Emerging Trace Contaminants: Prevalence and Treatment Options

Rajendra P. Bhattarai, P.E., BCEEAustin Water, City of Austin

Austin, Texas

June 17, 2016

Summer Seminar

Emerging Issues in the Water/Wastewater Industry

San Antonio, Texas

Acknowledgements• Dr. James M. Lazorchack, EPA• Dr. Angela Batt, EPA• Dr. Marc Mills, EPA• Dr. Mitchell Kostich, EPA• Dr. Desmond Lawler, The University of Texas at Austin• Dr. Wayne Parker, University of Waterloo• Dana White, Austin Water• Associated staff at 50 WWTPs

Presentation Outline

• Background

• Ecosystem and Human Health Impacts

• EPA Study of 50 large U.S. WWTP Effluent

• Results of EPA Study

• Treatment options

• Questions and Comments

Emerging Contaminants or Microconstituents

• Pharmaceuticals, Personal Care Products (PPCPs)

• Endocrine-Disrupting Compounds (EDCs)

• Contaminants of emerging concern (CECs)

• Micropollutants

• Natural (coffee, soy, apples and pears), as well as synthetic (industrial chemicals, medicines, personal care products such as soap, toothpaste, lotions and perfumes)

4

Background• Measurable levels of anthropogenic chemicals

in all waters

• Not a new issue

• Earliest published papers of ETCs in North American waters from 1960s and 1970s

• EPA Report on pharmaceuticals in water (1975)

• First report of endocrine disruption in fish downstream of WWTP outfalls (1996)

• More contaminants detected now due to better analytical technology

5

Background (continued…)

• National headlines with USGS publication of a study of 130 U.S. streams in Environmental Science and Technology (Kolpin et al., 2002)

• Detectable concentrations of organic compounds – including steroids, insect repellant, caffeine, antimicrobial agents, fire retardants and detergent metabolites – that are generally associated with wastewater, were found in 80% of streams sampled

• Lost in the ensuing noise was the relevance of the detectable levels of contaminants

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Extremely Low Concentrations

• mg/L = parts per million = 1 sec in 12 days

• μg/L = parts per billion = 1 sec in 32 years

• ng/L = parts per trillion = 1 sec in 32,000 years

or

• One Tylenol tablet dissolved in 26 Olympic-size pools

• What about pg/L, fg/L, åg/L, zg/L and yg/L?

• What will we find?

7

8

Ecosystem and Human Health Impacts• Feminization of male fish

• Reproductive abnormalities in alligators

• Female reproductive abnormalities

• “Gender-bending” in aquatic mammals

• Confused fish, Impotent Alligators

• Human health effects: not observed yetWhat am I?

Not even Viagra can help me!

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10

Occurrence and Potential for Human Health Impacts of Pharmaceuticals in the Water System

No definitive link hasbeen reported orestablished betweenhuman exposure topharmaceuticalsin drinking water andhuman health risk. Put another way,there is no knownimpact on humanhealth.

-GWRC (2009)

Synthesis of nine reports that address the occurrence and potential for human health impacts of pharmaceuticals in the water system (GWRC, 2009)

EPA Municipal Effluent CEC Study

• Assess concentration and magnitude of emerging contaminants in municipal WWTP effluents

• 50 large WWTP discharging to non-marine waters in the contiguous U.S.

• 24-hr composite samples collected: Dec 2010 – Mar 2011

• 54 highest priority pharmaceuticals, 8 steroids, Bisphenol A (BPA), 19 Nonylphenols, and 14 perfluorinated compounds

Geographical Distribution of Sampling Sites

50 Largest Plants (20% Population, 17% of discharge)

EPA Municipal Effluent Study Results

• Reporting limit (RL) = 3 x the EPA MDL (method detection limit) or the lowest calibration point, whichever is greater

• Numbers in parentheses are based on including estimated concentrations from samples that failed quantification criteria

EPA Municipal Effluent Study ResultsAnalyte RL

(ng/L)

Number of

detections

Mean

(ng/L)

Max

(ng/L)

10-Hydroxy-Amitriptyline - Metabolite 5 6 <RL <RL

Acetaminophen - Analgesic, Tylenol 5 7 79 (300) 1500 (4500)

