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Reclaimed Water Gray Water Emerging Contaminants by Chuck Graf Senior Hydrologist BIA Water Resources Technician Training July 31, 2012 Tucson, Arizona Our Path for this Session 1. Wastewater treatment and reclaimed water reuse in Arizona: A historical perspective 2. Arizona’s reclaimed water program 3. Gray water in Arizona 4. An introduction to emerging contaminants

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Page 1: Reclaimed Water Gray Water Emerging Contaminantsweb.sahra.arizona.edu/education2/wrtt/lecs/Graf...- livestock watering - concrete mixing Class B Reclaimed Water El Conquistador Golf

Reclaimed WaterGray Water

Emerging Contaminants

by

Chuck GrafSenior Hydrologist

BIA Water Resources Technician TrainingJuly 31, 2012

Tucson, Arizona

Our Path for this Session

1. Wastewater treatment and reclaimed water reuse in Arizona:A historical perspective

2. Arizona’s reclaimed water program

3. Gray water in Arizona

4. An introduction to emerging contaminants

Page 2: Reclaimed Water Gray Water Emerging Contaminantsweb.sahra.arizona.edu/education2/wrtt/lecs/Graf...- livestock watering - concrete mixing Class B Reclaimed Water El Conquistador Golf

Wastewater Treatment

• Haven’t determined when thefirst sewage treatment plant inArizona was built, but…

- In mid-Dec. 1899, Flagstaffaccepted construction of1.7 miles of sewer line

- at a cost of $8500!

The Sun, Flagstaff, December 30, 1899

Wastewater Treatment• Plan for Tucson sewer constructionon the books in 1900

• In 1931, Phoenix constructs15 million gallon per day (mgd)sewage treatment plant

- secondary treatment- chlorine disinfection of effluent

Plan of Sewerage for Tucson, Arizona, 1900

Arizona Sewage WorksAssociation members atPhoenix plant, 1937

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Wastewater Treatment

• Primary treatment – physical processes- screening and settling to remove particulate matter

• Secondary treatment – biological processes- microbial degradation of organic wastewater constituents- usually followed by settling, gravity filtration, and disinfection

• Tertiary treatment – advanced treatment processes- chemical treatment including advanced oxidation processes (AOP),pressure filtration such as RO, and/or other technologies

- usually targets pollutants or classes of pollutants that require morecomplete removal than provided by primary & secondary treatment

Management Options for WWTPs

• Surface water courses- discharge to dry streambeds,

streams, rivers, lakes, reservoirs

- most common method

• Infiltration- basins (rapid infiltration basins orRIBs) – tend to be smaller facilities

- trenches and beds – generallyvery small facilities

Roger Road WWTP Outfall into Santa Cruz River, Tucson(USGS photo)

Infiltration basin,Glendale, AZ

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Management Options for WWTPs

• Recharge (i.e., managed infiltration)- not considered or regulated as “disposal”- a significant practice, usually in ADWRActive Management Areas (AMAs), to reducegroundwater overpumping

- ADWR gives credits in AMAs that offset limitson groundwater pumping

• Reuse (more on this in a moment)- not considered or regulated as “disposal”

“It doesn’t go off the planet, so it has to go somewhere.” -Anonymous

Wheeling reclaimed water around,Gilbert Riparian Preserve

Ft. Huachuca recharge pond

Clean Water Act—A Major Step Forward

• The 1972 CWA requires all major facilities dischargingto a surface watercourse to obtain a NPDES permit– NPDES: National Pollutant Discharge Elimination System

• EPA delegates permit issuance to ADEQ– called an AZPDES Permit in Arizona

• ADEQ has issued AZPDES permits to ~125 WWTPs– 75% of all AZPDES permits are for WWTPs– Other 25% are for power plants, mines, other industrial

& miscellaneous discharges

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Clean Water Act Permitting for WWTPs

• In the past, NPDES generally has required only secondary treatment for WWTPs

• NPDES permittees must meet SWQS established for the designated use(s) of the water into which the discharge occurs

