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Determination of pharmaceuticals in sewage sludge and biochar from hydrothermal carbonization using different quantification approaches and matrix effect studies

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Abstract

Producing valuable biochar from waste materials using thermal processes like hydrothermal carbonization (HTC) has gained attention in recent years. However, the fate of micropollutants present in these waste sources have been neglected, although they might entail the risk of environmental pollution. Thus, an HPLC-MS/MS method was developed for 12 pharmaceuticals to determine the micropollutant load of biochar, which was made from sewage sludge via HTC within 4 h at 210 °C. Pressurized liquid extraction was applied to extract the compounds. Because of the high load of co-extracted matter, matrix effects in HPLC-MS/MS were investigated using matrix effect profiles. Interfering compounds suppressed 50 % of the phenazone signal in sewage sludge and 70 % in biochar, for example. The quantification approaches external calibration, internal standard analysis, and standard addition were compared considering recovery rates, standard deviations, and measurement uncertainties. The external analysis resulted in decreased or enhanced recovery rates. Spiking before LC-MS/MS compensated instrumental matrix effects. Still, recovery rates remained below 70 % for most compounds because this approach neglects sample losses during the extraction. Internal standards compensated for the matrix effects sufficiently for up to five compounds. The standard addition over the whole procedure proved to compensate for the matrix effects for 11 compounds and achieved recovery rates between 85 and 125 %. Additionally, results showed good reproducibility and validity. Only sulfamethoxazole recovery rate remained below 70 % in sewage sludge. Real sample analysis showed that three pharmaceuticals were detected in the biochar, while the corresponding sewage sludge source contained 8 of the investigated compounds.

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References

  1. Scholz RW, Ulrich AE, Eilitta M, Roy A (2013) Sustainable use of phosphorus: a finite resource. Sci Total Environ 461:799–803. doi:10.1016/j.scitotenv.2013.05.043

    Article  Google Scholar 

  2. Wiechmann B, Dienemann C, Kabbe C, Brandt S, Vogel I, Roskosch A (2012) Klärschlammentsorgung in der Bundesrepublik Deutschland

  3. Bergius F (1913) Production of hydrogen from water and coal from cellulose at high temperatures and pressures. J Soc Chem Ind 32(9):462–467. doi:10.1002/jctb.5000320904

  4. Funke A, Ziegler F (2010) Hydrothermal carbonization of biomass: a summary and discussion of chemical mechanisms for process engineering. Biofuels Bioprod Biorefin 4(2):160–177. doi:10.1002/bbb.198

    Article  CAS  Google Scholar 

  5. Weiner B, Baskyr I, Poerschmann J, Kopinke FD (2013) Potential of the hydrothermal carbonization process for the degradation of organic pollutants. Chemosphere 92(6):674–680. doi:10.1016/j.chemosphere.2013.03.047

    Article  CAS  Google Scholar 

  6. Clarke BO, Smith SR (2011) Review of ‘emerging’ organic contaminants in biosolids and assessment of international research priorities for the agricultural use of biosolids. Environ Int 37(1):226–247. doi:10.1016/j.envint.2010.06.004

    Article  CAS  Google Scholar 

  7. Chen YS, Yu G, Cao QM, Zhang HB, Lin QY, Hong YW (2013) Occurrence and environmental implications of pharmaceuticals in Chinese municipal sewage sludge. Chemosphere 93(9):1765–1772. doi:10.1016/j.chemosphere.2013.06.007

    Article  CAS  Google Scholar 

  8. Huang YJ, Cheng MM, Li WH, Wu LH, Chen YS, Luo YM, Christie P, Zhang HB (2013) Simultaneous extraction of four classes of antibiotics in soil, manure and sewage sludge and analysis by liquid chromatography-tandem mass spectrometry with the isotope-labelled internal standard method. Anal Methods-Uk 5(15):3721–3731. doi:10.1039/C3ay40220g

    Article  CAS  Google Scholar 

  9. Martin J, Camacho-Munoz D, Santos JL, 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. J Hazard Mater 239:40–47. doi:10.1016/j.jhazmat.2012.04.068