Albuterol - Bronchodilator, Ventolin 9.7 27 14 35

Alprazolam - Anxiety, Xanax 9.1 15 10 31

Amitriptyline – Antidepressant, Elavil 5 20 11 110

Amlodipine - High Blood Pressure 5 11 6.9 18

Amphetamine - ADD, Adderall 1.6 5 3.5 40

Atenolol – Beta Blocker, Hypertension 6 48 940 3000

Atorvastatin - Cholesterol, Lipitor 38 4 <RL <RL

3rd

EPA Municipal Effluent Study ResultsAnalyte RL

(ng/L)

Number of

detections

Mean

(ng/L)

Max

(ng/L)

Benztropine - Parkinson’s Disease 10 0 ND ND

Carbamazepine - Epilepsy, Tegretol 4.4 48 97 (140) 240 (460)

Ciprofloxacin - Antibiotic, Cipro 10 30 67 (72) 260 (320)

Clonidine - Blood Pressure & Anxiety 35 0 ND ND

Desmethylsertraline - Sertraline metabolite 9.4 9 9.9 (10) 24

Diltiazem - Blood Pressure, Cardizem 2.8 41 85 340

Diltiazem-desmethyl (Diltiazem metabolite) 1.6 34 24 100

Enalapril - Blood Pressure, Cardizem 1 9 4.6 38

Enalapril - Blood Pressure, Cardizem 11 13 13 32

3rd

9th

EPA Municipal Effluent Study ResultsAnalyte RL

(ng/L)

Number of

detections

Mean

(ng/L)

Max

(ng/L)

Enalaprilat - Enalapril metabolite 9 5 14 (18) 150

Florfenicol - Bovine Rsprtry Disease 60 0 ND ND

Fluocinonide - Eczema, Lidex 10 0 ND ND

Fluoxetine - Antidepressant, Prozac 2.8 18 8.7 31

Fluticasone - Corticosteroid, Flonase 19 0 ND ND

Furosemide - Blood Pressure, Lasix 38 45 280 (350) 810 (2100)

Gemfibrozil - Lowering Lipid, Lopid 10 38 420 (480) 2300

Hydrochlorothiazide - Blood Pressure 10 50 1100 (1200) 2800

Hydrocodone - Analgesic, Cough med 3.8 22 22 (24) 92 (100)

5th

1st

EPA Municipal Effluent Study ResultsAnalyte RL

(ng/L)

Number of

detections

Mean

(ng/L)

Max

(ng/L)

Hydrocortisone - Anti-inflammation 25 0 ND ND

Ibuprofen - NSAID, Advil, Motrin 12 23 460 (690) 4200 (4600)

Lincomycin - Antibiotic 8 0 ND ND

Lisinopril - Blood Pressure, Prinivil 45 23 180 (1700) 3300 (13000)

Melengestrol acetate - Anml Cntrcptv 9 0 ND ND

Methylprednisolone - Corticosteroid 25 0 ND ND

Metoprolol - Blood Pressure, Toprol 14 49 410 (450) 660 (1200)

Norethindrone - Oral Contraceptive 6.9 0 ND ND

Norfluoxetine - Fluoxetine metabolite 7.2 8 7.7 15

2nd

EPA Municipal Effluent Study ResultsAnalyte RL

(ng/L)

Number of

detections

Mean

(ng/L)

Max

(ng/L)

Norverapamil - Active Metabolite of Verapamil 4.4 25 5.8 20

Ofloxacin - Antibiotic, Floxin, Ocuflox 10 44 160 660

Oxycodone - Pain Killer, Opioid, Oxycontin 2.5 30 53 310

Paroxetine - Antidepressant, Paxil 5 0 ND ND

Prednisolone - Anti-inflammatory, cancers 11 0 ND ND

Prednisone - Corticosteroid, Anti-inflammatory 30 0 ND ND

Progesterone - Oral Contraceptive 188 2 <RL <RL

Progesterone - Oral Contraceptive 9 0 ND ND

Promethazine - Antihistamine, Phenadoz 5 0 ND ND

6th

EPA Municipal Effluent Study ResultsAnalyte RL

(ng/L)

Number of

detections

Mean

(ng/L)

Max

(ng/L)

Propoxyphene - Analgesic, Opioid, Darvon 16 12 17 34 (46)

Propranolol - Blood Pressure, Inderal 4.4 44 33 260

Ranitidine - Heartburn, Zantac 11 19 120 1400

Sertraline - Antidepressant, Zoloft 5 32 21 71

Simvastatin - Choloesterol, Zocor 41 12 <RL <RL

Sulfadimethoxine - Pet Antibacterial, Albon 1 0 ND ND

Sulfamethazine - Veterinary Antibacterial, 10 1 12 87

Sulfamethoxazole - Antibiotic, Bactrim 1.6 40 910 2900

Sulfamethoxazole - Antibiotic, Bactrim 1 44 330 1000

6th

6th

EPA Municipal Effluent Study ResultsAnalyte RL

(ng/L)

