Environmental Monitoring and Assessment

, Volume 184, Issue 11, pp 6735–6748 | Cite as

Application of chemometrics in understanding the spatial distribution of human pharmaceuticals in surface water

  • Najat Ahmed Al-Odaini
  • Mohamad Pauzi Zakaria
  • Muniirah Abdul Zali
  • Hafizan Juahir
  • Mohamad Ismail Yaziz
  • Salmijah Surif


The growing interest in the environmental occurrence of veterinary and human pharmaceuticals is essentially due to their possible health implications to humans and ecosystem. This study assesses the occurrence of human pharmaceuticals in a Malaysian tropical aquatic environment taking a chemometric approach using cluster analysis, discriminant analysis and principal component analysis. Water samples were collected from seven sampling stations along the heavily populated Langat River basin on the west coast of peninsular Malaysia and its main tributaries. Water samples were extracted using solid-phase extraction and analyzed using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) for 18 pharmaceuticals and one metabolite, which cover a range of six therapeutic classes widely consumed in Malaysia. Cluster analysis was applied to group both pharmaceutical pollutants and sampling stations. Cluster analysis successfully clustered sampling stations and pollutants into three major clusters. Discriminant analysis was applied to identify those pollutants which had a significant impact in the definition of clusters. Finally, principal component analysis using a three-component model determined the constitution and data variance explained by each of the three main principal components.


Human pharmaceuticals Aquatic pollution Chemometrics Langat River Malaysia 



This work was financially supported by funding from Malaysia’s Ministry of Science, Technology and Innovation (MOSTI) under the Science Fund (project number 5450100). The authors would like to thank the Public Health Lab of the Veterinary Department under the Ministry of Agriculture and Agro-Based Industry and Fisheries for their generous support in the performance of the LC-MS/MS procedures. The authors are grateful to the Sewage Service Department for providing the sewage information in the Langat basin.


