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Occurrence of naproxen, ibuprofen, and diclofenac residues in wastewater and river water of KwaZulu-Natal Province in South Africa

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Abstract

The present paper reports a detailed study that is based on the monitoring of naproxen, ibuprofen, and diclofenac in Mbokodweni River and wastewater treatment plants (WWTPs) located around the city of Durban in KwaZulu-Natal Province of South Africa. Target compounds were extracted from water samples using a multi-template molecularly imprinted solid-phase extraction prior to separation and quantification on a high-performance liquid chromatography equipped with photo diode array detector. The analytical method yielded the detection limits of 0.15, 1.00, and 0.63 μg/L for naproxen, ibuprofen, and diclofenac, respectively. Solid-phase extraction method was evaluated for its performance using deionized water samples that were spiked with 5 and 50 μg/L of target compounds. Recoveries were greater than 80% for all target compounds with RSD values in the range of 4.1 to 10%. Target compounds were detected in most wastewater and river water samples with ibuprofen being the most frequently detected pharmaceutical. Maximum concentrations detected in river water for naproxen, ibuprofen, and diclofenac were 6.84, 19.2, and 9.69 μg/L, respectively. The concentrations of target compounds found in effluent and river water samples compared well with some studies. The analytical method employed in this work is fast, selective, sensitive, and affordable; therefore, it can be used routinely to evaluate the occurrence of acidic pharmaceuticals in South African water resources.

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References

  • Agunbiade, F. O., & Moodley, B. (2014). Pharmaceuticals as emerging organic contaminants in Umgeni River water system, KwaZulu-Natal, South Africa. Environmental Monitoring and Assessment, 186, 7273–7291.

    Article  CAS  Google Scholar 

  • Agunbiade, F. O., & Moodley, B. (2016). 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, 35(1), 36–46.

    Article  CAS  Google Scholar 

  • Amdany, R., Chimuka, L., & Cukrowska, E. (2014). Determination of naproxen, ibuprofen and triclosan in wastewater using the polar organic chemical integrative sampler (POCIS): a laboratory calibration and field application. Water South Africa, 40(3), 407–414.

    CAS  Google Scholar 

  • Amdany, R., Moya, A., Chimuka, L., & Cukrowska, E. (2015). Optimization of the temperature for the extraction of pharmaceuticals from wastewater by a hollow fiber silicone membrane. Analytical Letters, 48, 2343–2356.

    Article  CAS  Google Scholar 

  • Anderson, J. C., Joudan, S., Shoichet, E., Cuscito, L. D., Alipio, A. E. C., Donaldson, C. S., Khan, S., Goltz, D. M., Rudy, M. D., Frank, R. A., Knapp, C. W., Hanson, M. L., & Wong, C. S. (2015). Reducing nutrients, organic micropollutants, antibiotic resistance, and toxicity in rural wastewater effluent with subsurface filtration treatment technology. Ecological Engineering, 84, 375–385.

    Article  Google Scholar 

  • Bayen, S., Zhang, H., Desai, M. M., Ooi, S. K., & Kelly, B. C. (2013). Occurrence and distribution of pharmaceutically active and endocrine disrupting compounds in Singapore’s marine environment: influence of hydrodynamics and physical-chemical properties. Environmental Pollution, 182, 1–8.

    Article  CAS  Google Scholar 

  • Bux, F., & Kasan, H. C. (1994). A microbiological survey of ten activated sludge plants. Water South Africa, 20, 61–72.

    Google Scholar 

  • Carmona, E., Andreu, V., & Pico, Y. (2014). Occurrence of acidic pharmaceuticals and personal care products in Turia River Basin: from waste to drinking water. Science of the Total Environment, 484, 53–63.

    Article  CAS  Google Scholar 

  • Caro, E., Marce, R. M., Cormack, P. A. G., Sherrington, D. C., & Borrull, F. (2005). Selective enrichment of anti-inflammatory drugs from river water samples by solid-phase extraction with a molecularly imprinted polymer. Journal of Separation Science, 28, 2080–2085.

    Article  CAS  Google Scholar 

  • Dahane, S., Gil Garcia, M. D., Martinez Bueno, M. J., Ucles Moreno, A., Martinez Galera, M., & Derdour, A. (2013). Determination of drugs in river and wastewaters using solid-phase extraction by packed multi-walled carbon nanotubes and liquid chromatography-quadrupole-linear ion trap-mass spectrometry. Journal of Chromatography A, 1297, 17–28.

