ENDOCRINE DISRUPTORS DOKUZ EYLUL UNIVERSITY DEPARTMENT OF ENVIRONMENTAL ENGINEERING PROF.DR. ILGI KAPDAN

QUESTIONS What are they? What are their adverse affects? What are their sources? How can they be treated?

What are Endocrine Disruptors? Endocrine disruptors are man-made synthetic chemicals and natural phytoestrogens (naturally occurring plant- or fungal metabolite-derived estrogen) that act on the endocrine systems of humans and animals by mimicking, blocking and/or interfering in some manner with the natural instructions of hormones to cells. 

Classification of EDCs: Natural Hormones Estrogenic: natural hormones that block or mimick the activity of the hormones in the body Androgenic: Testesteron hormones Thyrodial: That act on thydrodial gland Phytoestrogen: hormones from plants

Classification of EDCs: Chemicals Persistent Organohalogens: Dioxins and furans, PBBs, PCBs, Hexachlorobenzene, Octachlorostyrene, Pentachlorophenol Pesticides: 2,4,5-T, 2,4-D, alachlor, aldicarb, d-trans allethrin, amitrole, atrazine, benomyl, beta-HCH, carbaryl, chlordane, chlozolinate, - cyhalothrin,cis-nonachlor, cypermethrin, DBCP, DDT, DDT metabolites, dicofol, dieldrin, endosulfan, esfenvalerate, ethylparathion, fenvalerate, h-epoxide,heptachlor, iprodione, kelthane, kepone, ketoconazole, lindane, linurone, malathion, mancozeb, maneb, methomyl, methoxychlor, metiram, metribuzin, mirex, nitrofen, oxychlordane, permethrin, procymidone, sumithrin, synthetic pyrethroids, toxaphene, trans-nonachlor, tributyltin oxide, trifluralin, vinclozolin, zineb, ziram

Phthalates: Di-ethylhexyl phthalate (DEHP), Butyl benzyl phthalate (BBP), Di-n-butyl phthalate (DBP), Di-n-pentyl phthalate (DPP), Di-hexyl phthalate (DHP), Di-propyl phthalate (DprP), Dicyclohexyl phthalate (DCHP), Diethyl phthalate (DEP), Metals: Arsenic, Cadmium, Lead, Mercury Other: Penta- to Nonyl-Phenols, Bisphenol A, Bisphenol F, Styrene dimers and trimers, Benzo(a)pyrene, ethane dimethane, sulphonate, tris-4-(chlorophenyl), methane, tris-4-(chlorophenyl), methanol, Benzophenone, N-butyl benzene, 4-nitrotoluene, 2,4- dichlorophenol, Cyanazine, Diethylhexyl adipate More EDCs: ordinary household products (breakdowns products of detergents and associated surfactants, including nonylphenol and octylphenol

More about clasification Strong effect at low concentration Natural Steroid Estorogenler βE2:17βestradiol E3:estriol E1:estrone EE2:17αethinyestradiol Synthetic estrogenler: EE2:17αethinyestradiol: Birth control pills Weak effect at high concentrtaions Phytoestrogens Industrial Chemicals

What are the affects of EDCs? Just a few of the health effects. . Birth Defects Neurologic disorders Endometriosis Diabetes mellitus Immunological disorders Early Puberty in young girls Cancers: breast, colon, cervix, testicular, brain and central nervous system Non-Hodgkin's lymphoma Reduced physical stamina Genital birth defects: Hypospadias & Cryptorchidism Reduced anogenital distance in male Reduced sperm counts

What are the affects of EDCs? Enlarged prostates and cancer Developmental, Behavioral and Mental Disorders: Anger, Inattention, Decreased mental capacity Learning disabilities,  Dyslexia, Attention deficit/hyperactivity disorder (ADHD), Autism Propensity to violence Decreases in stamina, gross and fine eye-hand coordination Reduced motor skills and eye-hand coordination Reduced memory and intelligence Intellectual retardation