• For aquatic & wildlife uses, standards for some constituents are more stringent than MCLs

APP – Another Major Safeguard

• The Aquifer Protection Permit Program is an Arizona-uniqueprogram to protect groundwater quality

• Any person with a discharge that will, in reasonable probability,reach an aquifer must obtain an APP

• In 2001, ADEQ set stringent APP technology standards for WWTPs(Best Available Demonstrated Control Technology or BADCT)

• All new & expanding WWTPs must employ high-performance, tertiary treatment

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APP BADCT for WWTPs• All new or expanding WWTPs with a designcapacity of more than 0.25 mgd must achieve:

- Pathogen-free effluent• Routinely no detectable E. coli

- Nitrogen removal to below the 10 mg/l DW standard• WWTPs normally produce 45 – 70 mg/l

- Non-turbid discharge (using filtration)*≤ 2 NTU (24-hr average; never to exceed 5 NTU)

- Odor control

• Many Arizona plants have been upgraded to meet new facility BADCT

*Required for Class A+ rating for reuse

Advanced treatment & odor controlat Gilbert Neely WWTP

Reclaimed Water Use in Arizona

• 90% of reuse occurs in just four states, Arizona being one

Why Arizona?

• Driven by need

• Comprehensivelegal framework

Source: Western Water, July/August 2008

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Driven by Need for WaterArizona was one of the first states to reuse treated wastewater

• Grand Canyon Village – 1926

• Toilet flushing• Boiler feed for power generation• Water for steam locomotives

Driven by Need for WaterLater milestones for reuse of treated wastewater

• Phoenix 23rd Avenue WWTP – 1932• Agriculture

• 1st reclaimed water rules, ADHS – Jan 1972

• Phoenix 91st Avenue WWTP – 1983• Delivery to Palo Verde Nuclear Generating Station

Phoenix 91st Ave WWTP APS Palo Verde NuclearGenerating Station

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Driven by Need for Water

• First full-scale engineered recharge project involvingreclaimed water began operating in 1989

• Tucson Sweetwater Recharge Facility

Comprehensive Regulatory Framework

• Clear legislative authority granted to ADEQ in 1999

• Reclaimed water quality standards

• Permit program for the direct reuse ofreclaimed water

• Technical standards for open channel andpipeline conveyances

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Comprehensive Regulatory Framework

• ADEQ completely transformed its reclaimedwater rules, becoming effective Jan. 16, 2001

• Fosters reuse while protecting water quality andhuman health

• Aquifer Protection Permit (APP)—reclaimed waterquality is controlled at & responsibility of the WWTP

• Reclaimed Water Permit (RWP)—regulates useand application by the end user

• Reclaimed WQS—5 classes of reclaimed waterestablished: A+, A, B+, B, C

Photo: Southwest Hydrology, Jan/Feb 2010

Comprehensive Legal Framework• By court decision, WWTPs own their treated wastewater and havecontrol over disposal or distribution for reuse

• For WWTPs intending to distribute water for reuse, ADEQ indicatesthe applicable RWQS class in the plant’s APP- WWTP must monitor to ensure that the RWQS are met

• ADEQ has adopted technical standards for openchannel and pipeline (“purple pipe”) conveyances

• ADEQ issues Reclaimed Water Permits for end use- O&M is relatively straightforward because water quality

is maintained by the WWTP under its APP

• ADEQ has established allowed end uses for each RWQS class

City of Tucson

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• Little chance of contact by general public

• Allowed uses include:

- pasture for non-dairy animals

- livestock watering (non-dairy animals)

- irrigation of sod farms

- irrigation of fiber, seed, forage & similar crops

- silviculture

Class C Reclaimed Water

• Total retention time in wastewater stabilization ponds: ≥ 20 days

• Fecal coliform (cfu/100 ml): < 1000* (4 of last 7 samples)

< 4000 (single sample maximum)

