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Presentation On
Seminar
Entitled
“ENDOCRINE DISRUPTING CHEMICALS”
Master of Technology (Environmental Engineering)
SUBMITTED BY Tulsi Makwana (P17EN011)
Guide: Dr. M. Mansoor Ahammed
Associate Professor (CED)
CIVIL ENGINEERING DEPARTMENT
S. V. NATIONAL INSTITUTE OF TECHNOLOGY
SURAT – 395007, GUJARAT (INDIA) YEAR 2017-2018
Introduction
 Endocrine system is a system which includes variety of glands, producing hormones
which regulates the growth, development, reproduction, and behaviour.
 Chemicals with the potential to elicit negative effects on the endocrine system of
humans and wildlife are termed as Endocrine Disrupting Chemicals (EDC).
 An exogenous agent that interferes with the synthesis, secretion, transport, binding,
action, or elimination of natural hormones in the body that are responsible for the
maintenance of homeostasis, reproduction, development, and/or behaviour. (USEPA)
2
Classification
 Natural and synthetic estrogen or steroids. - Estradiol, testosterone, ethynylestradiol, etc.
 Pharmaceuticals. - Acetaminophen, diclofenac(pain-killer), etc.
 Personal care products (PPCPS) - Caffeine, oxybenzone (sunscreen), etc.
 Industrial chemicals. - Bisphenol A, Phthalate, Nonylphenol, etc.
 Pesticides. - Atrazine, DDT, etc.
 Combustion by-products. - Dioxin, etc.
3
4
Exposure
 Major exposure pathways for humans to many EDCs are through inhalation of air and
particles, consumption of contaminated food and drinking water, and through direct
dermal contact.
 Human exposure to these chemicals in the environment is a critical concern with
unknown long-term impacts.
 Consumer goods are another potential source of exposure to endocrine disruptors.
 The toxic effects of EDCs have resulted in the restriction of their use in countries
where evidence of extensive exposure is ample.
5
Effects
 Any system in the body controlled by hormones can be derailed by hormone
disruptors.
 EDCs have been attributed as a cause of following problems:
• Deformations of the body (including limbs).
• Breast cancer.
• Prostate cancer.
• Thyroid and other cancers.
• Reproductive disturbance.
• Cognitive and brain development problems
• Development of learning disabilities.
6
Analysis
 EDCs at trace concentration levels and with extremely diverse groups, make the
detection and analysis procedures quite challenging.
 Currently, the most prevailing methodological approach designed to analyse EDCs
incorporates a mass-based analysis process.
 Mass-based methods employing mass spectrometry (MS) show relatively low
detection limits as compared to other methods.
 Various combinations of instruments and detectors can be applied to obtain improved
analytical results, such as GC/MS, HPLC/MS, LC/UV, and GC/tandam mass
spectrometer, etc.
7
Extraction methods
Solid phase extraction Solid phase micro-extraction Liquid phase micro-extraction
(SPE) (SPME) (LPME)
8
Ultra-high-Performance Liquid Chromatography-Tandem
Mass spectrometry
9
Treatment
 Activated carbon.
 Sub-micron sized resin particles.
 Ozonation and Advanced oxidation process.
 Membrane fouling during UF process.
 Hybrid constructed wetland.
 Photodegradation.
10
Activated carbon
 AC’s ability to adsorb a large number of chemical substances and to be
regenerated has made the process one of the most effective and
economically feasible processes.
 Applied mainly in two forms; a powdered (PAC) and a granular one
(GAC) in packed bed filters.
 Various carbons with different base materials such as coal, coconut, and
wood can be used.
 GAC adsorption was effective in removal of EDCs with high Kow value.
11
Activated carbon
 GAC adsorption was effective in removing EDCs at the empty bed contact time
(EBCT) of 15 min.
 Nonylphenol and BPA were effectively adsorbed onto all carbons.
 Since the microbes residing at the used carbons already accustomed to amitrol, the
used carbons removed amitrol better than the virgin carbon.
 BPA removal 40% for coconut based carbon, Nonylphenol removal 76% for coal
based carbon.
 Not recommended for Amitrol as 9-87% passed through GAC column.
12
Ozonation and Advanced Oxidation Process.
 This is a group of chemical-oxidative processes called advanced oxidation processes
(AOP), characterized by the generation of hydroxyl ions.
 The hydroxyl radical is a strong oxidant.
H2O2 + hν → 2 HO•
Fe3+ + H2O → Fe2+ + H+ + HO•
 Ozonation is the dark oxidation method most used in the removal of new emergent
pollutants.
