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| Scientific Investigations Report 2008–5173 |
In cooperation with the Ohio Water Development Authority; National Park Service; Cities of Aurora, Bedford, Bedford Heights, Solon, and Twinsburg; Portage and Summit Counties; and in collaboration with the Ohio Environmental Protection Agency
By J.S. Tertuliani, D.A. Alvarez, E.T. Furlong, M.T. Meyer, S.D. Zaugg, and G.F. Koltun
This report is available below as a 69-page PDF for viewing and printing.
The U.S. Geological Survey—in cooperation with the Ohio Water Development Authority; National Park Service; Cities of Aurora, Bedford, Bedford Heights, Solon, and Twinsburg; and Portage and Summit Counties—and in collaboration with the Ohio Environmental Protection Agency, did a study to determine the occurrence and distribution of organic wastewater compounds (OWCs) in the Tinkers Creek watershed in northeastern Ohio. In the context of this report, OWCs refer to a wide range of compounds such as antibiotics, prescription and nonprescription pharmaceuticals, personal-care products, household and industrial compounds (for example, antimicrobials, fragrances, surfactants, fire retardants, and so forth) and a variety of other chemicals.
Canisters containing polar organic integrative sampler (POCIS) and semipermeable membrane device (SPMD) media were deployed instream for a 28-day period in Mayand June 2006 at locations upstream and downstream from seven wastewater-treatment-plant (WWTP) outfalls in the Tinkers Creek watershed, at a site on Tinkers Creek downstream from all WWTP discharges, and at one reference site each in two nearby watersheds (Yellow Creek and Furnace Run) that drain to the Cuyahoga River. Streambed-sediment samples also were collected at each site when the canisters were retrieved.
POCIS and SPMDs are referred to as “passive samplers” because they sample compounds that they are exposed to without use of mechanical or moving parts. OWCs detected in POCIS and SPMD extracts are referred to in this report as “detections in water” because both POCIS and SPMDs provided time-weighted measures of concentration in the stream over the exposure period. Streambed sediments also reflect exposure to OWCs in the stream over a long period of time and provide another OWC exposure pathway for aquatic organisms.
Four separate laboratory methods were used to analyze for 32 antibiotic, 20 pharmaceutical, 57 to 66 wastewater, and 33 hydrophobic compounds. POCIS and streambed-sediment extracts were analyzed by both the pharmaceutical and wastewater methods. POCIS extracts also were analyzed by the antibiotic method, and SPMD extracts were analyzed by the hydrophobic-compound method. Analytes associated with a given laboratory method are referred to in aggregate by the method name (for example, antibiotic-method analytes are referred to as “antibiotic compounds”) even though some analytes associated with the method may not be strictly classified as such. In addition, some compounds were included in the analyte list for more than one laboratory method. For a given sample matrix, individual compounds detected by more than one analytical method are included independently in counts for each method.
A total of 12 antibiotic, 20 pharmaceutical, 41 wastewater, and 22 hydrophobic compounds were detected in water at one or more sites. Eight pharmaceutical and 37 wastewater compounds were detected in streambed sediments. The numbers of detections at reference sites tended to be in the low range of detection counts observed in the Tinkers Creek watershed for a given analytical method. Also, the total numbers of compounds detected in water and sediment at the reference sites were less than the total numbers of compounds detected at sites in the Tinkers Creek watershed.
With the exception of hydrophobic compounds, it was common at most sites to have more compounds detected in samples collected downstream from WWTP outfalls than in corresponding samples collected upstream from the outfalls. This was particularly true for antibiotic, pharmaceutical, and wastewater compounds in water. In contrast, it was common to have more hydrophobic compounds detected in samples collected upstream from WWTP outfalls than downstream.
Caffeine, fluoranthene, N,N-diethyl-meta-toluamide (DEET), phenanthrene, and pyrene were detected in water at all sites in the Tinkers Creek watershed, irrespective of whether the site was upstream or downstream from a WWTP. Some, but not all of these compounds, also were detected in water at the reference sites; however, concentrations generally were at the low end of the range of concentrations observed in the Tinkers Creek watershed.
