Emerging Contaminants in U'S' Waters

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Emerging Contaminants in U.S. Waters
USEPA 22nd Annual Region VI Pretreatment
Association Workshop, August 8, 2006 Little Rock,
Arkansas
By Kent Becher-USGS Water Science Center Fort
Worth, TX
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Acknowledgments
Dana Kolpin, Iowa City, IA Ed Furlong, Denver,
CO Herb Buxton, Trenton, NJ Larry Barber,
Boulder, CO Kymm Barnes, Iowa City, IA Doug
Schnoebelen, Iowa City, IA Bill Andrews, Oklahoma
City, OK Paul Stackelberg, Troy, NY Mark Becker,
Oklahoma City, OK Greg Delzer, Rapid City,
SD Kathy Lee, Mounds View, MN Jessica Hopple,
Trenton, NJ
Mike Focazio, Reston, VA James Gray, Boulder,
CO Sheridan Haack, Lansing, MI Mike Meyer,
Lawrence, KS Colleen Rostad, Denver, CO Steve
Zaugg, Denver, CO
And Many Others
The Toxics Program toxics.usgs.gov
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What Are Emerging Contaminants?

• Emerging contaminants (ECs) are organic
  compounds including hormones, food additives,
  detergents, and pharmaceuticals that typically
  occur in parts-per-trillion or parts-per-billion
  concentrations in water.
• These contaminants are called emerging because
  methods for their analyses are experimental and
  analytical method development is on-going.
• The health effects to humans and biota from
  long-term exposure to small concentrations are
  unknown.

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Organizational Framework

• Methods Development.
• Occurrence.
• Sources and Source Pathways.
• Transport and Fate.
• Ecological Effects.

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• Methods Development

• Special emphasis
• PhAC
• HAC

What we find in the environment often depends on
what we look for and how hard we look.

• 158 Compounds in Water
• 45 Antibiotics
• 12 Prescription Drugs
• 8 Nonprescription Drugs
• 14 Hormones and Steroids
• 79 Household and
• Industrial Compounds

• 83 Compounds in Sediment
• 3 Antibiotics
• 12 Prescription Drugs
• 7 Nonprescription Drugs
• 61 Household and
• Industrial Compounds

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Target Compounds - Antibiotics
(SPE and LC/MS in positive-ion mode w/ SIM)
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Target Compounds - Human Prescription and
Nonprescription Drugs
(SPE and HPLC/ES-MS in positive-ion mode w/ SIM)
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Target Compounds Industrial and Household-use
Chemicals
(SPE and GC/MS w/ SIM)
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Target Compounds Industrial and Household-use
Chemicals (Cont.)
(SPE and GC/MS w/ SIM)
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II.Occurrence
The first step in the road to understanding the
fate of a contaminant is determining if
contamination is actually taking place.

• What compounds enter the environment?
• At what levels do they occur?
• In what mixtures do they occur?

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National Reconnaissance Studies
- Streams (1999-2000) - Ground Water (2000) -
Sources of Drinking Water (2001) - Streambed
Sediment (2002)
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USGS 1999 National Stream Study

• Sampled 139 streams in 30 states
• 62 CAFO basins
• 52 Urban basins
• 17 Mixed land use
• 8 Minimally developed

Web sitehttp//toxics.usgs.gov/regional/emc.html
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1999 National Study Monitoring Network
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Detection Frequency () by Group
Steroids (4) Nonprescrip. Drugs (5) Insect
Repellant (1) Detergent Meta. (5) Disinfectants
(3) Plasticizers (7) Fire Retardants
(2) Antibiotics (22) Insecticides (7) PAHs
(6) Hormones (11) Prescription Drugs
(14) Antioxidants (5) Fragrances (2) Solvent (1)
0 20 40 60 80 100
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Concentration by Group
(75th Percentile)
Detergent Meta. (5) Steroids (4) Plasticizers
(7) Disinfectants (3) Nonprescrip. Drugs
(5) Antioxidants (5) Fire Retardants
(2) Antibiotics (22) Insect Repellant
(1) Insecticides (7) PAHs (6) Hormones
(11) Prescription Drugs (14) Fragrances
(2) Solvent (1)
ppb

