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Pharmaceuticals and Personal Care Products (PPCPs), Hormones, and Alkylphenol Ethoxylates (APEs) in the North Shore
Channel of the Chicago River
Todd Nettesheim, Elizabeth Murphy, Great Lakes National Program Office, USEPA, Chicago, ILLawrence Zintek, Chicago Regional Laboratory, USEPA, Chicago, ILClifford P. Rice, Nuria Lozano, Agricultural Research Service, USDA, Beltsville, MDHeiko L. Schoenfuss, St. Cloud State University, St. Cloud, MNJames M. Lazorchak, Angela L. Batt, Marc A. Mills, USEPA ORD, Cincinnati, OHLarry B. Barber, James L. Gray, USGS, Boulder, CODavid Lordi, Sam Dennison, Tom Minarik, Metropolitan Water Reclamation District of Greater Chicago, Chicago, IL
SETAC North America 28th Annual MeetingWednesday, November 14, 2007
AcknowledgementsAcknowledgements
Other collaborators USGS National Water Quality Laboratory in Golden, CO U.S. EPA Office of Water – John Wathen and Leanne Stahl Tetra Tech – Blaine Snyder and Jennifer Pitt Baylor University Clarkson University, SUNY-Oswego, SUNY-Fredonia Illinois DNR – Rob Miller and Jim Langbein Exelon Corp – John Petro
Captains of the MWRD PC-1 boat MWRD R&D Laboratory staff Countless others at MWRD who helped to collect fish
and effluent samples
Things I plan to talk about…Things I plan to talk about…
Objectives of studyStudy locationStudy designPreliminary results
Objectives of Study
Supplemental study to EPA’s National Fish Tissue Study
The four main objectives of the supplemental study are to: Determine if there is reproductive impairment to resident
fish; Estimate effluent and stream concentrations of PPCPs,
APEs, hormones, and general chemistry Estimate whole fish concentrations of PPCPs, APEs, and
hormones; and Document seasonal differences in concentrations of these
compounds in effluent, stream, and fish. Strengthen collaborative ventures
Things I plan to talk about…
Objectives of studyStudy location
DowntownChicago
Study Location
North Side WRP•333 MGD•Serves 1.3 million people •Secondary treatment•Sludge pumped to another WRP
North Shore Channel•Man-made (early 1900s)•Effluent dominated•Recreational fishery
Things I plan to talk about…Things I plan to talk about…
Objectives of studyStudy locationStudy design
Study Design – Objective 1Study Design – Objective 1
Determine reproductive impairment Analyze fish blood for vitellogenin (vtg) Perform mRNA analyses for vtg in livers Examine livers for abnormalities Examine fish gonads for imposex and
abnormalities (histopathology) Examine fish brains for abnormalities
Large mouth bass and common carp Sexually mature fish
Local reference sites analyzed for control Lake Michigan and Braidwood cooling pond
Collaborative partners St. Cloud State University ORD Cincinnati
Study Design – Objective 2Study Design – Objective 2
Estimate effluent and stream concentrations of PPCPs and Hormones
USGS Boulder and Golden, CO, Labs – Conduct weekly analysis of stream and effluent samples using OWC 1433 (75 organic waste water contaminants including some personal care products); Pharma 9003 (34 prescription and non-prescription drugs); and hormones method (20 natural and synthetic sex hormones)
EPA ORD NERL – Conduct weekly analysis of stream and effluent samples for 56 pharmaceuticals and metabolites using SPE and UPLC/MS/MS (Sprng only)
EPA ORD NRMRL – Conduct weekly analysis of stream and effluent samples for 8 hormones using SPE and GC/MS (Spring only)
Study Design – Objective 2 (cont.)Study Design – Objective 2 (cont.)
Estimate effluent and stream concentrations of APEs and general chemistry
EPA Central Regional Laboratory (CRL) –Analyze of 2-3 effluent samples per week and weekly stream samples for long chain APEOs (NP3-18EO and OP2-12EO) and NP1EC and NP2EC using direct injection LC/MS; and NP, NP1EO, NP2EO, OP, and BPA using CLLE and GC/MS.
