The ABCs of ECs:Emerging Contaminants

in the Environment

byChuck Graf

AWI Associate DirectorLiaison to the Arizona Department of Environmental Quality

…and emerging terminology, too!

ECEC Emerging ContaminantsEmerging ContaminantsECCECC Emerging Contaminants of ConcernEmerging Contaminants of ConcernCECCEC Contaminants of Emerging ConcernContaminants of Emerging ConcernOWCOWC Organic Wastewater Contaminants (Chemicals/Compounds)Organic Wastewater Contaminants (Chemicals/Compounds)PPCPPPCP Pharmaceuticals & Personal Care ProductsPharmaceuticals & Personal Care ProductsPACPAC Pharmaceutically Active Chemicals (or Compounds)Pharmaceutically Active Chemicals (or Compounds)PIEPIE Pharmaceuticals in the EnvironmentPharmaceuticals in the EnvironmentEDCEDC Endocrine Disrupting Compounds (or Chemicals)Endocrine Disrupting Compounds (or Chemicals)EACEAC Endocrine Active CompoundsEndocrine Active CompoundsMCMC MicroconstituentsMicroconstituentsAOCAOC Anthropogenic Organic CompoundsAnthropogenic Organic CompoundsAWIAWI Anthropogenic Waste IndicatorsAnthropogenic Waste IndicatorsTOrCTOrC Trace Organic CompoundTrace Organic Compound

Questions to Answer

• What are they?• How do they get into the

environment?• Where do they end up?• What is their impact?• What can we do?

Carbamazepine

PPCPs (or is it OWCs?) Burst Onto the Scene!

Daughton and Jones-Lepp, 2001 Kolpin and others, 2002American Chemical Society Environmental Science & Technology

EC, OWC, AWI, TOrC: What are they?

• Human drugs• Veterinary drugs• Antibiotics• Hormones• Steroids• Detergents• Plastics additives• Antioxidants

• Flame retardants• Disinfection byproducts• Fumigants• Fragrances• Insecticides• Insect repellents• Natural phytoestrogens

– alfalfa, legumes

Other Emerging (Re-emerging?) Contaminants

• Tungsten• Cobalt• Germanium• Molybdenum• Strontium• Vanadium• Nanomaterials• Naegleria fowleri• Vibrio cholerae

• Perchlorate• Arsenic• Sulfate• TDS

Perchlorate ion

Our definition for today

Organic chemicals that are…

• Not commonly monitored• Demonstrated to occur in the

environment• Believed to have the potential

to create an ecosystem or human health risk

Polybrominateddiphenyl ether

(PBDE)flame retardant

2002 USGS Reconnaissance: A Milestone Consciousness-Raising Study

• USGS sampled 95 chemicals, 130 sites– Veterinary & human antibiotics– Prescription & non-prescription drugs– Steroids & hormones– Plasticizers– Insecticides– Detergent metabolites

• Targeted waters with likely OWC occurrence

USGS Samples Sites and Results

• USGS sampled 4 sites in AZ below WWTPs– Santa Cruz River below Nogales IWWTP– Santa Cruz River below Pima County Ina Rd

WWTP– Outfall below Phoenix 91st WWTP– Gila River at Gillespie Dam (45 mi below 91st Ave

WWTP)• 17 to 38 chemicals detected at each site• Highest levels in US for 16 chemicals

– Plasticizers (Bis-phenol A)– Detergent metabolites (4-nonylphenol) – Estrogen replacements (Equilin)– Birth control drugs (17β-estradiol)

Bis-phenol A

Concentration Limbo (How Low Can You Go?)

• Grams per liter (g/l)– parts per thousand

• Sea water (NaCl: 35 g/l– 35,000 ppm

Concentration Limbo (How Low Can You Go?)

• Milligrams per liter (mg/l)– parts per million

• Nitrate: 10 mg/l– Drinking water MCL– Protects from “blue baby

syndrome

Concentration Limbo (How Low Can You Go?)

• Micrograms per liter (µg/l)– parts per billion (ppb)

• Arsenic: 10 µg/l– Drinking water MCL– Protect from carcinogenetic

effects

Concentration Limbo (How Low Can You Go?)

