Grantee Research Project Results
2003 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, 2002 through September 20, 2003
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 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.
The secondary objectives of this research project are to: (1) develop new high performance lqiuid chromatography (HPLC)-electrospray ion-mass spectrometry (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) 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 method development, in field-and laboratory-based process studies, and with developing collaborations with a variety of groups that complement our capabilities.
Four significant developments were made with respect to method development: (1) We were able to reproduce the U.S. Geological Survey (USGS) method for high volume pharmaceuticals as a result of Mark Benotti’s visit to the USGS Denver lab for several weeks. After identifying differences in analytical approaches, successful intercalibrations were conducted. The method has been applied to a wide range of groundwater samples collected around Long Island and Cape Cod. (2) New graduate student Haifei Yin developed an approach (a modification of a published HPLC-fluorescence method using a precolumn rather than postcolumn UV photo-isomerization) to successfully determine fluorescent whitening agents diaminostilbene and distrylbiphenyl in wastewater and affected groundwater samples. The structures of these compounds contain stilbene moieties and have recently been found to have significant estrogenic activity in fish assay experiments. We found them in relatively high concentrations (approximately 4 ppb) in a septic tank plume at levels that were consistent with treated wastewater, suggesting that they may be mobile in the subsurface under certain conditions. (3) Significant progress has been made on the challenging problem of analyzing intact steroid estrogen conjugates (three sulfate and three glucuride conjugates of E1 and E2. Instrument detection limits (approximately 0.1 ng/L) that are sufficient to provide environmental fate information under realistic environmental conditions were achieved by either HPLC-MS-MS or HPLC-time of flight (TOF)-MS. Isotope surrogates were either located or synthesized; however, a tremendous amount of sample purification (selective solid-phase extraction washing following by anion exchange HPLC prior to HPLC-MS analysis) has been needed to remove enough suppression of ionization and isobaric interferences caused by matrix from extracts of environmental samples. Present method detection limits in wastewater samples are 0.5–1 ng/L using HPLC-TOF-MS, and the results of MS-MS will be soon completed. We have focused much energy on this analysis because of the potential for soluble conjugates to be more mobile in groundwater and because it is known that free estrogens (or other pharmacologically active contaminants) can be released from conjugated forms that are often excreted by mammals. (4) Many soluble polymers (polyoxyethylene and polyoxypropylene) have been identified during our HPLC-TOF-MS analysis of high volume pharmaceuticals. In this method, we have limited our mass/charge window to 100–1,000 Da/z. For several of these polymeric series, we see compounds that have mass/charge ratios up to 1,000 and are multiply charged with up to 5 sodium or ammonium adducts, meaning that molecular weights up to 5,000 amu are being detected. We will be spending more effort determining what these polymers (in addition to polyethylene and polypropylene glycols) are, exploring approaches for detecting other classes of water soluble polymer, determining whether we can extend our analysis up to 15,000-20,000 amu by opening our mass window, and beginning to assess whether some water soluble polymers might turn out to be valuable tracers of wastewaters in surface and groundwater environments.
We have characterized the distribution of PPCPs around 10 sites where there is discharge to ground of treated wastewaters or from multi-family septic tanks (2 on Cape Cod). Results from two sites are especially promising. One site on Long Island is a plume generated by treated wastewater from the Woodhaven Nursing home, in which four in-place downstream wells and one up-stream well yielded results that characterized differential transport of over 20 PPCPs identified in the wastewater effluent. Surprisingly, caffeine and the caffeine metabolite paraxanthine were among the four PPCPs that appeared to be transported with the most conservative behavior. We hypothesize that there may be a threshold concentration for microbial utilization that leads to selection of acclimated populations that can metabolize caffeine at high concentrations (e.g., ppb to near ppm) that can support growth, but microbial transformations may be much more limited under lower ppt concentrations found in this plume. Similar findings (i.e., apparently near conservative short-term behavior of caffeine and paraxanthine) were observed in surface water samples collected in wastewater-affected Jamaica Bay this year. Sorption experiments showed relatively poor correlation between the extent of sorption and the tendency for PPCPs to be found in downgradient wells, although PPCPs with very high sorption (Kd > 100 L/kg) were not found to migrate. At the Cape Cod septic tank sites, we found very high levels of alkylphenol ethoxylate metabolites (over 100 ppb), steroid estrogens (E1+E2 > 100 ng/L), fluorescent whitening agent, and selected PPCPs in samples proximate to the leachfield at one of the sites that was also the most reducing (it was anoxic) of the two. We will go back to this site to characterize the plume in more detail.
Finally, we have established much more effective collaborations with the local Suffolk County Department of Health and the local USGS office in Coram, Long Island. Both of these groups have been generous with providing state-of-the-art groundwater sampling capabilities and have obtained permission for us to sample privately operated sites around eastern Long Island. The Silent Spring Institute has begun collaboration with us and provided the support and access to sampling at the Cape Cod septic sites. They are interested in sources and transport of estrogenic or endocrine disrupting compounds in groundwaters receiving septic tank inputs. We have initiated a collaboration with Larry Barber and James Gray at the Denver USGS to provide complementary analyses of tracers and hormones in future sampling on Cape Cod. Finally, we have collaborated with Ed Furlong (e.g., offering for his group unique supporting confirmation of carbamezapine in drinking waters using the accurate mass/elemental formula estimation provided by the HPLC-TOF-MS). Mike Thurman and Imma Ferrer from the USGS have also spent significant time in our laboratory evaluating the unique capabilities of the TOF (see manuscript below with Ph.D. student Benotti).
In addition, two presentations were made on our pharmaceutical and estrogen studies at the 2003 Long Island Groundwater Conference held at Brookhaven National Laboratory (June, 2003). Invited seminars were given by Dr. Brownawell on the results from this project at Johns Hopkins University and the University of California (UC) at Riverside. Finally, Dr. Brownawell and Dan Schlenk from UC Riverside gave an all day workshop (October, 2002) for California Cooperative Extension on Pharmaceuticals and Personal Care Products; approximately 15 regulators and drinking water professionals attended.
Future Activities:
A multi-investigator (USGS investigators Barber and Gray along with Silent Spring) project is planned to study the transport of a wide variety of PPCPs in the septic plume at the multi-family site on Cape Cod that has the anoxic conditions. Ground radar has been used to identify the plume and several wells are being placed at different depths and distances. The USGS group is adding a set of additional tracers (e.g., eicosatrienoic acid and nitrilotriacetic acid) and the ability to measure ethinyl estradiol, which we do not measure with our immuno-affinity extraction method for steroid hormone analysis. A near-term priority is to finish the validation of the steroid conjugate work and to apply it at the Cape Cod site. More work on sorption an biodegradation is planned for Benotti’s thesis research and radiolabeled caffeine and estradiol will allow for detailed assessment of transformations of those target chemicals; the results of those studies will be compared to results of batch sorption and die-away experiments with a larger set of unlabeled compounds. Of special interest is the comparison of the fate of PPCPs within oxic and anoxic regimes of acclimated plumes to unacclimated control groundwater and priority personnel. Additional new directions include work on assessing the use of water soluble polymers (polyoxyethylene derived polymers and acrylate or acrylamide polymers) as potential tracers of wastewaters; the high solubility and known resistence to microbial degradation of some of these polymers and the detection of some of them in our groundwater samples lead us to hypothesize that they are good candidates as conservative tracers.
Journal Articles on this Report : 1 Displayed | Download in RIS Format
Other project views: | All 29 publications | 7 publications in selected types | All 6 journal articles |
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Type | Citation | ||
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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.