More about adverse effects Several studies showed that even low concentrations (ng/L) of bE2 can induce vitellogenin (VTG) in male species and rainbow trout (O mykiss) experimentally exposed to these chemicals. bE2 as low as 1 ng/L induces VTG in male trout. EE2 could induce VTG in male fish for a concentration as low as 0.1 ng/L. Nonyl-phenols is present in large amount in STPs sludge and would have as a consequence a diminution of fish reproduction in subsequent receiving water. Alkylphenols can have estrogenic effects in fish at concentrations from 1 to 10 mg/L In the aquatic environment, EDCs are easily bioavailable to fish through a variety of routes, including aquatic respiration, osmoregulation and maternal transfer of contaminants in lipid reserves of eggs

So !!!! Vitellogenin in male species Monosex cultures Effect on hormone system of the animals

Sources Emissions from steel foundries and motor vehicles (Pb, Hg), Incineration of chlorine containing products such as PVC in incinerators ( PCB), Pesticides ( such as chlorinated ones) Industrial Wastewater ( plastic, pulp and paper etc) Municiple Wastewater ( estrogens)

Exposure to EDCs in daily life The most insidious EDs are man-made synthetic chemicals. We are routinely exposed to them in most areas of our daily lives at home, work and play. Known and suspected EDs come in products we have been led to believe have been thoroughly tested for the safety of our health and the environment. The list includes; health and beauty aids (cosmetics, sunscreens, perfumes, soaps); pharmaceuticals (birth control pills); dental sealants; solvents; surfactants; Pesticides plastics (PVC [2], polystyrene aka Styrofoam®, and others).

Chemical structure Alkylphenols : Nonyl phenol ( NP): Surfactants Pesticides Detergents Octyl phenol (OP) Alkyl phenol ( AP) Ethyloxylate (EO)

Bisphenols Bisfenol A: Sentetik östrogen Fungicides Antioxidant Chemicals in production of plastics Epoxy production

PHTHALATES

Treatment Biological degradation and transformation occur aerobically by biological oxidation in activated sludge, trickling filters, or anaerobically in the sewage system or anaerobic sludge digesters. Not all compounds are completely broken down or converted to biomass in STP operating the activated sludge process. Estrogenic alkylphenols and steroid estrogens, for example, found in STP effluent are the breakdown products of incomplete biodegradation of their respective parent compounds. Field data suggested that the activated sludge process can remove over 85% of bE2, E3, and EE2, while the removal performance for E1 appears to be less and more variable

Whereas high removals of E3, bE2, and EE2 were achieved, no more than 69% of E1 were removed by activated sludge treatment and in 4 out of 30 events, E1 outlet levels were even larger than inlet levels. bE2 can be transformed to E1 aerobic and anaerobic biodegradation of bE2 indicated a rapid degradation of bE2 to E1 but no any other stable major metabolites. Furthermore, Estrogens are either excreted in urine as glucuronide or sulfated conjugates in both humans and animals. E1 appears to be the most important natural EDC, considering that: 1- The amount of the E1 species discharged from STPs into the receiving water was more than ten times larger than bE2 species, 2- E1 has half the estrogenic potency of bE2, and 3- Some E1-3S fraction could be converted to E1 in the aquatic environment.

Primary treatment alone is nor sufficient Secondary treatment involving activated sludge reduces significantly all estrogens concentrations. A long SRT appears to have a positive influence on the activated sludge system ability to eliminate estrogens. bE2 and E3 are very efficiently removed compared to E1 and EE2 is somewhat lower. On the other hand, the main estrogens removal mechanism in the activated sludge system seems to be sorption to sludge particles and/or microbiological degradation.

Research Needs Inventory study to determine EDC concentrations in wastewater, surface water, natural waster etc. Method development for measurement of EDCs in sediment, water , wastewater and treatment sludges. Determination of microbial population which is capable of degrading estrogenic EDCs. Investigation on treatment processes to achieve concentrations in effluent below estrogenic limits Investigations on operating conditions of biological treatment plants for complete removal of estrogenic EDCs. Determination of biological degradation by-products Determination of conditions during natural degradation of estrogenic EDCs by UV, oxidation in such as surface water