Groundwater Impact Project - PNCWA PNCWA... · Groundwater Impact Project: Monitoring for Pharmaceuticals and Personal ... measurable PPCP’s in its sewage? ... §The types of contaminants

Groundwater Impact Project:Groundwater Impact Project:Monitoring for Pharmaceuticals and Personal Monitoring for Pharmaceuticals and Personal

Care Products from a Wastewater Lagoon Care Products from a Wastewater Lagoon and Land Application Siteand Land Application Site

by by Tressa NicholasTressa Nicholas

DEQ Wastewater AnalystDEQ Wastewater AnalystEngineering Thesis StudyEngineering Thesis Study

OverviewOverview

Ø Quick Background l How pharmaceuticals get into our

environment l The concernsl The concerns

Ø Review project investigating pharmaceuticals from a wastewater treatment site.

Contaminants of ConcernContaminants of ConcernØØ Trace chemicals are found in waters Trace chemicals are found in waters

around the world.around the world.ØØ Insufficient data on 87,000 chemicals.Insufficient data on 87,000 chemicals.ØØ 2000 new chemicals introduced yearly.2000 new chemicals introduced yearly.ØØ 2000 new chemicals introduced yearly.2000 new chemicals introduced yearly.

The ConcernThe Concern

•• CarcinogenicCarcinogenic•• Promote antimicrobial Promote antimicrobial

resistanceresistanceresistanceresistance

•• Biologically activeBiologically active

Pharmaceuticals and Personal Care Pharmaceuticals and Personal Care Products (PPCPs)Products (PPCPs)

ØØ Products used by individuals for health or cosmetic reasons Products used by individuals for health or cosmetic reasons ØØ Prescription and over the counter medicines, shampoos, Prescription and over the counter medicines, shampoos,

sunscreens, fragrances... sunscreens, fragrances...

Pharmaceuticals and Personal Pharmaceuticals and Personal Care ProductsCare Products (PPCPs)(PPCPs)

are introduced to the environment when:are introduced to the environment when:

ØØ Pass out of the body.Pass out of the body.ØØ Washed off the body.Washed off the body.ØØ Washed off the body.Washed off the body.ØØ Placed in the trash. Placed in the trash. ØØ Drugs are flushed down the toilet.Drugs are flushed down the toilet.

Pathways for PPCPs residuesPathways for PPCPs residuesPharmaceuticals and Personal Care Products: medicines, soaps, fragrances, sunscreens, shampoos

Excretion or disposal(Hospital effluent)

Excretion(private household)

Solid waste disposal(unused medicine)

Wastewater collection system Waste disposal siteWastewater collection system Waste disposal site

Sewage Treatment

Surface Water

Sewage Sludge

Drinking Water

Ground Water

Soil

Sewage systems are not Sewage systems are not equipped for PPCP removalequipped for PPCP removal

Picture of one of fourteen New York City Picture of one of fourteen New York City Wastewater Treatment FacilitiesWastewater Treatment Facilities

ConcernConcern

Ø How does a drug optimized for a human target act on other species?

Example: Serotonin re-uptake inhibitors i.e. Prozac, Zoloft, Luvox, and Paxil.

Ø Humans: regulates sleep, appetite, mood.

Ø Frogs: Thyroid signaling.Ø Clams: regulates reproductive

Ø Similar targets could govern different processes in different species.

Ø Clams: regulates reproductive processes.

PPCP ProjectPPCP ProjectØØ Could a small community in Idaho that Could a small community in Idaho that

uses wastewater lagoons be producing uses wastewater lagoons be producing measurable PPCP’s in its sewage? measurable PPCP’s in its sewage?

ØØ And if so, could the PPCP’s be getting And if so, could the PPCP’s be getting ØØ And if so, could the PPCP’s be getting And if so, could the PPCP’s be getting into the groundwater?into the groundwater?

What is a Facultative Lagoon?What is a Facultative Lagoon?

ØØ A pond that holds wastewater.A pond that holds wastewater.ØØ Frequently used in small communities.Frequently used in small communities.ØØ More than 7000 in use in the United States .More than 7000 in use in the United States .

Facultative LagoonsFacultative Lagoons

ØØ Wastewater is treated via physical, biological, Wastewater is treated via physical, biological, and chemical processes. and chemical processes.

Facultative lagoon treatment of PPCP’s?

