Microconstituents: Emerging Pollutants We Should Care About

2. Microconstituents “Pollutants we should care about” Pure Water Forum and Shenandoah Valley Wastewater Treatment Plant Network Deborah DeBiasi, Water Division - VPDES Permits September 26th, 2019 deborah.debiasi@deq.virginia.gov 804-698-4028 Virginia Department of Environmental Quality

3. What are microconstituents? Natural and manmade substances in environment • Human and Veterinary drugs – prescription and OTC (Over The Counter) drugs • Pet products and supplements • Food Supplements – nutraceuticals (aka vitamins), caffeine, nicotine, fragrances • Sun-screen agents • Lotions, shampoos, soaps, deodorants, toothpaste • Cosmetics • Fire Retardants – PBDEs (polybrominated diphenyl ethers (penta, octa, deca), Organophosphate substitutions • Industrial Chemicals – bisphenol A, phthalates, PFAs, PFOS • Pesticides – bactericides, herbicides, fungicides, insecticides

4. Names for this topic • CPC– Compounds of Potential Concern • PC - Pollutants of Concern • EC - Emerging Contaminants – (USGS) • CEC- Contaminants of Emerging Concern (AWRA-American Water Resources Assoc, EPA) • PPCP – Pharmaceuticals and Personal Care Products (name coined by Dr. Christian Daughton, EPA in 1999) • Microconstituents –(WEF -Water Environment Federation) .

5. Endocrine Disrupting Compounds • An endocrine disruptor is a synthetic chemical that either mimics or blocks hormones and disrupts the body's normal functions when absorbed into the body. Natural products in environment (oak tree leaves, other decaying matter), household cleaners, personal care products, pharmaceuticals, pesticides, processed foods, plants (contain natural compounds called phytoestrogens), plastics, industrial chemicals, animal and veterinary sources, air deposits of fire retardants, etc. https://www.epa.gov/endocrine-disruption- Endocrine Disruptor Screening Program (EDSP) List of EDCs – approx 10,000 chemicals • Some products will contain this statement (or something similar) on the label, “Do not use if you are pregnant or breast-feeding” or “Do not expose children under 5 years of age” which could indicate the product contains EDCs

6. Endocrine System • Glands that produce and secrete hormones • Hormones regulate growth, metabolism, sexual development and function • Pituitary gland, hypothalamus, thyroid gland, parathyroid glands, adrenal glands, pineal body, reproductive glands, pancreas

7. Sunscreens Physical mineral sun blockers • titanium dioxide • zinc oxide Usually white but some more sheer Safe and effective Covering up with clothing best! Chemical sun blockers • oxybenzone* - in 2/3 sunscreen products, also in chapstick • octinoxate* Usually clear • Potential hormone disruptor • Allergenic, absorbed thru skin • Found in blood, urine, and breast milk * Banned in Hawaii beginning of 2021 – can kill developing coral, feminize fish, endocrine disruptor for fish, sea urchins, coral and shrimp

8. Benefits and Deterrents of Sun Exposure Sun exposure: +Vitamin D uptake in body prevents osteoporosis and bone fractures +Benefits children to make strong bones and prevent rickets +Lower risk of MS +May benefit people with MS +10-15 (or 5-30) minutes of sun exposure 2-3 times/week is all body needs. - Too much sun causes sunburn and may contribute to skin cancers Little to no sun exposure Need Vitamin D supplement Vitamin D deficiency is risk factor for cardiovascular issues like heart attacks, high BP, diabetes, and some cancers. Need minimum 600 IUs daily - Brittle bones - osteoporosis

9. How do Pharmaceuticals get into the Environment? • Purposeful disposal to sink or toilet • Both public sewer systems and septic systems (pumped and hauled) end up at wastewater treatment plants • Purposeful disposal to trash • Showering/bathing/washing hands of medications applied externally • Pass-through of medications into urine containing 10 – 90 % of ingested medications

