Grantee Research Project Results
Final Report: Occurrence and Fate of Pharmaceuticals and Personal Care Products in Groundwater Environments
EPA Grant Number: R829007Title: Occurrence and Fate of Pharmaceuticals and Personal Care Products in Groundwater Environments
Investigators: Brownawell, Bruce J. , Iden, Charles R.
Institution: The State University of New York at Stony Brook
EPA Project Officer: Page, Angela
Project Period: September 21, 2001 through September 20, 2004 (Extended to September 20, 2005)
Project Amount: $495,955
RFA: Drinking Water (2000) RFA Text | Recipients Lists
Research Category: Drinking Water , Water Quality , Water
Objective:
The primary objectives of the proposed study are to:
1. Determine the distribution of a wide range of highly used, toxicologically-significant pharmaceuticals, hormones, and personal care products (PPCPs) in point source discharges and in groundwaters that receive those discharges; and
2. Assess the likelihood of migration of PPCPs through sand-gravel aquifers using a combination of field observation, and laboratory-based process studies.
Secondary objectives are to:
1. Develop new HPLC-ESI-MS methods to determine hormone conjugates in wastewater effluents and groundwaters to determine the possible role of conjugates in solubilizing and transporting hormones in groundwaters; and
2. Compare the distribution and likely behavior of PPCPs in subsurface/groundwater environments with that observed in surface waters. This will help determine relative risks associated with discharge of human wastes to surface waters or subsurface environments.
Approach:
The vulnerability of groundwaters to contamination with PPCP discharges will be studied by comparing the groundwater distributions of PPCPs in areas of different land use (i.e., sewered vs. unsewered residential communities) and by determining distributions in groundwaters affected by known point source of PPCPs to the subsurface (sewage treatment plant discharges, landfill leachates, and cesspools). Laboratory sorption and transformation studies will support interpretations and test hypotheses generated from the field data.Summary/Accomplishments (Outputs/Outcomes):
We were able to address each of the primary and secondary objectives of the grant. A newly purchased Micromass LC-T HPLC-time-of-flight (TOF)-MS system served as the primary analytical tool to be used for the project. We were able demonstrate both outstanding sensitivity (signal to noise in environmental matrices that is intermediate between common single and triple quadrupole instruments) with full spectral resolution (that allows us to search for both targeted and nontargeted analytes at ultratrace levels), sufficient dynamic range for quantitative analysis when testing, and unique selectivity capabilities that allowed for a high level of confirmation of analytes through accurate mass (usually within 2.0 mDa) and elemental composition estimation that is complementary to that obtained by MS-MS analysis. The resolution of the TOF analyzer (resolution of 6000-7000) was sufficient to reduce greatly nominal same mass interferences for many analytes, sometimes using only minimal sample clean-up. We were able to use this instrument to provide meaningful detection of a range of high volume pharmaceuticals in groundwaters, municipal wastewaters, and estuarine surface waters; of selected steroid estrogens and alkyphenol ethoxylate metabolites in sediments and in groundwaters in a septic tank plume; and of homologous of polyoxyethylene and polyoxypropylene derivatives in wastewaters and groundwater.
Key analytical method developments included unique methods for isolating and detecting the glucuronide and sulfate conjugates of steroid estrogens and for steroid estrogens in sediment/soil matrices. With the assistance of Ed Furlong at the USGS lab in Denver, we were also able to successfully adapt a USGS method for a suite of 22 high volume pharmaceuticals to our analysis using the HPLC-TOF-MS. Great effort was expended developing the method for the steroid estrogen conjugates that was sufficiently sensitive (0.1 ng/L MDL) to provide new understandings of their occurrence and fate, as problems were encountered related to separating them from same mass interferences and very rapid transformations that occur in wastewater samples after collection. These problems were overcome with highly refined and multiple chromatographic clean-up approaches, use of HPLC-MS-MS, and immediate addition of acid to wastewater samples to stop enzymatic deconjugation of glucuronides in samples. We, and now other investigators, have determined from direct analysis of conjugates that the glucuronide conjugates of estrogens excreted in wastewater systems are extensively transformed (in part to free estrogen) during transport in sewer lines to municipal treatment plants; both glucuronide and sulfate conjugates are efficiently removed by activated sludge sewage treatment; and that the sulfate conjugates (esp. E1-3S) are somewhat more stable and can be detected at levels approaching free estrogens in sewage effluent streams. Preservation of glucuronides could only be achieved through acidification and not by microbial poisons, such as sodium azide, mercury, and formaldehyde. Furthermore, steroid estrogen conjugates were almost completely transformed in a septic tank system on Cape Cod, suggesting that septic tanks may not be a major source of more soluble conjugates to groundwaters.