• Nanograms per liter (ng/l)– parts per trillion (ppt)

• 17α-ethynylestradiol: 6 ng/l– Synthetic estrogen used in

birth-control pills– Endocrine-disrupting effects

Q. So, just what does non-detect mean?

A. Certainly not zero! At 6 ng/l, there arestill 12,000,000,000 (12 trillion) molecules of the estrogen in a liter of water

A Spectrum of Concentrations

NaCl 250,000 mg/l Heavy salt brineNaCl 35,000 mg/l SeawaterTDS 500 mg/l EPA DW aesthetic limitNitrate 10 mg/l Drinking water MCLArsenic .01 mg/l Drinking water MCL17α-Ethynylestradiol .000006 mg/l Hormonally active

EDCs: A Subset of ECs

What is an endocrine disrupting compound?

“ an exogenous substance or mixture that alters function(s) of the endocrine system and consequently causes adverse health effects in an intact organism, or its progeny….”

World Health Organization, 2002

Some Suspected/Known EDCs

Synthetic Compounds Natural CompoundsSynthetic hormones: Sex steroids:

birth control 17β-estradiol (the primary vertebrate estrogen)hormone therapy drugs testosteronegrowth steroids

Agricultural compounds: Phytoestrogens:organochlorine pesticides naturally occurring plant compoundschlordeconeendosulfan

Industrial compounds:phenolicsnonyl- and octylphenolsBisphenol APDBE flame retardantsphthalate plasticizersPCBsPAHs

Bis(2-ethylhexyl)phthalate

How do EDCs act?

• Reduce hormone production in endocrine glands

• Mimic or counteract hormones at target tissues

• EDC categories– Estrogenic– Androgenic– Thyroid-active

Normal Hormone Function

Adapted from Nicole Fales, Absar Alum, and Morteza AbbaszadeganArizona State University

Hormone Mimicking

Adapted from Nicole Fales, Absar Alum, and Morteza AbbaszadeganArizona State University

Hormone Mimicking

Adapted from Nicole Fales, Absar Alum, and Morteza AbbaszadeganArizona State University

Hormone Blocking

Adapted from Nicole Fales, Absar Alum, and Morteza AbbaszadeganArizona State University

Documented effects of EDCs in wildlife• Abnormal blood hormone levels• Masculinization of females• Feminization of males• Intersex individuals (reproductive

organs of both sexes)• Malformed reproductive organs• Skewed sex ratios• Embryo mortality (incl. eggshell

thinning in birds of prey)• Deformities• Modified immune system• Altered thyroid function• Brain and neurological problems• Reproductive tissue cancers• Altered bone density and structure Source: Center for Bioenvironmental Research, Tulane and Xavier Universities

Denver Post (September 6, 2006)

EDCs in the News

Courtesy of Dr. David Quanrud, Univ. of Arizona

“Collapse of a fish population after exposure to a synthetic estrogen,”Kidd, et al., Proc. of the National Academy of Sciences, 2007.

• 7-year field study at Canadian research lake in Ontario• Fathead minnow population collapsed after 2 years of estrogen addition• 17α-ethynylestradiol added at 5-6 ng/l

Untreated Lake Treated lake

Length Distribution

EE2 added

Speculated effects of EDCs in humans

• Reductions in male fertility and declines in the numbers of males born

• Abnormalities in male reproductive organs

• Female reproductive diseases including fertility problems, early puberty, and early reproductive senescence

• Increases in mammary, ovarian, and prostate cancers

2008 WERF study conclusion: “No definitive evidence of harm to human health—research suggests watchful caution, but not alarm.”

Analysis of Emerging Contaminants

How are these measured in environmental samples?

