Sludge Removal of Nonsteroidal Anti-Inflammatory Drugs during Wastewater Treatment Studied by Direct Hollow Fiber Liquid Phase Microextraction

Abstract

In this study, the fate of four common anti-inflammatory drugs (ketoprofen, naproxen, diclofenac and ibuprofen) within a wastewater treatment plant was investigated. A previously developed direct hollow fiber liquid phase microextraction method was applied to water as well as sludge samples collected from the primary, secondary and tertiary treatment respectively and the final analysis was performed by liquid chromatography quadropole time of flight tandem mass spectrometry. Enrichment factors ranged from 1400 to 3900 times depending on analyte and matrix. Method detection limits ranged from 0.3 to 14 ng/L for the different analytes and matrices. The overall sludge removal was 9%, 3%, 13% and 1% for ketoprofen, naproxen, diclofenac and ibuprofen respectively, thus indicating that of the studied compounds, ketoprofen and diclofenac to the largest extent partition into the sludge. For both substances, the largest fraction was found in secondary sludge (60% and 80% respectively of the total amount detected in the sludge). For naproxen and ibuprofen, the largest fraction were on the other hand detected in primary and tertiary sludge respectively, indicating that the affinity to the different sludge types might vary among the four drugs. The overall low sludge removal confirms existing theories that partitioning into sludge is only a minor removal mechanism for the investigated compounds. Nevertheless, naproxen and ibuprofen are still efficiently removed from the water during treatment (100% and 97 % total removal respectively) suggesting that these compounds are highly susceptible to biodegradation while ketoprofen and diclofenac (66% and 67% total removal respectively) appear more persistent.

Share and Cite:

E. Larsson, A. Rabayah and J. Jönsson, "Sludge Removal of Nonsteroidal Anti-Inflammatory Drugs during Wastewater Treatment Studied by Direct Hollow Fiber Liquid Phase Microextraction," Journal of Environmental Protection, Vol. 4 No. 9, 2013, pp. 946-955. doi: 10.4236/jep.2013.49109.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1] I. Maijó, F. Borrull, C. Aguilar and M. Calull, “Determination of Anti-Inflammatory Drugs in River Water by sweeping-Micellarelectrokinetic Capillary Chromatography,” Journal of Liquid Chromatography and Related Technologies, Vol. 35, No. 15, 2012, pp. 2134-2147.
[2] N. Migowska, M. Caban, P. Stepnowski and J. Kumirska, “Simultaneous Analysis of Non-Steroidal Anti-Inflammatory Drugs and Estrogenic Hormones in Water and Wastewater Samples Using Gas Chromatography-Mass Spectrometry and Gas Chromatography with Electron Capture Detection,” Science of the Total Environment, Vol. 441, 2012, pp. 77-88.
[3] M. Villar Navarro, M. Ramos Payan, R. Fernández-Torres, M. A. Bello-López, M. Callejón and M. A. Guiráum-Pérez, “Capillary Electrophoresis Determination of Nonsteroidal Anti-Inflammatory Drugs in Wastewater Using Hollow Fiber Liquid-Phase Microextraction,” Electrophoresis, Vol. 32, No. 16, 2011, pp. 2107-2113. doi:10.1002/elps.201100105
[4] Apotekens Service (Service of the Pharmacies), Sales Data for Pharmaceuticals in Sweden, 2011.