MWRD – Analyze 2-3 effluent samples per week and a stream sample for general chemical parameters (e.g. N-NH3, BOD, SS, etc.)
Study Design – Study Design – Objective 3Objective 3
Estimate whole fish concentrations of PPCPs, APEs, and hormones (sexually mature fish)
USDA - Conduct analyses on whole fish homogenates and fillet tissue for alkylphenols and alkylphenol ethoxylates (NP, NP1-4EO, OP, OP1-4EO). 6 large mouth bass from NSC and 3 large mouth bass from reference site 3 fillet composite samples from National Fish Tissue study 3 small mouth bass from national reference location (New Mexico)
USGS - Conduct analysis of whole fish homogenates using OWC 1433 (75 organic waste water contaminants including some personal care products) and hormones method (20 natural and synthetic sex hormones) 3 large mouth bass from NSC and 3 large mouth bass from reference site
Clarkson University - Conduct analysis of whole fish homogenates for PCBs, OC pesticides, BFRs, Hg, and dioxins. 6 large mouth bass from NSC and 3 large mouth bass from reference site
Study Design – Objective 4Study Design – Objective 4
Document seasonal differences in concentrations of these compounds in effluent, stream, and fish. Fall 2006 campaign
Effluent and stream samples collected from September to October 24 large mouth bass collected for National Fish Tissue study 12 large mouth bass collected for this study 9 large mouth bass collected from local reference site (Lk Michigan)
Spring 2007 campaign Effluent & stream samples collected from February to April 24 large mouth bass collected for National Fish Tissue study 9 large mouth bass & 14 common carp collected for this study 12 large mouth bass, 13 carp and 2 catfish from Braidwood
Things I plan to talk about…Things I plan to talk about…
Objectives of studyStudy locationStudy designPreliminary results
Estrogenic Effects on FishEstrogenic Effects on FishFall 2006Fall 2006
Summary of fish sex and occurrence of vitellogenin in Fall 2006 Collection
North Shore Channel
Outer Chicago Harbor
Immature fish (w/ VTG) 4 (0%) 0
Male fish (w/ VTG) 5 (60%) 4 (0%)
Female fish (w/ VTG) 3 (100%) 5 (100%)
Estrogenic Effects on FishEstrogenic Effects on Fish(values mean ± standard error) Spring 2007(values mean ± standard error) Spring 2007
Parameter Largemouth Bass Common Carp
Effluent Braidwood Effluent Braidwood
Male Female Male Female Male Female Male Female
Sample size
1 8 8 4 9 5 11 2
Weight (g) 1050 949±64
998±110
941±114
3176±466
3518±779
2222±207
1889±874
VTG (µg/mL)
3.3 7±1.8 0.08±0.05
9.3±5.1 38±17 38900±9334
29±12 48350±31950
NPEs in Large Mouth Bass
0.0
500.0
1000.0
1500.0
2000.0
2500.0
3000.0
3500.0
4000.0
4500.0
5000.0
NSC fall ref fall NSC spring ref spring
Co
ncen
tratio
n, n
g/g
NP NP1EO NP2EO NP3EO NP4EO
* Below MDL
* * * * ** * **
Percent Compound DetectedFall 2006 & Spring 2007 Collections
0.0% 10.0% 20.0% 30.0% 40.0% 50.0% 60.0% 70.0% 80.0% 90.0% 100.0%
NP
NP1EO
NP2EO
NP3EO
OP
BPA
NP1EC
NP2EC
Percent detected
Stream Effluent
Nonylphenol and Nonylphenol Ethoxylatesin Northside WRP Effluent
0
2000
4000
6000
8000
10000
12000
14000
14-S
ep-0
6
18-S
ep-0
6
22-S
ep-0
6
26-S
ep-0
6
2-O
ct-0
6
6-O
ct-0
6
10-O
ct-0
6
14-O
ct-0
6
18-O
ct-0
6
24-O
ct-0
6
28-F
eb-0
7
6-M
ar-0
7
12-M
ar-0
7
16-M
ar-0
7