 Removals higher than 90% can be achieved for several compounds, such as,
pesticides, anti-inflammatories, antiepileptics, antibiotics and natural and synthetic
estrogens by using ozone dose from 0.1 – 30 mg/L.
13
Ozonation and Advanced Oxidation Process.
 UV/H2O2 and titanium dioxide photocatalysis are the light oxidation processes most
used to destroy EDCs and PPCPs.
 Removals higher than 98% were obtained by using TiO2 photocatalysis, estrogens
(17β-estradiol, estrone and 17α- ethinylestradiol), bisphenols and antiepileptics.
 In order to achieve high removals, large irradiation times were required compared with
dark ozonation processes.
 The range of H2O2 concentrations used went from 0.1 to 1 mol/L.
14
Membrane fouling during UF process.
 EDC elimination by fouled membrane was better than
clean membrane.
 Clean membrane had only 5%–34% removal rate of
EDCs, while fouled membrane had 10%–76% removal
rate of EDCs.
 Cake layers formed under different pressures had
different abilities on retaining different EDCs.
 With increase in pressure, fouling potential of feed
dropped. However, cake resistance and average specific
resistance both increased with pressure rising.
15
Hybrid Constructed Wetland
Schematic diagram of hybrid constructed wetland (Singapore)
16
Hybrid Constructed Wetland
 The overall removal of EDCs in the hybrid CW system were greater than 77.2%.
 Several compounds, such as BPA (bisphenol A), CA (clofibric acid), and SMZ
(Sulfamethazine), exhibited excellent removal efficiencies (>99.9%).
 The open-air aerobic lagoons were found to be effective in the elimination of most
EDCs.
 The reed beds also allowed for the effective removal of the majority of PPCPs and
EDCs, especially ACT (Acetaminophen), GFZ (Gemfibrozil), DEET (N, N-diethyl-m-
toluamide), CF (Caffeine), DCF (diclofenac), and CA.
17
Sub-micron sized resin
 For SMR, the mechanism for adsorption is non-
specific.
 The high removal efficiency is also related to the SMR
concentration used.
 Lower efficiencies are due to lower contact time.
 For 2–14 ppb of 17-β estradiol (E2), 17-α
ethinylestradiol (EE2), estrone (E1) and bisphenol A
(BPA), the maximum percent removals achieved were
98%, 80%, and 87%, respectively.
Removal of E2, EE2, and BPA with SMR
18
Photodegradation (Sunlight)
 Solar irradiation for removing EDCs from water and
wastewater is an environmentally friendly.
 No degradation of E1 and E2 occurs in the absence of
either light or catalyst (TiO2), demonstrating the
importance of the joint actions of the two.
 50% of E1 and 55% of E2 degraded after 75 h of
solar irradiation.
 The degradation rate is not dependent on the initial
chemical concentration.
Degradation of E1 and E2 over time by
solar irradiation in the presence of TiO2
19
Photodegradation (UV light)
Compound Removal (%)
4-tert-Octylphenol 90
4-Nonylphenol 83
Bisphenol A 93
Estrone 60
17β Estradiol 83
17a-Ethynylestradiol NA
16a-Hydroxyestrone 81
Levels of selected EDCs in different sites from Horsham STP
(Site 1: influent; site 2: post sedimentation tank;
site 3: post biological filters; site 4: final effluent.)
20
Photodegradation (UV light)
 In the absence of TiO2 or UV light, the changes in
the concentrations of both E1 (Estrone) and E2
(Estradiol) were negligible.
 98% of the initial E1 was decomposed under UV
light within 16 min.
 Overall, Bisphenol A showed the highest removal
efficiency (90–96%).
 UV photodegradation is far more efficient than
solar irradiation.
21
Summary
 Endocrine disruptors are chemicals that can interfere with endocrine (or hormone)
systems at certain doses.
 As their concentrations are very less in terms of ‘ng/L’ or ‘μg/L’, they need to be
determined by very sensitive measuring systems such as LC-MS.
 Various treatment methods Advanced Oxidation Process, Activated carbon method,
Ozonation, Sub micron-sized resins, photodegradation, membrane, ultrafiltration,
constructed wetlands, etc. gave high removal efficiencies for specific compounds.
22
References
 Changa, Hyun-Shik, Chooa, Kwang-Ho, Leeb, Byungwhan, Choia, Sang-June, 2009, The methods of
identification, analysis, and removal of endocrine disrupting compounds (EDCs) in water, Journal of Hazardous
Materials 172 (2009) 1–12.