[5] B. Quinn, F. Gagné and C. Blaise, “The Effects of Pharmaceuticals on the Regeneration of the Cnidarian, Hydra attenuata,” Science of the Total Environment, Vol. 402, No. 1, 2008, pp. 62-69. doi:10.1016/j.scitotenv.2008.04.039
[6] B. Quinn, F. Gagné and C. Blaise, “Evaluation of the Acute, Chronic and Teratogenic Effects of a Mixture of Eleven Pharmaceuticals on the Cnidarian, Hydra attenuata,” Science of the Total Environment, Vol. 407, No. 3, 2009, pp. 1072-1079. doi:10.1016/j.scitotenv.2008.10.022
[7] A. C. Mehinto, E. M. Hill and C. R. Tyler, “Uptake and Biological Effects of Environmentally Relevant Concentrations of the Nonsteroidal Anti-inflammatory Pharmaceutical Diclofenac in Rainbow Trout (Oncorhynchus mykiss),” Environmental Science and Technology, Vol. 44, No. 6, 2010, pp. 2176-2182. doi:10.1021/es903702m
[8] J. Martín, D. Camacho-Munoz, J. L. Santos, E. Aparicio and E. Alonso, “Occurence of Pharmaceutical Compounds in Wastewater and Sludge from Wastewater Treatment Plants: Removal and Ecotoxicological Impact of Wastewater Discharges and Sludge Disposal,” Journal of Hazardous Materials, Vol. 239-240, 2012, pp. 40-47. doi:10.1016/j.jhazmat.2012.04.068
[9] A. Jelic, M. Gros, A. Ginebreda, R. Cespedes-Sánchez, F. Ventura, M. Petrovic and D. Barceló, “Occurence, Partition and Removal of Pharmaceuticals in Sewage Water and Sludge during Wastewater Treatment,” Water Research, Vol. 45, No. 3, 2011, pp. 1165-1176. doi:10.1016/j.watres.2010.11.010
[10] R. L. Oulton, T. Kohn and D. M. Cwiertny, “Pharmaceuticals and Personal Care Products in Effluent Matrices: A Survey of Transformation and Removal during Wastewater Treatment and Implications for wastewater management,” Journal of Environmental Monitoring, Vol. 12, No. 11, 2010, pp. 1956-1978. doi:10.1039/c0em00068j
[11] P. Gao, Y. Ding, H. Li and I. Xagoraraki, “Occurence of Pharmaceuticals in a Municipal Wastewater Treatment Plant: Mass Balance and Removal Processes,” Chemosphere, Vol. 88, No. 1, 2012, pp. 17-24. doi:10.1016/j.chemosphere.2012.02.017
[12] V. G. Samaras, A. S. Stasinakis, D. Mamais, N. S. Thomaidis and T. D. Lekkas, “Fate of Selected Pharmaceuticals and Syntehtic Endocrine Disrupting Compounds during Wastewater Treatment and Sludge Anaerobic Digestion,” Journal of Hazardous Materials, Vol. 244-245, 2013, pp. 259-267. doi:10.1016/j.jhazmat.2012.11.039
[13] P. Falas, H. R. Andersen, A. Ledin and J. La Cour Jansen, “Occurrence and Reduction of Pharmaceuticals in the Water Phase at Swedish Wastewater Treatment Plants,” Water Science and Technology, Vol. 66, No. 4, 2012, pp. 783-791. doi:10.2166/wst.2012.243
[14] Q. Huang, Y. Yu, C. Tang, K. Zhang, J. Cui and X. Peng, “Occurrence and Behavior of Non-Steroidal Anti-Inflammatory Drugs and Lipid Regulators in Wastewater and Urban River Water of the Pearl River Delta, South China,” Journal of Environmental Monitoring, Vol. 13, 2011, pp. 855-863. doi:10.1039/c1em10015g
[15] J. Radjenovic, M. Petrovic and D. Barcelo, “Fate and Distribution of Pharmaceuticals in Wastewater and Sewage Sludge of the Conventional Activated Sludge (CAS) and Advanced Membrane Bioreactor (MBR) Treatment,” Water Research, Vol. 43, No. 3, 2009, pp. 831-841. doi:10.1016/j.watres.2008.11.043
[16] D. Bendz, N. A. Paxéus, T. R. Ginn and F. J. Loge, “Occurrence and Fate of Pharmaceutically Active Compounds in the Environment, a Case Study: Hoje River in Sweden,” Journal of Hazardous Materials, Vol. 122, No. 3, 2005, pp. 195-204. doi:10.1016/j.jhazmat.2005.03.012
