Source: TENNESSEE STATE UNIVERSITY submitted to NRP
ASSESSMENT OF EMERGING CONTAMINANTS IN SURFACE WATER OF RURAL AND URBANIZING WATERSHEDS.
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
Reporting Frequency
Annual
Accession No.
1025265
Grant No.
(N/A)
Cumulative Award Amt.
(N/A)
Proposal No.
(N/A)
Multistate No.
(N/A)
Project Start Date
Dec 1, 2020
Project End Date
Sep 30, 2023
Grant Year
(N/A)
Program Code
[(N/A)]- (N/A)
Recipient Organization
TENNESSEE STATE UNIVERSITY
3500 JOHN A. MERRITT BLVD
NASHVILLE,TN 37209
Performing Department
Agricultural and Environmental Sciences
Non Technical Summary
Emerging contaminants such as human pharmaceuticals, are becoming pollutants of concern in freshwater systems. The potential pathways include, but not limited to their consumption, low human metabolic capability and improper disposal of unused products. With rural community development and potential urban sprawl, high consumption of pharmaceutical products in Middle Tennessee abounds. Pharmaceuticals have been detected nationwide in different environmental matrices including wastewater effluents and surface water. Moreover, in recent studies pharmaceuticals have also been detected in rivers draining rural and urbanizing watersheds in Middle Tennessee. On a national scale, pharmaceuticals that were detected as indicated in published literature, included steroids, prescription drugs such as antibiotics, anti-depressants, anti-inflammatory drugs, hormones and over the counter (OTC) drugs. Their concentration ranges from parts per trillion to parts per billion in sewage treatment plants effluent and surface water environment especially around outfall discharges. It is noteworthy that many of these chemicals are suspected or are potential endocrine-disrupting chemicals, as well as having the potential for adverse environmental effects in freshwater systems. The central hypothesis of this study is that the incidence of Pharmaceuticals in surface water in urbanizing and rural watersheds exist, partly due to catchment land uses and outfall discharges. Therefore, the overarching goal of the study is to provide a comprehensive assessment of two broad classes of pharmaceuticals based on their end-use for heart treatment ailments and as anti-inflammatory drugs. These class of pharmaceuticals were selected based on their production volumes, availability based on over-the-counter sales, the number of prescriptions being filled, and their extended uses.
Animal Health Component
0%
Research Effort Categories
Basic
90%
Applied
0%
Developmental
10%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
11202102050100%
Knowledge Area
112 - Watershed Protection and Management;

Subject Of Investigation
0210 - Water resources;

Field Of Science
2050 - Hydrology;
Goals / Objectives
The overarching goal of the study is to provide a comprehensive assessment of two broad classes of pharmaceuticals based on their end-use for heart treatment ailments and as anti-inflammatory drugs. These class of pharmaceuticals were selected based on their production volumes, availability based on over-the-counter sales, the number of prescriptions being filled, and their extended uses.Therefore, the objectives of the study are:1. To quantitatively determine anti-inflammatory drugs such as Ibuprofen, Naproxen, and Diclofenac in surface water using chromatographic methods.2. To quantitatively determine cardiovascular drugs such as Clofibric acid, Metoprolol, Atenolol, and Propranolol in surface water using chromatographic methods.3. To quantify temporal variation of the pharmaceuticals of interest in surface water in Middle Tennessee.4. To determine water quality parameters that could affect the concentration or fate of the pharmaceuticals of interest detected in the surface water.
Project Methods
Two counties from Middle Tennessee namely, Rutherford and Warren counties, will be chosen for the study. These counties are chosen because: 1) the rivers to be monitored, drain urbanizing and rural watersheds respectively in Middle Tennessee; 2) because of the watersheds proximity to the University (TSU) main campus. The watershed and the associated rivers are Stones River and Collins River sub-watersheds.Sampling of rivers in the watersheds for the emerging contaminants and physico-chemical water quality parameters will be conducted in three seasons per year throughout the study period. Specifically, the river sampling will take place in the Summer, Fall and Spring; with the initial sampling beginning during the Spring of 2021 and while mindful of the COVID-19 guidelines or restrictions. In each season, water samples will be collected for six consecutive weeks. Grab samples will be collected during base flow (normal flow conditions) and after rainstorm events for each sampling site, using Teflon bailers.The bailers are used as a form of protection from venomous snakes that may be found in the area. The bailers will be casted into the river at the sampling site and dragged to shore when full. The water in the bailer will then be emptied into a three-liter LDPE (low density polyethylene) sample containers. This amount of water is needed in order to quantitatively get a good concentration of the pharmaceuticals of interest. The containers will be kept on ice and transported to the lab, where they will be kept in a freezer at -20 degrees centigrade before analysis within 14 days. Duplicate samples will be collected for the pharmaceutical analysis, and at the same time in-situ monitoring of water quality parameters of interest will be conducted in the river. The water quality parameters of interest are pH, turbidity, specific conductance, total dissolved solids, dissolved oxygen, and temperature.An Eureka (Eureka Water Probes, Austin TX) multi-parameter data logger or sonde will be used. The data logger is interfaced with the applicable sensors and will be deployed in the streams to at least a 45 cm depth. The data loggers will be calibrated according to instrument specifications. A minimum of two readings will be taken in situ, and then the average will be obtained and used for further analysis. During sampling, visual observation of aquatic habitats and wildlife present in the rivers will also be noted. During sampling, gloves will be used in order to prevent cross contamination. The samples that will be kept in the freezer will be analyzed for pharmaceuticals of interest using LC/MS/MS or GC/MS/MS. HPLC grade organic solvents will be used, as well as analytical standards of the pharmaceutical of interest..Sample preparation prior to chromatographic analysis is a critical step in the analysis of these pharmaceuticals of interest. Sample preparation can significantly improve the accuracy, selectivity, and precision of the analysis.Therefore, solid phase extraction (SPE) will be used to extract the emerging contaminants of interest from the river water samples. Solid phase extraction is a widely used technique used during sample preparation. The amount of co-extracted natural organic matter needs to be extremely minimized to achieve a successful analysis. Consequently, SPE protocol will be used to separate compounds in the water samples based on their polarities and solubility in specific solvents.

Progress 12/01/20 to 09/30/21

Outputs
Target Audience:Watershed association's members/stakeholders; The State regulatory agency (Tennessee Department of environment and conservation); Local water services; Water quality researchers, Conference attendees and Students Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest?Too soon to report results. What do you plan to do during the next reporting period to accomplish the goals?Analyze the water samples collected in the summer of 2021 with GC/MS/MS. Monitor the two rivers for the pharmaceuticals of interest in spring of 2022. Develop one manuscript for publication. Be active in the local drug take back campaign. Make presentation of our findings at a conference or symposium yet to be determined.

Impacts
What was accomplished under these goals? While the research is ongoing, two rivers weresampled for six weeks during the summer of 2021 for pharmaceuticals of interest. Theintent is toshow the incidenceof pharmaceuticals in surface water in rural and urbanizing watersheds. The targeted pharmaceuticalsare Ibuprofen, Naproxen,Diclofenac,Clofibric acid, Metoprolol, Atenolol, and Propranolol.The rivers include Collins River in Warren County and Stones River in Rutherford County. These rivers drained rural and urbanizing watersheds respectively in Middle Tennessee. The pharmaceuticals were extracted from the water samples using the solid phase extraction protocol.

Publications