 Choi, Keun J., Kim, Sang G., Kim, Chang W., Kim, Seung H., 2005, Effects of activated carbon types and
service life on removal of endocrine disrupting chemicals: amitrol, nonylphenol, and bisphenol-A, Chemosphere
58 (2005) 1535–1545.
 Esplugas, Santiago, Bila, Daniele M., 2007, Ozonation and advanced oxidation technologies to remove EDCs
and PPCPs in water effluents, Journal of Hazardous Materials 149 (2007) 631–642.
 Esteve, C., Herrero, L., Gómara, B., Quintanilla-López, J. E., 2016, Fast and simultaneous determination of
endocrine disrupting compounds by ultra-high-performance liquid chromatography tandem mass spectrometry,
Talanta 146(2016)326–334.
 Hu, Zunfang, Si, Xiurong, Zhang, Zheyun, Wen, Xianghua, 2014, Enhanced EDCs removal by membrane
fouling during the UF process, Desalination 336 (2014) 18–23.
 Katsigiannis, A., Noutsopoulos, C., Mantziaras, J., Gioldasi, M., 2015, Removal of emerging pollutants through
Granular Activated Carbon, Chemical Engineering Journal 280 (2015) 49–57.
23
References
 Murray, Audrey, Edward, Banu Örmeci1, Lai, P. C., Use of sub-micron sized resin particles for removal of
endocrine disrupting compounds and pharmaceuticals from water and wastewater, journal of environmental
science 51 (2017) 256–264.
 Sawyer, C. N., McCarty, P. L., and Parkin, G. F., Chemistry for Environmental Engineering and Science (Fifth
edition), Mc Graw Hill education.
 Stavros, S., Androutsopoulosb, Vasilis P, Tsatsakisc, Aristeidis M., Spandidos, Demetrios A., (2017), Human
exposure to endocrine disrupting chemicals: effects on male and female reproductive systems, Environmental
Toxicology and Pharmacology 51 (2017) 56–70.
 Yi, Xinzhu, Tran, Ngoc Han, Yin, T., He, Y., 2017, Removal of selected PPCPs, EDCs, and antibiotic resistance
genes in landfill leachate by a full-scale constructed wetlands system, Water research.
 Zhou, John L., Zhang, Y., 2008, Occurrence and removal of endocrine disrupting chemicals in wastewater,
Chemosphere 73 (2008) 848–853.
24
“
”
If You Change Nothing,
Nothing Will Change…
THANK YOU
25

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Endocrine Disrupting Chemicals

  • 1. Presentation On Seminar Entitled “ENDOCRINE DISRUPTING CHEMICALS” Master of Technology (Environmental Engineering) SUBMITTED BY Tulsi Makwana (P17EN011) Guide: Dr. M. Mansoor Ahammed Associate Professor (CED) CIVIL ENGINEERING DEPARTMENT S. V. NATIONAL INSTITUTE OF TECHNOLOGY SURAT – 395007, GUJARAT (INDIA) YEAR 2017-2018
  • 2. Introduction  Endocrine system is a system which includes variety of glands, producing hormones which regulates the growth, development, reproduction, and behaviour.  Chemicals with the potential to elicit negative effects on the endocrine system of humans and wildlife are termed as Endocrine Disrupting Chemicals (EDC).  An exogenous agent that interferes with the synthesis, secretion, transport, binding, action, or elimination of natural hormones in the body that are responsible for the maintenance of homeostasis, reproduction, development, and/or behaviour. (USEPA) 2
  • 3. Classification  Natural and synthetic estrogen or steroids. - Estradiol, testosterone, ethynylestradiol, etc.  Pharmaceuticals. - Acetaminophen, diclofenac(pain-killer), etc.  Personal care products (PPCPS) - Caffeine, oxybenzone (sunscreen), etc.  Industrial chemicals. - Bisphenol A, Phthalate, Nonylphenol, etc.  Pesticides. - Atrazine, DDT, etc.  Combustion by-products. - Dioxin, etc. 3
  • 4. 4
  • 5. Exposure  Major exposure pathways for humans to many EDCs are through inhalation of air and particles, consumption of contaminated food and drinking water, and through direct dermal contact.  Human exposure to these chemicals in the environment is a critical concern with unknown long-term impacts.  Consumer goods are another potential source of exposure to endocrine disruptors.  The toxic effects of EDCs have resulted in the restriction of their use in countries where evidence of extensive exposure is ample. 5
  • 6. Effects  Any system in the body controlled by hormones can be derailed by hormone disruptors.  EDCs have been attributed as a cause of following problems: • Deformations of the body (including limbs). • Breast cancer. • Prostate cancer. • Thyroid and other cancers. • Reproductive disturbance. • Cognitive and brain development problems • Development of learning disabilities. 6