[17] M. Carballa, F. Omil, J. M. Lema, M. Llompart, C. García-Jares, I. Rodríguez, M. Gómez and T. Ternes, “Behavior of Pharmaceuticals, Cosmetics and Hormones in a Sewage Treatment Plant,” Water Research, Vol. 38, No. 12, 2004, pp. 2918-2926. doi:10.1016/j.watres.2004.03.029
[18] J. Martín, M. D. Camacho Munoz, J. L. Santos, I. Aparicio and E. Alonso, “Distribution and Temporal Evolution of Pharmaceutically Active Compounds Alongside Sewage Sludge Treatment. Risk Assessment of Sludge Application onto Soils,” Journal of Environmental Management, Vol. 102, 2012, pp. 18-25. doi:10.1016/j.jenvman.2012.02.020
[19] A. Jelic, M. Petrovic and D. Barceló, “Multi-Residue Method for Trace Level Determination of Pharmaceuticals in Solid Samples Using Pressurized Liquid Extraction Followed by Liquid Chromatography/Quadropole-Linear Ion Trap,” Talanta, Vol. 80, No. 1, 2009, pp. 363-371. doi:10.1016/j.talanta.2009.06.077
[20] T. A. Ternes, N. Herrmann, M. Bonerz, T. Knacker, H. Siegrist and A. Joss, “A Rapid Method to Measure the Solid-Water Distribution Coefficient (Kd) for Pharmaceuticals and Musk Fragrances in Sewage Sludge,” Water Research, Vol. 38, No. 19, 2004, pp. 4075-4084. doi:10.1016/j.watres.2004.07.015
[21] E. Sagristà, E. Larsson, M. Ezoddin, M. Hidalgo, V. Salvadó and J. A. Jonsson, “Determination of Non-Steroidal Anti-Inflammatory Drugs in Sewage Sludge by Direct Hollow Fiber Supported Liquid Membrane Extraction and Liquid Chromatography-Mass Spectrometry,” Journal of Chromatography A, Vol. 1217, No. 40, 2010, pp. 6153-6158. doi:10.1016/j.chroma.2010.08.005
[22] T. Okuda, N. Yamashita, H. Tanaka, H. Matsukawa and K Tanabe, “Development of Extraction Method of Pharmaceuticals and Their Occurrences Found in Japanese Wastewater Treatment Plants,” Environment International, Vol. 35, No. 20, 2009, pp. 815-820. doi:10.1016/j.envint.2009.01.006
[23] H. Jiang, B. Hu, B. Chen and W. Zu, “Hollow Fiber Liquid Phase Microextraction Combined with Graphite Furnace Atomic Absorbtion Spectrometry for the Determination of Methylmercury in Human Hair and Sludge Samples,” Spectrochimca Acta, Part B, Vol. 63, No. 7, 2008, pp. 770-776. doi:10.1016/j.sab.2008.04.011
[24] T. Vasskog, O. Bergersen, T. Anderssen, E. Jenssen and T. Eggen, “Depletion of Selective Serotonine Reuptake Inhibitors during Sewage Sludge Composting,” Waste Management, Vol. 29, No. 11, 2009, pp. 2808-2815.
[25] C. Basheer and H. K. Lee, “Hollow Fiber Membrane-Protected Solid-Phase Microextraction of Triazine Herbicides in Bovine Milk and Sewage Sludge Samples,” Journal of Chromatography A, Vol. 1047, No. 2, 2004, pp. 189-194.
[26] V. A. Syd, “Environmental Report,” 2011. http://www.vasyd.se/SiteCollectionDocuments/Vatten%20och%20avlopp/Avloppsvatten/Miljorapporter/Miljorapport_2010_Kallby.pdf
[27] K. F. Bardstu, T. S. Ho, K. E. Rasmussen, S. Pedersen-Bjergaard and J. A. Jonsson, “Supported Liquid Membranes in Hollow Fiber Liquid Phase Microextraction (LPME). Practical Considerations in the Three-Phase Mode,” Journal of Separation Science, Vol. 30, No. 9, 2007, pp. 1364-1370. doi:10.1002/jssc.200600486
[28] H. K. Lee, K. E. Rasmussen and S. Pedersen-Bjergaard, “Environmental and Bioanalytical Applications of Hollow Fiber Membrane Liquid-Phase Microextraction: A Review,” Analytica Chimica Acta, Vol. 624, No. 2, 2008, pp. 253-268. doi:10.1016/j.aca.2008.06.050
[29] J. A. Jonsson, “Membrane Extraction: General Overview and Basic Techniques,” In: J. Pawliszyn and H. Lord, Eds., Comprehensive Sampling and Sample Preparation, Academic Press, Oxford, 2012, pp. 461-474. doi:10.1016/B978-0-12-381373-2.00049-1