10. How to reduce the amount of pharmaceuticals in the environment Education of public to dispose of medications properly • Take unused/unwanted medications to Drug Take Back events for disposal, or dispose of in an authorized collection box. Remove your identification information and address from the container. Collected drugs are ultimately incinerated. • Trash disposal: English Spanish German Chinese http://www.deq.virginia.gov/Programs/Water/PermittingCompliance/PollutionDischargeElimination/Microconstituents.aspx • Where possible, reduce the amount of medications and nutraceuticals (dietary supplements) ingested • Only take medications that are appropriate for the illness/condition • Do not take medications longer than necessary or as directed • Have your doctor review all of the medications and supplements that you take to make sure combinations won’t be a problem

11. Drug Disposal Options Drug collection boxes are available at participating police stations and many pharmacies 2019 https://takebackday.dea.gov/

12. Total pounds collected to dateNationally –10,878,950 Virginia – 354,012 Interesting trend – Spring collections higher than fall Click on icon to see how all the states did with the April 2019 Drug Take Back event

13. FDA Guidance on Drug Disposal FDA list of Drugs to flush In 2007, the FDA advised that 13 drugs be flushed down the toilet instead of thrown in the trash In January 2012, the FDA advised that 32 drugs be flushed down the toilet instead of thrown in the trash In November 2013, the FDA advised that 36 drugs be flushed instead of trashed In April 2016, the FDA advised that 45 drugs be flushed instead of thrown in the trash April 2018, the FDA posted a list of 49 drugs to be flushed. From Don McLean’s song “Vincent” – “They would not listen, they're not listening still. Perhaps they never will…”

14. Virginia Guidance PLEASE do NOT DISPOSE of ANY MEDICATIONS by FLUSHING or washing down the sink! Don’t take the chance that it could end up in your drinking water!

15. The “circle” of microconstituents 7. Clean water back to you 3. Biosolids to farmland or landfill 1.Sewage to WW Treatment plant 6. Wastewater discharge 4. Leachate or garbage juice to WW Treatment plant 2. Treated effluent to river 5. Water intake for Water Treatment Plant

16. Why don’t Treatment Plants remove microconstituents? Water Treatment Plant https://www.youtube.com/watch?v=A2FmNrEmowE All Treatment Plants have steps 1, 2 and 5. Most Treatment Plants have steps 1, 2, 3 and 5 Many are adding step 4 to remove nutrients, which helps remove estrogenic compounds

17. What is the contribution from septic systems? • Can do a decent job removing acetaminophen, caffeine, and alkyphenols (in cleaning products) • Less effective removing TCEP (carcinogenic flame retardant), carbamazepine, and antibiotic sulfamethoxazone • Contaminants can get into groundwater, which may be source of drinking water for household • Users need to avoid household products with harmful ingredients Well Casing Septic systems are a major source of emerging contaminants in drinking water June 26, 2017

18. What do you contribute from personal care products (PCPs)? In 2007, the average person used 9 PPCPs a day. Most recent number is 15 PPCPs per person per day. PPCPs include lotions, powders, soaps, gels, colognes, sprays, toothpaste, make-up, medication, etc. Think about every product, medication or caffeine/nicotine product you used since you got up. Read the list of ingredients – remember: EVERYTHING GOES SOMEWHERE! Do you need to use all of them? Can you substitute something less toxic to the environment? Can you reduce the antibacterial products you use and stay healthy?

19. Do we need all the drugs and supplements that we take? • Pill to sleep • Pill to stay awake • Pill to give energy • Pill to calm down • Pill to lose weight • Pill to gain weight • Pill to stop reproduction • Pill to encourage fertility • Pill for pain • Pill for ulcer from pain pill • Supplements and vitamins Would changes in diet, habits, physique help instead of another pill?