22-M
ar-0
7
28-M
ar-0
7
3-A
pr-0
7
9-A
pr-0
7
13-A
pr-0
7
19-A
pr-0
7
Co
nce
ntr
atio
n (
ng
/L)
0.0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
Tem
per
atu
re (
F)
NP NP1EO NP2EO Temperature
APEs Concentrations versus TemperatureFall 2006 & Spring 2007 Collections
R2 = 0.8403
R2 = 0.4942 R2 = 0.7681
0
2000
4000
6000
8000
10000
12000
14000
45.0 50.0 55.0 60.0 65.0 70.0 75.0
Temperature (F)
Con
cent
rati
on (n
g/L
)
NP NP1EO NP2EO Linear (NP) Linear (NP2EO) Linear (NP1EO)
APEs in Northside WRP Effluent and Downstream ChannelFall 2006 & Spring 2007 Collections
0
1000
2000
3000
4000
5000
6000
7000
8000
NP NP1EO NP2EO NP3EO OP BPA
Con
cent
ratio
n (n
g/L
)
Effluent Stream
NPECs in Northside WRP and Downstream ChannelFall 2006 and Spring 2007 Collections
05000
10000150002000025000300003500040000
NP1EC NP2EC
Con
cent
ratio
n (n
g/L
)
Effluent Stream
Bioconcentration Factor (BCF) for Bioconcentration Factor (BCF) for NPEsNPEs
BCF = Concentration in fish / Concentration in BCF = Concentration in fish / Concentration in waterwater
NP = 130-230NP = 130-230 NP1EO = 450-630NP1EO = 450-630 NP2EO = 200-480NP2EO = 200-480 NP3EO = 40-60NP3EO = 40-60
These values agree quite well with the values These values agree quite well with the values published by Mitchelmore and Rice 2006.published by Mitchelmore and Rice 2006.
NP = 280NP = 280 NP1EO = 1713NP1EO = 1713 NP2EO = 693NP2EO = 693
Pharmaceuticals in Effluent and Stream Samples
0 20 40 60 80 100 120
atenololclonidine
oxycodoneamphetaminehydrocodone
triamtereneenaliprilat
metoprololenalipril
propanololdiltiazem
diltiazem-desmethylverapamil
norverapamilpropoxyphene
amlodipinelisinopril
ciprofloxacintrimethoprim
sulfamethoxazoleamitriptyline-10-OH
promethazineparoxetine
amitriptylinebenztropinealprazolam
norfluoxetinefluoxetine
sertraline-desmethylsertraline
liothyroninelevothyroxine
acetaminophenprednisone
prednisolonecarbamazepinebetamethasone
methylprednisolonenorethindronetestosterone
valsartanfluocinonideatrovastatinfluticasone
progesteronesimvastatintheophylline
hydrochlorothiazideibuprofen-2-hydroxy
furosemidewarfaringlipizide
ibuprofenhydrocortisone
gemfibrozilglyburide
% detect
Pharmaceuticals in Effluent and Stream Pharmaceuticals in Effluent and Stream Samples Samples (for those with eyesight worse than 20/10)(for those with eyesight worse than 20/10)
Pharmaceuticals present at high ppt to ppb Lisinopril Valsartan Hydrochlorothiazide Ibuprofen-2-hydroxy Gemfibrozil
Pharmaceuticals present at mid ppt Atenolol Metoprol Diltiazem Ciprofloxacin Trimethoprim Carbamazepine Furosemide ibuprofen
Pharmaceuticals not detected Clonidine Oxycodone Propoxyphene Amitriptyline-10-OH Alprazolam Liothyronine Levothyroxine Acetaminophen Prednisone, Prednisolone,
Betamethasone, Methylprednisolone Norethindrone Testosterone Fluocinonide Fluticasone Progesterone Simvastatin Theophylline Warfarin Glipizide Hydrocortisone glyburide
Summary and Next Steps
Collaboration is KEY! Estrogenic effects present
What is the significance?
Fish tissue concentrations vary along with effluent and stream concentrations
Similar BCFs in fall and spring
Wastewater effluent is a soup of 1000s of compounds Much more data to come
Hormones is effluent, stream and fish PPCPs in effluent, stream and fish