Drinking water Treatment

Wastewater Treatment

River

ØØ Series of treatment Series of treatment lagoons lagoons

ØØ Land application to Land application to 260 acres. 260 acres.

Project SiteProject Site

Lagoons

260 acres. 260 acres.

ØØ Site permitted since Site permitted since 1989.1989.Land

Application Site

LagoonsLagoons

ØØ 9 lagoons 9 lagoons collect, treat and collect, treat and store wastewater.store wastewater.

ØØ Lagoons leak or Lagoons leak or

1

6

3

24

5

Lagoons leak or Lagoons leak or seep.seep.

98

7

ØØ Can water from the lagoon be reaching Can water from the lagoon be reaching groundwater wells? groundwater wells?

Groundwater Flow is South to SoutheastGroundwater Flow is South to Southeast

Lagoons

Groundwater flowLand

Application Site

Groundwater flow

AquifersAquifers

SoilsSoils

Fractured Basalt Fractured Basalt

waterwater

Flow direction Flow direction

Regional AquiferRegional AquiferConfining layer rockPerched aquiferPerched aquifer

AquifersAquifers

SoilsSoils

Fractured Basalt Fractured Basalt

waterwater


Regional AquiferRegional AquiferConfining layer rock is leakyPerched aquiferPerched aquifer

Lagoon SeepageLagoon Seepage

SoilsSoils

Fractured Fractured Basalt Basalt

lagoon lagoon lagoon lagoon

Perched aquiferPerched aquifer


Confining “leaky” layer rock

Regional AquiferRegional Aquifer

wellwell







wellwell













Idaho Wastewater Rules Idaho Wastewater Rules IDAPA 58.01.16.493IDAPA 58.01.16.493

ØØ Lagoons constructed after April 21, 2007 Lagoons constructed after April 21, 2007 must leak less than must leak less than 1/8 inch per day 1/8 inch per day (3400 gallons per acre per day).(3400 gallons per acre per day).

ØØ Existing lagoons constructed before that Existing lagoons constructed before that date may leak up to date may leak up to 1/4 inch per day 1/4 inch per day (6800 gallons per acre per day). (6800 gallons per acre per day).


3

4

5

2 1

6

Ø This system leaks approximately 250 Million Gallons.

7

8 9

Ø Meets state requirements.

ØØ Are pharmaceuticals (PPCPs) traveling Are pharmaceuticals (PPCPs) traveling with the water that is seeping?with the water that is seeping?

Sample SitesSample Sites

HeadworksHeadworks

Storage Lagoon Storage Lagoon

Shallow Wells Shallow Wells Shallow Wells Shallow Wells

GroundwaterFlow

Sample SitesSample Sites

Seven Private Seven Private Domestic WellsDomestic WellsDomestic WellsDomestic Wells

Quality Assurance Quality Assurance Project PlanProject Plan

Similar to procedures for using EPA Method 1669 (i.e., “clean hands/dirty hands” procedures) for Sampling Ambient Water for Trace Metals.

PPCPs listPPCPs list

ØØ Acetaminophen Acetaminophen ––analgesic, antipyreticanalgesic, antipyretic

ØØ Caffeine Caffeine –– CNS stimulantCNS stimulant

ØØ CarbamazepineCarbamazepine --anticonvulsantanticonvulsant

ØØ EsteroneEsterone -- steroidsteroid

ØØ IbuprofenIbuprofen-- nonsteroidal anti nonsteroidal anti inflammatoryinflammatory

ØØ Iopromide Iopromide –– contrast agentcontrast agent

ØØ ProgestroneProgestrone -- steroidsteroid

ØØ Sulfamethoxazole Sulfamethoxazole --antibioticantibiotic

ØØ EsteroneEsterone -- steroidsteroid

ØØ EsteradiolEsteradiol,, 17B 17B -- steroidsteroid

ØØ Ethyl Ethyl EstradiolEstradiol -- steroidsteroid

ØØ FluoxetineFluoxetine --antidepresssantantidepresssant

ØØ GemfibrozilGemfibrozil –– HDL drugHDL drug

antibioticantibiotic

ØØ TestosteroneTestosterone -- steroidsteroid

ØØ Triclosan Triclosan -- antisepticantiseptic

ØØ Trimethoprim Trimethoprim ––Bacteriostatic antibioticBacteriostatic antibiotic

