Emerging Contaminants and Water Supply/Watershed Protection

Transcription

1 Emerging Contaminants and Water Supply/Watershed Protection Presented by Scott A. Grieco, PE Vice President Industrial Water/Wastewater Treatment 1

2 EMERGING CONTAMINANTS EMERGING = new Recent findings of existence and effects at ppt or ng/l concentrations CONTAMINANTS = harmful (?): Endocrine system and epigenetics Immune system Regulatory system Chronic effect at low dosages? Synergistic i effect?

3 A Matter of Scale 1 M (1 g/l) 3

4 A Matter of Scale Ceramic Coffee Mug 10 1 M Marble 10 2 M Grain of sand 10 3 M (mm) (mg/l) 4

5 A Matter of Scale Human hair 10 4 M Yeast cell 10 5 M Pain pigment M (µm) (µg/l) 5

6 A Matter of Scale Tobacco smoke 10 7 M Protein molecule 10 8 M Organic molecule 10 9 M (nm) (ng/l) 6

7 What is a ng/l? Our dose of 2 Excedrin is dissolved in 10 9 L to create a ng/l Tanker truck 5,500 gallons 42 ft long How many tanker truck of water are needed to dilute our 2 Excedrin to 1 ng/l? 7

8 What is a ng/l? 48,000 Tanker Trucks 8

9 What Are Emerging Contaminants? Compounds Pharmaceuticals Personal care products Antibiotics Sterols and hormones Endocrine disrupters Herbicides/pesticides Flame retardants Others Varying chemical properties Dissimilar structures and functional groups Molecular size Polarity Solubility

10 What are Emerging Contaminants? 4 Studies (Estevez, 2010); (Pal, 2012); (Stuart, 2010); (Murray, 2012) 117 ECs Metabolites of ECs May be more persistent or toxic Splenda & Aspartame are being found like an EC Metabolite Personal Care Product Pharmaceutical 4 AA Caffeine Acetominophen Gadolinium Sulfamethoxazole 4 AAA Cashmeran Amidotrizoic acid Gemfibrozil Sulfapyridine 4 FAA Celestolide Androstenedione Glibenclamide Sulfathiazole Fenofibric acid DEET Atenolol Hydrochlorothiazide Sulpiride 4 MAA Galaxolide Azithromycin Hydrocodone Telmisartan Paraxanthine Hydrocinnamic acid Benzafibrate Ibuprofen Testosterone Methyl dihydrojasmonate Butalbital Indomethacine Tramadol Musk Ketone Carbamazepine Iopromide Trimethoprim Nonylphenol Carisooprodol Irbesartan Venlafaxine Oxybenzone Chloramphenicol Ketoprofen Salicylic acid Ciprofloxacin Ketoroloc Tonalide Clindamycine Loratidine Triclocarban Codeine Mefenamic acid Triclosan Diazepam Meprobamate Diclofenac Methadone Industrial Dilantin Metoprolol Diphenhydramine Nadolol Atrazine Methylbenzotriazole Eprosartan Naproxen Benzotriazole Methoxychlor Erythyromycin Norfloxacin Bis(2 ethylhexyl)phthalate Metolachlor 17β Estradiol Ofloxacin Bisphenol A 4 Nitrophenol Estriol Oxycodone Clofibric acid Octylphenol (p tert) Estrone Pentoxifylline DDT Perfluoroheptanoic acid (PFHpA) 17α Ethynyl estradiol Pravastatin Diazinon Perfluorohexanoate (PFHxA) Famotidine Progesterone Dicamba Perfluorooctanic acid (PFOA) Fexofenadine Propranolol Dieldrin Perfluorooctanesulfonic acid (PFOS) Fenofibrate Propyphenazone Dimethyl phthalate Terbutylazine Fluconazole Ranitidine Diuron Tributylphosphate (TBP) Fluoxetine Sotalol 2 Ethylhexyldiphenyl y y phosphate p Tris(2 butoxyethyl)phosphate y)p p (TBEP) Furosemide Sulfamethazine Lindane Tris(2 chloroethyl)phosphate (TCEP) MCPA Tris(2 chloroisopropyl)phosphate (TCPP) Mecoprop Tris(isobutyl)phosphate (TIBP) 10

11 Sources of ECs 11

12 Ubiquitous Nature of ECs An example comprehensive study 2009 study by Loos et. al. 122 river sampling stations 27 countries 35 compounds 12

13 Status of EC regulations Technological breakthroughs have outpaced the regulatory practices. No existing limiting regulations EDC priority list was first reported by the EU 66 chemicals A further 52 chemicals were identified Recently the total list included 564 chemicals. 147 compounds are likely to be environmentally persistent in the environment (Bolong, 2009) EPA has CCL3, which is not nearly as comprehensive or focused on EDCs Certain states (CA, MN, NY) have independent lists FDA requires ecological testing of pharmaceuticals when environmental concentration exceeds 1 μg/l. 13

14 Health concerns regarding EC s Many are classified as Potentially carcinogenic Impactful to the endocrine system, disrupting cellular development and hormonal function There still is a scarcity of data on human health and ecosystem effects: At environmental levels In multi component mixture Chronic or generational effects