    Article  Google Scholar 

  10. Peysson W, Vulliet E (2013) Determination of 136 pharmaceuticals and hormones in sewage sludge using quick, easy, cheap, effective, rugged and safe extraction followed by analysis with liquid chromatography-time-of-flight-mass spectrometry. J Chromatogr A 1290:46–61. doi:10.1016/j.chroma.2013.03.057

    Article  CAS  Google Scholar 

  11. Boxall ABA, Rudd MA, Brooks BW, Caldwell DJ, Choi K, Hickmann S, Innes E, Ostapyk K, Staveley JP, Verslycke T, Ankley GT, Beazley KF, Belanger SE, Berninger JP, Carriquiriborde P, Coors A, DeLeo PC, Dyer SD, Ericson JF, Gagne F, Giesy JP, Gouin T, Hallstrom L, Karlsson MV, Larsson DGJ, Lazorchak JM, Mastrocco F, McLaughlin A, McMaster ME, Meyerhoff RD, Moore R, Parrott JL, Snape JR, Murray-Smith R, Servos MR, Sibley PK, Straub JO, Szabo ND, Topp E, Tetreault GR, Trudeau VL, Van Der Kraak G (2012) Pharmaceuticals and personal care products in the environment: what are the big questions? Environ Health Persp 120(9):1221–1229. doi:10.1289/Ehp.1104477

    Article  Google Scholar 

  12. Avbersek M, Somen J, Heath E (2011) Dynamics of steroid estrogen daily concentrations in hospital effluent and connected waste water treatment plant. J Environ Monitor 13(8):2221–2226. doi:10.1039/C1em10147a

    Article  CAS  Google Scholar 

  13. Niessen WMA, Manini P, Andreoli R (2006) Matrix effects in quantitative pesticide analysis using liquid chromatography-mass spectrometry. Mass Spectrom Rev 25(6):881–899. doi:10.1002/Mas.20097

    Article  CAS  Google Scholar 

  14. Seira J, Claparols C, Joannis-Cassan C, Albasi C, Montrejaud-Vignoles M, Sablayrolles C (2013) Optimization of pressurized liquid extraction using a multivariate chemometric approach for the determination of anticancer drugs in sludge by ultra high performance liquid chromatography-tandem mass spectrometry. J Chromatogr A 1283:27–38. doi:10.1016/j.chroma.2013.01.114

    Article  CAS  Google Scholar 

  15. Gosetti F, Mazzucco E, Zampieri D, Gennaro MC (2010) Signal suppression/enhancement in high-performance liquid chromatography tandem mass spectrometry. J Chromatogr A 1217(25):3929–3937. doi:10.1016/j.chroma.2009.11.060

    Article  CAS  Google Scholar 

  16. Stahnke H, Reemtsma T, Alder L (2009) Compensation of matrix effects by postcolumn infusion of a monitor substance in multiresidue analysis with LC-MS/MS. Anal Chem 81(6):2185–2192. doi:10.1021/Ac802362s

    Article  CAS  Google Scholar 

  17. Chen XJ, Bester K (2009) Determination of organic micro-pollutants such as personal care products, plasticizers and flame retardants in sludge. Anal Bioanal Chem 395(6):1877–1884. doi:10.1007/s00216-009-3138-5

  18. Saleh A, Larsson E, Yamini Y, Jonsson JA (2011) 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 sewage sludge. J Chromatogr A 1218(10):1331–1339. doi:10.1016/j.chroma.2011.01.011

    Article  CAS  Google Scholar 

  19. Stahnke H, Kittlaus S, Kempe G, Alder L (2012) Reduction of matrix effects in liquid chromatography-electrospray ionization-mass spectrometry by dilution of the sample extracts: how much dilution is needed? Anal Chem 84(3):1474–1482. doi:10.1021/Ac202661j

    Article  CAS  Google Scholar 

  20. Navarro I, Sanz P, Martínez MA (2011) Analysis of perfluorinated alkyl substances in Spanish sewage sludge by liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem 400(5):1277–1286. doi:10.1007/s00216-011-4655-6

