Skip to main content
SpringerLink
Log in

Popular pharmaceutical residues in hospital wastewater: quantification and qualification of degradation products by mass spectroscopy after treatment with membrane bioreactor

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

The occurrence of drugs in wastewater has been considered an imminent risk to the population, for the treatments used are usually ineffective. The presence of four popular drug residues (metformin, paracetamol, tetracycline, and enalapril) in hospital effluents, by using ultra-fast liquid chromatography tandem mass spectrometry (UFLC-MS/MS) with electrospray (ESI) ionization, and removal/degradation by membrane bioreactor (MBR) system are investigated in this study. For analysis method, all standard calibration curves showed satisfactory linearity (R 2 ≥ 0.993) within a relatively wide range. The recovery was between 70.4 and 105.0 %, and the relative standard deviation (RSD) values were within the ranges of 8.2 and 13.5 %. The effluent samples were collected at the end of the process treated in a bench-scale MBR treatment system and preconcentrated on solid-phase extraction (SPE) cartridges. Following that procedure, the chemical analysis demonstrated that the MBR system was effective in enalapril 94.3 ± 7.63 %, tetracycline 99.4 ± 0.02 %, and paracetamol 98.8 ± 0.86 % removal. However, the polar metformin was less effectively removed (35.4 ± 12.49 %). Moreover, the degradation products were investigated using high-resolution mass spectrometry (HRMS) by quadrupole–time of flight (Q-TOF), which has been indicated a tetracycline metabolite. In order to investigate the environmental impact, the wastewater potential risk was evaluated. The risk quotient (RQ) by measure environmental concentration (MEC) and its predicted no effect concentration (PNEC) ratio (RQ = MEC/PNEC) was between 0.003 (enalapril) to 0.815 (paracetamol). Finally, this work demonstrates that UFLC-MS/MS (ESI-Q) is a sensitive and selective method for drug analysis in wastewater and with ESI-Q-TOF has the accuracy required for determining the degradation products of these compounds. Also, it indicated that membrane bioreactor systems represent a new generation of processes that have proved to outperform conventional treatment showing better effluent quality. The removal capacity studied in this work demonstrates the efficiency of this process.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Abhilash TN (2012) Pharmaceuticals in Environment: a review on its effect. Res J Chem Sci 2(1):103–105

    Google Scholar 

  • Abuin S, Codony R, Compañó R, Granados M, Prat MD (2006) Analysis of macrolide antibiotics in river water by solid-phase extraction and liquid chromatography–mass spectrometry. J Chromatogr A 1114:73–81

    Article  CAS  Google Scholar 

  • Al Aukidy M, Verlicchi P, Jelic A, Petrovic M, Barcelò D (2012) Monitoring release of pharmaceutical compounds: occurrence and environmental risk assessment of two WWTP effluents and their receiving bodies in the Po Valley, Italy. Sci Total Environ 438:15–25

    Article  CAS  Google Scholar 

  • Al Qarni H, Collier P, O’Keeffe J, Akunna J (2016) Investigating the removal of some pharmaceutical compounds in hospital wastewater treatment plants operating in Saudi Arabia. Environ Sci Pollut Res. doi:10.1007/s11356-016-6389-7

    Google Scholar 

  • Ávila C, Reyes C, Bayona JM, García J (2013) Emerging organic contaminant removal depending on primary treatment and operational strategy in horizontal subsurface flow constructed wetlands: influence of redox. Water Res 47:315–325

    Article  Google Scholar 

  • Bisceglia KJ, Yu JT, Coelhan M, Bouwer EJ, Roberts AL (2010) Trace determination of pharmaceuticals and other wastewater-derived micropollutants by solid phase extraction and gas chromatography/mass spectrometry. J Chromatogr A 1217:558–564

    Article  CAS  Google Scholar 

  • Bueno MJM, Ulaszewska MM, Gomez MJ, Hernando MD, Fernández-Alba AR (2012) Simultaneous measurement in mass and mass/mass mode for accurate qualitative and quantitative screening analysis of pharmaceuticals in river water. J Chromatogr A 1256:80–88