* 99.9% - 99.999% removal compared to raw sewage

Class C Reclaimed WaterLimits and Monitoring

E. coli bacteria

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• For restricted access uses (access by general public is controlled)

• Some Class B uses allowed in rule

- surface irrigation of an orchard or vineyard

- golf course irrigation

- restricted access landscape irrigation

- landscape impoundment

- dust control

- pasture for milking animals

- livestock watering

- concrete mixing

Class B Reclaimed Water

El Conquistador Golf Course, Oro Valley

• Fecal coliform (cfu/100 ml): < 200 (4 of last 7 daily samples)

< 800 (single sample maximum)

Compare to ADEQ Surface WQS for E. coli for “partial-body contact”:

< 126 (geometric mean of last 4 samples)

< 575 (single sample maximum)

• To gain Class B+ rating: Nitrogen removed to below 10 mg/l

Class B Reclaimed WaterLimits and Monitoring

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• For open access uses (access by general public is uncontrolled)

• Some Class A uses allowed in rule

- irrigation of food crops

- recreational impoundments

- residential/schoolyard landscape irrigation

- other open access landscape irrigation

- toilet & urinal flushing

- fire protection systems

- spray irrigation of an orchard or vineyard

- snowmaking

Class A Reclaimed Water

Northern Arizona University

• Turbidity (by filtration): ≤ 2 NTU (24-hr average)

≤ 5 NTU (never to exceed)

• Fecal coliform: No detectable (4 of last 7 daily samples)

< 23 cfu/100 ml (single sample maximum)

Compare to ADEQ Surface WQS for E. coli for “full-body contact”:

< 126 cfu/100 ml (geometric mean of last 4 samples)

< 235 cfu/100 ml (single sample maximum)

• To gain Class A+ rating: Nitrogen removed to below 10 mg/l

Class A Reclaimed WaterLimits and Monitoring

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Reclaimed Water Quality vs.Canal Water Quality

• For 2001 rule, ADEQ relied heavily on 1996 EPAReuse Manual for standards and allowed uses

• ADEQ also reviewed Salt River Projectcanal sampling records

• SRP had collected 61 fecal coliform (FC)samples throughout canal system – Highest (cfu/100 ml) > 16,000– Mean = 2360– Median = 500– Lowest = 17

• Compare to RWQS– Class A = 0– Class B = 200– Class C = 1000

Reclaimed Water Quality vs.Canal Water Quality

• SRP collected 300 turbidity samples at South Canal & intake to Val Vista Drinking Water Treatment Plant– Highest (NTU) = 500– Mean = 34– Median = 14– Lowest = 6 (twice)

• Class A, A+ standard= 2 (24-hr avg)= 5 (never to exceed)

• SRP canal water has irrigated residential yards, parks & schoolyards since 1928

SRP Residential Irrigation, Phoenix

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Reclaimed Water Permits

• ADEQ issues Reclaimed Water Permits to ensure the safe end use of reclaimed water

• ADEQ issues two types of permits for end use

1. A single end user permit

2. A reclaimed water agent permit for an entity thatassumes responsibility for multiple end users of reclaimed water

Single End User Permits

• Permits available for all 5 classes—A+, A, B+, B, C

• Allows permit holder (say a farmer) to receive reclaimedwater from a WWTP authorized by its APP to distributewater of that class

• Permit includes O&M, signage, and other requirements

• Permit holder must keep records & report volumes,areas of use, and other information to ADEQ

• Uncomplicated requirements for A+ and B+ permitsbecause supplied water meets drinking water standardfor total nitrogen

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Reclaimed Water Agent Permit

• Agent is responsible for the reuse of reclaimed water by all theend users it acts as agent for

• Agent must have a contract with each end user

• Agent keeps records and reports to ADEQ rather than end user

• Agent is the compliance/enforcement entity of record for ADEQ

Reclaimed Water Agent Permits

• ADEQ has issued 47 agent permits to date representing severalthousand residential, municipal & industrial, and agricultural users