  1. Al-Odaini, N. A., Zakaria, M. P., Yaziz, M. I., & Surif, S. (2010). Multi-residue analytical method for human pharmaceuticals and synthetic hormones in river water and sewage effluents by solid-phase extraction and liquid chromatography-tandem mass spectrometry. Journal of Chromatography. A, 1217, 6791–6806.CrossRefGoogle Scholar
  2. Bendz, D., Paxeus, N. A., Ginn, T. R., & Loge, F. J. (2005). Occurrence and fate of pharmaceutically active compounds in the environment, a case study: Hoje River in Sweden. Journal of Hazardous Materials, 122, 195–204.CrossRefGoogle Scholar
  3. Benotti, M. J., Trenholm, R. A., Vanderford, B. J., Holady, J. C., Stanford, B. D., & Snyder, S. A. (2008). Pharmaceuticals and Endocrine Disrupting Compounds in U.S. Drinking Water. Environmental Science & Technology, 43, 597–603.CrossRefGoogle Scholar
  4. Boyd, G. R., Palmeri, J. M., Zhang, S., & Grimm, D. A. (2004). Pharmaceuticals and personal care products (PPCPs) and endocrine disrupting chemicals (EDCs) in stormwater canals and Bayou St. John in New Orleans, Louisiana, USA. Science of the Total Environment, 333, 137–148.CrossRefGoogle Scholar
  5. Calamari, D., Zuccato, E., Castiglioni, S., Bagnati, R., & Fanelli, R. (2003). Strategic Survey of Therapeutic Drugs in the Rivers Po and Lambro in Northern Italy. Environmental Science & Technology, 37, 1241–1248.CrossRefGoogle Scholar
  6. Castiglioni, S., Bagnati, R., Fanelli, R., Pomati, F., Calamari, D., & Zuccato, E. (2005). Removal of Pharmaceuticals in Sewage Treatment Plants in Italy. Environmental Science & Technology, 40, 357–363.CrossRefGoogle Scholar
  7. Christensen, F. M. (1998). Pharmaceuticals in the Environment–A Human Risk? Regulatory Toxicology and Pharmacology, 28, 212–221.CrossRefGoogle Scholar
  8. Comeau, F., Surette, C., Brun, G. L., & Losier, R. (2008). The occurrence of acidic drugs and caffeine in sewage effluents and receiving waters from three coastal watersheds in Atlantic Canada. Science of the Total Environment, 396, 132–146.CrossRefGoogle Scholar
  9. Costanzo, S. D., Murby, J., & Bates, J. (2005). Ecosystem response to antibiotics entering the aquatic environment. Marine Pollution Bulletin, 51, 218–223.CrossRefGoogle Scholar
  10. Cui, C., Ji, S., & Ren, H. (2006). Determination of Steroid Estrogens in Wastewater Treatment Plant of A Controceptives Producing Factory. Environmental Monitoring and Assessment, 121, 407–417.CrossRefGoogle Scholar
  11. Glassmeyer, S. T., Hinchey, E. K., Boehme, S. E., Daughton, C. G., Ruhoy, I. S., Conerly, O., Daniels, R. L., Lauer, L., McCarthy, M., Nettesheim, T. G., Sykes, K., & Thompson, V. G. (2009). Disposal practices for unwanted residential medications in the United States. Environment International, 35, 566–572.CrossRefGoogle Scholar
  12. Goncalves, C., Esteves Da Silva, J. C. G., & Alpendurada, M. F. (2006). Chemometric interpretation of pesticide occurence in soil samples from an intensive horticulture area in north Portugal. Analytica Chimica Acta, 560, 164–171.CrossRefGoogle Scholar
  13. Halling-Sorensen, B., Nors Nielsen, S., Lanzky, P. F., Ingerslev, F., Holten Lutzhoft, H. C., & Jorgensen, S. E. (1998). Occurrence, fate and effects of pharmaceutical substances in the environment- A review. Chemosphere, 36, 357–393.CrossRefGoogle Scholar
  14. Heberer, T., Schmidt-Bäumler, K., & Stan, H. J. (1998). Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part I: Drug Residues and other Polar Contaminants in Berlin Surface and Groundwater. Acta hydrochimica et hydrobiologica, 26, 272–278.CrossRefGoogle Scholar
  15. IWK (2010). Indah Water Konsortium Sdn Bhd. Retrieved May 2010 from http://www.iwk.com.my/
  16. Johnson, R. A., & Wichern, D. W. (2007). Applied multivariate statitical analysis. New Jersey, USA: Pearson Education Inc.Google Scholar
  17. Jones, O. A., Voulvoulis, N., & Lester, J. N. (2002). Aquatic environmental assessment of the top 25 English prescription pharmaceuticals. Water Research, 36, 5013–5022.CrossRefGoogle Scholar
  18. Jones, O. A., Lester, J. N., & Voulvoulis, N. (2005). Pharmaceuticals: a threat to drinking water? Trends in Biotechnology, 23, 163–167.CrossRefGoogle Scholar