1. Individual chemical measurement– no adopted standard methods for the vast bulk of compounds of interest (or

no method at all!)– quantification much more difficult than detection/identification– high cost of analysis– drinking water easier; soil, sediment, wastewater & biosolids harder– In Dec 2007, EPA published but did not promulgate the following methods

• 1694—Pharmaceuticals and Personal Care Products (74 compounds)• 1698—Steroids and hormones (29 compounds)• 1699—Pesticides (61 compounds)

INTE

NS

ITY

TIME

a. Naproxen analgesicb. Dilantin anti-seizurec. Diclofenac anti-arthriticd. Ibuprofen analgesice. Tetrabromobisphenol A flame retardantf. Triclosan antibiotica

b

c

d

e f

ADHS Liquid Chromatography

Tandem Mass Spectrometer

(LCMS/MS)

Analysis of Emerging Contaminants

• Just coming out of the research labs into commercial labs

• Emphasis so far is on analysis of drinking water

• Differing methods are in use (EPA, state, commercial, and USGS & other research labs)

– analytes vary– differing equipment and analytical approaches– differing extraction methods

• RFP recently issued by AWWA to look at current laboratory practice:

– list of analytes– reporting limits– instrumentation– extraction procedures– quality control measures– cost

Analysis of Emerging Contaminants

• Commercial lab cost is still stratospheric– Estrogens and other hormones - $455

• Estradiol and ethynyl estradiol• 9 compounds total

– Fragrances - $390• Galaxolide and tonalid (2 compounds total)

– Pharmaceutically active compounds (List 1) - $520• Ibuprofen, aspirin, triclosan• 30 compounds total

– Pharmaceutically active compounds (List 2) - $520• Acetominophen, caffeine, carbamazepine, Prozac• 40 compounds total

– Phenolic endocrine disrupting chemicals - $390• Bisphenol A, nonylphenol• 8 compounds total

• One well, one “full” scan - $2275 !!

Analysis of Emerging Contaminants

2. Bioassays: A second approach to measurement

For EDCs, measurement of collective impactTotal estrogenic activity

- estrogen receptor is incorporated into test- records binding of any estrogen or mimicking compound

- good screening tool because much cheaper- no adopted standard method- interferences are common- specific causation chemical(s) aren’t identified

Analysis of Emerging Contaminants

Yeast Estrogen Screen (YES) Bioassay

← Std

Cytoplasm

E

R

R E

E

Cytoplasm

= Receptor

R

hER β-gal

CPRGyellow

CPRGred

lac-z

RE

=Estrogens

Cytoplasm

RR

RR EE

EE

Cytoplasm

= Receptor

RR

hER β-gal

CPRGyellow

CPRGred

lac-z

RE

RREE

=Estrogen

AWIs in the Environment

ECs in Soil Irrigated with Reclaimed Water

• Colorado study of lawn and golf course sprinkler irrigation of reclaimed water

• 19 PPCPs tested in reclaimed water and in soil to a depth of 1 ft

• Accumulations detected in soil of (among others)– Cotinine (nicotine metabolite)– Fluoxetine (antidepressant)– Sulfamethoxazole (antibiotic)– Carbamazepine (antiepileptic)

• Leaching occurred below 1 ft• Soil organic matter is controlling factor in

retention/leaching

Kinney, C.A., Presence and Distribution of Wastewater-derived Pharmaceuticals in Soil Irrigated with Reclaimed Water, 2006.

Fluoxetine (Prozac)

ECs in Reclaimed Water & GroundwaterTucson Mesa Tucson Mesa

Compound (ng/l) Class WWTP WWTP Well* Well**

Carbamazepine Antiepileptic ND 175 455 115Primidone Antiepileptic 110 202 115 140

Ibuprofen Analgesic 3380 16 ND NDNaproxen Analgesic 6280 8 20 NDGemfibrozil Lipid regulator 1235 ND ND NDPropyphenazone Analgesic 20 ND 15 ND

4-Nonylphenol Detergent metabolite 40,000 DEET Insect repellent 1,100

* Groundwater travel time: 2-4 weeks**Groundwater travel time: 6-18 months

Pima County Rogers Road WWTP is a secondary plant w/o nitrification-denitrification.Mesa Northwest WWTP is a tertiary plant with nitrification-denitrification.

