Emerging contaminants in the Great Lakes present a new threat to human and ecological health due to chal- lenges associated with tracking and understanding their impacts. The workshop presenters will discuss how large water and wastewater utilities approach the issue of emerging contaminants, highlight the challenges, and provide recommendations for future action. This presentation was given by Lon Couillard, Water Quality Manager, Milwaukee Water Works.

1. Milwaukee Water Works
Chemicals of Emerging
Concern in the Great
Lakes
HOW Conference
September 2013
Lon A. Couillard
Water Quality Manager

2. Milwaukee Water Works
Ozonation Facilities and Treatment
Established in 1998
Major Water Quality goals identified at that time:
• Disinfection of pathogens (Cryptosporidium)
• Disinfection by-products reduction
• Taste & odor control
• Oxidation of organics (Biological Filtration)

3. Milwaukee Water Works
Much New information has come
along since 1998 - Emerging
Pollutants list continues to grow
• Endocrine disruptors
• Pharmaceuticals
• Brominated flame retardants
• Personal care products

4. What are the sources of these new emerging
contaminants?
• Sewage treatment plant discharges
• Disposal of expired and unused consumer products,
including prescription drugs
• Farm animal feed additives, veterinary drugs
• Consumer products including Over-the counter (OTCs)
containing antimicrobials, fragrances, dyes, etc
• medical wastes from/used in diagnostic procedures

5. State and Federal Regulatory Agenda
recognizes this emerging contaminant
trend as well:
UCMR (Unregulated contaminant monitoring rule)
sampling & monitoring required of selected water
utilities -
UCMR- Phase 1 in 2005
UCMR- Phase 2 in 2008
UCMR- Phase 3 started in 2013

6. Milwaukee Water Works
Early Monitoring Program
In 2004, started the Endocrine Disruptor
testing; two component groups
• Estrogenic compounds and hormones
• Phenolic endocrine disruptor compounds
• Total list of 18 specific parameters

7. Milwaukee Water Works
Early Monitoring Program
• Started Pharmaceuticals & Personal Care Products
PPCPs in 2005
Acetaminophen
Caffeine
Carbamazepine
Cotinine
Tylosin
DEET
Ibuprofen
Lincomycin
Sulfadimethoxine
Sulfamethazine Sulfamethoxazole
Sulfamethoxazole
Triclosan
Trimethoprim 1, 7-Dimethylxanthine
• This list is 1/2 animal antibiotics

8. Milwaukee Water Works
Environmental Monitoring Program is a
Constantly Evolving Process
• Data and information gathering phase
• Locating labs that can perform tests
• Dealing with changing detection limits
• Media coverage
• Surge of information on the Internet

9. Milwaukee Water Works
Important Notes:
• There is a knowledge gap between
what we purchase and use as
consumers, and what water utilities and
environmental labs are able to monitor
in the environment
• Case in point -

10. Top 60 Prescribed Prescription Drugs, 2010*
1. Hydrocodone/APAP
2. Amoxicillin
3. Hydrocodone/APAP
4. Lipitor
5. Levothyroxine Sodium
6. Lisinopril
7. Simvastatin
8. Plavix
9. Nexium
10. Singulair
11. Metoprolol Tartrate
12. Simvastatin
13. Lexapro
14. Synthroid
15. Azithromycin
16. Crestor
17. Levothyroxine Sodium
18. Proair HFA
19. Metformin HCl
20. Sertraline HCl
21. Ibuprofen (Rx)
22. Metoprolol Succinate
23. Azithromycin
24. Zolpidem Tartrate
25. Advair Diskus
26. Furosemid
27. Hydrochlorothiazide
28. Omeprazole (Rx)
29. Trazodone HCl
30. Lisinopril
31. Simvastatin
32. Diovan
33. Tramadol HCl
34. Oxycodone/APAP
35. Cymbalta
36. Warfarin Sodium
37. Amlodipine Besylate
38. Omeprazole (Rx)
39. Oxycodone/APAP
40. Amlodipine Besylate
41. Sulfamethoxazole/ Trimethoprim 42. Seroquel
43. Promethazine HCl
44. Ventolin HFA
45. Fluticasone Propionate
46. Alprazolam
47. Clonazepam
48.
Amoxicillin Trihydrate/ Potassium Clavulanate
49. Hydrochlorothiazide
50.
Warfarin Sodium
51. Diovan HCT
52. Actos
Pravastatin Sodium
54. Oxycodone/APAP
55. Vitamin D (Rx)
Fluoxetine HCl
57. Alprazolam
58. Lantus
Atenolol
60. Fluconazole
*Data Courtesy of RxList.com 2012
53.
56.
59.

