Abstract
Due to concerns about ecotoxicological effects of pharmaceuticals and other micropollutants released from wastewater treatment plants, activated carbon adsorption is one of the few processes to effectively reduce the concentrations of micropollutants in wastewater. Although aimed mainly at apolar compounds, polar compounds are also simultaneously removed to a certain extent, which has rarely been studied before. In this study, adsorption isotherm and batch kinetic data were collected with two powdered activated carbons (PACs) to assess the removal of the polar pharmaceuticals 5-fluorouracil (5-Fu) and cytarabine (CytR) from ultrapure water and wastewater treatment plant effluent. At pH 7.8, single-solute adsorption isotherm data for the weak acid 5-Fu and the weak base CytR showed that their adsorption capacities were about 1 order of magnitude lower than those of the less polar endocrine disrupting chemicals bisphenol A (BPA) and 17-α-ethinylestradiol (EE2). To remove 90 % of the adsorbate from a single-solute solution 14, 18, 70, and 87 mg L−1 of HOK Super is required for EE2, BPA, CytR, and 5-Fu, respectively. Effects of solution pH, ionic strength, temperature, and effluent organic matter (EfOM) on 5-Fu and CytR adsorption were evaluated for one PAC. Among the studied factors, the presence of EfOM had the highest effect, due to a strong competition on 5-Fu and CytR adsorption. Adsorption isotherm and kinetic data and their modeling with a homogeneous surface diffusion model showed that removal percentage in the presence of EfOM was independent on the initial concentration of the ionizable compounds 5-Fu and CytR. These results are similar to neutral organic compounds in the presence of natural organic matter. Overall, results showed that PAC doses sufficient to remove >90 % of apolar adsorbates were able to remove no more than 50 % of the polar adsorbates 5-Fu and CytR and that the contact time is a critical parameter.
Similar content being viewed by others
References
ASTM (2003) ASTM Standard Practice for Determination of Adsorptive Capacity of Activated Carbon by Aqueous Phase Isotherm Technique, D 3860–98, Reapproved 2003
Gillogly TET, Snoeyink VL, Elarde JR, Wilson CM, Royal EP (1998) 14C-MIB adsorption on PAC in natural water: a new way of measuring very low concentrations of MIB allows calculation of the PAC dose needed to mitigate odors caused by MIB. J Am Water Works Assoc 90(1):98–100
Johnson AC, Jurgens MD, Williams RJ, Kummerer K, Kortenkamp A, Sumpter JP (2008) Do cytotoxic chemotherapy drugs discharged into rivers pose a risk to the environment and human health? An overview and UK case study. J Hydrol 348(1–2):167–175
Jones OAH, Green PG, Voulvoulis N, Lester JN (2007) Questioning the excessive use of advanced treatment to remove organic micropollutants from wastewater. Environ Sci Technol 41(14):5085–5089
Joss A, Siegrist H, Ternes TA (2008) Are we about to upgrade wastewater treatment for removing organic micropollutants? Water Sci Technol 57(2):251–255
Kiffmeyer T, Gotze HJ, Jursch M, Luders U (1998) Trace enrichment, chromatographic separation and biodegradation of cytostatic compounds in surface water. Fresenius J Anal Chem 361(2):185–191
Knappe DRU, Matsui Y, Snoeyink VL, Roche P, Prados MJ, Bourbigot MM (1998) Predicting the capacity of powdered activated carbon for trace organic compounds in natural waters. Environ Sci Technol 32(11):1694–1698
Kosjek T, Heath E (2011) Occurrence, fate and determination of cytostatic pharmaceuticals in the environment. TrAC Trends Anal Chem 30(7):1065–1087. doi:10.1016/j.trac.2011.04.007
Kovalova L, McArdell CS, Hollender J (2009) Challenge of high polarity and low concentrations in analysis of cytostatics and metabolites in wastewater by hydrophilic interaction chromatography/tandem mass spectrometry. J Chromatogr A 1216(7):1100–1108
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(3):1536–1545
Lehnberg K, Kovalova L, Kazner C, Wintgens T, Schettgen T, Melin T, Hollender J, Dott W (2009) In: Kim YJ, Platt U, Gu MB, Iwahashi H (eds) Atmospheric and biological environmental monitoring: removal of selected organic micropollutants from WWTP effluent with powdered activated carbon and retention by nanofiltration. Springer, Heidelberg
Li L, Quinlivan PA, Knappe DRU (2002) Effects of activated carbon surface chemistry and pore structure on the adsorption of organic contaminants from aqueous solution. Carbon 40(12):2085–2100
Lipp P, Gross H-J, Tiehm A (2012) Improved elimination of organic micropollutants by a process combination of membrane bioreactor (MBR) and powdered activated carbon (PAC). Desalination Water Treat 42(1–3):65–72
Mahnik SN, Rizovski B, Fuerhacker M, Mader RM (2004) Determination of 5-fluorouracil in hospital effluents. Anal Bioanal Chem 380(1):31–35