HeadworksDetection

Limit

Analytes ng/L ng/L

Acetaminophen 17700 1

Caffeine 7920 1

Carbamazepine 92 5

Esterone 16 1

Gemfibrozil 440 1

Ibuprofen 1820 1

Iopromide 17 5

Headworks Headworks

GroundwaterFlow

Iopromide 17 5

Progestrone 520 1

Sulfamethoxazole 158 1

Triclosan 43 5

Trimethoprim 40 1

Esteradiol, 17B No detect 1

Ethyl Estradiol No detect 5

Fluoxetine No detect 1

Testosterone No detect 1

Headworks Headworks

Analytes ng/L

Caffeine 48

Carbamazepine 64

Esterone 450

Esteradiol, 17B 49

Ethyl Estradiol 62

Gemfibrozil 880Storage LagoonStorage Lagoon

GroundwaterFlow

Gemfibrozil 880

Sulfamethoxazole 87Storage LagoonStorage Lagoon

AcetaminophenCaffeineMood stabilizing DrugEstrogensXray Contrast MediaAntibacterial

wellwell




AcetaminophenCaffeineCarbamazepineEstrogensX-ray Contrast MediaSulfamethoxazole




Sulfamethoxazole




CarbamazepineSulfamethoxazole







Carbamazepine found in lagoon, shallow well, and deeper wells in similar concentrations

Carbamazepine

Headworks




0102030405060708090

100

1

ng/L

Date

Pond 8

MW2

Sample 11

Sample 12

CarbamazepineCarbamazepine

Ø anticonvulsant, antineuralgic, antimanic,

Ø antidiuretic, antipsychotic.

Ø Potential Indicator for wastewater

C15H12N2O

Log Kow: 2.45

antipsychotic.

Analytes Detection Limit Headworks Pond 8 MW 2 MW2

ng/L ng/L ng/L ng/L ng/L

Carbamazepine 5 92 64 77 82

CarbamazepineCarbamazepine

Ø Rainbow Trout: Very low doses changed oxidative metabolism in liver cells.

Gagné, F., C. Blaise and C. André. 2006. Occurrence of pharmaceutical products in a municipal effluent and toxicity to Rainbow trout (Oncorhynchus mykiss) hepatocytes. Ecotoxicology and Environmental Safety 43(3): 329–336.




Sulfamethoxazole found in lagoons, shallow well, and deeper wells with carbamazepine

Sulfamethoxazole




020406080

100120140160180

1

ng/L

Date

Headworks

Pond 8

MW2

Sample 11 500 ft well

Sample 12 300 ft well

First lagoon First lagoon Storage lagoon Storage lagoon SewerSewer

AntiAnti--Bacterial: Bacterial: SulfamethoxazoleSulfamethoxazole

Ø Used primarily in combination with other medicines, known as Bactrim or Septra.

WW treatment may expose bacteria and create strains that are anti-biotic resistant.

SewerSewer

Bacteria Exposed Bacteria Exposed for 22 daysfor 22 days

ØØ Bacteria Bacteria exposed all exposed all winterwinter

AntiAnti--bacterialbacterial

Wastewater ponds are often duck ponds.Waterfowl migrate.

How Resistance SpreadsHow Resistance Spreads

Ø From “The Landscape of Antibiotic Resistance ,” Environmental Health Perspectives Volume 117 Number 6 June 2009

Estrogens:Estrogens: Found in: shampoos, foods, drugsFound in: shampoos, foods, drugs

In addition to reproductive development it effects:

Body StructureBody Structure:: accelerate accelerate growth, metabolism, reduce bone growth, metabolism, reduce bone resorption.resorption.

Protein synthesisProtein synthesis:: increase liver increase liver production of certain proteins.production of certain proteins.

Blood:Blood: Increase platelet Increase platelet Blood:Blood: Increase platelet Increase platelet adhesiveness, increase HDL and adhesiveness, increase HDL and decrease LDL.decrease LDL.

Fluid BalanceFluid Balance:: influence sodium influence sodium and water retention, increase cortisol.and water retention, increase cortisol.

GI Tract:GI Tract: reduce bowel motility and reduce bowel motility and increase cholesterol in the bile.increase cholesterol in the bile.

Cancer:Cancer: breast cancers may be breast cancers may be hormone sensitive. hormone sensitive.


Side Chain

Estrogen

Side Chain

Estrogen

Estrogen

SewerSewer

No No EstrogensEstrogens

TreatmentTreatmentEstrogensEstrogens

Estrogen conjugated with hydrophilic side chain.