15 Health concerns regarding EC s Recent studies have measured: Impacts on fish reproduction and asexuality (Kavanagh, 2004) Large mammal reproduction (Catriona, 2005) Human embryonic cell function (Pomati, 2006) Potential synergistic at environmental concentrations (Silva, 2002). 15

16 Health concerns regarding EC s Schriks, 2010 Study of 50 EC s From a toxicological point of many ECs are not a direct concern for human health. The sub lethal effects of these compounds are largely unknown. Need better understanding of the potential mixture effects of EC s 16

17 How are we treating EC s? Local Study with O Brien & Gere & USGS 14 studies from 2006 to 2013 Wastewater Treatment plant effluents Receiving waters Drinking water sources Treated drinking water Locations North America Europe Asia Australia

18 How are we treating EC s? Biological Physical/Chemical Advanced Treatment New Research

19 Biological Treatment 19

20 Municipal WWTP Upstate NY example Wastewater from Municipal WWTP with a Pharmaceutical Industrial User Previous study showing high pharmaceutical concentrations Contributes to a drinking water supply Objective Evaluate removal of opiates in wastewater Unit Operations at WWTP Extended aeration activated sludge Microfilters UV Disinfection

21 WWTP Effluent Concentrations Pharmaceutical Average Effluent Concentration (ug/l) Range (ug/l) Butalbital to 116 Codeine to 7.4 Hydrocodone to 60 Metaxalone to 480 Methadone to 55 Methylphenidate to 9.6 Oxycodone 1, to 2,100 Piperonyl butoxide to 1.1 Tramadol to 1.3 Temazepam <

22 POTW EFFLUENTS 17alpha-ethynylestradiol (EE2) testosterone ng/l 7 beta-estradiol (E2), 2,4 DCP, azithromycin, BHT, bupropion, ciproflaxin, estrone (E1), fluoxetine, malathion, norfloxacin, paracetamol, setraline ATH(Traseolide), BHA, cimetidine, dehydronifedipine, diazepam, dlitiazem, diphenhydramine, indolebutyric acid, lindane, primidone, benzophenone Carbaryl, chlorpyrifos, diazinon, diethylphthalate, estriol (E3), fenofibrate, phenazone, propanolol, triclocarban, trimethoprim Sulfamethoxazole, TCEP, Tetrachloroethene, venlaflaxin Gemfibrozil, HHCB, iopromide, lincomycin, roxithromycin 4-methylphenol, 4-OP (mono,di) Eos, bis-2-ethylhexylhphthalate, clofibric acid, fenobiric acid AHTN, atenolol, bezfibrate, cholesterol, DEET, diclofenac, erythromycin, Fluoranthene, ketoprofen, mefenamic acid, metoprolol, naproxen, Pyrene, TDCPP, triclosan 1,4 Dichlorobenzene, acetaminophen, atrazine, carbamazepine, nonylphenol, phthalic anhydride Bisphenol A, Ibuprofen, NonylPhenol, NPEOs, TBEP, TCPP

23 Biological WWTP Increasing SRT can improve removal for some ECs PPT Bisphenol A Effluent Concentration vs. Treatment SRT BP-A Data from Reference Papers SRT

24 Biological Wastewater Treatment Biological processes can treat many of the identified ECs. Constraints to consider Concentration Configuration System Operation Example ECs persistent through aerobic systems: carbamazepine, erythromycin, hydrochlorothiazide, indomethacine, metoprolol, and tris(2 chloroethyl) phosphate (TCEP) Persistent ECs not effectively treated within mesophilic or thermophilic anaerobic systems Key issue for sludge digestion & biosolids disposal 30% solids = 70% water 24

25 Biological Wastewater Treatment Improve existing treatment Increase SRT Alternative technologies Membrane bioreactor (MBR) Enhanced Powered Activated Carbon Treatment (PACT) For the most persistent constituents additional treatment will likely be required. Many ECs lack adequate study diazinon, dieldrin, dilantin, iopromide, methoxychlor, musk ketone, 4 nitrophenol, nonylphenol, perfluoro organic acids 25

26 Physical/Chemical Treatment 26

27 Applications of Physical/Chemical Treatment 2007 AWWARF Report (Snyder et. al.) Water Treatment Filtration Settling Chemical Disinfection (Chorine, Ozone, UV) Carbon adsorption Reverse Osmosis (RO) Tertiary Treatment for Biological i l 27

28 Technologies Process Adsorption Oxidation Advanced Oxidation (AOP) Membrane Filtration Technology Activated Carbon Zeolite Chlorination Chloramine oxidation Ultraviolet light Ozone Ozone/hydrogen peroxide UV/Ozone UV/hydrogen peroxide UV/titanium dioxide Nano-filtration (NF) Reverse Osmosis (RO)

29 Activated Carbon Natural Material Bituminous coal Coconut shell Wood Heterogeneous Chemical differences (functional groups, metals) Pore sizes 29