  • 7. Analysis  EDCs at trace concentration levels and with extremely diverse groups, make the detection and analysis procedures quite challenging.  Currently, the most prevailing methodological approach designed to analyse EDCs incorporates a mass-based analysis process.  Mass-based methods employing mass spectrometry (MS) show relatively low detection limits as compared to other methods.  Various combinations of instruments and detectors can be applied to obtain improved analytical results, such as GC/MS, HPLC/MS, LC/UV, and GC/tandam mass spectrometer, etc. 7
  • 8. Extraction methods Solid phase extraction Solid phase micro-extraction Liquid phase micro-extraction (SPE) (SPME) (LPME) 8
  • 10. Treatment  Activated carbon.  Sub-micron sized resin particles.  Ozonation and Advanced oxidation process.  Membrane fouling during UF process.  Hybrid constructed wetland.  Photodegradation. 10
  • 11. Activated carbon  AC’s ability to adsorb a large number of chemical substances and to be regenerated has made the process one of the most effective and economically feasible processes.  Applied mainly in two forms; a powdered (PAC) and a granular one (GAC) in packed bed filters.  Various carbons with different base materials such as coal, coconut, and wood can be used.  GAC adsorption was effective in removal of EDCs with high Kow value. 11
  • 12. Activated carbon  GAC adsorption was effective in removing EDCs at the empty bed contact time (EBCT) of 15 min.  Nonylphenol and BPA were effectively adsorbed onto all carbons.  Since the microbes residing at the used carbons already accustomed to amitrol, the used carbons removed amitrol better than the virgin carbon.  BPA removal 40% for coconut based carbon, Nonylphenol removal 76% for coal based carbon.  Not recommended for Amitrol as 9-87% passed through GAC column. 12
  • 13. Ozonation and Advanced Oxidation Process.  This is a group of chemical-oxidative processes called advanced oxidation processes (AOP), characterized by the generation of hydroxyl ions.  The hydroxyl radical is a strong oxidant. H2O2 + hν → 2 HO• Fe3+ + H2O → Fe2+ + H+ + HO•  Ozonation is the dark oxidation method most used in the removal of new emergent pollutants.  Removals higher than 90% can be achieved for several compounds, such as, pesticides, anti-inflammatories, antiepileptics, antibiotics and natural and synthetic estrogens by using ozone dose from 0.1 – 30 mg/L. 13
  • 14. Ozonation and Advanced Oxidation Process.  UV/H2O2 and titanium dioxide photocatalysis are the light oxidation processes most used to destroy EDCs and PPCPs.  Removals higher than 98% were obtained by using TiO2 photocatalysis, estrogens (17β-estradiol, estrone and 17α- ethinylestradiol), bisphenols and antiepileptics.  In order to achieve high removals, large irradiation times were required compared with dark ozonation processes.  The range of H2O2 concentrations used went from 0.1 to 1 mol/L. 14
  • 15. Membrane fouling during UF process.  EDC elimination by fouled membrane was better than clean membrane.  Clean membrane had only 5%–34% removal rate of EDCs, while fouled membrane had 10%–76% removal rate of EDCs.  Cake layers formed under different pressures had different abilities on retaining different EDCs.  With increase in pressure, fouling potential of feed dropped. However, cake resistance and average specific resistance both increased with pressure rising. 15
  • 16. Hybrid Constructed Wetland Schematic diagram of hybrid constructed wetland (Singapore) 16
  • 17. Hybrid Constructed Wetland  The overall removal of EDCs in the hybrid CW system were greater than 77.2%.  Several compounds, such as BPA (bisphenol A), CA (clofibric acid), and SMZ (Sulfamethazine), exhibited excellent removal efficiencies (>99.9%).  The open-air aerobic lagoons were found to be effective in the elimination of most EDCs.  The reed beds also allowed for the effective removal of the majority of PPCPs and EDCs, especially ACT (Acetaminophen), GFZ (Gemfibrozil), DEET (N, N-diethyl-m- toluamide), CF (Caffeine), DCF (diclofenac), and CA. 17
