EMERGING ORGANIC MOLECULES (EDCs) IN URBAN WATERSHED AND RUNOFF

Department of Civil Engineering Indian Institute of Technology Delhi

New Delhi 110016  

Dr. A. K. Mittal

CONTENTS– Introduction

– Sources of these compounds

– Global and Indian scenario

– Delhi: a metro city

– Need of study

– Scope of the study

– Methodology

Conventional Water Pollutants

COD

BOD

TSS

TS

TKN

pH

EC

Carbon

Solids

Proteins

Salts

Industrial Activities

Heavy Metals

Emerging Organic

Compounds

Water Pollution

Emerging Organic

Compounds

HC

PAHs

PCBs

THMs

Surfactants

Pesticides

PPCPs/PhACs

EDCs

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

Selected EDCs Categories

• Pesticide Residues Include

• Organochlorine Pesticides• Organophosphorous

Pesticides

• Pharmaceutical and Personal Care Products (PPCPs)

include

• NSAIDs• Antibiotics• Antiepileptic drugs• Other Compounds

– 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

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.

• 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

Sources……………………

Entry root for Pesticides

Ground Residue

Active Ingredients

Biodegradation

Plant Uptake

Pesticide Applied

Leaching

Volatilization

Run Off

Ground Water

House Hold Drugs

Sewer Networks

STPs

Surface Water Ground water

Drinking Water

Open Drains

Hospitals Veterinary Drugs

Urine & Dung

SoilSludge

Entry root for PhACs/PPCPs

– 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

Present Status

Presence of Pesticides and Pharmaceutical Residues in different

Waterbodies Global and Indian Scenario and

Impacts associated

Analytical Techniques Used in

Detection

Pesticides and PPCPs: Global scenarioPesticide Residues in water• Presence – Around the Global

River Water China 0.1-3.8 Zhang et al, 2004

In PPB

Brazil 0.02-1.0 Rissato et al, 2006

Spain <0.1

0.12-0.60

BDL-17

R-Mozaz et al., 2004

Darco et al, 2008

Tariq et al, 2007

Ghana

Pakistan

Lakes

1.22-14.3 Yang et al, 2007Yunnan, China

27-70 Oezmen et al, 2008Sariyar, Turkey

5.82 Tariq et al, 2007Rawal, Pakistan

40-60Punjab, Pakistan

0.3-8.5 Mitchell et al, 2005Australia

0.03-1.59 Fatta et al, 2007Cyprus

Ground Water

Tariq et al, 2007

Industrial Waste Water

In PPBPesticide Residues in water• Presence – Around the Global

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

Presence of Pharmaceutical Residues in different water segments

Sr No

Type Compound Reference & Country Reported

1. Drinking Water

Diclofenac Wasik et al, 2006 (Poland)

Ibuprofen Araujo et al, 2008 (Venezuela)

Naproxen

2. Surface Waters

Diclofenac Heberer 2002 (Germany)

Ibuprofen

Diazepam Terens, 2001 (Germany)

Caffeine

Estrol Kolpin et al, 2002 (USA)

Clofibric acid Wasik et al, 2006 (Poland)

Naproxen Rederson et al, 2002 (Germany)

Cont.

3. Sewage effluents Diazepam Suchara et al, 2008 (Brazil)

Diclofenac

4. Biosolids Estrone Ternes et al, 2001 (Germany)

17B-estradiol

5. Sea Water Diclofenac

6. Waste Water Acetylsalicylic acid Ternes et al, 2001 (Germany)

Diazepam

Chloramphenicol

Cont.

Sr No Type Compound Reference

6. Wastewater Diclofenac Stackelberg et al, 2007 (USA)

Ibuprofen

17B-estradiol Jurgensen and Surensen, 2000 (Germany)17A-estradiol

Estrol

Caffeine Gomez et al, 2007 (Spain)

Carbamazepine

Acetaminophen

Nonylphenol Kolpin et al, 2002 (Germany)

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.

300

0.44

0.182

30

0.33

7

2.4

0.02

10

4.7 1-710

4

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

In PPB

PPCPs/PhACs : No Study Reported

?

