JWARP  Vol.12 No.3 , March 2020
Detection of Human Pharmaceuticals in the Surface Water of East Fork Stones River
Abstract: Pharmaceuticals have been detected nationwide in different environmental matrices including wastewater effluents and surface water. In recent studies, pharmaceuticals have also been found in aquatic plants, fish tissues and plasma of shark bulls. 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. We conducted a monitoring study to detect the presence of pharmaceuticals in East fork of the Stones River located in Rutherford County in Middle Tennessee. East Fork Stones River is a six (6) order river that drains a large portion of Rutherford County including Murfreesboro, Tennessee. Grab water samples were collected from Stones River for three seasons: (summer and fall of 2014 and 2015 and winter of 2015 and 2016) each year. Water quality parameters were also determined in situ using Eureka Water ProbesTM multi-parameter sondes. Water samples were analyzed for the presence of pharmaceutical compounds using GC-MS. Chemical Abstract Service Registry Numbers (CASRN or CAS) for detected pharmaceuticals were identified. Pharmaceuticals detected included those used for treatment of chronic alcoholism (Disulfiram: CAS # 97-77-8), a compound (Thiazolidine: CAS # 504-78-9) in the drug Thiazolidinedione which is used for the treatment of type II diabetes, a compound associated with the prevention of anti-inflammatory conditions (Methyl palmitate: CAS # 112-39-0), and emollient in skincare (Undecane: CAS # 1120-21-4). While the quantitative concentrations of these drugs were not determined in this study, their qualitative presence in surface water is noteworthy.
Cite this paper: Kaur, R. , Akuley-Amenyenu, A. , Garner, K. and Dennis, S. (2020) Detection of Human Pharmaceuticals in the Surface Water of East Fork Stones River. Journal of Water Resource and Protection, 12, 240-259. doi: 10.4236/jwarp.2020.123015.

[1]   Ahmed, M.B., Zhou, J.L., Ngo, H.H., Guo, W., Thomaidis, N.S. and Xu. J. (2017) Progress in the Biological and Chemical Treatment Technologies for Emerging Contaminant Removal from Wastewater: A Critical Review. Journal of Hazardous Materials, 323, 274-298.

[2]   Agunbiade, F.O. and Moodley, B. (2015) Occurrence and Distribution Pattern of Acidic Pharmaceuticals in Surface Water, Wastewater, and Sediment of the Msunduzi River, Kwazulu-Natal, South Africa. Environmental Toxicology and Chemistry, 31, 36-46.

[3]   Brun, G.L., Bernier, M., Losier, R., Doe, K., Jackman, P. and Lee, H.B. (2006) Pharmaceutically Active Compounds in Atlantic Canadian Sewage Treatment Plant Effluents and Receiving Waters, and Potential for Environmental Effects as Measured by Acute and Chronic Aquatic Toxicity. Environmental Toxicology and Chemistry, 25, 2163-2176.

[4]   Carucci, A., Cappai, G. and Piredda, M. (2006) Biodegradability and Toxicity of Pharmaceuticals in Biological Wastewater Treatment Plants. Journal of Environmental Science and Health, Part A, 41, 1831-1842.

[5]   Benotti, M.J. and Brownawell, B.J. (2009) Microbial Degradation of Pharmaceuticals in Estuarine and Coastal Seawater. Environmental Pollution, 157, 994-1002.

[6]   Belhaj, D., Baccar, R., Jaabiri, I., Bouzid, J., Kallel, M., Ayadi, H. and Zhou, J.L. (2015) Fate of Selected Estrogenic Hormones in an Urban Sewage Treatment Plant in Tunisia (North Africa). Science of the Total Environment, 505, 154-160.

[7]   Ekpeghere, K.I., Lee, J.W., Kim, H.Y., Shin, S.K. and Oh, J.E. (2017) Determination and Characterization of Pharmaceuticals in Sludge from Municipal and Livestock Wastewater Treatment Plants. Chemosphere, 168, 1211-1221.

[8]   Gao, L., Shi, Y., Li, W., Niu, H., Liu, J. and Cai, Y. (2012) Occurrence of Antibiotics in Eight Sewage Treatment Plants in Beijing, China. Chemosphere, 86, 665-671.