Fate Through a WWTP

Influent

EffluentInfluent

Biosolids(Sludge)

Treated Wastewater(Reclaimed Water)

WWTPUnit

Processes

Estrogen Removal: 8 Arizona WWTPsEDC Removal, EDC Removal,

WWTP Location Type Liquid (%) Total (%)Roger Rd* Tucson Secondary 37 21Ina Road Tucson Tertiary 76 58Rio de Flag Flagstaff Tertiary 73 50Sundog Prescott Tertiary 89 84American Gulch Payson Tertiary 99 99Randolph Park Tucson Tertiary 99 9991st Avenue Phoenix Tertiary 99 99Avra Valley Tucson Tertiary 99 99

*Pima County Rogers Road WWTP is a secondary plant without nitrification-denitrification.All others are tertiary plants with nitrification-denitrification.

2008 WERF study conclusion: Advanced treatment for nutrient reductioncan provide additional TOrC removal.

Note: EDC Removals calculated from YES bioassay results.

WWTP Performance: Next Steps• More fully determine removal efficiencies of unit processes within WWTP

– Wastewater– Sludge

• Determine how to optimize EC removal in existing unit processes• Develop new unit treatment processes targeting removal of recalcitrant or harmful ECs

Raw Sewage PrimarySedimentation

BiologicalTreatment

Secondary Clarifier

TreatedWastewater

Bar Screen

Digested Sludge

1º Sludge

Centrate

Dewatered Sludge(Biosolids)

Pharmaceuticals in AZ water vs. Therapeutic Dose

Max Conc Years forDrug Use (ng/l) Medium Location Therapeutic Dose*Carbamazepine Antiepileptic 455 GW Below Tucson WWTPs 30Primidone Antiepileptic 202 WW Mesa NW 340Ibuprofen Analgesic 3380 WW Roger Rd, Tucson 20Naproxen Analgesic 6280 WW Roger Rd, Tucson 27Gemfibrozil Lipid regulator 1235 WW Roger Rd, Tucson 1300Diclofenic Antiepileptic 80 WW Roger Rd, Tucson 17,000Ciprofloxacin Antibiotic 30 WW Roger Rd, Tucson 6.7Sulfamethoxazole Antibiotic 1900 WW Roger Rd, Tucson 290Cimetidine Antiacid 580 WW Roger Rd, Tucson 47017α-EE Birth control 81 WW 91st Ave, Phx 0.08 (30 days)

*Years to reach therapeutic dose drinking 2 liters of water per day at indicated concentration level.

GW = GroundwaterWW = Wastewater collected from or below an outfall of a sewage treatment plant

Dealing with the EC Problem

• Regulatory approaches

– Drinking water standards (federal--EPA)– BADCT for WWTPs (state--ADEQ)– Reclaimed WQS (state--ADEQ)

• Non-regulatory approaches

– Pharmaceutical take back programs– Source & disposal control approaches to keep PPCPs out of the sewer– More, better, cheaper, faster analytical methods– Better screening/modeling methods to identify harmful existing and new chemicals– More research on occurrence, fate, transport, treatability, and human and

ecosystem effects– Models to more accurately assess endocrine disrupting potential of chemicals in

humans and aquatic wildlife

Drinking Water Standards: One Regulatory Approach

• EPA Contaminant Candidate List (CCL 3)– Released February 2008– 7500 potential contaminants identified– Screening criteria applied to 560– 104 contaminants selected for CCL3 (organics, metals, microbials)– 87 organic chemicals on list

• Many pesticides, herbicides, industrial chemicals• A few plasticizers• A few disinfection byproducts• No pharmaceuticals• Almost none of the chemicals of current EDC concern

– Process involves more information gathering and drinking water surveillance– Eventual standard setting if appropriate

• Bottom line: MCLs are still years in the making

In the meantime…

• Reuse of reclaimed water is significant and will only become an even more important part of Arizona’s water budget

• Much ongoing research at Arizona’s 3 state universities to determine occurrence, impacts, and treatability, but more research is needed

• Already a significant political issue– Arizona Snowbowl– New WWTP near Sedona– New Bisbee WWTP– Lake Havasu City WWTP– Pinetop-Lakeside drinking water system expansion

Final Words

“There is a lot we don’t know about

trace organics in wastewater.”--Dr. David Quanrud,

University of Arizona