Grantee Research Project Results
2004 Progress 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 Period Covered by this Report: September 21, 2003 through September 20, 2004
Project Amount: $495,955
RFA: Drinking Water (2000) RFA Text | Recipients Lists
Research Category: Drinking Water , Water Quality , Water
Objective:
The primary objectives of this research project are to: (1) determine the distribution of a wide range of highly used, toxicologically significant hormones and pharmaceuticals 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.
The secondary objectives of the research project are to: (1) develop new high performance liquid chromatography (HPLC)-electrospray ion-mass spectrometry (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) c ompare 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.
Progress Summary:
Progress has been made in completing intensive development of methods to detect sulfate and estrogen conjugates in wastewaters and groundwater and in conducting detailed field-based experiments, in which we have studied the occurrence and transport of PPCPs and estrogens in groundwater at two upper glacial aquifer sites that receive points sources of wastewaters.
We overcame several difficulties to complete and validate a sensitive new method to detect sulfate and glucuronide conjugates of the steroid estrogens E1 and E2, which are measured readily in many wastewaters. The conjugates have held our interest because: (1) it has been well documented that free estrogens are not readily transported in several subsurface environments because of sorption to aquifer solids and possible microbial degradation; (2) conjugates are the form of estrogens excreted by mammals and, being much more soluble, have the potential to migrate rapidly through groundwaters; and (3) the preponderance of attempts to study the role of conjugates has measured them indirectly (through enzymatic deconjugation and quantification by difference), an approach that has never been validated. We finished what turned out to be a very difficult method this year and have applied the method to a study on the fate of steroid estrogens in a sewage treatment plant and in a groundwater plume from a multi-family septic tank on Cape Cod.
During this year, our HPLC-MS-MS method was improved and refined in numerous ways related to sample clean up and chromatography. Our most significant work, however, was related to understanding and controlling conjugate transformations of analytes and surrogate standards during sampling and analysis. Synthesis of C-14 labeled glucuronide conjugates was a critical achievement, which allowed us to complete this part of the study. In sewage influent and effluent samples, microbially mediated conjugate transformations are very rapid (minutes in many cases), and reliable results for conjugates, as well as free estrogens released by enzymatic hydrolysis, cannot be obtained without immediate preservation of the samples. In sewage influent, we found that the strong biocide mercuric chloride was an effective preservative, but azide and formalin were not. In effluent samples (high levels of extracellular hydrolases and lower organic matter in the matrix), however, mercury was not sufficient to stop conjugate transformation, but acidification to pH 2 (thus de-activating responsible enzymes) was. With our methods, we were able to obtain method detection limits for most of the twelve conjugates at levels approaching 0.1 ng/L. In a sewage treatment plant receiving secondary treatment with activated sludge, we found that glucuronide conjugates are very labile and had been largely transformed even before wastewaters reached the plants; those glucuronide conjugates that did make it to the plant were efficiently degraded during secondary treatment.
On the other hand, sulfate conjugates of estrone and estradiol were more stable and became more quantitatively important during the treatment process. The E2, 3-sulfate was the most stable conjugate, and, in sewage effluent, it was three times higher in concentration than the free E1 and E2. We also showed that a mixture of glucuronidases, often used to deconjugate estrogens in water and wastewater samples, did not efficiently hydrolyze E2, 3-sulfate, suggesting that there could be a significant, previously unrecognized source of steroid estrogens to surface waters coming from well operated sewage treatment plants. More work on other treatment plants is needed to see if these findings can be generalized. It is also important to extend this approach to the assessment of the role of conjugates with the more potent synthetic estrogen EE2.
Analysis of steroid estrogens and their conjugates in a septic tank groundwater plume (combined inputs from five year-round cottages) showed that free estrogens E1 and E2 were elevated highly compared to municipal wastewaters (combined concentrations exceeding 100 ng/L on three separate sampling dates) and that relatively little degradation occurred between the septic tank and the wells within the anaerobic portion of the plume extending 22 feet from the leachfield. Good evidence for hormone degradation and the oxidation of E2 to E1, however, is seen at the periphery of the plume where oxic or suboxic conditions prevail. In contrast to relative preservation of the sulfate conjugates during aerobic treatment, all of the conjugates are largely transformed in the anaerobic septic system; a small amount of sulfate conjugates (this time E1, 3-sulfate) is found within the plume, but at only a small percentage of the levels of free estrogens.