    Article  CAS  Google Scholar 

  • Dai, C., Zhang, J., Zhang, Y., Zhou, X., Duan, Y., & Liu, S. (2012). Selective removal of acidic pharmaceuticals from contaminated lake water using multi-templates molecularly imprinted polymer. Chemical Engineering Journal, 211-212, 302–309.

    Article  CAS  Google Scholar 

  • Duan, Y., Dai, C., Zhang, Y., & Ling-Chen. (2013). Selective trace enrichment of acidic pharmaceuticals in real water and sediment samples based on solid-phase extraction using multi-templates molecularly imprinted polymers. Analytica Chimica Acta, 758, 93–100.

    Article  CAS  Google Scholar 

  • Farre, M., Ferrer, I., Ginebreda, A., Figueras, M., Olivella, L., Tirapu, L., Vilanova, M., & Barcelo, D. (2001). Determination of drugs in surface water and wastewater samples by liquid chromatography-mass spectrometry: methods and preliminary results including toxicity studies with Vibrio fischeri. Journal of Chromatography A, 938, 187–197.

    Article  CAS  Google Scholar 

  • Farrington, K., & Regan, F. (2007). Investigation of the nature of MIP recognition: the development and characterisation of a MIP for ibuprofen. Biosensors and Bioelectronics, 22(6), 1138–1146.

    Article  CAS  Google Scholar 

  • Gilart, N., Marce, R. M., Fontanals, N., & Borrull, F. (2013). A rapid determination of acidic pharmaceuticals in environmental waters by molecularly imprinted solid-phase extraction coupled to tandem mass spectrometry without chromatography. Talanta, 110, 196–201.

    Article  CAS  Google Scholar 

  • Gracia-Lor, E., Sancho, J. V., Serrano, R., & Hernandez, F. (2012). Occurrence and removal of pharmaceuticals in wastewater treatment plants at the Spanish Mediterranean area of Valencia. Chemosphere, 87, 453–462.

    Article  CAS  Google Scholar 

  • Gros, M., Petrovic, M., Ginebreda, A., & Barcelo, D. (2010). Removal of pharmaceuticals during wastewater treatment and environmental risk assessment using hazard indexes. Environment International, 36, 15–26.

    Article  CAS  Google Scholar 

  • K’oreje, K. O., Vergeynst, L., Ombaka, D., De Wispelaere, P., Okoth, M., Van Langenhove, H., & Demeestere, K. (2016). Occurrence patterns of pharmaceutical residues in wastewater, surface water and groundwater of Nairobi and Kisumu city, Kenya. Chemosphere, 149, 238–244.

    Article  Google Scholar 

  • Kermia, A. E. B., Fouial-Djebbar, D., & Trari, M. (2016). Occurrence, fate and removal efficiencies of pharmaceuticals in wastewater treatment plants (WWTPs) discharging in the coastal environment of Algiers. Comptes Rendus Chimie, 19(8), 963–970.

    Article  CAS  Google Scholar 

  • Kosma, C. I., Lambropoulou, D. A., & Albanis, T. A. (2014). Investigation of PPCPs in wastewater treatment plants in Greece: occurrence, removal and environmental risk assessment. Science of the Total Environment, 466-467, 421–438.

    Article  CAS  Google Scholar 

  • Koutsouba, V., Heberer, T., Fuhrmann, B., Schmidt-Baumler, K., Tsipi, D., & Hiskia, A. (2003). Determination of polar pharmaceuticals in sewage water of Greece by gas chromatography-mass spectrometry. Chemosphere, 51, 69–75.

    Article  CAS  Google Scholar 

  • Larsson, E., al-Hamimi, S., & Jonsson, J. A. (2014). Behaviour of nonsteroidal anti-inflammatory drugs and eight of their metabolites during wastewater treatment studied by hollow fibre liquid phase microextraction and liquid chromatography mass spectrometry. Science of the Total Environment, 485-486, 300–308.

    Article  CAS  Google Scholar 

  • Lindqvist, N., Tuhkanen, T., & Kronberg, L. (2005). Occurrence of acidic pharmaceuticals in raw and treated sewages and in receiving waters. Water Research, 39, 2219–2228.