Side chain is detached

EstrogensEstrogensEsteroneEsterone -- steroidsteroidEsteradiolEsteradiol, 17B , 17B -- steroidsteroidEthyl Ethyl EstradiolEstradiol –– steroidsteroid

•Estrogen molecules conjugate with hydrophillic side groups.

•Conjugates are easily cleaved during treatment which can reform the original pharmaceutical.


WW treatment may increase relevant environmental concentrations.

SewerSewer

No No EstrogensEstrogens

TreatmentTreatmentEstrogensEstrogens

Estrogens: Toxicity EffectsEstrogens: Toxicity Effects

Ø Rainbow Trout: Estrogenic compounds may be more potent and may create issues with liver cell stress and viability. Its suspected of creating increase female/male ratios, sexual immaturity and intersex issues.

ØØ GagnéGagné, F., C. , F., C. BlaiseBlaise and C. André. 2006. and C. André. 2006. Occurrence of pharmaceutical Occurrence of pharmaceutical products in a municipal effluent and toxicity to Rainbow trout (products in a municipal effluent and toxicity to Rainbow trout (OncorhynchusOncorhynchusmykissmykiss) ) hepatocyteshepatocytes. . EcotoxicologyEcotoxicology and Environmental Safetyand Environmental Safety 43(3): 32943(3): 329––336.336.

Total Nitrogen Total Nitrogen TN (Total Nitrogen) = TKN + nitrate + nitrite = organic nitrogen + TN (Total Nitrogen) = TKN + nitrate + nitrite = organic nitrogen +

ammonia + nitrate + nitrite. ammonia + nitrate + nitrite. TKN = organic nitrogen + ammonia. TKN = organic nitrogen + ammonia.

25.00

30.00

Total Nitrogen

0.00

5.00

10.00

15.00

20.00

11/14/2007

mg/L

Sample Date

Headworks

Pond 8

Monitoring well

Regional wells



Perched aquiferPerched aquiferSulfamethoxazole and carbamazepine found in shallow well and deeper wells where nitrate levels were at ambient levels




GroundwaterFlow

HeadworksHeadworks Analytes ng/L

Acetaminophen 17700

Caffeine 7920

Carbamazepine 92

Esterone 16

Gemfibrozil 440

Ibuprofen 1820

Iopromide 17

Progestrone 520

Sulfamethoxazole 158

Triclosan 43

Trimethoprim 40

Deeper wellsDeeper wellsCarbamazepine 80

Sulfamethoxazole 3.1

Caffeine 48

Carbamazepine 64

Esterone 450

Esteradiol, 17B 49

Ethyl Estradiol 62

Gemfibrozil 880

Sulfamethoxazole 87

Storage lagoonStorage lagoon

Acetaminophen 21

Caffeine 12 36

Carbamazepine 77 82

Esterone 120

Ethyl Estradiol 9

Iopromide 6.8

Sulfamethoxazole 1.1 5.8

Shallow wellShallow well

Wastewater Treatment will Wastewater Treatment will create two paths: create two paths:

Effluent OutEffluent OutSewage InSewage Inchemical reactions

Liquid and SolidsLiquid and Solids

Lagoon

Seepage Seepage

Biosolids/ Sludge

BiosolidsBiosolids

ØØ In Idaho 60% of municipal solids are reclaimed In Idaho 60% of municipal solids are reclaimed by land applicationby land application

BiosolidsBiosolids USGS StudyUSGS Study§ 55 of 87 chemicals were detected in at least one of the samples collected, (45 chemicals found in a single sample).

§25 of 87 chemicals were found in every sample. This includes: an antimicrobial disinfectant (triclosan), a musk fragrance (tonalide), an antihistamine (diphenhydramine), and an antiepileptic drug (carbamazepine).

ØØ Kinney, Furlong., 2006, Kinney, Furlong., 2006, Survey of organic wastewater contaminants in Survey of organic wastewater contaminants in biosolidsbiosolids destined for destined for land applicationland application: Environ Science and : Environ Science and TechnTechn, v. 40, no. 23, p. 7207, v. 40, no. 23, p. 7207--7215, 7215, doi:10.1021/es0603406.doi:10.1021/es0603406.

§The biosolids were more similar than different.§ Produced by a variety of treatment processes. § Served vastly different sized cities and towns.§ The types of contaminants and their relation to each other did not vary greatly between the biosolids tested.