[9]   Huang, J.J., Hu, H.Y., Tang, F., Li, Y., Lu, S.Q. and Lu, Y. (2011) Inactivation and Reactivation of Antibiotic Resistant Bacteria by Chlorination in Secondary Effluents of a Municipal Wastewater Treatment Plant. Water Research, 45, 2775-2781.

[10]   Zhu, Y.G., Johnson, T.A., Su, J.Q., Qiao, M., Guo, G.X. and Stedtfeld, R.D. (2013) Diverse and Abundant Antibiotic Resistance Genes in Chinese Swine Farms. Proceedings of the National Academy of Sciences of the United States of America, 110, 3435-3440.

[11]   Daughton, C.G. and Ternes, T.A. (1999) Pharmaceuticals and Personal Care Products in the Environment: Agents of Subtle Change? Environmental Health Perspectives, 107, 907-938.

[12]   Papageorgiou, M., Kosma, C. and Lambropoulou, D. (2016) Seasonal Occurrence, Removal, Mass Loading and Environmental Risk Assessment of 55 Pharmaceuticals and Personal Care Products in a Municipal Wastewater Treatment Plant in Central Greece. Science of the Total Environment, 543, 547-569.

[13]   Blair, B.D., Crago, J.P., Hedman, C.J. and Klaper, R.D. (2013) Pharmaceuticals and Personal Care Products Found in the Great Lakes above Concentrations of Environmental Concern. Chemosphere, 93, 2116-2123.

[14]   Rubirola, A., Llorca, M., Rodriguez-Mozaz, S., Casas, N., Rodriguez-Roda, I. and Barceló, D. (2014) Characterization of Metoprolol Biodegradation and Its Transformation Products Generated in Activated Sludge Batch Experiments and in Full Scale WWTPs. Water Research, 63, 21-32.

[15]   Richmond, E.K., Grace, M.R., Kelly, J.J., Reisinger, A.J., Rosi, E.J. and Walters, D.M. (2017) Pharmaceuticals and Personal Care Products (PPCPs) Are Ecological Disrupting Compounds (EcoDC). Elementa: Science of the Anthropocene, 5, 66.

[16]   Caldas, S.S., Rombaldi, C., De Oliveira Arias, J.L., Marube, L.C. and Primel, E.G. (2016) Multi-Residue Method for Determination of 58 Pesticides, Pharmaceuticals and Personal Care Products in Water Using Solvent Demulsification Dispersive Liquid-Liquid Microextraction Combined with Liquid Chromatography-Tandem Mass Spectrometry. Talanta, 146, 676-688.

[17]   De, V., Gaffney, J., Almeida, C.M.M., Rodrigues, A., Ferreira, E., Jo-Ao Benoliel, M., Eepal, S.A., et al. (2015) Occurrence of Pharmaceuticals in a Water Supply System and Related Human Health Risk Assessment.

[18]   Deo, R.P. (2014) Pharmaceuticals in the Surface Water of the USA: A Review. Current Environmental Health Reports, 1, 113-122.

[19]   Ebele, A.J., Abou-Elwafa Abdallah, M. and Harrad, S. (2017) Pharmaceuticals and Personal Care Products (PPCPs) in the Freshwater Aquatic Environment. Emerging Contaminants, 3, 1-16.

[20]   Madikizela, L.M., Tavengwa, N.T. and Chimuka, L. (2017) Status of Pharmaceuticals in African Water Bodies: Occurrence, Removal and Analytical Methods. Journal of Environmental Management, 193, 211-220.

[21]   Daughton, C. (2007) Green Pharmacy: Preventing Pharmaceutical Pollution. Journal of Ecology and Toxicology, 4-13.

[22]   Riemenschneider, C., Al-Raggad, M., Moeder, M., Seiwert, B., Salameh, E. and Reemtsma, T. (2016) Pharmaceuticals, Their Metabolites and Other Polar Pollutants in Field-Grown Vegetables Irrigated with Treated Municipal Wastewater. Journal of Agricultural and Food Chemistry, 64, 5784-5792.