  19. Juahir, H., Zain, S. M., Aris, A. Z., Yusoff, M. K., & Mokhtar, M. B. (2009). Spatial assessment of Langat river water quality using chemometrics. Journal of Environmental Monitoring, 12, 287–295.CrossRefGoogle Scholar
  20. Juahir, H., Zain, S. M., Yusoff, M. K., Hanidza, T. I. T., Armi, A. S. M., Toriman, M. E., & Mokhtar, M. (2010). Spatial water quality assessment of Langat River Basin (Malaysia) using environmetric techniques. Environmental Monitoring and Assessment, 173, 1–17.Google Scholar
  21. Kasprzyk-Hordern, B., Dinsdale, R. M., & Guwy, A. J. (2009a). Illicit drugs and pharmaceuticals in the environment - Forensic applications of environmental data, Part 2: Pharmaceuticals as chemical markers of faecal water contamination. Environmental Pollution, 157, 1778–1786.CrossRefGoogle Scholar
  22. Kasprzyk-Hordern, B., Dinsdale, R. M., & Guwy, A. J. (2009b). Illicit drugs and pharmaceuticals in the environment - Forensic applications of environmental data. Part 1: Estimation of the usage of drugs in local communities. Environmental Pollution, 157, 1773–1777.CrossRefGoogle Scholar
  23. Kim, J.-W., Jang, H.-S., Kim, J.-G., Ishibashi, H., Hirano, M., Nasu, K., Ichikawa, N., Takao, Y., Shinohara, R., & Arizono, K. (2009). Occurrence of Pharmaceutical and Personal Care Products (PPCPs) in Surface Water from Mankyung River, South Korea. Journal of Health Science, 55, 249–258.CrossRefGoogle Scholar
  24. Kolpin, D. W., Furlong, E. T., Meyer, M. T., Thurman, E. M., Zaugg, S. D., Barber, L. B., & 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.CrossRefGoogle Scholar
  25. Kosjek, T., Heath, E., & Krbavcic, A. (2005). Determination of non-steroidal anti-inflammatory drug (NSAIDs) residues in water samples. Environment International, 31, 679–685.CrossRefGoogle Scholar
  26. Kruawal, K., Sacher, F., Werner, A., Muller, J., & Knepper, T. P. (2005). Chemical water quality in Thailand and its impacts on the drinking water production in Thailand. Science of the Total Environment, 340, 57–70.CrossRefGoogle Scholar
  27. KTA Tenaga, S.B. (2005). Sungai Langat Integrated River Basin Management Study. M. o. N. R. a. Environment: Kuala Lumpur.Google Scholar
  28. Langford, K. H., & Thomas, K. V. (2009). Determination of pharmaceutical compounds in hospital effluents and their contribution to wastewater treatment works. Environment International, 35, 766–770.CrossRefGoogle Scholar
  29. Liu, C.-W., Lin, K.-H., & Kuo, Y.-M. (2003). Application of factor analysis in the assessment of groundwater quality in a blackfoot disease area in Taiwan. Science of the Total Environment, 313, 77–89.CrossRefGoogle Scholar
  30. Loos, R., Gawlik, B. M., Locoro, G., Rimaviciute, E., Contini, S., & Bidoglio, G. (2009). EU-wide survey of polar organic persistent pollutants in European river waters. Environmental Pollution, 157, 561–568.CrossRefGoogle Scholar
  31. Mas, S., de Juan, A., Tauler, R., Olivieri, A. C., & Escandar, G. M. (2010). Application of chemometric methods to environmental analysis of organic pollutants: A review. Talanta, 80, 1052–1067.CrossRefGoogle Scholar
  32. Mendiguchia, C., Moreno, C., Galindo-Riano, M. D., & Garcia-Vargas, M. (2004). Using chemometric tools to assess anthropogenic effects in river water: A case study: Guadalquivir River (Spain). Analytica Chimica Acta, 515, 143–149.CrossRefGoogle Scholar
  33. Nakada, N., Tanishima, T., Shinohara, H., Kiri, K., & Takada, H. (2006). Pharmaceutical chemicals and endocrine disrupters in municipal wastewater in Tokyo and their removal during activated sludge treatment. Water Research, 40, 3297–3303.CrossRefGoogle Scholar
  34. Nakada, N., Kiri, K., Shinohara, H., Harada, A., Kuroda, K., Takizawa, S., & Takada, H. (2008). Evaluation of Pharmaceuticals and Personal Care Products as Water-soluble Molecular Markers of Sewage. Environmental Science & Technology, 42, 6347–6353.CrossRefGoogle Scholar
  35. NMUS. (2006). Malaysian Statistics on Medicine. Kuala Lumpur: Ministry of Health Malaysia.Google Scholar