• Top 6 agent permits (based on number of end users)- City of Tucson

• 18 golf courses• 39 parks• 52 schools (incl. University of Arizona)• more than 700 single family homes

- Lake Havasu City- City of Flagstaff

• 60 reuse sites listed in latest agent report to ADEQ- City of Cottonwood- Anthem- Arrowhead Ranch, Glendale

Irrigating athletic fieldwith reclaimed water,University of Arizona

Reclaimed water pumps,City of Flagstaff

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Design RWQS

WWTP Flow (mgd) Reuse? Class Comment

1. Phoenix 91st Avenue 204.5 Yes B+ 60-70 mgd to PVNGS; much to agric.

2. Phoenix 23rd Avenue 63 Yes B+

3. Pima County Roger Rd 41 Yes B

4. Pima County Ina Road 37.5 Yes B New (A+) & old treat. trains combined

5. Mesa Greenfield 24 Yes A+

6. Scottsdale Water Campus 23.6 Yes A+ Includes managed recharge facility

7. Mesa Northwest 18 Yes A+ Includes managed recharge facility

8. Tolleson 17.5 Yes B

Arizona’s Program: A Positive Force

Arizona’s 12 Largest WWTPs

Design RWQS

WWTP Flow (mgd) Reuse? Class Comment

9. Nogales International 17.2 No Not classed But new plant meets A+

10. Surprise South 16.3 Yes A+

11. Chandler Airport 15 Yes A+

12. Yuma 12 No Not classed Discharges to Colorado River

Arizona’s 12 Largest WWTPs

Upgrading the Ina Road WWTP, Tucson

Photo: Tucson Citizen

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How Has ADEQ’s Program Worked?“Celebrating the Return of the Fish”

• In 2009, the Nogales International WWTP was finally upgradedfrom sub-C to A+ class treatment

• In 2 yrs, the downstream Santa Cruz River went from long deadto clear and live with native fish

Impact of ComprehensiveLegal Framework

• High-quality wastewater is produced, whichallows safe reclaimed use by end users

• Result: High-performance treatment,balanced with appropriate end-userequirements, has turned once poor-quality wastewater “to be gotten rid of”into a resource

Town of Payson Green Valley Lake

Pumping Reclaimed Water,Surprise, AZ

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Arizona’s Reclaimed Water Program:The Current Story

• 65% of sewage treatment plants inAZ now distribute treated wastewaterfor reuse (203 WWTPs)

• 340 single end user permits issued

• 47 agent permits issued to date

• 10 of the 12 largest WWTPs in AZnow distribute high-quality treatedwastewater for reuse Tucson golf course irrigated

by reclaimed water

• Current individual end user permits by reclaimed water class

• A+ 72%

• A 2%

• B+ 13%

• B 9%

• C 3%

Rapid Transition toHigh-Performance Treatment

Freestone Park, Gilbert Sun Lakes, Maricopa County

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Gray Water: Is Spelling It OurBiggest Impediment To Its Use?

Gray water

Graywater

Grey water

Greywater

In this presentation, “gray water” is usedbecause that is the spelling in Arizona law.

Photo by Brad Lancaster

Gray Water Reuse

• “Gray water” means wastewater from clothes washers, bathtubs, showers, and sinks– excludes kitchen sinks, dishwashers, and toilets

• Simple requirements for home use

• No actual application submittal

• Estimated 200-300,000 homeowner gray water users in Arizona

Page 20: Reclaimed Water Gray Water Emerging Contaminantsweb.sahra.arizona.edu/education2/wrtt/lecs/Graf...- livestock watering - concrete mixing Class B Reclaimed Water El Conquistador Golf

Gray Water Use In Arizona

• Sources of gray water named by users- 71% -- clothes washers- 16% -- bathroom sinks, tubs, showers- 12% -- kitchen sinks

• Average age of systems: 9.2 years

• Only 2 respondents reported storing gray water

• 10% reported some type of treatment (filtering, chlorine)