    Article  Google Scholar 

  • Carballa M, Omil F, Alder AC, Lema JM (2006) Comparison between the conventional anaerobic digestion of sewage sludge and its combination with a chemical or thermal pre-treatment concerning the removal of pharmaceuticals and personal care products. Water Sci Technol 8:109–117

    Article  Google Scholar 

  • Carlsson C, Johansson A-K, Alvan G, Bergman K, Kuhler T (2006) Are pharmaceuticals potent environmental pollutants? Part I: environmental risk assessments of selected active pharmaceutical ingredients. Sci Total Environ 364:67–87

    Article  CAS  Google Scholar 

  • Celiz MD, Pérez S, Barceló D, Aga DS (2009) Trace analysis of polar pharmaceuticals in wastewater by LC–MS–MS: comparison of membrane bioreactor and activated sludge systems. J Chromatogr Sci 47:19–25

    Article  CAS  Google Scholar 

  • Chon K, KyongShon H, Cho J (2012) Membrane bioreactor and nanofiltration hybrid system for reclamation of municipal wastewater: removal of nutrients, organic matter and micropollutants. Bioresour Technol 122:181–188

    Article  CAS  Google Scholar 

  • Dang HQ, Nghiem LD, Price WE (2014) Factors governing the rejection of trace organic contaminants by nanofiltration and reverse osmosis membranes. Desalin Water Treat 52:4–6

    Article  Google Scholar 

  • Dvorák L, Svojitka J, Wanner J, Wintgens T (2013) Nitrification performance in a membrane bioreactor treating industrial wastewater. Water Res 47:4412–4421

    Article  Google Scholar 

  • Eggen T, Asp TN, Grave K, Hormazabal V (2011) Uptake and translocation of metformin, ciprofloxacin and narasin in forage- and crop plants. Chemosphere 85:26–33

    Article  CAS  Google Scholar 

  • EMEA (2006) Europe Medicines Agency, Committee for medicinal products for human use (CHMP). http://www.emea.europa.eu/pdfs/human/swp/444700en.pdf. Accessed 14 Jan 2015

  • Escher BI, Baumgartner R, Koller M, Treyer K, Lienert J, McArdell CS (2011) Environmental toxicology and risk assessment of pharmaceuticals from hospital wastewater. Water Res 45:75–92

    Article  CAS  Google Scholar 

  • Farré M, Pérez S, Kantiani L, Barceló D (2008) Fate and toxicity of emerging pollutants, their metabolites and transformation products in the aquatic environmental. Trends Anal Chem 27:991–1007

    Article  Google Scholar 

  • Fatta D, Nikolaou A, Achilleos A, Meriç A (2007) Analytical methods for tracing pharmaceutical residues in water and wastewater. Trends Anal Chem 26:515–533

    Article  CAS  Google Scholar 

  • Garcia-Rodríguez A, Matamoros V, Fontàs C, Salvadó V (2013) The influence of light exposure, water quality and vegetation on the removal of sulfonamides and tetracyclines: a laboratory-scale study. Chemosphere 90:2297–2302

    Article  Google Scholar 

  • Grung M, Kallqvist T, Sakshaug S, Skurtveit S, Thomas KV (2008) Environmental assessment of Norwegian priority pharmaceuticals based on the EMEA guideline. Ecotoxicol Environ Saf 71:328–340

    Article  CAS  Google Scholar 

  • Halling-Sorensen B, Nielsen SN, Lanzky PF, Ingerslev F, Lutzhoft HCH, Jorgensen SE (1998) Occurrence, fate and effects of pharmaceutical substances in the environment—a review. Chemosphere 36:357–394

    Article  CAS  Google Scholar 

  • Ham BM (2008) Even electron mass spectrometry with biomolecule applications. Wiley Blackwell, England