The fate of a wide assortment of other PPCPs and wastewater contaminants also has been studied at the Cape Cod septic tank site. In general, there is significant transport of most PPCPs and wastewater contaminants within the anaerobic plume. Caffeine is one contaminant that is degraded under anaerobic conditions, and there is a measured, corresponding increase in the caffeine metabolite paraxanthine along the plume. Alkylphenol ethoxylate metabolites and the fluorescent whitening agent DAS are elevated in the plume, with total metabolite concentrations on the order of 100 and 3 μg/L, respectively. EDTA concentrations also are elevated highly (about 35 μg/L) and it appears to be the most conservative of all the wastewater contaminants analyzed. At the fringes of the anaerobic plume and in samples where wastewater-affected groundwater has been oxidized (e.g., at the water table), EDTA and total nitrogen levels remain little changed, whereas many of the other contaminants largely are depleted. Oxidized samples have lower total concentrations and much higher ratios of more oxidized alkylphenol ethoxylate carboxylates and estrone compared to alkylphenol ethoxylates and b-estradiol that are likely precursors of former contaminants.
We are planning additional work at the Cape Cod site that also will include microbial degradation tests with C-14-labeled caffeine, E2, and some of the conjugates of E2. Experiments with radio-labeled compounds and unlabeled PPCPs will be designed to understand better the conditions (oxygen, microbial acclimation, contaminant concentration) under which selected wastewater is persistent or degraded. During Year 3 of the project we submitted and had accepted a manuscript for determining steroid estrogens in sediments and soils using HPLC-time of flight (TOF)-MS. We will use this method to better understand the role of sorption on the transport of estrogens at the Cape Cod site. We also will dig additional wells to characterize the axial extent of the plume for distances greater than 22 feet, and, through our partnership with the U.S. Geological Survey (USGS), we will measure of polyfluorinated PFOS contaminants that should be readily detectable in wastewater.
At another site on Long Island, where the biologically treated effluent from a nursing home is discharged to a shallow upper glacial aquifer, Ph.D. student Mark Benotti has measured the distribution of a series of 24 PPCPs in downgradient wells. He is planning to conduct additional microbiological and sorption experiments to understand better why some of the PPCPs are readily mobile and others are not. Interestingly, caffeine appears to be transported relatively conservatively at the Long Island site.
We also developed the use of water-soluble polymers as tracers of wastewater in groundwater and surface water environments. In what remains relatively preliminary work, we have used HPLC-TOF-MS to characterize small polyethylene oxide and polypropylene oxide polymers, as well as polyethoxylated sorbitols (ingredients of Tween products) of up to 5000 amu. Seventeen such series of polymers have been identified in wastewaters and a number of those have been confirmed in both surface and groundwater samples impacted by wastewater. Because of the large size of water-soluble polymers, they should be relatively resistant to microbially mediated intracellular reactions and thus have a good chance to be sensitive and stable tracers of wastewaters in subsurface environments. In the next year, we hope to confirm the identity of these homologous series, to conduct better tests of persistence in groundwaters, and to extend our approach with MALDI-TOF analysis to look for higher molecular weight water soluble polymers, including polyacrylates and methacrylates.
Our collaborations with the Suffolk County Department of Health, the Silent Spring Institute in Newton, Massachusetts, and the USGS laboratories in Lawrence, Kansas, Boulder, Colorado, and Arvada, Colorado, have continued and grown. We presently are preparing a series of papers detailing our joint results from these efforts.
Future Activities:
Activities for the next year are discussed in the Progress Summary/Accomplishments section. A major goal for the next several months is to complete the four manuscripts presently in preparation and submit them for publication.
Journal Articles on this Report : 3 Displayed | Download in RIS Format
Other project views: | All 29 publications | 7 publications in selected types | All 6 journal articles |
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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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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, drinking water, groundwater, wastewater fate, pharmaceuticals and personal care products, environmental estrogens, environmental monitoring, health risk assessment, drinking water contaminants, fate and transport,, RFA, Scientific Discipline, Water, Ecosystem Protection/Environmental Exposure & Risk, Wastewater, Environmental Chemistry, Health Risk Assessment, Fate & Transport, Analytical Chemistry, Environmental Monitoring, Drinking Water, monitoring, fate and transport, aquifer characteristics, human health effects, pharmaceuticals, exposure and effects, pharmacokinetics, estrogen, transformation studies, exposure, other - risk assessment, chemical contaminants, personal care products, kinetic studies, treatment, wastewater systems, hormones, wastewater discharges, drinking water contaminants, effluents, drinking water system, groundwaterRelevant Websites:
http://www.msrc.sunysb.edu/people/brownawell.htm Exit
Progress 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.