0 1.0 2.0 3.0
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Most Commonly Detected Compounds
Detection Median Compound
Freq. Detect (ppb) coprostanol
85.7 0.088 cholesterol
84.3 0.83 N-N-diethyltoluamide 74.1
0.06 caffeine 70.6 0.1
tri(2-chloroethyl)phos. 57.6 0.1
triclosan
57.6 0.14 4-nonylphenol 50.6
0.8 NPEO1 45.9 1 ethanol,
2-butoxy-phos. 45.9 0.51 OPEO1
43.5 0.2
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1999 Ntl. StudyResults Summary

• ECs were detected in 80 of samples
• 82 of 95 ECs were detected
• EC concentrations were generally low
• 5 of top 30 compounds were gt 1 ppb 25 sites
  had gt 6 ppb total ECs
• Few health standards or guidelines were exceeded
• (Only 14 of the 95 ECs had standards)
• Detection of multiple ECs was common
• 35 had gt 10 ECs

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Drinking Water Sources Recon

• PWS serving 1,000 to 8M
• 25 states and PR
• 25 GW and 49 SW

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National Reconnaissance Studies
Source Water Recon (Frequency of Occurrence)

• A few ECs occur more frequently
• - Most ECs are not (or infrequently) detected

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National Reconnaissance Studies
Source Water Recon (Co-occurrence)

• MOST targeted compounds are NOT detected alone
• Concentrations of mixtures are generally low
• Detections and concentrations higher in SW than GW

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Bed Sediment

• Another reservoir for ECs
• Water and bed sediment
• collected at 44 stream sites

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Comparison of results 44 stream sites
Stream Water Bed Sediment
Cotinine 81.8 34.1 Carbamazepine 59.1 72.7
Caffeine 54.5 29.5 Acetaminophen 36.4 25.0
Dehydronifedipine 36.4 63.6 Sulfamethoxazole
36.4 6.8 Codeine 34.1
6.8 Diphenhydramine 27.3 68.2 Trimethoprim 22.
7 27.3 Diltiazem 20.4 43.2 Cimetidine 13.6
34.1 Fluoxetine 4.5 63.6 Thiabendazole
2.2 43.2
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EC Concentrations by Matrix
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Summary - National Recon Studies
SW GW S DW B Sed
(N139) (N47) (N74) (N51)
Non_drugs 81 15 64 50
Antibiotics 48 30 26
53 Pharms 32 6
23 100 Det metabs 69 32
19 -- DEET 74
9 19 -- Caffeine
71 (.08) 13 (.02) 54 (.02) 24 (2.3)
Fluoxetine 1 4
1 100
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III. Sources and Source Pathways
Modified from Halling-Sorenson (1998)
To effectively minimize environmental
contamination, it is necessary to understand
potential contaminant origins and pathways to the
environment.
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Sources of Emerging Contaminants

• WWTPs
• Domestic septic systems
• Industrial discharges (medical)

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Source Characterization Study - 2004
Its a dirty job, !
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Septic System - Example

• Multi-family household
• Both liquid and solid waste sampled

Select Liquid Pharm Results (mg/L)
Ctet ND Carbamazepine 0.05 Epi-Ctet
ND Caffeine 38 Iso-Ctet
0.64 Acetaminophen 45 Iso-Epi-Ctet
0.26 Cotinine 1.7 Tet ND Epi-Tet
ND Ofloxacin 0.32
Select PCP Results
Liquid Solid
(mg/L) (mg/kg) AHTN ND
18000 Triclosan 2.0
19000 p-nonylphenol 18 55000
Results Provisional
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Swine Waste Example Results

• 5000 head finishing operation
• Both liquid and solid waste sampled
• Antibiotics used as feed additive