[30] A. Saleh, E. Larsson, Y. Yamini and J. A. Jonsson, “Hollow Fiber Liquid Phase Microextraction as a Preconcentration and Clean-Up Step after Pressurized Hot Water Extraction for the Determination of Non-Steroidal Anti-Inflammatory Drugs in Sewge Sludge,” Journal of Chromatography A, Vol. 1218, No. 10, 2011, pp. 1331-1339. doi:10.1016/j.chroma.2011.01.011
[31] E. Sagristà, J. M. Cortés, E. Larsson, V. Salvadó, M. Hidalgo and J. A. Jonsson, “Comparison of Two Extraction Methods for the Determination of Selective Serotonine Reuptake Inhibitors in Sewage Sludge by Hollow Fiber Liquid Phase Microextraction,” Journal of Separation Science, Vol. 35, 2012, pp. 2460-2468. doi:10.1002/jssc.201200257
[32] R. Seth, E. Webster and D. Mackay, “Continued Development of a Mass Balance Model of Chemical Fate in a Sewage Treatment Plant,” Water Research, Vol. 42, No. 3, 2008, pp. 595-604. doi:10.1016/j.watres.2007.08.004
[33] I. S. Turovskiy and P. K. Mathai, “Wastewater Sludge Processing,” John Wiley and Sons, Inc., Hoboken, 2006. doi:10.1002/047179161X
[34] M. Horsing, A. Ledin, R. Grabic, J. Fick, M. Tysklind, J. la Cour Jansen and H. R. Andersen, “Determination of Sorption of Seventy-Five Pharmaceuticals in Sewage Sludge,” Water Research, Vol. 45, No. 15, 2011, pp. 4470-4482. doi:10.1016/j.watres.2011.05.033
[35] H. Sun, D. Zhu and J. Mao “Sorption of Polar and Non-Polar Aromatic Compounds to Two Humic Acids with Varied Structural Heterogeniety,” Environmental Toxicology and Chemistry, Vol. 27, 2008, pp. 2449-2456. doi:10.1897/08-124.1
[36] J. M. Cortés, E. Larsson and J. A. Jonsson, “Study of the Uptake of Non-Steroid Anti-Inflammatory Drugs in Wheat and Soybean after the Application of Sewage Sludge as a Fertilizer,” Science of the Total Environment, Vol. 449, 2013, pp. 385-389. doi:10.1016/j.scitotenv.2013.01.061
[37] K. M. Onesios, J. T. Yu and E. J. Bouwer, “Biodegradation and Removal of Pharmaceuticals and Personal Care Products in Treatment Systems: A Review,” Biodegradation, Vol. 20, No. 4, 2009, pp. 441-466. doi:10.1007/s10532-008-9237-8
[38] J. B. Quintana, S. Weiss and T. Reemtsma, “Pathways and Metabolites of Microbial Degradation of Selected Acidic Pharmaceuticals and Their Occurrence in Municipal Wastewater Treated by a Membrane Bioreactor,” Water Research, Vol. 39, No. 12, 2005, pp. 2654-2664. doi:10.1016/j.watres.2005.04.068
[39] M. Lahti and A. Oikari, “Microbial Transformation of Pharmaceuticals Naproxen, Bisoprolol and Diclofenac in Aerobic and Anaerobic Environments,” Archives of Environmental Contamination and Toxicology, Vol. 61, No. 2, 2011, pp. 202-210. doi:10.1007/s00244-010-9622-2
[40] J. Leinert, K. Güdel and B. I. Escher, “Screening Method for Ecotoxicological Hazard Assessment of 42 Pharmaceuticals Considering Human Metabolism and Excretory Routes,” Environmental Science and Technology, Vol. 41, No. 12, 2007, pp. 4471-4478. doi:10.1021/es0627693
[41] M. Schmitt-Jansen, P. Bartels, N. Adler and R. Altenburger, “Phytotoxicity Assessment of Diclofenac and Its Phototransformation Products,” Analytical and Bioanalytical Chemistry, Vol. 387, No. 4, 2007, pp. 1389-1396. doi:10.1007/s00216-006-0825-3
[42] M. Isidori, M. Lavorgna, A. Nardelli, A. Parrella, L. Previtera and M. Rubino, “Ecotoxicity of Naproxen and Its Phototransformation Products,” Science of The Total Environment, Vol. 348, No. 1-3, 2005, pp. 93-101. doi:10.1016/j.scitotenv.2004.12.068
[43] S. Peréz and D. Barceló, “First Evidence for Occurrence of Hydroxylated Human Metabolites of Diclofenac and Aceclofenac in Wastewater Using QqLIT-MS and QqTOFMS,” Analytical Chemistry, Vol. 80, No. 21, 2008, pp. 8135-8145. doi:10.1021/ac801167w

Copyright © 2024 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.