20. Microconstituents are everywhere ALL municipal sewage, regardless of location, will contain microconstituents. Issue is not unique to any particular municipal area. Each geographic area will differ only with respect to the types, quantities, and relative abundances of individual contaminants. Microconstituents can transport by air as well as by water. Microconstituents are being found in all tested waterways, and are usually ‘present’ in drinking tap water and bottled water. ‘Present’ does not mean they are harmful.

21. Antibacterial Soaps • Often contain triclosan (liquid soaps) and triclocarban (bar soaps)– synthetic anti-microbial agent and EPA registered pesticide • Not any more effective than soap and water for washing hands • By Sept 6 2017, hand soaps with triclosan and triclocarban for home use should be removed from shelves • Use in health care allowed but discouraged • Most triclosan passes through wastewater treatment plants or ends up in the sludge - very persistent and toxic to marine life. • May contribute to development of mutant bacteria that are antibiotic resistant. Discourage use in residential and public areas where possible. Products with triclosan

22. Bis-Phenol A, or BPA • Used in clear, hard plastics (polycarbonate plastic and epoxy resins) since 1957. All 3’s Some 7’s • Has weak but detectable hormone-like properties • Some states looking at laws to prohibit BPA from being used in baby bottles and products. Some manufacturers making substitutions now. • Removal of BPA for food and drink applications is difficult. Replacement product must be corrosion resistant, withstand high temps used for sterilization and processing, and be chemically compatible with foods, and not add odor or taste. • Reduce exposure by using glass baby bottles, stainless water bottles, food products not in cans.

23. BP-A sources • Canned foods and drinks • Reusable water bottles (Polycarbonate plastic #7, or “PC”) • Note: Most water and sodas are in flexible, clear plastic bottles made of polyethylene terephthalate, or PET – no BPA. • Plastics with #1, 2, 4, or 5 do not contain BPA either • Canned sodas and beer • Fast food, particularly burgers • Carbonless register receipts – BPA absorbed through skin, inhaled, or ingested 23

24. BP-A and the 50+ “relatives” - BPS, BPF, BPAF, BPZ, BPP, BHPF, and the list goes on BP-A can be substituted with BPS (bisphenol-S) or BHPF (Fluorene-9-bisphenol) – no real difference in toxicity Public Health term: “Regrettable substitution” – replacement of one harmful chemical by another possibly equally or more harmful chemical Endocrine disruptors – affect fertility in men and women, can affect growth and development, cause obesity, diabetes 24

25. Plastic recycling hints • #3, PVC and PUR – polyurethane are the most toxic of the plastics. • #7 is next worst, since the components are unknown • Only recycle #1, #2, or #5 plastics • Trash black plastic – made from recycled electronic waste. It can’t be recycled again. 25

26. Phthalate – the everywhere chemical! • Phthalates are a group of chemicals used in: • soft plastic toys for babies, pets, adults • vinyl flooring and wall covering • “new car smell” • detergents • lubricating oils • food packaging • pharmaceuticals • blood bags and tubing • in about 75% of personal care products such as cosmetics, fragrances, nail polish, hair sprays, soaps, and shampoos.

27. Phthalates and Human Health • Exposure is through • Ingestion of food or drink that is in containers containing phthalates • Inhalation of dust from items containing phthalates • Skin contact with products made with phthalates • Once in the body, they are converted into metabolites that exit in urine • Women have higher levels of phthalates than men • May affect reproduction or development (endocrine disruptor) • Wash hands well after handling • Avoid products with phthalates where possible 27

28. Phthalates Alters development of reproductive tract, mostly with males – can cause deformity and affect fertility – possible carcinogen. Exposure during fetal development and puberty can help cause an array of complications like genital birth defects, infertility, asthma, and lower IQ Correlation of higher levels of phthalates with cardiovascular disease, type-2 diabetes, and high blood pressure for males DEHP - diethylhexyl phthalate is a plasticizer used to soften PVC (EU prohibits DEHP at levels greater than 0.1% by weight) https://www.atsdr.cdc.gov/toxfaqs/tf.asp?id=377&tid=65 Used in IV bags, tubing, blood collection machines. Red Cross is buying some DEHP-free equipment with attrition. For DEHP free equipment sources http://www.noharm.org/ Blood bags with DEHP should not be used with infants or children with compromised immunities FDA urges alternatives, like ethylene vinyl acetate (EVA) bags which are available except for packed red blood cells