30 Activated Carbon

31 Oxidation Oxidizing Reactions break chemical bonds and destroy organic compounds Complete Oxidation Organic (C H O N S) + Oxidant CO 2 + H Salts Incomplete oxidation Organic (C H O N S) + Oxidant Smaller Organics Effectiveness based on: Chemical structure Electrochemistry (Types / Number of Bonds) Configuration of organic Molecule Relative power of oxidant

32 Oxidation Conventional oxidation Chlorination UV Advanced oxidation Hydroxyl radical generation (OH ) Ozone (O 3 )/Ultraviolet (UV) Ultraviolet (UV)/Hydrogen Peroxide (H 2 O 2 ) UV/Titanium dioxide (TiO 2 ) h O3 H 2 O 2 OH O2 H

33 AOP Reactor Reactor & Chemical Recirc Control UV Reactor HOCl, Ozone, H 2 O 2 Injection Recirc Pump

34 Chlorination

35 UV

36 Ozone 36

37 UV/H 2 O 2 (Advanced Oxidation) 37

38 RO / NF Permeate: Clean Water Reject: Concentrate with ECs Generally 70 85% recovery (15 30% reject) Can configure with high recovery (<10% reject) 38

39 RO / NF RO removal is generally >85% (Xu, 2005; Kim 2007; Kimura 2004) carbamazepine (85 91%) erythromycin (>98%) tris(2 chloroethyl)phosphate (95%) iopromide (99%) Removals influenced by Molecular weights Electro chemical properties / surface charge of the membrane Concerns using RO The concentrate stream will contain a smaller volume higher concentration of ECs As tertiary treatment to biological, adequate protection of the RO through pretreatment such as MBR or UF will be required 39

40 New Research Removal of TCEP from Aqueous Solutions by Adsorption with Zeolites SUNY ESF: Dr. Bandaru Ramarao 40

41 Tris (2 chloroethyl) Phosphate (TCEP) Flame retardant and plasticizer Textiles, upholstery (drapes, rugs, furniture, clothes) PVCs, Foams (automobiles, electronics) Organophosphate Ester Usage stats 2001: Global usage 186,000 metric tons (Hartmann, 2004) Production has been in decline since the 1980s (safer products) 250 tons of TCEP are imported / produced in US (NRDC, 2010) OPEs are not chemically conjugated and can be released to the environment (Reemtsma, 2008)

42 TCEP Health Concerns EU TCEP possibly linked to cancer and fertility impairment US, Canada Probably of harm to humans at any level Minnesota: Listed as EC California: linked to cancer and reproductive toxicity NY: prohibits sale of any child care product containing TCEP

43 Extent of TCEP Across the Globe In East Antarctica snow samples (Cheng, 2013) In the Arctic atmosphere (Moller 2012) Within German urban and rural rain (Regnery, 2010) Oceans higher than other pollutants (Andresen, 2007) Bio monitoring study in Germany (Schindler, 2009) Studied metabolite {bis(2 chloroethyl)phosphate} Up to 27.5 µg/l in urine of 50% of the general population studied

44 Why Focus on TCEP? Environmentally persistent Small, hydrophilic molecule Aquifers 20 to 45 years old 0.1 to 0.6 µg/l in surface water The most frequently detected compound of the ECs investigated (Glassmeyer, 2005) TCEP is not being removed from the water cycle through current conventional treatment: Biological <20% GAC 20 50% Oxidaton <20%

45 Zeolite Alumino silicate based material Porous material in a crystalline framework Uniform pore size (typically 0.5 to 1 nm) High surface area (400 to 800 m 2 /g) Exchangeable cations Variety of natural and synthesized zeolites

46 Zeolite Framework substituted aluminum negative charge Charge balanced by additional (+) charge Crystal framework defects cause terminal silanol groups Si(OH), Si(OH) 2, Si(OH) 3 Increased aluminum increased hydrophilicity Evaluated 25:1 and 300:1 (Si:Al ratio) materials

47 Zeolite advantages Consistent chemical structure Consistent tpore size Adsorption is improved when there is close proximity between molecule and adsorbent surface 47

48 Adsorption testing Isotherm experiments: 10 mg/l TCEP in DI water Evaluated ph values of 5, 7, and 10 SU EtblihdI Established Isotherms using 2 models dl q e q e qmaxk 1 k L c c L k Rce 1 a c R e g e e 25:1 Si:Al 300:1 Si:Al

49 Observations / Findings Achieved >99% removal with zeolite Significant improvement of adsorption at acidic ph value (<5 SU) 300:1 material showed 50% greater adsorption capacity Material showed 50% less polar surface area Application works well in real waters Natural organic material Salts TCEP removal was not reacted i.e., hydrolyzed to similar structure Zeolite can be regenerated

50 Summary There are many trace contaminants being detected Regulations & Science of risk assessment are lagging gbehind technology of detection Still lacking science of chronic low doses and mixture effects Separate discussion of eco health versus human health Many ECs are treatable with existing technology One size does not fit all for treatment Municipalities may require upgrades and/or polishing treatment Smaller list of ECs will need advanced treatment or new technology 50

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