Select Liquid Pharm Results (mg/L)
Ctet 700 mg/L Carbamazepine ND Epi-Ctet
61 Caffeine 0.05 Iso-Ctet
1250 Acetaminophen ND Iso-Epi-Ctet
1150 Cotinine ND Tet 140 Epi-Tet 155
Select PCP Results
Liquid Solid
(mg/L) (mg/kg) AHTN
ND Triclosan
ND p-nonylphenol ND
Results Provisional
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Chemical Indicator Study - 2002
Site Locations 10 WWTP Settings upstream (10)
effluent (35) 1st downstream (32) 2nd
downstream (24) 2 Background settings (2)
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Most Frequently Detected Compounds
Cotinine (92.5) Caffeine (70.0) Cholesterol
(90.0) DEET (70.0) Carbamazepine (82.5)
Tributylphosate (70.0) Tonalide (80.0)
Ethanol,2-b,p (70.0) Tri(dcp)phosphate (77.5)
Benzophenone (67.5) Tri(2-ce)phosphate (75.0)
Diltiazem (67.5) 3,4-dcp isocyanate (72.5)
NPEO2 (62.5) b-sitosterol (72.5) NPEO1
(62.5) Codeine (72.5) Triclosan (62.5) Ethyl
citrate (72.5) 3b-coprostanol
(60.0) Sulfamethoxazole (72.5) Trimethoprim
(60.0)
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Antimicrobials in Swine Waste Lagoons, 1998-2002

• Antibiotics found in all swine
  waste lagoons sampled (N78)
• Compound Med Max mg/L
• Ctet 90 19 1000
• Smth 85 6.2 6000
• Linc 75 25 1200
• Tet 60 1.4 150
• Oxtet 50 10 410
• Sdimx 25 2.5 150
• Tylosin 25 0.2 0.5
• Total residues gt 6 mg/L.

• Antibiotics found proximal to poultry farms in
  Ohio (joint research with CDC)
• Multiple classes
  Sarafloxacin Oxytetracycline
  Sulfadimethoxine

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Antibiotics in Fish Hatcheries

• Initial Recon
• - Detected in 15 of samples
• - SDM (12), OTC (4)

Follow-up (3 hatcheries) - Detected in 31 of
samples - SDM (23), OM (17), OTC (8) - Max
conc 36 mg/L - Variable persistence - SDM
(48 d), OM (28 d), OTC (20 d) - Detections in
untreated raceways
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Plants Vary In Ability To Reduce ECs
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Antidepressants - Background
Various compounds used - SSRIs (Fluoxetine,
Sertraline, Paroxetine, Citalopram, Fluvoxamine)
- SSNRIs (Venlafaxine, Duloxetine) -
Bupropion Widely prescribed - Sertraline
(14), Fluoxetine (28), Effexor (36), Paxil (52),
Celexa (71) Veterinary uses - Companion
animals Detected in water and streambed
sediment - Degradates important Detected in
fish tissue - Brooks et al., 2005, Environ.
Toxicol. Chem., v. 24, p. 464-469.
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Mini-Balances selected SSRIs
New York state WWTP
grit removal
chlorination/ dechlorination
primary clarifier
trickling filter
sand filter
screen
Pump Station
sand filter effluent
primary effluent
secondary effluent
final effluent
all units in ng/L
Fluoxetine 29.1
51.2 21.3 19.2
Norfluoxetine 11
nd lt1 lt1
Sertraline 26.3
8.57 6.57 12.0
Results Provisional
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Mini-Balances selected nonSSRIs