11. Milwaukee Water Works
Our PPCP list – 2010
Pharmaceuticals & Personal Care Products
Acetaminophen Antipyrine Atenolol Azithromycin Bacitracin Bezafibrate
Caffeine Carbadox Carbamazepine Chloramphenicol Chlorotetracycline
Ciprofloxacin Clofibric acid Cotinine DEET Diclofenac Dilantin
Diazepam Diltiazem Doxycycline Enrofloxacin Erythromycin Fluoxetine
(Prozac) Gemfibrozil Ibuprofen Iopromide Lasalocid Levothyroxine
(Synthroid) Lincomycin Meprobamate Monensin
Naproxen Narasin Nicotine Norfloxacin Oleandomycin
Oxytetracycline Paraxanthine Penicillin-G Penicillin-V
Prednisone Primidone Roxithromycin Salinomycin Simvastatin
Sulfachloropyridazine Sulfadiazine Sulfadimethoxine Sulfamerazine
Sulfamethazine Sulfamethizole Sulfamethoxazole Sulthiazole
Tetracycline Theobromine Theophylline Triclosan Trimethoprim
Tylosin Virginiamycin M1

12. Problems and Challenges of Current Analytical
Methodologies*
• Certified methods not readily available
• Significant method variation in sensitivity,
recoveries, and precision
• Significantly varied QC criteria from lab to
lab
• Significant matrix effects
• Optimum sample preservation not established
• Lack of standardization on sample stability and
hold time
*Water Research Foundation Report # 4167,
March 2012

13. Problems and Challenges of Current Analytical
Methodologies*
common, due to lab
and water, data is
suspect
Mass Balance Figure published in Journal of Environmental Monitoring, 8:9 (2006) by Peck, A. and Hornbuckle,
K. Environmental Sources, Occurrence, and Effects of Synthetic Musk Fragrances

14. Milwaukee Water Works
Lessons Learned so far
• Expect the unexpected
• False-positives are common, due to lab
and cross-contamination
• Ways to minimize surprise detects – collect in
duplicate, require both a lab blank and a trip
blank, collect at two points in treatment process
• If the contaminant is found in the finished
water but not your source water, data is
suspect

15. Ozone Oxidation of Endocrine Disruptors and Pharmaceuticals
• In recent study of drinking water treatment,
the majority of target compounds (36) were
removed by > 90% at ozone doses
commonly used for disinfection*
• Only 6 of 36 compounds showed removals
less than 50% in finished drinking waters
Implementation of ozone for water treatment is likely
The most cost effective measure for removing the majority of PPCPs
* Data courtesy of WRF Report # 91188, Published 2007
Shane A. Snyder at al.

16. Treatability of Algal Toxins Using Ozone Oxidation Technologies
• Cyanobacteria and their toxins are an emerging
water quality concern
• Studies conducted using Microcystis algal species
have shown that Microcystis toxin (m-LR) is effectively
destroyed by ozonation
• Ozone doses as low as 0.4 ppm achieved significant
m-LR removals (>97 %) at or below pH 7*
* data provided courtesy of WRF Report #2839
published July 2010

17. As the great philosopher POGO once said,
We have met the enemy, and he is us
In this case, we have met the polluter,
and he is us.
We as citizens and consumers purchase
the products that end up in our environment

18. What can we do? As citizens and consumers?
We can purchase more environmentally-friendly products
• Buy fragrance-free and dye-free laundry
detergent products
• Purchase allergen-free lotion for hands and feet Often
labeled as Hypoallergenic
• Use less products containing syn musks –
dryer
sheets, hair and body sprays
• Purchase biodegradable shampoos and
body
washes – better for our environment