29. Phthalate reductions/removals Some manufacturers taking phthalates out of products due to customer complaints: Avon, Johnson & Johnson, S.C. Johnson, Estee Lauder, Revlon, Unilever, Disney. Check here to see if phthalates are in products: http://www.ewg.org/skindeep/ Phthalates Action Plan Summary.  US Environmental Protection Agency. Rulemaking 2012 https://www.epa.gov/sites/production/files/2015-09/documents/phthalates_actionplan_revised_2012-03-14.pdf DEHP is tested for at public water supplies and regulated under the Safe Drinking Water Act

30. PFAs, per- and polyfluroalkyl substances EPA health advisory of 0.07 µg/l – no plans to change the advisory. No MCL (maximum contaminant level) for drinking water, not listed as a haz waste, with CERCLA or RCRA. https://www.amwa.net/article/epa-outlines-path-forward-pfas Some states adopting more stringent endpoints. See IRTC (Interstate Technology and Regulatory Council) website - https://pfas-1.itrcweb.org/fact-sheets/ Table 4-1 presents the available PFAS water values, Table 4-2 has soil values established by the USEPA, each pertinent state, or country (Australia, Canada and Western European countries) Table 5-1 summarizes the differences in the PFOA values, Table 5-2 summarizes the differences in the PFOS values for drinking water in the United States.

31. PFAS – the “Forever Chemicals Per- and polyfluroalkylsubstances – used to make water-, grease- and stain-repellent coatings Teflon introduced in 1946, PFOA used by Dupont to make Teflon, PFOS used by 3M to make Scotchgard. Manufacture, use and importation of both effectively banned in the US DuPont no longer makes or uses PFOA – however, Chemours (spin-off of DuPont) makes a replacement called Gen-X Exposure can cause Testicular, kidney, liver and pancreatic cancer Increased cholesterol Harmful effect to developing fetus or breastfeeding infant Low infant birth weights Effects on immune system and thyroid Weight gain in humans PFAS chemicals are persistent - remain in body and environment for decades

32. Products containing PFAS or PFOS Some grease-resistant paper, fast food containers/wrappers, microwave popcorn bags, pizza boxes, and candy wrappers Nonstick cookware Stain resistant coatings used on carpets, upholstery, and other fabrics Water resistant clothing Cleaning products Personal care products (shampoo, dental floss) and cosmetics (nail polish, eye makeup) Paints, varnishes, and sealants Firefighter turnout gear, firefighting foams

33. Oldies but goodies – and NO PFOA! Best if pans were made 1939-1968 Newer Revere Ware does not have a circle or reference to a patent 33

34. Cast Iron Cookware – No PFOA! 34

35. PFAS Exposure Routes Drinking contaminated municipal water or private well water Eating fish caught from water contaminated by PFAS (PFOS, in particular) Accidentally swallowing contaminated soil or dust Eating food that was packaged in material that contains PFAS Using some consumer products such as non-stick cookware, stain resistant carpeting, and water repellant clothing. Note: Only small amount PFAs can get through skin. Showering, bathing, washing dishes should not increase exposure.