ØØ Victor Hugo wrote in his book Les Victor Hugo wrote in his book Les MiserablesMiserables, , ØØ “…the history of men is reflected in the “…the history of men is reflected in the

history of sewers…history of sewers…

WastewaterWastewater

ØØ In 2004, 2.6 billion people in In 2004, 2.6 billion people in the world did not have basic the world did not have basic sanitation. Wastewater sanitation. Wastewater treatment often doesn’t treatment often doesn’t happen.happen.

The World’s WastewaterThe World’s Wastewater

ØØ In the Northeast Pacific 98 % In the Northeast Pacific 98 % of domestic wastewater is of domestic wastewater is discharged without treatment discharged without treatment

ØØ In the In the CarribbeanCarribbean 90 % is 90 % is discharged without treatment discharged without treatment

ØØ Picture Source: UNEP, David Tapia Munoz, Picture Source: UNEP, David Tapia Munoz, TophamTopham PicturepointPicturepoint

Wastewater ReuseWastewater Reuse

ØØ Eliminates the need for Eliminates the need for discharge to discharge to surface water.surface water.Can Can be the primary source of irrigation be the primary source of irrigation ØØ Can Can be the primary source of irrigation be the primary source of irrigation water for nutrient utilization water for nutrient utilization by cropsby crops

Wastewater ReuseWastewater ReuseCan Can be a source of aquifer recharge.be a source of aquifer recharge.

Global Sustainability, Reuse and Global Sustainability, Reuse and Recycling of Wastewater and Recycling of Wastewater and BiosolidsBiosolids

ØØ Population and density Population and density create water challengescreate water challenges•• Affordable and SustainableAffordable and Sustainable SocietySociety

EconomyEconomy

ØØ Water quality goals need to Water quality goals need to be health based be health based ll Detection ≠ safe Detection ≠ safe ll NonNon-- detect ≠ riskdetect ≠ risk

EnvironmentEnvironment

Risk = Toxicity x ExposureRisk = Toxicity x ExposureThere are no systematic studies demonstrating that much lower than therapeutic doses will cause direct harm in exposed humans, however:

Ø Hypersensitivity

Ø Indirect health effects (i.e. antibiotic resistance)

Ø Incomplete data for reliable benchmarks for chronic low dose exposure

Ø Multiple chemical low dose exposure

Ø Indirect effects from harm to other species in the environment

An early water regulation:

“No one shall with malice pollute the waters where they issue publicly.

Should anyone pollute them, Should anyone pollute them, his fine

shall be ten thousand sesterti.”

(approx. $600)Source: Sextus Julian Frontinus, Water Commissioner of the City of Rome, 97 CE

ThoughtsThoughtsØ 100% probability of chronic low dose exposure over

your lifetime, to a mixture of chemicals that are unknown endocrine disruptors.

Ø Unknown Effectsl From the organism to the population.l From acute to chronic exposure.l To understanding of the processes and consequences of system

disruption.From single chemical to multi-chemical exposure and dose l From single chemical to multi-chemical exposure and dose understanding.

Ø Mitigation: Probability + Impact • Can you reduce the impact of Drugs (endocrine disruptors) or

carcinogens?• Can you reduce the probability of exposure?

Pharmaceuticals and Personal Pharmaceuticals and Personal Care ProductsCare Products (PPCPs)(PPCPs)

are introduced to the environment when:are introduced to the environment when:

ØØ Pass out of the body.Pass out of the body.ØØ Washed off the body.Washed off the body.ØØ Washed off the body.Washed off the body.ØØ Placed in the trash. Placed in the trash. ØØ Drugs are flushed down the toilet.Drugs are flushed down the toilet.

PPCP Project SummaryPPCP Project Summary

Ø Don’t Flush Drugs Down the Toilet!

Chemicals change us. Chemicals change us.

a dash of a dash of triclosantriclosan,… ,… a pinch of a pinch of caffeine,.. caffeine,.. mix in some mix in some antianti--depressants,depressants,depressants,depressants,….a little ….a little

fire fire retardant….retardant….only a bit of only a bit of atrazineatrazine……and and estrogens estrogens and…..and…..

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Groundwater Impact Project - PNCWA PNCWA... · Groundwater Impact Project: Monitoring for Pharmaceuticals and Personal ... measurable PPCP’s in its sewage? ... §The types of contaminants