New York state WWTP
grit removal
chlorination/ dechlorination
primary clarifier
trickling filter
sand filter
screen
Pump Station
sand filter effluent
primary effluent
secondary effluent
final effluent
all units in ng/L
Bupropion 201
110 105 92.1
Venlafaxine 1190 1320
610 556
Results Provisional
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Study Design
Drinking Water Treatment Research
Paul Stackelberg
Raw water
Screening
Site 1
decant
Raw Recycled
Site 2
Settled
Site 3
Sludge
Site 7
Disinfected
Site 4
to composite sample
Influent
GAC
Site 5
Metering pump
2nd disinfection
Effluent
Site 6
Clear well (finished water)
Constant head tank
Distribution
24-hour composite samples
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Investigating Effects of Drinking-Water Treatment
(New Jersey)
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ECs Detected in Finished Water
3 to 15 compounds detected per sample
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Percent Reduction in Concentration from Raw to
Finished Water
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IV. Transport and Fate
In order to minimize ecologic effects, it is
essential to understand how a contaminant moves
and is altered in the environment.
(Barber and others, 1995)
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In-stream Study
Fourmile Creek (IA) - Reach 10.6 km -
Drainage Area 160 km2 - Gradient 1 m/km -
HRT 23 hours - Population 27,000 Boulder
Creek (CO) - Reach 9.7 km - Drainage Area
790 km2 - Gradient 4 m/km - HRT 6 hours
- Population 174,000
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Lagrangian Studies

• Sample the same mass of water as it moves
  downstream.
• Useful for evaluating chemical reactions within
  the water mass.
• Useful for determining what chemicals are
  conservative and what chemicals may be reduced.

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Time of Travel
Dye Injection
Leading Edge
Peak
Trailing Edge
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Lagrangian Sampling6 Sites on Boulder Creek6
Sites on Fourmile Creek
Sample Same Parcel of Water

• Churn-Splitting for Separate Analyses

Width and Depth Integrated Composite

• Clean Sampling Protocols

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Comprehensive Chemical Analysis

• Field Measurements (12)
• Inorganic
• major ions (30)
• nutrients (20)
• trace elements (44)
• Organics
• DOC/TOC
• Biological (6)
• OWC (68)
• Pharmaceuticals (34)
• Antibiotics (39)
• Pesticides (52)

gt300 determinations in triplicate at 12 sites
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Paired Watershed Study Tracer Testing

• Boulder Creek (Boulder, CO)
• Reach 9.7 km
• Drainage Area 790 km2
• Gradient 4 m/km
• Population Density 220 people/km2
• Hydraulic Residence Time 6 hr
• Four Mile Creek (Ankeny, IA)
• Reach 10.6 km
• Drainage Area 160 km2
• Gradient 1 m/km
• Population Density 170 people/km2
• Hydraulic Residence Time 23 hr

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Carbamazepine
Cotinine
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OWC Fate and Transport
Fourmile Creek
Boulder Creek
82 effluent
37 effluent
Preferential removal of EDTA relative to
NPEC Apparent in-stream attenuation was greater
in Fourmile Creek Removal consistent with
Fe3-EDTA photolysis
43 9
85 59
9 4
56 36
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Tonalide in Fourmile Creek
Water Sediment (mg/L)
(mg/kg)
Site 1 0.021 lt25 (-0.1 km)
Site 2 3.1 2000 (0 km) Site 4
0.7 580 (2.9 km) Site 5 0.4
200 (8.4 km)
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V. Ecological Effects

• Contaminant uptake
• Endocrine Disruption
• Antibiotic Resistance
• Pathogens

Our ability to measure contaminants currently
exceeds our understanding of their environmental
effects.
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Integration of Chemical and Biological Research
Fish Work - Community structure - Health
assessment
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Why study the biota?

• Critical link between the water-chemistry and the
  environment.
• What compounds are important?
• Treatment plants may not be able to remove
  everything some compounds may have a higher
  priority.
• How are certain compounds affecting the biota?
• Endrocrine disruption
• Abnormalities.
• Implications for food chain and warning signs.

