Grantee Research Project Results
2002 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, 2001 through September 20, 2002
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 this research project are to: (1) develop new high performance liquid 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) 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.
Progress Summary:
A primary accomplishment of Year 1 of the project was to finish the construction of a new environmental mass spectrometry facility with the Marine Sciences Research Center under the direction of project director Dr. Brownawell. During the fall of 2001 , we conducted experiments that provided the basis for selecting and purchasing a Micromass LC-T HPLC-time-of-flight (TOF)-MS system as the primary analytical tool to be used for the research project. In collaboration with Ed Furlong at the U.S. Geological Survey (USGS) and Curt Heine at Micromass (a division of Waters, Inc.) , we were able to 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 allow 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 6,000-7,000) is sufficient to greatly reduce nominal same mass interferences for many analytes using only minimal sample clean-up.
After the instrument arrived and electronic problems finally were corrected (5 months after the promised installation date), we were able to finish a useful comparison between the TOF and single quadrupole and magnetic resonance microscopy analysis with a triple quadrupole instrument that provided the basis for the manuscript by Benotti, et al. While waiting for the instrument, we developed sensitive HPLC-MS-MS methods for PPCP analysis on our VG Quattro system. Low instrument detection levels could not be matched, however, with even groundwater matrices because of the susceptibility of the older electrospray source to matrix-affected suppression of ionization. One useful feature of the TOF analysis that we discovered is that it is not uncommon for there to be false detections and interferences in many LC/MS analyses in which only a parent ion is scanned in selected ion monitoring mode. For example, many samples of wastewater and surface water that were analyzed this year had apparent caffeine and caffeine metabolite paraxanthine detections that turned out to be C-13 isotope mass spectral peaks of much larger co-eluting analytes, which had base peaks one mass unit lower than the targeted analytes. HPLC-TOF-MS was able to elucidate this problem because of the inherent full spectral sensitivity and because of accurate mass measurement discrepancies of the putative caffeine/paraxanthine peaks.
We also developed a method to reproduce the high volume PPCP method of Ed Furlong at USGS. In addition, we performed first screening level analyses in treated and untreated municipal wastewaters, highly sewage-impacted Jamaica Bay, and local groundwaters from a selection of monitoring wells within 100-200 feet of treated wastewater discharges to leachfields or pits from Seldon Sanitary District and local nursing and retirement homes. While clear detections of several PPCPs (most abundant being caffeine, paraxanthine, carbamezapine, and sulfamethoxazole) were detectable readily in the 2-200 ng/L range, more work is required on method recoveries.
A highly qualified group of personnel have been recruited to support this project. Mass spectrometry operator and facility manager Joe Ruggieri was hired with extensive experience in GC/MS and environmental QA/QC. He now supervises and is responsible primarily for maintenance of the HPLC-TOF-MS system. After a long search for a highly qualified post doc, we have hired biochemist Sharanya Reddy who brings great biochemical and pharmacological expertise to the group as well as three years of HPLC-MS analysis with her. She recently successfully reproduced the synthesis of the immuno-affinity columns that former Ph.D. student Lee Ferguson developed for selective isolation of steroid estrogens. Reddy is starting to modify our aqueous method to sediments and soils so that we can better understand whether the fate of estrogens in groundwater is controlled more by sorption or by microbial transformation. Over the next year, she will work on developing a method for analyzing intact sulfate and glucuronide conjugates of estrogens in wastewaters and groundwaters that receive wastewater loads. Finally Ph.D. student Mark Benotti has been working hard on extraction and analysis of PPCPs; he is collaborating with Ed Furlong and hopes to do a dissertation that contrasts the distributions and fate of representative PPCPs in groundwater and estuarine surface waters. It is our plan to leverage this study with additional funding to involve additional graduate students and collaborators to work on a broader range of pharmaceutically active and wastewater contaminants at some of our better groundwater sites.
Among the practical applications of our study are: identification of pharmaceutically active contaminants or classes of structures that are most likely to migrate into aquifers; assessment of the distributions of PPCPs in an aquifer system highly stressed with treated wastewaters and a high density of cesspools; new method development for difficult to analyze contaminants (e.g., soluble steroid conjugates) and detailed assessment of the advantages and disadvantages of LC-TOF as a tool for trace level environmental applications.
Future Activities:
We will work closely with Ed Furlong at the USGS in Denver to identify discrepancies in recoveries of selected PPCPs; survey for occurrence and levels of PPCPs at in-place monitoring wells at a variety of locations on Long Island that are proximate to on-site treatment discharges to ground from municipal treatment plants, hospitals, nursing and retirement homes; to develop methods to determine sulfate and glucuronide conjugates of estrone and beta-estradiol in wastewater and groundwater; and to begin laboratory and field based studies to access processes that limit transport of PPCPs in upper glacial aquifer deposits.
Journal Articles:
No journal articles submitted with this report: View all 29 publications for this projectSupplemental 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.