The occurrence and fate of pharmaceuticals and other estrogenic contaminants was studied in two upper glacial aquifer settings: at 18 sites from Long Island proximate to and away from known sources with on-site sewage treatment plants, and in a plume emanating from a septic tank serving multiple cottages on Cape Cod. Only a few pharmaceuticals (including caffeine, paraxanthine, sulfamethoxazole, acetaminophen, and carbamezapine) were frequently detected on Long Island, consistent with relatively low extents of sorption of these compounds with aquifer solids measured in lab experiments. Pharmaceuticals with higher aquifer/water partitioning (Kd > 50; e.g., diltiazem and cimetidine) were not observed to migrate significantly in a nursing home derived plume that was sampled on three dates. Preliminary results from sorption experiments as a function of pH, suggest that it is a key variable (especially for pharmaceuticals with basic functional groups) in affecting migration of many pharmaceuticals in the subsurface, with greater mobility found at higher pH. At the Cape Cod site, there was a suboxic plume that extended at least 20 feet from the leach field, within which a number of wastewater contaminants persisted and readily migrated (including steroid estrogens, alkylphenol ethoxylate metabolites, acetaminophen, caffeine, paraxanthine, and two fluorescent whitening agents). However, at the oxic fringes of the plume, where other wastewater tracers were present, concentrations of these same chemicals was greatly attenuated as a result of rapid (days or less) removal. Microbial degradation is inferred as the dominant removal process in the oxic portions of the plume. The same wastewater contaminants were detected at much lower levels in an oxic plume from another septic tank. The septic plume study illustrates that pharmacologically active wastewater contaminants might migrate away from septic systems that fail to maintain oxygen in their plumes.
We also determined the occurrence and studied the fate of pharmaceuticals in estuarine surface waters with studies conducted in sewage impacted Jamaica Bay, NY, an estuary whose major source of freshwater is from municipal wastewater and combined sewer overflows (CSO) during large precipitation events. Sixteen pharmaceuticals were detected in the Bay on multiple sampling dates, and twelve were consistently ubiquitous throughout the Bay and just outside its mouth. Under dry weather conditions, the near linear relationship for each pharmaceutical with salinity was consistent with their common wastewater source, dilution of measured wastewater concentrations, and relatively slow removal in the Bay over the timescales of mixing (days to weeks). However, laboratory incubations with Jamaica Bay and NY Bight seawater samples showed that some pharmaceuticals (nicotine, acetaminophen, and diltiazem) were transformed by microbially mediated processes on timescales of a couple of days, and would not serve as reliable tracers of wastewater over longer timescales. Pharmaceuticals that could be easily detected in the Bay but were not transformed significantly over 4 to 7 weeks included cotinine, carbamezapine, hydrocodone, sulfamethoxazole and trimethoprim; these compounds might make the best long term tracers of wastewater in surface water environments. Caffeine and its metabolite paraxanthine degraded at intermediate and variable rates with half-lives of caffeine as fast as 5 days. While these compounds are often present at the highest and most easily detected concentrations, more work on microbial degradation would be needed to assess the conditions where they might best be used as persistent wastewater tracers in the field. The effect of a large (10” of rain) CSO event on the distribution of pharmaceucticals in Jamaica Bay was also studied. As predicted by a simple model of concentrations in the freshwater source, the effect of the rain was to dilute (3 – 10 times) the concentrations in the Bay of pharmaceuticals (as a function of salinity) that were inefficiently removed by sewage treatment plants; in contrast, the concentrations of efficiently removed acetaminophen and nicotine were little changed as the effect of raw wastewater that bypassed sewage treatment was balanced by the effects of dilution by rainwater.