Number of

detections

Mean

(ng/L)

Max

(ng/L)

Testosterone - Steroid Hormone 3.5 0 ND ND

Testosterone - Steroid Hormone 1 0 ND ND

Theophylline - Asthma, Theolair 88 4 <RL (88) <RL (100)

Triamterene - Diuretic, Dyrenium 1.3 35 37 170

Trimethoprim - Antibiotic, Primsol 2.5 37 170 370

Trimethoprim - Antibiotic, Primsol 1 40 90 210

Valsartan - Blood Pressure, Diovan 11 40 1600 (1700) 5300 (8200)

Verapamil - Blood Pressure 2.5 39 26 97

Warfarin - Blood Thinner, Coumadin 11 0 ND ND

10th

10th

Comparison of Detected Values with Australian Guidelines for Drinking Water Augmentation

AnalyteDetected

Mean,μg/L

DWG, μg/L

Atenolol 0.94 NA

Carbamazepine 0.097 100

Diltiazem 0.085 60

Furosemide 0.28 NA

Hydrochlorothiazide 1.1 NA

Metoprolol 0.41 25

Ofloxacin 0.16 NA

Propranolol 0.033 40

Sulfamethoxazole 0.33 35

Trimethoprim 0.09 70

Valsartan 1.6 NA

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Summary of 63 Pharmaceuticals plus Metabolites Across all 50 Effluents

9 pharmaceuticals (14%) detected at or above 1 μg/L42 (84%) effluents with 1-8 pharmaceuticals > 0.7 μg/L or higher

0

5

10

15

20

25

30

35

0 10 20 30 40 50 60

Det

ects

Across 50 Plants

# of Detects out of 63 Pharmaceuticals

0

5000

10000

15000

20000

25000

0 10 20 30 40 50 60

To

tal

ng/L

Across 50 Plants

Total Mass of Pharmaceuticals Detected

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Prepared by Joel Allen U.S. EPA ORD

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Summary of 8 Hormones across all 50 Effluents

EE2 found in 49 (98%) effluent 44 (88%) > PNEC of 0.35 ng/L Estradiol found in 30 (60%) effluents 29 effluents have both EE2 and E2

0

1

2

3

4

5

6

7

8

9

0 10 20 30 40 50 60

De

tect

s

# Detects over 50 Plants

# of Hormones Detected out of 8 Analyzed

0.00

20.00

40.00

60.00

80.00

100.00

120.00

0 10 20 30 40 50 60

ng/

L

Over 50 Plants

Total Mass of Hormones

25

Prepared by Joel Allen U.S. EPA ORD

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Summary of 32 Alkylphenols and Nonylphenol Across all 50 Effluents

0

5

10

15

20

25

0 10 20 30 40 50 60

# D

ete

cts

Across 50 Plants

Total AP/NP Detects 32

0

50000

100000

150000

200000

250000

300000

350000

0 10 20 30 40 50 60

ng/

L

Across 50 Plants

Total Mass AP/NP

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Prepared by Joel Allen U.S. EPA ORD

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Summary of 15 PFAA (PFCs) across all 50 Effluents

0

2

4

6

8

10

12

14

16

0 10 20 30 40 50 60

# D

ete

cte

d

Across 50 Plants

# of PFAA Detects out of 15 Analytes

0

200

400

600

800

1000

1200

1400

1600

0 10 20 30 40 50 60

ng/

L

Mass Across 50 Plants

Total Mass PFAAs (PFCs)

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Perfluoroalkyl Acids PFAA (PFCs)

Prepared by Joel Allen U.S. EPA ORD

C3A = PFPAC4A = PFBAC5A = PFPeAC6A = PFHxAC7A = PFHpAC8A = PFOAC9A = PFNAC10A= PFDAC11A= PFUdAC12A= PFDoAC13A= PFTrDAC4S = PFBSC6S = PFHxSC8S = PFOS

30

Prepared by Joel Allen U.S. EPA ORD

Illegal Drugs in European Wastewater

Modified from Stephanie Fox, io9.com. From Kevin Thomas et al, Science of the Total Environment, August 2012