Source: Survey by Water CASA and the U of A in 2000

Photo by Brad Lancaster

More Survey Results

• Only 11% reported below ground irrigation- no drip systems were reported

• Of non-users, commonest response was “don’t know how”

• Preserving the lifetime of the septic tank may be a factorin much gray water reuse- septic tanks serve 20% of Arizona’s population

Septic tank installation in rural Arizona

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Increased Interest in Larger-Scale,Non-household Gray Water Projects

• ADEQ has issued 8 permits since 2005 for larger-scale,non-household use

• Interesting variations in sources, treatment approaches,and end uses- urban learning center- college buildings- campground- recreational vehicle park- prison showers and laundries- major corporation test facility

Hidden Oasis RV Park, Wickieup, AZ

Arizona State University,Barrett Honors College, Tempe, AZ

• Permit issued: 2009• Design flow: 7000 gal/day• Sources: Showers, sinks, drinking water fountains fromclassrooms and dormitories for 200 students

• Lift station, storage tanks, recirculating sand filter,mechanical filter, flow meter

• Irrigates 0.60 acre of turf,desert plants

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Henkel Laundry Development Lab,Dial Corporation, Scottsdale, AZ

• Permit issued: 2010• Design flow: 500 gal/day• Source: 32 washing machines for testing detergents• Storage tank, basket strainer, sand filter, bag filter• System limits gray water irrigation to 500 gal/day• Irrigates desert trees, shrubs, smaller plants

WWTPUnit

Processes

Influent

Treated Wastewater(Reclaimed Water)Biosolids

(Sludge)

Emerging Contaminants• Reuse of reclaimed water has brought the issue of

emerging contaminants to the fore nationally

• Reuse of treated wastewater is a significant part of the AZ water budget

• ADEQ’s 2001 rules were developed to ensure safety from pathogens & protect groundwater from nitrogen contamination

– emerging contaminants were not yet on the horizon

• Intensified interest now in understanding– occurrence and fate– human health and aquatic impacts– enhancing removal in WWTPs

Page 23: Reclaimed Water Gray Water Emerging Contaminantsweb.sahra.arizona.edu/education2/wrtt/lecs/Graf...- livestock watering - concrete mixing Class B Reclaimed Water El Conquistador Golf

…and emerging terminology, too!EC Emerging Contaminants

ECC Emerging Contaminants of Concern

CEC Contaminants of Emerging Concern

OWC Organic Wastewater Contaminants (Chemicals/Compounds)

PPCP Pharmaceuticals & Personal Care Products

PAC Pharmaceutically Active Chemicals (or Compounds)

PIE Pharmaceuticals in the Environment

EDC Endocrine Disrupting Compounds (or Chemicals)

EAC Endocrine Active Compounds

MC Microconstituents

AOC Anthropogenic Organic Compounds

AWI Anthropogenic Waste Indicators

TOrC Trace 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

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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, TOrC, or CEC: 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

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Other Emerging (Re-emerging?) Contaminants

• Tungsten• Cobalt• Germanium• Molybdenum• Strontium• Vanadium• Chromium-6• Nanomaterials

• Perchlorate

• Arsenic

• Sulfate

• TDS

Perchlorate ion

Some Emerging Microbial Contaminants

• Naegleria fowleri - protozoan parasite

• Legionella - bacterium

• Vibrio cholerae – bacterium

• Hepatitus A – virus

• Norovirus

Naegleria fowleri

amoeba flagellate cyst

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Today, we will mainly focus on:

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

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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

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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

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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

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EDCs: A Subset of CECs

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

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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

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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

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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

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Documented effects of EDCs in wildlife• 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

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“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.”

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Analysis of Emerging Contaminants

How are these measured in environmental samples?

1. Individual chemical measurement– no adopted standard methods for many compounds (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)

INT

EN

SIT

Y

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

• 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 !!