Expected Results:
This project will fill important data gaps with respect to the distribution, transport, and fate of a wide range of PPCPs in groundwaters. Measurements of PPCPs in groundwaters near potentially important sources would provide valuable end-member information with which to estimate risk to drinking water supplies. Given the low detection limits afforded by HPLC-ESI-MS, it will be possible make PPCP concentration measurements in groundwater that will typically be much lower than those in source waters, assuring that it will be possible to make useful interpretations from those data concerning fate and transport. This groundwater-based study will complement other recent or concurrent studies of surface waters in the U.S. and abroad by other investigators, and provide a greater knowledge base needed for comparing relative risks for disposal PPCPs to surface and subsurface environments. The data generated in this project will also provide the most comprehensive study to date of environmental estrogens in groundwaters.Journal Articles on this Report : 6 Displayed | Download in RIS Format
| Other project views: | All 29 publications | 7 publications in selected types | All 6 journal articles |
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Benotti MJ, Brownawell BJ. Distributions of pharmaceuticals in an urban estuary during both dry-and wet-weather conditions. Environmental Science & Technology 2007;41(16):5795-5802. |
R829007 (Final) |
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Benotti MJ, Brownawell BJ. Microbial degradation of pharmaceuticals in estuarine and coastal seawater. Environmental Pollution 2009;157(3):994-1002. |
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Reddy S, Brownawell BJ. Analysis of estrogens in sediment from a sewage-impacted urban estuary using high-performance liquid chromatography/time-of-flight mass spectrometry. Environmental Toxicology and Chemistry 2005;24(5):1041-1047. |
R829007 (2004) R829007 (Final) |
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Reddy S, Iden CR, Brownawell BJ. Analysis of steroid conjugates in sewage influent and effluent by liquid chromatography-tandem mass spectrometry. Analytical Chemistry 2005;77(21):7032-7038. |
R829007 (2004) R829007 (Final) |
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Swartz CH, Reddy S, Benotti MJ, Yin H, Barber LB, Brownawell BJ, Rudel RA. Steroid estrogens, nonylphenol ethoxylate metabolites, and other wastewater contaminants in groundwater affected by a residential septic system on Cape Cod, MA. Environmental Science & Technology 2006;40(16):4894-4902. |
R829007 (Final) |
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Thurman EM, Ferrer I, Benotti M, Heine CE. Intramolecular isobaric fragmentation: a curiosity of accurate mass analysis of sulfadimethoxine in pond water. Analytical Chemistry 2004;76(5):1228-1235. |
R829007 (2003) R829007 (2004) R829007 (Final) |
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Supplemental Keywords:
pharmaceuticals, estrogens, groundwater, tracers, HPLC-MS, RFA, Scientific Discipline, Ecosystem Protection/Environmental Exposure & Risk, Water, Health Risk Assessment, Fate & Transport, Environmental Chemistry, Analytical Chemistry, Wastewater, Drinking Water, Environmental Monitoring, wastewater systems, treatment, kinetic studies, hormones, wastewater discharges, monitoring, chemical contaminants, effluents, personal care products, pharmacokinetics, estrogen, pharmacuticals, drinking water system, drinking water contaminants, fate and transport, groundwater, pharmaceuticals, exposure, other - risk assessment, transformation studies, human health effects, aquifer characteristicsRelevant Websites:
http://www.somas.stonybrook.edu/people/brownawell.html ExitProgress and Final Reports:
Original AbstractThe perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Conclusions drawn by the principal investigators have not been reviewed by the Agency.