from Fish farms • Animal dung and urine • Feed additives for animals

10. Active Ingredients Entry root for Pesticides Pesticide Applied Biodegradation Volatilization Plant Uptake Run Off Leaching Ground Residue Ground Water

11. Ground water Entry root for PhACs/PPCPs House Hold Drugs Veterinary Drugs Hospitals Urine & Dung Sewer Networks Open Drains Sludge STPs Soil Surface Water Drinking Water

12. Introduction • Sources of these compounds • Literature review • Global and Indian scenario • Delhi: a metro city • Need of study • Scope of the study • Methodology • Work done

13. Present Status Presence of Pesticides and Pharmaceutical Residues in different Waterbodies Global and Indian Scenario and Impacts associated Analytical Techniques Used in Detection

14. 0.1-3.8 0.02-1.0 BDL-17 0.12-0.60 <0.1 Pesticides and PPCPs: Global scenario In PPB Pesticide Residues in water • Presence – Around the Global River Water China Zhang et al, 2004 Brazil Rissato et al, 2006 R-Mozaz et al., 2004 Spain Ghana Darco et al, 2008 Pakistan Tariq et al, 2007

15. 1.22-14.3 27-70 5.82 0.03-1.59 0.3-8.5 40-60 • Pesticide Residues in water • Presence – Around the Global In PPB Yang et al, 2007 Yunnan, China Sariyar, Turkey Oezmen et al, 2008 Lakes Tariq et al, 2007 Rawal, Pakistan Punjab, Pakistan Tariq et al, 2007 Ground Water Australia Mitchell et al, 2005 Industrial Waste Water Cyprus Fatta et al, 2007

16. PhACs/PPCPs • Presence – Global (mainly in waste water and wastewater disposing drains) • Main Compounds- NSAIDs and Antibiotics • Concentration ranges from sub pg/L to ug/L. How Detection become possible at such low level with complex matrix? GC-MS LC-MS

17. Presence of Pharmaceutical Residues in different water segments Cont.

18. Cont.

20. Indian scenarioPesticides Residues in Water • Total pesticide consumption is 41350 MT (NCIPM, 2006) • Present in all the major rivers, open wells, sea water, estuaries, lakes and ponds. • Concentration is much higher than the prescribed safe limit of 1PPB. • Ground Water also severely affected in some areas under intensive agriculture practices and the areas under severe water scarcity • 300 times more than safe limit in Ground Water in Rajasthan, where ground water is a major source for drinking water • Yamuna River, pesticide is present all along its length and the concentration varies from PPB level to PPM level.

21. 4 7 30 300 4.7 1-710 0.33 0.44 2.4 10 0.182 0.02 In PPB Kaushik et al, 2007; Sharma et al, 2005; Rajendran and Subramanian, 1997 ; Kumari et al 2006 ; Singh and Gupta, 2002 ; Luo et al, 1997 ; Shukla et al., 2006 ; Jayashree and Vasudevan, 2006; Sankararamakrishnan et al, 2005; Pandit et al, 2006

22. PPCPs/PhACs : No Study Reported ?

23. Introduction • Sources of these compounds • Literature review • Global and Indian scenario • Delhi: a metro city • Need of study • Scope of the study • Methodology • Work done

24. DELHI- Population explosion and Sewage generation POPULATION GROWTH • Delhi, the capital of India, has a population of over 15 million. It has grown by more than 300% since 1971 and expected to increase 23million by 2021 at a growth rate to 26.4%. • Presently about 3364 mld water is distributed by Delhi Jal Board (DJB) in Delhi. • It is estimated that about 3267 mld of wastewater is generated in Delhi including 218 mld from industrial sources

25. Drains out falling in River Yamuna • Part of the wastewater generated is collected through underground sewers and transported to the treatment plants and balance flows into the river Yamuna through 17main drains. 1. NAJAFGARH DRAIN 2. MAGAZINE ROAD DRAIN 3. SWEEPERS COLONY DRAIN 4. KHYBER PASS DRAIN 5. METCALF HOUSE DRAIN 6.MORI GATE DRAIN 7. TONGA STAND DRAIN 8. CIVIL MILL DRAIN 9. DELHI GATEDRAIN 10. SEN N..H.DRAIN 11. DRAIN NO.12A • The total treatment capacity of the 30 STPs was observed as 2330 mld. The actual treatment of sewage during November-December 2004 was found only 1478 mld (about 63% of the treatment capacity) 12. DRAIN NO.14 13. BARAPULA DRAIN 14. MAHARANI BAGH DRAIN 15. KALKAJI DRAIN 16. TUGHLAKABAD DRAIN 17. SHAHDARA OUTFALL DRAIN

26. Environmental Effects of Pesticidal and Pharmaceutical Residues in waterbodies Effect on aquatic ecosystem: • Deteriorate the quality of waterbody, making the water unfit for drinking and other purposes • Decrease in biodiversity of aquatic ecosystem • Affect the life of aquatic flora and fauna, resulting from changes in growth pattern upto death of organisms • Entry of Pesticides Residues in to food-chain

27. Environmental effects……………….cont. • Bioaccumulation and bioconcentration at various trophic levels results high risk to the organism at higher trphic level. • Human beings being at highest trophic level are at highest risk • Affect the central nervous system (CNS) of the living organism • Constant exposure of PPCPs, results in the malfunctioning of endocrine glands • Development of Resistant bacterial species