Carbamazepine, sulfamethoxazole, trimethoprim, and hexahydrohexamethylcyclopentabenzopyran (HHCB) were detected in water at 100 percent of the sites downstream from WWTP outfalls, yet their frequency of detection at sites upstream from outfalls was statistically less (occurring in about 29 percent or less of the samples). None of these compounds were detected in water at the Yellow Creek reference site, and only two of the compounds (carbamazepine and sulfamethoxazole) were detected at the Furnace Run site. HHCB, a synthetic musk used in some personal care products, has been shown to demonstrate antiestrogenic activity and is thought to disrupt endocrine function in fish.
Fifteen wastewater compounds (2,6-dimethylnaphthalene, 2-methylnaphthalene, 3-methyl-1H-indole, anthraquinone, acetophenone, benzo[a]pyrene, β-sitosterol, bis(2-ethylhexyl) phthalate, carbazole, cholesterol, fluoranthene, indole, naphthalene, p-cresol, and pyrene) were detected in streambed sediments at all sites in the Tinkers Creek watershed, irrespective of whether the site was upstream or downstream from a WWTP. Three of the fifteen compounds (benzo[a]pyrene, bis(2-ethylhexyl) phthalate, and p-cresol) are known or suspected endocrine disruptors.
Many of the pharmaceutical compounds detected in sediment also were detected in water. One notable exception was miconazole, which was detected in more than a quarter of the streambed-sediment samples yet never detected in water. In contrast, some pharmaceutical compounds (such as trimethoprim and carbamzepine) that were detected in water at all sites downstream from WWTP outfalls were either not detected or detected at a much lower frequency in streambed sediments.
Abstract
Introduction
Purpose and Scope
Study Area
Methods
Passive Sampling Technology
Polar Organic Chemical Integrative Samplers (POCIS)
Semipermeable Membrane Devices (SPMDs)
Sampling-Site Selection and Sampler Deployment
Streambed-Sediment Sampling
Laboratory Analyses
Reporting of Data
Quality Control
Trip Blanks
Field Replicates
Reagent and Matrix Spikes
Method Blanks and Surrogate and Internal Standards
Results
Compounds in Water
Antibiotic Compounds
Pharmaceutical Compounds
Wastewater Compounds
Hydrophobic Compounds
Compounds in Streambed Sediments
Pharmaceutical Compounds
Wastewater Compounds
Summary and Conclusions
References Cited
Appendix A. Detailed Analytical Methods and Passive Sampling Theory
POCIS and SPMD Media Preparation and Extraction
Chemical Analysis of POCIS and SPMD Extracts
Chemical Analysis of Streambed Sediments
Passive Sampling Theory
Estimation of Ambient Water Concentrations
References Cited
Appendix B. Organic Wastewater Compound Analytes and Reporting Levels, by Sample Media and Analytical Method
References Cited
Appendix C. Quality-Control Data
Appendix D. Organic Wastewater Compounds in Polar Organic Chemical Integrative Sampler (POCIS) Extracts
Appendix E. Organic Wastewater Compounds in Semipermeable Membrane Device(SPMD) Extracts
Appendix F. Organic Wastewater Compounds in Streambed Sediments
(This report contains 9 figures and 31 tables.)
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Suggested Citation:
Tertuliani, J.S., Alvarez, D.A., Furlong, E.T., Meyer, M.T, Zaugg, S.D., and Koltun, G.F., 2008, Occurrence of organic wastewater compounds in the Tinkers Creek watershed and two other tributaries to the Cuyahoga River, Northeast Ohio: U.S. Geological Survey Scientific Investigations Report 2008–5173, 60 p.
For further information on USGS water-resources activities in Ohio, visit the USGS Ohio Water Science Center Home Page
U.S. Geological Survey
Ohio Water Science Center
6480 Doubletree Ave.
Columbus OH 43229-1111
Phone: (614) 430-7700
FAX: (614) 430-7777
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