[23]   Sui, Q., Zhao, W., Cao, X., Lu, S., Qiu, Z., Gu, X. and Yu, G. (2017) Pharmaceuticals and Personal Care Products in the Leachates from a Typical Landfill Reservoir of Municipal Solid Waste in Shanghai, China: Occurrence and Removal by a Full-Scale Membrane Bioreactor. Journal of Hazardous Materials, 323, 99-108.

[24]   Ekberg, B.M.P. and Pletsch, B.A. (2011) Pharmaceuticals and Personal Care Products (PPCPs) in the Streams and Aquifers of the Great Miami River Basin. The Miami Conservancy District.

[25]   Focazio, M.J., Kolpin, D.W., Barnes, K.K., Furlong, E.T., Meyer, M.T., Zaugg, S.D., Barber, L.B. and Thurman, M.E. (2008) A National Reconnaissance for Pharmaceuticals and Other Organic Wastewater Contaminants in the United States-II) Untreated Drinking Water Sources. Science of the Total Environment, 402, 201-216.

[26]   Kolpin, D.W., Furlong, E.T., Meyer, M.T., Thurman, E.M., Zaugg, S.D., Barber, L.B. and Buxton, H.T. (2002) Pharmaceuticals, Hormones and Other Organic Wastewater Contaminants in U.S. Streams, 1999-2000: A National Reconnaissance. Environmental Science & Technology, 36, 1202-1211.

[27]   Sgroi, M., Roccaro, P., Korshin, G.V., Greco, V., Sciuto, S., Anumol, T., Snyder, S.A. and Vagliasindi, F.G.A. (2017) Use of Fluorescence EEM to Monitor the Removal of Emerging Contaminants in Full Scale Wastewater Treatment Plants. Journal of Hazardous Materials, 323, 367-376.

[28]   de Wilt, A., van Gijn, K., Verhoek, T., Vergnes, A., Hoek, M., Rijnaarts, H. and Langenhoff, A. (2018) Enhanced Pharmaceutical Removal from Water in a Three Step Bio-Ozone-Bio Process. Water Research, 138, 97-105.

[29]   Miralles-Cuevas, S., Oller, I., Agüera, A., Llorca, M., Sánchez Pérez, J.A. and Malato, S. (2017) Combination of Nanofiltration and Ozonation for the Remediation of Real Municipal Wastewater Effluents: Acute and Chronic Toxicity Assessment. Journal of Hazardous Materials, 323, 442-451.

[30]   Troger, R., Klockner, P., Ahrens, L. and Wiberg, K. (2018) Micropollutants in Drinking Water from Source to Tap-Method Development and Application of a Multiresidue Screening Method. Science of the Total Environment, 627, 1404-1432.

[31]   Zhang, S., Gitungo, S., Axe, L., Dyksen, J.E. and Raczko, R.F. (2016) A Pilot Plant Study Using Conventional and Advanced Water Treatment Processes: Evaluating Removal Efficiency of Indicator Compounds Representative of Pharmaceuticals and Personal Care Products. Water Research, 105, 85-96.

[32]   Brooks, B.W. (2018) Urbanization, Environment and Pharmaceuticals: Advancing Comparative Physiology, Pharmacology and Toxicology. Conservation Physiology, 6, cox079.

[33]   Weber, F.A., Bergmann, A., Hickmann, S., Ebert, I., Hein, A., et al. (2015) Pharmaceuticals in the Environment-Global Occurrences and Perspectives. Environmental Toxicology and Chemistry, 35, 823-835.

[34]   Bartrons, M. and Penuelas, J. (2017) Pharmaceuticals and Personal Care Products in Plants. Trends in Plant Science, 22, 194-203.

[35]   Bhalsod, G.D., Chuang, Y.H., Jeon, S., Gui, W., Li, H., Ryser, E.T., Guber, A.K. and Zhang, W. (2018) Uptake and Accumulation of Pharmaceuticals in Overhead- and Surface-Irrigated Greenhouse Lettuce. Journal of Agricultural and Food Chemistry, 66, 822-830.

[36]   Deo, R.P. (2014) Pharmaceuticals in the Surface Water of the USA: A Review. Current Environmental Health Reports, 1, 113-122.

[37]   Foltz, J., Mottaleb, M.A., Meziani, M.J. and Islam, M.R. (2014) Simultaneous Detection and Quantification of Select Nitromusks, Antimicrobial Agent and Antihistamine in Fish of Grocery Stores by Gas Chromatography-Mass Spectrometry. Chemosphere, 107, 187-193.