28. Reported effects of Pesticidal and PPCPs Residues on living beings

29. Reported effects………………………….cont.

30. Other harmful effects on human beings: • Reduction in sperm density • Development of testicular cancer • Cryptorchism • Hypospadias • Breast cancer

31. Introduction • Sources of these compounds • Literature review • Global and Indian scenario • Delhi: a metro city • Need and Scope of work • Methodology • Work done

32. NEED OF THE STUDY To know and Understand the- • Status of emerging molecules, Pesticides and PPCPs in Delhi’s waterbodies • Their concentration in different STPs and CETPs, as these are acting as point source for these emerging molecules • Contribution of the sources from various sectors i.e. Domestic and Industrial Sector • Contamination level of various drains by these emerging molecules • Checking the removal efficiency of the STPs for these new molecules • The total load of these molecules in Delhi’s watershed • Ground water contamination by leaching of these pollutants, if any

33. SPECIFIC SCOPE OF THE WORK • Development of suitable extraction and determination methods of Pesticides and PPCPs from complex matrixes like wastewater, sewage and sludge etc • Understanding hydrologic and geochemical factors affecting EDCs in Delhi Watershed • Removal of these pollutant by sewage treatment plants • Source identification for these pollutants • Development of database for the emerging molecules in Delhi watershed • To ensure the safe drinking water supply from DJBs borewells and drinking water treatment plants, by monitoring the drinking water for these pollutants.

34. Knowledge gaps • No literature is available on status of Pharmaceutical residues in Indian subcontinent. • Delhi stretch of Yamuna is worst polluted, but no information on Phamaceutics in Yamuna despite YAP I being over and YAP II in progress • Being a metro city, Delhi is one of the high drug consumption city of India, so the expected concentration of the Pharmaceutical Residues in the wastewater should be more. • Though SPME is a very recent developed preconcentration technique for organic volatiles, but still there is no report available on SPME from India.

36. Introduction • Sources of these compounds • Literature review • Global and Indian scenario • Delhi: a metro city • Need and Scope of work • Methodology • Work done

37. Selected Sampling Sites

38. THE PARTS OF THE SYSTEM TO BE INVESTIGATED ARE • STPs • CETPs • Wastewater from Medical Care Units • Drains • Yamuna River • Ground Water from Bore wells

39. Approach and Methodology Drains CETPs Yamuna River STPs Sampling TubeWell Filtration Acidification & Preconcentration LLE SPME SPE Analysis by GC, GC/MS, HPLC,LC/MS

40. Preconcentration Techniques • Liquid Liquid Extraction (LLE)- LLE, also known as solvent extraction and partitioning, is a method to separate compounds based on their relative solubilities in two different immiscible liquids i.e. water and an organic solvent. • Solid Phase Extraction (SPE) SPE, is based on the preferential affinity of the desired solutes over solid adsorbents, known as, stationary phase through which the sample is passed. Then the solid adsorbent is desorbed by suitable organic solvents. • Solid Phase Micro Extraction (SPME) SPME, is a solvent free sample preparation technique in which the compound of interest is adsorbed over polymeric fibers (PDMS, DVB, PEG etc) and the same is desorbed directly in the inlet of the instrument.

41. LLE 500 mL Water Sample Preconcentration 15 % DEE in n- Hexane N- Hexane DCM DEE Analysed by GC-ECD and GCMS Most Suitable solvent is 15% DEE in n-Hexane

42. SPE Pressure Reading SPE Manifold Vacuum Pump Waste Collection Flask Laboratory prepared sample of Acetaminophen and Ibuprofen were prepared and loaded in the SPE cartridge @ 10 mL per minute. The cartridge were washed with 0.1N HCl and 5% MeOH. After washing, the compounds were eluted with MeOH/MTBE/NH4OH (20:75:5), as per standard method for NSAIDs. Dried the extract over Na2SO4, and analysed the sample by GC-MS. The field sample (500 mL) was preconcentrated through 1cc and 6cc Oasis HLB SPE cartridge and analysis is under progress.

43. SPME The literature reported that the PDMS fiber is most suitable for the discussed pharmaceutical compounds. The SPME manual holder with PDMS fibers of 7 μm and 100 μm thickness procured from Sigma-Aldrich, USA.

44. Course Work The following courses have been completed: Advanced wastewater treatment (CEL796) 3 credits Environmental Impact Assessment (CEP797) 3 credits

45. Sampling • Samples were collected from Palla Wellfield area, three times in 2007-2008. This area covers 85 sampling points, representing each tubewell of the wellfield. • Samples of Nijamudeen site were collected in January 2008. • Wastewater sample from Vasantkunj STP was collected in May 2008.

46. Field Work • Selection of Field Sites • Drilling, Levelling • Sampling (GW and SW) Will be carried out with Battery operated pumps

47. Thanks Suggestions Please

48. Findings till date- Pesticide residue estimation in the Palla Wellfield area and the Results of April 2008 sampling campaign are • Conclusions • TW 180 and TW 24/60 are severely contaminated with Pesticides, more sampling campaigns are required to know the actual situation. • The Ranney Well (RW) yields poor quality water than TW as high negative pressure generated during pumping promotes transfer of more pollutants