    Google Scholar 

  • Han J, Qiu W, Hu J, Gao W (2012) Chemisorption of estrone in nylon microfiltration membranes: adsorption mechanism and potential use for estrone removal from water. Water Res 46:873–881

    Article  CAS  Google Scholar 

  • Heberer T (2002) Occurrence, fate, and removal of pharmaceutical residues in the aquatic environment: a review of recent research data. Toxicol Lett 131:5–17

    Article  CAS  Google Scholar 

  • Hernando MD, Mezcua M, Fernandez-Alba AR, Barcelo D (2007) Environmental risk assessment of pharmaceutical residues in wastewater effluents, surface waters and sediments. Talanta 69:334–342

    Article  Google Scholar 

  • Howard PH, Muir DCG (2011) Identifying new persistent and bioaccumulative organics among chemicals in commerce II: pharmaceuticals. Environ Sci Technol 45:6938–6946

    Article  CAS  Google Scholar 

  • Ibáñez M, Gracia-Lor E, Bijlsma L, Morales E, Pastor L, Hernández F (2013) Removal of emerging contaminants in sewage water subjected to advanced oxidation with ozone. J Hazard Mater 260:389–398

    Article  Google Scholar 

  • Jones OAH, Voulvoulis N, Lester JN (2005) Human pharmaceuticals in wastewater treatment processes. Crit Rev Environ Sci Technol 35:401–427

    Article  CAS  Google Scholar 

  • Kim M, Guerra P, Shah A, Parsa M, Alaee M, Smyth SA (2014) Removal of pharmaceuticals and personal care products in a membrane bioreactor wastewater treatment plant. Water Sci Technol 69:2221–2229

    Article  CAS  Google Scholar 

  • Kolpin DW, Furlog ET, Meyer MT, Thurman EM, Zaugg SD, Barber LB, Buxton HT (2002) Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999-2000: A national reconnaissance environmental science & technology. Environ sci Technol 36:1202–1211

  • Kosjek T, Heath E, Petrovic M, Barceló D (2007) Mass spectrometry for identifying pharmaceutical biotransformation products in the environmental. Trends Anal Chem 26:1076–1085

    Article  CAS  Google Scholar 

  • Kovalova L, Siegrist H, Singer H, Wittmer A, Mcardell CS (2012) Hospital wastewater treatment by membrane bioreactor: performance and efficiency for organic micropollutant elimination. Environ Sci Technol 46:1536–1545

    Article  CAS  Google Scholar 

  • Kümmerer K (2008) Pharmaceuticals in the environment—sources, fate, effects and risks, 3rd edn. Springer, Berlin, Heidelberg, pp 81–89

    Google Scholar 

  • Lacorte S, Fernandez-Alba AR (2006) Time of flight mass spectrometry applied to the liquid chromatographic analysis of pesticides in water and food. Mass Spec Ver 25:866–880

    Article  CAS  Google Scholar 

  • Langford KH, Thomas KV (2009) Determination of pharmaceutical compounds in hospital effluents and their contribution to wastewater treatment works. Environ Int 35:766–770

    Article  CAS  Google Scholar 

  • Lin AYC, Tsai YT (2009) Occurrence of pharmaceuticals in Taiwan’s surface waters: impact of waste streams from hospitals and pharmaceutical production facilities. Sci Total Environ 407:3793–3802

    Article  CAS  Google Scholar 

  • López-Serna R, Petrovic M, Barceló D (2012) Direct analysis of pharmaceuticals, their metabolites and transformation products in environmental waters using on-line TurboFlow™ chromatography–liquid chromatography–tandem mass spectrometry. J Chromatogr A 1252:115–129

    Article  Google Scholar 

  • Mohammed B, Amina D, Samira G (2013) Global approach and targeted approach in the management of hospital effluents. J Mater Sci Eng B 3:214–225

    CAS  Google Scholar 

  • Monsalvo VM, McDonald JA, Khan SJ, Le-Clech P (2014) Removal of trace organics by anaerobic membrane bioreactors. Water Res 49:103–112