    Article  CAS  Google Scholar 

  • Madikizela, L. M., & Chimuka, L. (2016). Determination of ibuprofen, naproxen and diclofenac in aqueous samples using a multi-template molecularly imprinted polymer as selective adsorbent for solid-phase extraction. Journal of Pharmaceutical and Biomedical Analysis, 128, 210–215.

    Article  CAS  Google Scholar 

  • Madikizela, L. M., Muthwa, S. F., & Chimuka, L. (2014). Determination of triclosan and ketoprofen in river water and wastewater by solid-phase extraction and high performance liquid chromatography. South African Journal of Chemistry, 67, 143–150.

    Google Scholar 

  • Madikizela, L. M., Mdluli, P. S., & Chimuka, L. (2016). Experimental and theoretical study of molecular interactions between 2-vinyl pyridine and acidic pharmaceuticals used as multi-template molecules in molecularly imprinted polymer. Reactive and Functional Polymers, 103, 33–43.

    Article  CAS  Google Scholar 

  • Mahkam, M., & Poorgholy, N. (2011). Imprinted polymers as drug delivery vehicles for anti-inflammatory drugs. Nature and Science, 9(5), 163–168.

    Google Scholar 

  • Martin, J., Camacho-Munoz, D., Santos, J. L., Aparicio, I., & Alonso, E. (2012). Occurrence 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, 239-240, 40–47.

    Article  CAS  Google Scholar 

  • Matongo, S., Birungi, G., Moodley, B., & Ndungu, P. (2015a). Pharmaceutical residues in water and sediment of Msunduzi River, KwaZulu-Natal, South Africa. Chemosphere, 134, 133–140.

    Article  CAS  Google Scholar 

  • Matongo, S., Birungi, G., Moodley, B., & Ndungu, P. (2015b). Occurrence of selected pharmaceuticals in water and sediment of Umgeni River, KwaZulu-Natal, South Africa. Environmental Science and Pollution Research, 22, 10298–10308.

    Article  CAS  Google Scholar 

  • Mhlanga, F. T., Brouckaert, C. J., Foxon, K. M., Fennemore, C., Mzulwini, D., & Buckley, C. A. (2009). Simulation of a wastewater treatment plant receiving industrial effluents. Water South Africa, 35, 447–454.

    CAS  Google Scholar 

  • Nzimande, S. B. T. (2014). Treated wastewater effluent as potential source of emerging bacterial pathogens in surface water, MSc thesis, University of KwaZulu-Natal, Durban.

  • Ort, C., Lawrence, M. G., Reungoat, J., & Mueller, J. F. (2010). Sampling for PPCPs in wastewater systems: comparison of different sampling modes and optimization strategies. Environmental Science and Technology, 44, 6289–6296.

    Article  CAS  Google Scholar 

  • Payan, M. R., Lopez, M. A. B., Torres, R. F., Navarro, M. V., & Mochon, M. C. (2011). Electromembrane extraction (EME) and HPLC determination of non-steroidal anti-inflammatory drugs (NSAIDs) in wastewater samples. Talanta, 85, 394–399.

    Article  CAS  Google Scholar 

  • Prasad, B. B., & Rai, G. (2013). Molecular structure, vibrational spectra and quantum chemical MP2/DFT studies toward the rational design of hydroxyurea imprinted polymer. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 105, 400–411.

    Article  CAS  Google Scholar 

  • Rigobello, E. S., Dantas, A. D. B., Bernardo, L. D., & Vieira, E. M. (2013). Removal of diclofenac by conventional drinking water treatment processes and granular activated carbon filtration. Chemosphere, 92(2), 184–191.

    Article  CAS  Google Scholar 

  • Rosal, R., Rodriguez, A., Perdigon-Melon, J. A., Petre, A., Garcia-Calvo, E., Gomez, M. J., Aguera, A., & Fernandez-Alba, A. R. (2010). Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonation. Water Research, 44, 578–588.

    Article  CAS  Google Scholar 

  • Santos, J. L., Aparicio, I., Alonso, E., & Callejon, M. (2005). Simultaneous determination of pharmaceutically active compounds in wastewater samples by solid-phase extraction and high-performance liquid chromatography with diode array and fluorescence detectors. Analytica Chimica Acta, 550, 116–122.