  • 18. Sub-micron sized resin  For SMR, the mechanism for adsorption is non- specific.  The high removal efficiency is also related to the SMR concentration used.  Lower efficiencies are due to lower contact time.  For 2–14 ppb of 17-β estradiol (E2), 17-α ethinylestradiol (EE2), estrone (E1) and bisphenol A (BPA), the maximum percent removals achieved were 98%, 80%, and 87%, respectively. Removal of E2, EE2, and BPA with SMR 18
  • 19. Photodegradation (Sunlight)  Solar irradiation for removing EDCs from water and wastewater is an environmentally friendly.  No degradation of E1 and E2 occurs in the absence of either light or catalyst (TiO2), demonstrating the importance of the joint actions of the two.  50% of E1 and 55% of E2 degraded after 75 h of solar irradiation.  The degradation rate is not dependent on the initial chemical concentration. Degradation of E1 and E2 over time by solar irradiation in the presence of TiO2 19
  • 20. Photodegradation (UV light) Compound Removal (%) 4-tert-Octylphenol 90 4-Nonylphenol 83 Bisphenol A 93 Estrone 60 17β Estradiol 83 17a-Ethynylestradiol NA 16a-Hydroxyestrone 81 Levels of selected EDCs in different sites from Horsham STP (Site 1: influent; site 2: post sedimentation tank; site 3: post biological filters; site 4: final effluent.) 20
  • 21. Photodegradation (UV light)  In the absence of TiO2 or UV light, the changes in the concentrations of both E1 (Estrone) and E2 (Estradiol) were negligible.  98% of the initial E1 was decomposed under UV light within 16 min.  Overall, Bisphenol A showed the highest removal efficiency (90–96%).  UV photodegradation is far more efficient than solar irradiation. 21
  • 22. Summary  Endocrine disruptors are chemicals that can interfere with endocrine (or hormone) systems at certain doses.  As their concentrations are very less in terms of ‘ng/L’ or ‘μg/L’, they need to be determined by very sensitive measuring systems such as LC-MS.  Various treatment methods Advanced Oxidation Process, Activated carbon method, Ozonation, Sub micron-sized resins, photodegradation, membrane, ultrafiltration, constructed wetlands, etc. gave high removal efficiencies for specific compounds. 22
  • 23. References  Changa, Hyun-Shik, Chooa, Kwang-Ho, Leeb, Byungwhan, Choia, Sang-June, 2009, The methods of identification, analysis, and removal of endocrine disrupting compounds (EDCs) in water, Journal of Hazardous Materials 172 (2009) 1–12.  Choi, Keun J., Kim, Sang G., Kim, Chang W., Kim, Seung H., 2005, Effects of activated carbon types and service life on removal of endocrine disrupting chemicals: amitrol, nonylphenol, and bisphenol-A, Chemosphere 58 (2005) 1535–1545.  Esplugas, Santiago, Bila, Daniele M., 2007, Ozonation and advanced oxidation technologies to remove EDCs and PPCPs in water effluents, Journal of Hazardous Materials 149 (2007) 631–642.  Esteve, C., Herrero, L., Gómara, B., Quintanilla-López, J. E., 2016, Fast and simultaneous determination of endocrine disrupting compounds by ultra-high-performance liquid chromatography tandem mass spectrometry, Talanta 146(2016)326–334.  Hu, Zunfang, Si, Xiurong, Zhang, Zheyun, Wen, Xianghua, 2014, Enhanced EDCs removal by membrane fouling during the UF process, Desalination 336 (2014) 18–23.  Katsigiannis, A., Noutsopoulos, C., Mantziaras, J., Gioldasi, M., 2015, Removal of emerging pollutants through Granular Activated Carbon, Chemical Engineering Journal 280 (2015) 49–57. 23
  • 24. References  Murray, Audrey, Edward, Banu Örmeci1, Lai, P. C., Use of sub-micron sized resin particles for removal of endocrine disrupting compounds and pharmaceuticals from water and wastewater, journal of environmental science 51 (2017) 256–264.  Sawyer, C. N., McCarty, P. L., and Parkin, G. F., Chemistry for Environmental Engineering and Science (Fifth edition), Mc Graw Hill education.  Stavros, S., Androutsopoulosb, Vasilis P, Tsatsakisc, Aristeidis M., Spandidos, Demetrios A., (2017), Human exposure to endocrine disrupting chemicals: effects on male and female reproductive systems, Environmental Toxicology and Pharmacology 51 (2017) 56–70.  Yi, Xinzhu, Tran, Ngoc Han, Yin, T., He, Y., 2017, Removal of selected PPCPs, EDCs, and antibiotic resistance genes in landfill leachate by a full-scale constructed wetlands system, Water research.  Zhou, John L., Zhang, Y., 2008, Occurrence and removal of endocrine disrupting chemicals in wastewater, Chemosphere 73 (2008) 848–853. 24
  • 25. “ ” If You Change Nothing, Nothing Will Change… THANK YOU 25