36. PFAS Contamination in the USA • DOD report on military bases with PFAs and PFOS issues – https://partner-mco-archive.s3.amazonaws.com/client_files/1524589484.pdf • Virginia - Langley-Ft. Eustis, NAS Oceana NALF Fentress, Norfolk Navy Base

37. Fire Retardants PBDEs – Poly-brominated diphenyl ethers (or BDEs), commonly referred to as penta, octa and deca ( i.e. penta-brominated diphenyl ether) considered Persistent Organic Pollutants (POPs) Used in furniture, carpets, vehicles, electronics - Showing up in sediment, water and air PBDEs leaching out of products and get in blood – can cause thyroid problems, developmental problems, carcinogenic Penta and Octa forms have been phased out – deca still used Organophosphate substitutes (TDCIPP and TPHP) showing up in blood too. May cause fertility problems, and linked to poorer cognitive function in children. tris (1,3-dichloro-2-propyl) phosphate (TDCPP). New substitute products should be thoroughly tested prior to marketing to make sure that they are safe.

38. Fire retardants • PBDEs are used in cell phones, remote controls, personal computers, computer monitors, textiles, electronics, cabinets and enclosures for electronics, foam cushioning, foam-based packaging materials, upholstery, carpet padding, paint products, and adhesives • Exposure through • Ingestion – eating contaminated food or water • Inhalation – breathing air or dust with PBDE emissions • Skin contact – touching items containing PBDEs • Concerns – endocrine disruptor, may cause liver, thyroid and neurodevelopmental dysfunction. Accumulates in body. • Children and pets have more exposure 38

39. Feeling Blue?

40. Argyria from silver ingestion • Paul Karason started turning blue 15 years after he began ingesting silver-based prep and colloidal silver to self medicate a skin condition. Stan Jones, bottom right • Argyria (ahr–JIR–e–uh), a blue-gray discoloration of your skin, eyes, internal organs, nails and gums. While argyria doesn't pose a serious health problem, it can be a cosmetic concern because it doesn't go away when you stop taking silver products. • Currently no FDA approved oral OTC or prescription drugs containing silver. • https://nccih.nih.gov/health/silver

41. Silver as Antibacterial Silver as antibacterial The Silver Institute promotes silver in medical supplies as biocide, in water purification systems, pools and spas (https://www.silverinstitute.org/site/) Silver or triclosan treated clothing for “anti-odor” and “anti-bacterial” purposes will release coatings with bleach detergents (~25% after 2 washes, up to 50% with more washes), discharging to sewers → POTWs → state waters. Bacteria mutate to survive, becoming more antibiotic resistant. The Mayo Clinic – Colloidal silver isn't considered safe or effective for any of the health claims manufacturers make. Silver has no known purpose in the body, nor is it an essential mineral, as some sellers of silver products claim. 3/25/15 EPA requires registration under pesticide law of products containing nanoscale (smaller than 1 micrometer) silver designed to control microbes.

42. Microbeads • Plastics disintegrate in the oceans and are ingested by aquatic organisms • Many PCPs contained microbeads like exfoliates, body washes, toothpastes • Seafood eating humans ingest up to 11,000 tiny pieces of plastic every year Larval perch with plastic beads • 2017 – illegal to sell a PCP with plastic microbeads Next issue is glitter, small pieces of plastic

43. Microplastics and Microfibers Photo shows a 3 mm (0.1 in) section of microfibers filtered from drain water of standard load of laundry magnified 120 X • Microfibers are made of plastic and chemical covered non-plastics • Breaking off clothes in the water, discharged through drain water • One fleece jacket could shed 250,000 pieces of fibers/wash 80 70 Human hair 70 µ wide 60 50 40 Naked eye can see 40 µ • 30 • 20 • 10 Red blood cell is 8 µ • 0 Microfibers are 3-60 µ

44. Microplastics and Microfibers 90% of collected samples have microplastics 89% microfibers, 11% plastic fragments One in 3 shellfish; 1 in 4 fin fish and 67% of all species tested from fish markets in California had microfiber in them Cows, pigs and chicken are fed fish meal Drain filters needed Cora Ball now available

45. http://www.deq.virginia.gov/programs/water/permittingcompliance/pollutiondischargeelimination/microconstituents.aspxhttp://www.deq.virginia.gov/programs/water/permittingcompliance/pollutiondischargeelimination/microconstituents.aspx