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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

Yeast Estrogen Screen(YES) Bioassay

← Std

Cytoplasm

E

R

R E

E

Cytoplasm

= Receptor

R

hER -gal

CPRGyellow

CPRGred

lac-z

=Estrogens

Cytoplasm

RR

RR EE

EE

Cytoplasm

= Receptor

RR

hER -gal

CPRGyellow

CPRGred

lac-z

=Estrogen

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CECs 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)

CECs in Reclaimed Waterand Groundwater

Tucson Mesa Tucson MesaCompound (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.

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Fate of CECs Through a WWTP

Influent

Biosolids(Sludge)

Treated Wastewater(Reclaimed Water)

WWTPUnit

Processes

Aeration basins at the Figueroa WWTP, Yuma

Estrogen Removal: 8 Arizona WWTPs

EDC 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 CEC removal.

Note: EDC Removals calculated from YES bioassay results.

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WWTP Performance: Next Steps

• More fully determine removal efficiencies of unit processes within WWTP– Wastewater

– Sludge

• Determine how to optimize CEC removal in existing unit processes

• Develop new unit processes targeting removal of recalcitrant or harmful ECs

Raw SewagePrimary

SedimentationBiologicalTreatment

Secondary Clarifier

TreatedWastewater

Bar Screen

Digested Sludge

1º Sludge

Centrate

Dewatered Sludge(Biosolids)

Pharmaceuticals in AZ water vs. Therapeutic Dose

Max Conc Years for

Drug Use (ng/l) Medium Location Therapeutic Dose*

Carbamazepine Antiepileptic 455 GW Below Tucson WWTPs 30

Primidone Antiepileptic 202 WW Mesa NW 340

Ibuprofen Analgesic 3380 WW Roger Rd, Tucson 20

Naproxen Analgesic 6280 WW Roger Rd, Tucson 27

Gemfibrozil Lipid regulator 1235 WW Roger Rd, Tucson 1300

Diclofenic Antiepileptic 80 WW Roger Rd, Tucson 17,000

Ciprofloxacin Antibiotic 30 WW Roger Rd, Tucson 6.7

Sulfamethoxazole Antibiotic 1900 WW Roger Rd, Tucson 290

Cimetidine Antiacid 580 WW Roger Rd, Tucson 470

17α-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 = Groundwater

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

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Dealing with the CEC Problem

• Non-regulatory approaches

– Pharmaceutical take back programs

– Source & disposal control approaches to keep CECs out of the sewer

– 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

Dealing with the CEC Problem

• Regulatory approaches– Drinking water standards (federal--EPA)

• Contaminant Candidate List 3 (CCL3)

– BADCT for WWTPs (state--ADEQ)

– Reclaimed WQS (state--ADEQ)

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Contaminant Candidate List

• EPA published CCL3 in 2009

– 104 chemicals– a dozen or so EDCs of interest to reclaimed water use– 6 metals– 12 microbial contaminants– monitoring required in public drinking water systems for

a reduced list of contaminants (UCMR 3)– results, along with toxicological and other studies, will

be used to establish numeric drinking water standards, if merited

Bottom Line: MCLs are still years in the making

However, The Good News• Unlike most states, AZ mandates high-performance treatment with

nitrogen removal in all new & expanding WWTPs• Corollary benefit: this treatment also greatly reduces CEC levels

– Nitrogen removal allows attack by a range of bacteria in the successive anoxic and oxic unit processes

– Longer residence time for nitrogen removal also aids the bacteria in their degradation of CECs

• Work by UA & others shows high CEC removal rates– Secondary treatment: 20-40%– Tertiary treatment with N-removal: 60-99%

• Overall, AZ is in much better shape than most other states in removing CECs from treated wastewater

• Recent Governor’s Blue Ribbon Panel on Water Sustainability recommends accelerating research on CECs in reclaimed water

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More InformationMore information on ADEQ’s reclaimed water program and water quality information generally is at: www.azdeq.gov.

Governor’s Blue Ribbon Panel Report is available at:www.azwater.gov.

ADEQ Main Office, Phoenix