Treatment for Emerging Contaminants• One single treatment not adequate

for large groups of contaminantsBetter removal at wastewater treatment plants with:• Longer detention times• Longer sludge age• Biological Nutrient Removal

– Anaerobic– Anoxic– Aerobic

• Natural Bacterial Enzymes• Cl2 moderately effective• O3 and H2O2 highly effective• Activated carbon highly effective• More research needed

Treatment for Emerging Contaminants• Advanced Oxidation

Processes (AOP)

• Use of highly reactive hydroxyl radicals (●OH)– Ozone

– Hydrogen Peroxide

– Ozone/Hydrogen Peroxide

– UV/Ozone

– UV/Hydrogen Peroxide

– UV/Hydrogen Peroxide/Ozone

Mobile Advanced Oxidation Process System

Source: Air Products

Membrane Treatment for Emerging Contaminants

Combination of Membranes and AOP

• Most direct potable reuse plants use a combination of membrane treatment followed by advanced oxidation processes

• Destroys even some of the most recalcitrant organic compounds

Direct Potable Reuse• Windhoek, Namibia (1968): First

Direct Potable Reuse in the World

• Initial: 1.1 million gal/day (MGD)

• Current: 5.5 MGD

Goreangab Water Reclamation Plant

Initial Treatment Plant Current Treatment Plant

Source: P. DuPisani

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Direct Potable Reuse• First Direct Potable Reuse in the

U.S. and Texas

• Colorado River Municipal Water District, Big Spring, Texas (2013): 2.1 MGD treated effluent; Produces 1.6 MGD drinking water.

• Microfiltration

• Reverse Osmosis

• Advanced Oxidation: UV and Hydrogen Peroxide

Source: David Sloan, Freese and Nichols39

Safe Drinking Water Act Standard Setting Processes

Source: Alan Roberson, Corona Environmental Engineering NPDWR – National Primary Drinking Water Regulations

CCL – Contaminant Candidate ListUCMR – Unregulated Contaminant Monitoring Rule

Third Unregulated Contaminant Monitoring Rule (UCMR 3)

• Seven Hormones

– 17-β-Estradiol

– 17-α-Ethynylestradiol(Ethinyl Estradiol)

– 16-α-Hydroxyestradiol(Estriol)

– Equilin

– Estrone

– Testosterone

– 4-Androstene-3,17-dione

• Six Perfluorinated Acids

– PerfluorooctanesulfonicAcid (PFOS)

– Perfluorooctanoic Acid (PFOA)

– Perfluorononanoic Acid (PFNA)

– PerfluorohexanesulfonicAcid (PFHxS)

– Perfluoroheptanoic Acid (PFHpA)

– PerfluorobutanesulfonicAcid (PFBS)

Take Home Messages• Pharmaceuticals and trace contaminants documented in

water for almost 50 years

• No definitive list – too many compounds

• Extremely low concentrations – difficult to sample and measure

• Watch out for erroneous data

• Can be treated using a variety of methods

• No technology is likely to achieve “zero”

• Toxicological relevance at detected levels?

• Ecological concerns must be addressed

• Need to look at mixture, not just at individual compounds

• Using some activity or equivalency approach would be better for risk assessments

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Take Home Messages• No known human health effects

• Long-term risk to humans from any single compound at sub-μg/L levels is negligible

• World Health Organization (2012): Virtually no risk to humans from exposure to pharmaceuticals in water

• Detection doesn’t mean adverse health effects

• Non-Detect doesn’t imply total absence or complete safety

• Concentration of some contaminants in water many times lower than what humans are exposed to through food, beverages and indoor air

• Give EPA’s Endocrine Disruptor Screening Program (EDSP), CCL, and UCMR a chance

• EPA’s UCMR 3 currently includes seven hormones and six perfluorinated compounds, among other parameters

Questions, Comments?

44

In Memoriam: Dr. Joseph F. Malina, Jr.(1935 - 2016)

• Teacher, Author, Mentor, Adviser, Friend

• Professor Emeritus, UT Austin, 2014-2016

• Professor, UT Austin, 1961-2014

• TWPCA President, 1975-1976

• WEAT Lifetime Achievement Award, 2005

• WEF Fellow, 2015

• WEF Gordon M. Fair Award, 1994

• WEF Arthur Sidney Bedell Award, 1984

• ASCE Fellow, 1980

• ASCE Arthur M. Wellington Prize, 2000

• Life Member of ASCE, AWWA and WEF

• 26 Ph.D. students, 166 M.S. students, and thousands of graduate and undergraduate students 45