EMERGING ORGANIC MOLECULES (EDCs) IN URBAN WATERSHED AND RUNOFF
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Transcript of EMERGING ORGANIC MOLECULES (EDCs) IN URBAN WATERSHED AND RUNOFF
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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
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CONTENTS– Introduction
– Sources of these compounds
– Global and Indian scenario
– Delhi: a metro city
– Need of study
– Scope of the study
– Methodology
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Conventional Water Pollutants
COD
BOD
TSS
TS
TKN
pH
EC
Carbon
Solids
Proteins
Salts
Industrial Activities
Heavy Metals
Emerging Organic
Compounds
Water Pollution
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Emerging Organic
Compounds
HC
PAHs
PCBs
THMs
Surfactants
Pesticides
PPCPs/PhACs
EDCs
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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
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Selected EDCs Categories
• Pesticide Residues Include
• Organochlorine Pesticides• Organophosphorous
Pesticides
• Pharmaceutical and Personal Care Products (PPCPs)
include
• NSAIDs• Antibiotics• Antiepileptic drugs• Other Compounds
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– 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
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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.
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• 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……………………
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Entry root for Pesticides
Ground Residue
Active Ingredients
Biodegradation
Plant Uptake
Pesticide Applied
Leaching
Volatilization
Run Off
Ground Water
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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
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– 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
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Present Status
Presence of Pesticides and Pharmaceutical Residues in different
Waterbodies Global and Indian Scenario and
Impacts associated
Analytical Techniques Used in
Detection
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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
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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
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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
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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.
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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.
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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)
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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.
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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
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PPCPs/PhACs : No Study Reported
?
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– 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
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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
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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)
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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
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• 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.
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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
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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
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Other harmful effects on human beings:
• Reduction in sperm density• Development of testicular cancer• Cryptorchism• Hypospadias• Breast cancer
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– Introduction
– Sources of these compounds
– Literature review
– Global and Indian scenario
– Delhi: a metro city
– Need and Scope of work
– Methodology
– Work done
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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
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• 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
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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.
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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
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– Introduction
– Sources of these compounds
– Literature review
– Global and Indian scenario
– Delhi: a metro city
– Need and Scope of work
– Methodology
– Work done
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Selected Sampling Sites
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THE PARTS OF THE SYSTEM TO BE INVESTIGATED ARE
• STPs • CETPs• Wastewater from Medical
Care Units• Drains • Yamuna River• Ground Water from Bore wells
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STPs
CETPs Drains Yamuna River
TubeWellSampling
Filtration
Acidification & Preconcentration
LLE SPE SPME
Analysis by
GC, GC/MS, HPLC,LC/MS
Approach and Methodology
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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.
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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
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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.
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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.
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Course Work
The following courses have been completed:
Advanced wastewater treatment (CEL796) 3 credits
Environmental Impact Assessment (CEP797) 3 credits
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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.
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• Selection of Field Sites
• Drilling, Levelling
• Sampling (GW and SW)
Field Work
Will be carried out with Battery operated pumps
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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