[38]   Huerta, B., Jakimska, A., Gros, M., Rodríguez-Mozaz, S. and Barceló, D. (2013) Analysis of Multi-Class Pharmaceuticals in Fish Tissues by Ultra-High-Performance Liquid Chromatography Tandem Mass Spectrometry. Journal of Chromatography A, 1288, 63-72.

[39]   Puckowski, A., Mioduszewska, K., Lukaszewicz, P., Borecka, M., Caban, M., Maszkowska, J. and Stepnowski, P. (2016) Bioaccumulation and Analytics of Pharmaceutical Residues in the Environment: A Review. Journal of Pharmaceutical and Biomedical Analysis, 127, 232-255.

[40]   Ramirez, A.J., Brain, R.A., Usenko, S., Mottaleb, M.A., O’Donnell, J.G., Stahl, L.L., Wathen, J.B., Snyder, B.D., Pitt, J.L., Perez-Hurtado, P., Dobbins, L.L., Brooks, B.W. and Chambliss, C.K. (2009) Pharmaceuticals and Personal Care Products in the Environment: Occurrence of Pharmaceuticals and Personal Care Products in Fish: Results of a National Pilot Study in the United States. Environmental Toxicology and Chemistry, 28, 2587-2597.

[41]   Tanoue, R., Nomiyama, K., Nakamura, H., Hayashi, T., Kim, J.-W., Isobe, T., Shinohara, R. and Tanabe, S. (2014) Simultaneous Determination of Polar Pharmaceuticals and Personal Care Products in Biological Organs and Tissues. Journal of Chromatography A, 1355, 193-205.

[42]   Zenker, A., Cicero, M.R., Prestinaci, F., Bottoni, P. and Carere, M. (2014) Bioaccumulation and Biomagnification Potential of Pharmaceuticals with a Focus to the Aquatic Environment. Journal of Environmental Management, 133, 378-387.

[43]   Goldstein, M., Shenker, M. and Chefetz, B. (2014) Insights into the Uptake Processes of Wastewater-Borne Pharmaceuticals by Vegetables. Environmental Science & Technology, 48, 5593-5600.

[44]   Pan, M., Wong, C.K.C. and Chu, L.M. (2014) Distribution of Antibiotics in Wastewater-Irrigated Soils and Their Accumulation in Vegetable Crops in the Pearl River Delta, Southern China. Journal of Agricultural and Food Chemistry, 62, 11062-11069.

[45]   Shenker, M., Harush, D., Ben-Ari, J. and Chefetz, B. (2014) Uptake of Carbamazepine by Cucumber Plants: A Case Study Related to Irrigation with Reclaimed Wastewater. Chemosphere, 82, 905-910.

[46]   Tanoue, R., Sato, Y., Motoyama, M., Nakagawa, S., Shinohara, R. and Nomiyama, K. (2012) Plant Uptake of Pharmaceutical Chemicals Detected in Recycled Organic Manure and Reclaimed Wastewater. Journal of Agricultural and Food Chemistry, 60, 10203-10211.

[47]   Wu, X., Conkle, J.L., Ernst, F. and Gan, J. (2014) Treated Wastewater Irrigation: Uptake of Pharmaceutical and Personal Care Products by Common Vegetables Under Field Conditions. Environmental Science & Technology, 48, 11286-11293.

[48]   Herklotz, P.A., Gurung, P., Heuvel, B.V. and Kinney, C.A. (2010) Uptake of Human Pharmaceuticals by Plants Grown under Hydroponic Conditions. Chemosphere, 78, 1416-1421.

[49]   Esplugas, S., Bila, D.M., Krause, L.G.T. and Dezotti, M. (2007) Ozonation and Advanced Oxidation Technologies to Remove Endocrine Disrupting Chemicals (EDCs) and Pharmaceuticals and Personal Care Products (PPCPs) in Water Effluents. Journal of Hazardous Materials, 149, 631-642.

[50]   University Wisconsin Green Bay (2005) Dissolved Oxygen. Lower Fox River Watershed Monitoring Program, Green Bay, WI.

[51]   USEPA (2015).

[52]   USGS (2015).