    Article  CAS  Google Scholar 

  • Mulroy A (2001) When the cure is the problem. Water Environ Technol 13:32–36

  • Niu J, Li Y, Wang W (2013) Light-source-dependent role of nitrate and humic acid in tetracycline photolysis: kinetics and mechanism. Chemosphere 92:1423–1429

    Article  CAS  Google Scholar 

  • Oliveira TS, Murphy M, Mendola N, Wong V, Carlson D, Waring L (2015) Characterization of pharmaceuticals and personal care products in hospital effluent and waste water influent/effluent by direct-injection LC-MS-MS. Sci Total Environ 518–519:459–478

    Article  Google Scholar 

  • Oosterhuis M, Sacher F, Ter Laak TL (2013) Prediction of concentration levels of metformin and other high consumption pharmaceuticals in wastewater and regional surface water based on sales data. Sci Total Environ 442:380–388

    Article  CAS  Google Scholar 

  • Petrovic M, Cruz HMS, Barceló D (2005) Liquid chromatography–tandem mass spectrometry for the analysis of pharmaceutical residues in environmental samples: a review. J Chromatogr A 1067:1–14

    Article  CAS  Google Scholar 

  • Pisarenko AN, Stanford BD, Yan D, Gerrity D, Snyder SA (2012) Effects of ozone and ozone/peroxide on trace organic contaminants and NDMA in drinking water and water reuse applications. Water Res 46:316–326

    Article  CAS  Google Scholar 

  • Pomati F, Netting AG, Calamari D, Neilan BA (2004) Effects of erythromycin, tetracycline and ibuprofen on the growth of Synechocystis sp. And Lemma minor. Aquat Toxicol 67:387–396

  • Reemtsma T, Jekel M (2007) Organic pollutants in the water cycle. Environ Eng Manag J 6:77–78

    Google Scholar 

  • Santos LHMLM, Gros M, Rodriguez-Mozaz S, Delerue-Matos C, Pena A, Barceló D, Montenegro MCBSM (2013) Contribution of hospital effluents to the load of pharmaceuticals in urban wastewaters: identification of ecologically relevant pharmaceuticals. Sci Total Environ 461:302–316

    Article  Google Scholar 

  • Scheurer M, Michel A, Brauch H-J, Ruck W, Sacher F (2012) Occurrence and fate of the antidiabetic drug metformin and its metabolite guanylurea in the environment and during drinking water treatment. Water Res 46:4790–4802

    Article  CAS  Google Scholar 

  • Shao B, Chen D, Zhang J, Wu Y, Sun C (2009) Determination of 76 pharmaceutical drugs by liquid chromatography–tandem mass spectrometry in slaughterhouse wastewater. J Chromatogr A 1216:8312–8318

    Article  CAS  Google Scholar 

  • Sharma P, Kumar M, Mathur N, Singh A, Bhatnagar P, Sogani M (2013) Health care industries: potential generators of genotoxic waste. Environ Sci Pollut Res 20:5160–5167

    Article  CAS  Google Scholar 

  • Shen J, Huang J, Ruan H, Wang J, Van der Bruggen B (2013) Techno-economic analysis of resource recovery of glyphosate liquor by membrane technology. Desalination 342:118–125

    Article  Google Scholar 

  • Shi X, Lefebvre O, Kwang NK, Yong NH (2014) Sequential anaerobic– aerobic treatment of pharmaceutical wastewater with high salinity. Bioresour Technol 153:79–86

    Article  CAS  Google Scholar 

  • Stalder T, Alrhmoun M, Louvet JN, Casellas M, Maftah C, Carrion C, Pons MN, Pahl O, Ploy MC, Dagot C (2013) Dynamic assessment of the floc morphology, bacterial diversity, and integron content of an activated sludge reactor processing hospital effluent. Environ Sci Technol 47:7909–7917

    Article  CAS  Google Scholar 

  • Standard methods for examination of water and wastewater (2012) APHA, 22nd ed. http://www.mwa.co.th/download/file_upload/SMWW_1000-3000.pdf. Accessed 19 Oct 2015.