    Article  CAS  Google Scholar 

  • Santos, J. L., Aparicio, I., Callejon, M., & Alonso, E. (2009). Occurrence of pharmaceutically active compounds during 1-year period in wastewaters from four wastewater treatment plants in Seville (Spain). Journal of Hazardous Materials, 164, 1509–1516.

    Article  CAS  Google Scholar 

  • Sebok, A., Vasanits-Zsigrai, A., Palko, G., Zaray, G., & Molnar-Perl, I. (2008). Identification and quantification of ibuprofen, naproxen, ketoprofen and diclofenac present in waste-waters, as their trimethylsilyl derivatives, by gas chromatography mass spectrometry. Talanta, 76, 642–650.

    Article  CAS  Google Scholar 

  • Sun, Q., Li, M., Ma, C., Chen, X., Xie, X., & Yu, C. (2016). Seasonal and spatial variations of PPCP occurrence, removal and mass loading in three wastewater treatment plants located in different urbanization areas in Xiamen, China. Environmental Pollution, 208, 371–381.

    Article  CAS  Google Scholar 

  • Wanda, E. M. M., Mamba, B. B., & Msagati, T. A. M. (2016). Determination of the water quality index ratings of water in the Mpumalanga and North West provinces, South Africa. Physics and Chemistry of the Earth, 92, 70–78.

    Article  Google Scholar 

  • Yu, J. T., Bouwer, E. J., & Coelhan, M. (2006). Occurrence and biodegradability studies of selected pharmaceuticals and personal care products in sewage effluent. Agricultural Water Management, 86, 72–80.

    Article  Google Scholar 

  • Yu, Y., Wu, L., & Chang, A. C. (2013). Seasonal variation of endocrine disrupting compounds, pharmaceuticals and personal care products in wastewater treatment plants. Science of the Total Environment, 442, 310–316.

    Article  CAS  Google Scholar 

  • Zhang, J., Zhang, Y., & Quan, X. (2012). Electricity assisted anaerobic treatment of salinity wastewater and its effects on microbial communities. Water Research, 46, 3535–3543.

    Article  CAS  Google Scholar 

  • Zhao, J., Ying, G., Wang, L., Yang, J., Yang, X., Yang, L., & Li, X. (2009). Determination of phenolic endocrine disrupting chemicals and acidic pharmaceuticals in surface water of the Pearl Rivers in South China by gas chromatography-negative chemical ionization-mass spectrometry. Science of the Total Environment, 407, 962–974.

    Article  CAS  Google Scholar 

  • Zorita, S., Boyd, B., Jonsson, S., Yilmaz, E., Svensson, C., Mathiasson, L., & Bergstrom, S. (2008). Selective determination of acidic pharmaceuticals in wastewater using molecularly imprinted solid-phase extraction. Analytica Chimica Acta, 626, 147–154.

    Article  CAS  Google Scholar 

  • Zorita, S., Martensson, L., & Mathiasson, L. (2009). Occurrence and removal of pharmaceuticals in a municipal sewage treatment system in the south of Sweden. Science of the Total Environment, 407, 2760–2770.

    Article  CAS  Google Scholar 

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Acknowledgements

This work is based on the research supported in part by the National Research Foundation (NRF) of South Africa for the Thuthuka grant, Unique Grant No. 93986. NRF is also thanked for funds allocated for lecturer replacement of Lawrence Mzukisi Madikizela. Our sampling team that consisted of Ms. SS Zunngu and Ms. NY Mlunguza is acknowledged. EThekwini Municipality and WWTPs personnel are thanked for sampling arrangements.

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  1. Department of Chemistry, Durban University of Technology, PO Box 1334, Durban, 4000, South Africa

    Lawrence Mzukisi Madikizela

  2. Molecular Sciences Institute, University of Witwatersrand, Private Bag x3, Johannesburg, 2050, South Africa

    Lawrence Mzukisi Madikizela & Luke Chimuka

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  1. Lawrence Mzukisi Madikizela
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  2. Luke Chimuka
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Correspondence to Lawrence Mzukisi Madikizela.

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Madikizela, L.M., Chimuka, L. Occurrence of naproxen, ibuprofen, and diclofenac residues in wastewater and river water of KwaZulu-Natal Province in South Africa. Environ Monit Assess 189, 348 (2017). https://doi.org/10.1007/s10661-017-6069-1

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