– 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

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

26.640.7

62.2

94.2

137.8

182.0

230.0

0

50

100

150

200

250

Popu

latio

n (in

Lac

s)

1Year

Decadal Growth of Population in Delhi

Population (in lacs)

1961 1971 1981 1991 2001 2011 2021

Drains out falling in River Yamuna

1. NAJAFGARH DRAIN 2. MAGAZINE ROAD DRAIN

3. SWEEPERS COLONY DRAIN4. KHYBER PASS DRAIN5. METCALF HOUSE DRAIN6.MORI GATE DRAIN

7. TONGA STAND DRAIN8. CIVIL MILL DRAIN

9. DELHI GATE DRAIN

11. DRAIN NO.12A12. DRAIN NO.14

10. SEN N..H.DRAIN

13. BARAPULA DRAIN14. MAHARANI BAGH DRAIN

16. TUGHLAKABAD DRAIN15. KALKAJI DRAIN

17. SHAHDARA OUTFALL DRAIN

• 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.

• 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)

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

• 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

Environmental effects……………….cont.

Reported effects of Pesticidal and PPCPs Residues on living beings

Sr. No. Compound Effects Reference

1. Pesticides mainly Herbicides

Birth defects in children Gerry, 2002

2. EDC mainly DDE Premature labor Wood et al, 2007

3. Pesticide Residue Reproductive dysfunction in vertebrates

Singh et al 2008

4. Diclofenac Deaths in Vultures Oak et al, 2004

Histopathological alterations in Rainbow trout

Schwaiger et al, 2004

Reported effects………………………….cont.

5. Antibiotics Development of various resistant bacteria

Kummerer, 2004

Death and decline in reproduction in standard test organisms like Vibrio fischeri, Daphnia magna, Moina macrocopa, and O. latipes

Park and Choi, 2008

6. Antiepileptic drug- Carbamazepine

Death of aquatic invertebrates

Oetken et al, 2005

7. NSAIDs (14 Drugs) Death of Xenopus laevis larvae

Richards and. Cole, 2006

Other harmful effects on human beings:

• Reduction in sperm density• Development of testicular cancer• Cryptorchism• Hypospadias• Breast cancer

– Introduction

– Sources of these compounds

– Literature review

– Global and Indian scenario

– Delhi: a metro city

– Need and Scope of work

– Methodology

– Work done

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

• 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.

SPECIFIC SCOPE OF THE WORK

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.

Targeted Compounds in water samples

Pesticides PPCPs

OCPs a-BHC NSAIDs Diclofenac

b-BHC Ibuprofen

g-BHC Hydroxyibuprofen

d-BHC Carboxyibuprofen

Heptachlor Acetylsalicylic acid

Aldrin Salicylic acid

Heptachlor epoxide Naproxen

Endosulphan-1-Acetaminophen/Paracetamol

p-p-DDE Antibiotics Ciprofloxacin

Endrin Chloramphenicol

Endosulphan-2- Erythromycines

p-p-DDD Norfluoxetine

Endrin sulphate Sulphomethoxazole

Endo sulphate Ampicilline

p-p-DDT Penicilline

Methoxychlore TOC & Others Caffeine

OPs Malathion Clofibric Acid

Chlorpyriphos Carbamazepine

– Introduction

– Sources of these compounds

– Literature review

– Global and Indian scenario

– Delhi: a metro city

– Need and Scope of work

– Methodology

– Work done

Selected Sampling Sites

THE PARTS OF THE SYSTEM TO BE INVESTIGATED ARE

• STPs • CETPs• Wastewater from Medical

Care Units• Drains • Yamuna River• Ground Water from Bore wells

STPs

CETPs Drains Yamuna River

TubeWellSampling

Filtration

Acidification & Preconcentration

LLE SPE SPME

Analysis by

GC, GC/MS, HPLC,LC/MS

Approach and Methodology

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.

LLE500 mL Water

Sample

Preconcentration

N- HexaneDCM

15 % DEE in n- HexaneDEE

Analysed by GC-ECD and GCMS

Most Suitable solvent is 15% DEE in n-Hexane

SPE

SPE Manifold

Pressure Reading

Waste Collection Flask

Vacuum Pump

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.

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.

Course Work

The following courses have been completed:

Advanced wastewater treatment (CEL796) 3 credits

Environmental Impact Assessment (CEP797) 3 credits

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.

• Selection of Field Sites

• Drilling, Levelling

• Sampling (GW and SW)

Field Work

Will be carried out with Battery operated pumps

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