  • Suarez S, Lema JM, Omil F (2009) Pre-treatment of hospital wastewater by coagulation–flocculation and flotation. Bioresour Technol 100:2138–2146

    Article  CAS  Google Scholar 

  • Tadkaew N, Hai FI, McDonald JA, Khan SJ, Nghiem LD (2011) Removal of trace organics by MBR treatment: the role of molecular properties. Water Res 45:2439–2451

    Article  CAS  Google Scholar 

  • Thomas KV, Dye C, Schlabach M, Langford KH (2007) Source to sink tracking of selected human pharmaceuticals from two Oslo city hospitals and a wastewater treatment works. J Environ Monit 9(12):1410–1418

    Article  CAS  Google Scholar 

  • Torres NH, Ferreira LFR, Americo JHP, Freguglia RMO, Moura-Andrade GCR, Tornisielo VL (2012) Analysis and occurrence of residues of the hormones estriol, 17alpha-ethinylestradiol and 17beta-estradiol in urban water supply by HPLC-DAD. IOSRJEN 2:984–989

    Article  Google Scholar 

  • Tunkel J, Howard PH, Boethling RS, Stiteler W, Loonen H (2000) Predicting ready biodegradability in the Japanese ministry of international trade and industry test. Toxicol Chem 19:2478–2485

    Article  CAS  Google Scholar 

  • Verlicchi P, Aukidy MA, Galletti A, Petrovic M, Barceló D (2012a) Hospital effluent: investigation of the concentrations and distribution of pharmaceuticals and environmental risk assessment. Sci Environ 430:109–118

    CAS  Google Scholar 

  • Verlicchi P, Al Aukidy M, Zambello E (2012b) Occurrence of pharmaceutical compounds in urban wastewater: removal, mass load and environmental risk after a secondary treatment—a review. Sci Total Environ 429:123–155

    Article  CAS  Google Scholar 

  • Wei L, Xiao-nong Y, Qun L, Hua Y, Yi-ke D, Wan-you W (2003) Clinical medication and interaction of drugs in animal medical science. J Southwest Univer National 29:709–712

    Google Scholar 

  • Yu Y, Wu L (2011) Comparison of four extraction methods for the analysis of pharmaceuticals in wastewater. J Chromatogr A 1218:2483–2489

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors are grateful to CAPES, FAPERGS, CNPq, and Department of Economic Development, Science and Technology of Rio Grande do Sul (SDECT) for the financial support. The authors declare that they have no conflicts of interest in the research.

Author information

Authors and Affiliations

  1. LBIOP—Laboratory of Biotechnology of Natural and Synthetics Products, Technology Department, Biotechnology Institute, University of Caxias do Sul, 1130, Francisco Getúlio Vargas St., CEP 95070-560, Caxias do Sul, Brazil

    M. Chiarello, L. Minetto & S. Moura

  2. LATAM—Laboratory of Environmental Technology, Technology Department, University of Caxias do Sul, 1130, Francisco Getúlio Vargas St., CEP 95070-560, Caxias do Sul, Brazil

    M. Chiarello, S. V. Della Giustina & L. L. Beal

Authors
  1. M. Chiarello
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. L. Minetto
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. S. V. Della Giustina
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. L. L. Beal
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. S. Moura
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to S. Moura.

Additional information

Responsible editor: Hongwen Sun

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chiarello, M., Minetto, L., Giustina, S.V.D. et al. Popular pharmaceutical residues in hospital wastewater: quantification and qualification of degradation products by mass spectroscopy after treatment with membrane bioreactor. Environ Sci Pollut Res 23, 16079–16089 (2016). https://doi.org/10.1007/s11356-016-6766-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-016-6766-2

Keywords

Search

Navigation