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Fish are weighed, measured, and examined.
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Blood sample is collected.
Sex of fish is determined
Liver is removed and flash frozen in cryogenic
vials
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Gonads, spleen and kidneys are examined and saved
for histopathology. Gill sample is collected and
preserved. Fish is frozen.
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Summary

• Contaminants that are not currently regulated are
  being detected in our streams, rivers, bed
  sediment, and in some cases drinking water.
• The health effects of mixtures of low
  concentrations of ECs on wildlife or humans are
  not known, but antibiotic resistance in bacteria
  is common, as are endocrine-disrupting effects in
  fish and amphibians.
• More studies on the fate and transport of these
  compounds need to be conducted and the search
  should continue to identify other compounds that
  may have an effect on biota and human health.

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WWTP Effluent Discharge Results in Endocrine
Disruption
White sucker (Catostomus commersoni)
(Norris and others, 2004)
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Occurrence of Antibiotics and Other Organic
Wastewater Compounds in Select Arkansas Streams

• Joel M. Galloway W. Reed Green
• USGS Arkansas Water Sciences Center
• Brian E. Haggard
• USDAARS PPPSRU
• Michael T. Meyer
• USGS Organic Chemistry Research Laboratory

Online report at http//pubs.usgs.gov/sir/2005/51
40/SIR2005-5140.pdf
U.S. Department of the Interior U.S. Geological
Survey
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Antibiotics and Other Organic Wastewater
Compounds (OWCs)

• The purpose of this study was to evaluate the
  occurrence of antibiotics and other OWCs in
  selected streams of northcentral and northwestern
  Arkansas.
• This project was completed as a joint effort
  between the USGS Arkansas Water Sciences Center,
  USDAARS, and the University of Arkansas.
• Samples were collected in April and May 2004 at
  18 sites upstream and downstream of WWTP
  discharges (including 1 site in an undeveloped
  basin)
• Four sites were also sampled in August 2004

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WaterQuality Monitoring Sites in NorthCentral
and Northwestern Arkansas
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RESULTS AND DISCUSSION

• One or more OWCs were found in water samples
  collected at the sites in this study, except at
  Spavinaw Creek near Mayesville.
• This catchment has a high density of poultry.
• Three OWCs were even found at North Sylamore
  Creek near Fifty-Six, including
• Caffeine (Nonprescription Drug)
• Phenol (Disinfectant)
• AHTN (Fragrances Flavors)

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number of constituents in group
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Percent of the total concentration of all
detected constituents
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RESULTS AND DISCUSSION

• Overall, 42 of the 108 targeted antibiotics and
  OWCs were detected at least once.
• Concentrations were generally low (lt1 mg L-1).
• Many concentrations were estimated, because they
  were less than the reporting limit (RL).
• However, a few chemical concentrations were
  greater than 1 mg L-1, including
• 3-b-Coprostanol, b-Sigmastanol, Cholesterol
• para-Nonylphenol (total), NPEO2, OPEO1
• AHTN (widely used musk fragrance)
• anhydro-Erythromycin

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RESULTS AND DISCUSSION

• Individual OWCs detected in greater than 50 of
  the water samples, including
• AHTN, Caffeine, para-Cresol and Phenol.
• None of the individual chemicals exceeded
  drinking water guidelines, health advisories, or
  aquatic life criteria.
• It was apparent that municipal WWTP effluent
  discharges significantly increased the number of
  detections (plt0.05) and total measured
  concentrations (plt0.10).

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Number of constituents detected
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RESULTS AND DISCUSSION

• Overall, four chemical categories produced the
  increase in the number of detections and total
  measured concentration downstream from municipal
  WWTP effluent discharges.
• Detergent Metabolites
• Fire Retardants
• Fragrances Flavors
• Steroids
• Antibiotics were only found in water samples
  collected downstream from municipal WWTP effluent
  discharges.

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Current Activities

• Evaluation of the transport and fate of
  antibiotics and other OWCs in effluent dominated
  streams.
• WholeReach Attenuation Factors
• Sediment Accumulation
• Samples will be collected at numerous sites
  downstream from WWTP discharges 3 times a year at
  different flow conditions
• Sites located on Mud Creek (Fayetteville WWTP),
  Spring Creek (Springdale WWTP), and Decatur
  Branch (Decatur WWTP)

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ANY QUESTIONS?