  36. Petrovic, M., Gonzalez, S., & Barceló, D. (2003). Analysis and removal of emerging contaminants in wastewater and drinking water. TrAC Trends in Analytical Chemistry, 22, 685–696.CrossRefGoogle Scholar
  37. Quintana, J. B., & Reemtsma, T. (2004). Sensitive determination of acidic drugs and triclosan in surface and wastewater by ion-pair reverse-phase liquid chromatography/tandem mass spectrometry. Rapid Communications in Mass Spectrometry, 18, 765–774.CrossRefGoogle Scholar
  38. Rodgers-Gray, T. P., Jobling, S., Morris, S., Kelly, C., Kirby, S., Janbakhsh, A., Harries, J. E., Waldock, M. J., Sumpter, J. P., & Tyler, C. R. (2000). Long-Term Temporal Changes in the Estrogenic Composition of Treated Sewage Effluent and Its Biological Effects on Fish. Environmental Science & Technology, 34, 1521–1528.CrossRefGoogle Scholar
  39. Rodriguez-Mozaz, S., Lopez de Alda, M. J., & Barcelo, D. (2004). Picogram per Liter Level Determination of Estrogens in Natural Waters and Waterworks by a Fully Automated On-Line Solid-Phase Extraction-Liquid Chromatography-Electrospray Tandem Mass Spectrometry Method. Analytical Chemistry, 76, 6998–7006.CrossRefGoogle Scholar
  40. Saim, N., Osman, R., Sari Abg Spian, D. R., Jaafar, M. Z., Juahir, H., Abdullah, M. P., & Ghani, F. A. (2009). Chemometric approach to validating faecal sterols as source tracer for faecal contamination in water. Water Research, 43, 5023–5030.CrossRefGoogle Scholar
  41. Stumpf, M., Ternes, T. A., Wilken, R.-D., Silvana Vianna, R., & Baumann, W. (1999). Polar drug residues in sewage and natural waters in the state of Rio de Janeiro, Brazil. Science of the Total Environment, 225, 135–141.CrossRefGoogle Scholar
  42. Thompson, R. E., Voit, E. O., & Scott, G. I. (2000). Statistical modeling of sediment and oyster PAH contaminant data collected at a south Carolina Estuary (complete and left-censored samples). Environmetrics, 11, 99–119.CrossRefGoogle Scholar
  43. Weigel, S., Bester, K., & Huhnerfuss, H. (2001). New method for rapid solid-phase extraction of large-volume water samples and its application to non-target screening of North Sea water for organic contaminants by gas chromatography–mass spectrometry. Journal of Chromatography. A, 912, 151–161.CrossRefGoogle Scholar
  44. Werner, J. J., McNeill, K., & Arnold, W. A. (2005). Environmental photodegradation of mefenamic acid. Chemosphere, 58, 1339–1346.CrossRefGoogle Scholar
  45. Wiegel, S., Aulinger, A., Brockmeyer, R., Harms, H., Loffler, J., Reincke, H., Schmidt, R., Stachel, B., von Tumpling, W., & Wanke, A. (2004). Pharmaceuticals in the river Elbe and its tributaries. Chemosphere, 57, 107–126.CrossRefGoogle Scholar
  46. Yamamoto, H., Nakamura, Y., Moriguchi, S., Nakamura, Y., Honda, Y., Tamura, I., Hirata, Y., Hayashi, A., & Sekizawa, J. (2009). Persistence and partitioning of eight selected pharmaceuticals in the aquatic environment: Laboratory photolysis, biodegradation, and sorption experiments. Water Research, 43, 351–362.CrossRefGoogle Scholar
  47. Ying, G.-G., Kookana, R. S., & Ru, Y.-J. (2002). Occurrence and fate of hormone steroids in the environment. Environment International, 28, 545–551.CrossRefGoogle Scholar
  48. Yu, C.-P., & Chu, K.-H. (2009). Occurrence of pharmaceuticals and personal care products along the West Prong Little Pigeon River in east Tennessee, USA. Chemosphere, 75, 1281–1286.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2011

Authors and Affiliations

  • Najat Ahmed Al-Odaini
    • 1
  • Mohamad Pauzi Zakaria
    • 1
  • Muniirah Abdul Zali
    • 1
  • Hafizan Juahir
    • 2
  • Mohamad Ismail Yaziz
    • 2
  • Salmijah Surif
    • 3
  1. 1.Centre of Excellence for Environmental Forensics, Faculty of Environmental StudiesUniversiti Putra MalaysiaSerdangMalaysia
  2. 2.Department of Environmental Science, Faculty of Environmental StudiesUniversiti Putra MalaysiaSerdangMalaysia
  3. 3.School of Environment and Natural Resources Science, Faculty of Science and TechnologyUniversiti Kebangsaan MalaysiaBangiMalaysia

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