Moreno-Castilla C (2004) Adsorption of organic molecules from aqueous solutions on carbon materials. Carbon 42(1):83–94
Newcombe G, Dixon D (2006) Interface science in drinking water treatment. Theory and Applications. Chapter 9: Surface chemistry effects in activated carbon adsorption of industrial pollutants (D.R.U. Knappe). Elsevier, London
Qi S, Adham SS, Snoeyink VL, Lykins Jr BW (1994) Prediction and verification of atrazine adsorption by powdered activated carbon. J Envir Eng Div, Am Soc Civ Engrs 120(1):202–218
Qi S, Schideman L, Marinas BJ, Snoeyink VL, Campos C (2007) Simplification of the IAST for activated carbon adsorption of trace organic compounds from natural water. Water Res 41(2):440–448
Rey RP, Padron AS, Leon LG, Pozo MM, Baluja C (1999) Ozonation of cytostatics in water medium. Nitrogen bases. Ozone Sci Eng 21(1):69–77
Robinson BJ, Hui JPM, Soo EC, Hellou J (2009) Estrogenic compounds in seawater and sediment from Halifax Harbour, Nova Scotia, Canada. Environ Toxicol Chem 28(1):18–25
Romanova D, Novotny L (1996) Chromatographic properties of cytosine, cytidine and their synthetic analogues. J Chromatogr B-Biomed Appl 675(1):9–15
Rossner A, Snyder SA, Knappe DRU (2009) Removal of emerging contaminants of concern by alternative adsorbents. Water Res 43(15):3787–3796. doi:10.1016/j.watres.2009.06.009
SciFinder Scholar (2011) CAS. American Chemical Society. https://scifinder.cas.org/. Accessed September 2011
Schreiber B, Schmalz V, Brinkmann T, Worch E (2007) The effect of water temperature on the adsorption equilibrium of dissolved organic matter and atrazine on granular activated carbon. Environ Sci Technol 41(18):6448–6453
Serrano D, Suarez S, Lema JM, Omil F (2011) Removal of persistent pharmaceutical micropollutants from sewage by addition of PAC in a sequential membrane bioreactor. Water Res 45(16):5323–5333
Toledo IB, Ferro-Garcia MA, Rivera-Utrilla J, Moreno-Castilla C, Fernandez FJV (2005) Bisphenol A removal from water by activated carbon. Effects of carbon characteristics and solution chemistry. Environ Sci Technol 39(16):6246–6250
Weissbrodt D, Kovalova L, Ort C, Pazhepurackel V, Moser R, Hollender J, Siegrist H, McArdell CS (2009) Mass flows of X-ray contrast media and cytostatics in hospital wastewater. Environ Sci Technol 43(13):4810–4817
Wirling J (2001) Implementation of Process-Integrated Waste Gas Cleaning Using Activated Lignite. In: A&WMA Specialty Conference on Hazardous Waste Combustors, A&WMA Specialty Conference on Hazardous Waste Combustors, March 28–30, 2001, Kansas City, KS, USA, March 28–30, 2001
Yu Q, Zhang R, Deng S, Huang J, Yu G (2009) Sorption of perfluorooctane sulfonate and perfluorooctanoate on activated carbons and resin: kinetic and isotherm study. Water Res 43(4):1150–1158
Yu J, Lv L, Lan P, Zhang S, Pan B, Zhang W (2012) Effect of effluent organic matter on the adsorption of perfluorinated compounds onto activated carbon. J Hazard Mater 225–226:99–106
Zoschke K, Engel C, Bornick H, Worch E (2011) Adsorption of geosmin and 2-methylisoborneol onto powdered activated carbon at non-equilibrium conditions: Influence of NOM and process modelling. Water Res 45(15):4544–4550. doi:10.1016/j.watres.2011.06.006
Zounkova R, Kovalova L, Blaha L, Dott W (2010) Ecotoxicity and genotoxicity assessment of cytotoxic antineoplastic drugs and their metabolites. Chemosphere 81(2):253–260. doi:10.1016/j.chemosphere.2010.06.029
Acknowledgments
This research project has been supported by a Marie Curie Early stage Research Fellowship of the European Community’s Sixth Framework Programme under contract number MEST-CT-2004-505169, as well as by the German Federal Ministry of Economics and Technology through the AiF - German Federation of Industrial Research Associations “Otto von Guericke”. The authors would like to thank Bettina Sterkele from Eawag, Switzerland for fruitful and inspiring discussions, Damian Helbling, also from Eawag, for revising the manuscript, Robert McLaughlan from University of technology Sidney for checking the quality of the English, as well as Wolfgang Dott, and Thomas Schettgens from University Hospital Aachen, Germany for providing the instrumentation and lab space.
Author information
Authors and Affiliations
Corresponding author
Additional information
Responsible editor: Vinod Kumar Gupta
Electronic supplementary material
Below is the link to the electronic supplementary material.
ESM 1
PDF 504 kb
Rights and permissions
About this article
Cite this article
Kovalova, L., Knappe, D.R.U., Lehnberg, K. et al. Removal of highly polar micropollutants from wastewater by powdered activated carbon. Environ Sci Pollut Res 20, 3607–3615 (2013). https://doi.org/10.1007/s11356-012-1432-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-012-1432-9