    Article  CAS  Google Scholar 

  21. Ding YJ, Zhang WH, Gu C, Xagoraraki I, Li H (2011) Determination of pharmaceuticals in biosolids using accelerated solvent extraction and liquid chromatography/tandem mass spectrometry. J Chromatogr A 1218(1):10–16. doi:10.1016/j.chroma.2010.10.112

    Article  CAS  Google Scholar 

  22. Göbel A, Thomsen A, McArdell CS, Alder AC, Giger W, Theiss N, Loffler D, Ternes TA (2005) Extraction and determination of sulfonamides, macrolides, and trimethoprim in sewage sludge. J Chromatogr A 1085(2):179–189. doi:10.1016/j.chroma.2005.05.051

  23. Ternes TA, Bonerz M, Herrmann N, Loffler D, Keller E, Lacida BB, Alder AC (2005) Determination of pharmaceuticals, iodinated contrast media and musk fragrances in sludge by LC/tandem MS and GC/MS. J Chromatogr A 1067(1–2):213–223. doi:10.1016/j.chroma.2004.10.096

  24. Radjenovic J, Jelic A, Petrovic M, Barcelo D (2009) Determination of pharmaceuticals in sewage sludge by pressurized liquid extraction (PLE) coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS). Anal Bioanal Chem 393(6–7):1685–1695. doi:10.1007/s00216-009-2604-4

  25. Herrero M, Martin-Alvarez PJ, Senorans FJ, Cifuentes A, Ibanez E (2005) Optimization of accelerated solvent extraction of antioxidants from Spirulina platensis microalga. Food Chem 93(3):417–423. doi:10.1016/j.foodchem.2004.09.037

    Article  CAS  Google Scholar 

  26. Runnqvist H, Bak SA, Hansen M, Styrishave B, Halling-Sorensen B, Bjorklund E (2010) Determination of pharmaceuticals in environmental and biological matrices using pressurised liquid extraction—are we developing sound extraction methods? J Chromatogr A 1217(16):2447–2470. doi:10.1016/j.chroma.2010.02.046

    Article  CAS  Google Scholar 

  27. Wang S, Cyronak M, Yang E (2007) Does a stable isotopically labeled internal standard always correct analyte response? A matrix effect study on a LC/MS/MS method for the determination of carvedilol enantiomers in human plasma. J Pharm Biomed 43(2):701–707. doi:10.1016/j.jpba.2006.08.010

    Article  CAS  Google Scholar 

  28. JCGM 100:2008. GUM 1995 with minor corrections. Evaluation of measurement data — Guide to the expression of uncertainty in measurement (2008)

  29. Stoob K, Singer HP, Stettler S, Hartmann N, Mueller SR, Stamm CH (2006) Exhaustive extraction of sulfonamide antibiotics from aged agricultural soils using pressurized liquid extraction. J Chromatogr A 1128(1–2):1–9. doi:10.1016/j.chroma.2006.06.048

    Article  CAS  Google Scholar 

  30. Reid BJ, Pickering FL, Freddo A, Whelan MJ, Coulon F (2013) Influence of biochar on isoproturon partitioning and bioaccessibility in soil. Environ Pollut 181:44–50. doi:10.1016/j.envpol.2013.05.042

    Article  CAS  Google Scholar 

  31. Yu XY, Ying GG, Kookana RS (2009) Reduced plant uptake of pesticides with biochar additions to soil. Chemosphere 76(5):665–671. doi:10.1016/j.chemosphere.2009.04.001

    Article  CAS  Google Scholar 

  32. Nieto A, Borrull F, Pocurull E, Marce RM (2010) Occurrence of pharmaceuticals and hormones in sewage sludge. Environ Toxicol Chem 29(7):1484–1489. doi:10.1002/etc.188

  33. Okuda T, Yamashita N, Tanaka H, Matsukawa H, Tanabe K (2009) Development of extraction method of pharmaceuticals and their occurrences found in Japanese wastewater treatment plants. Environ Int 35(5):815–820. doi:10.1016/j.envint.2009.01.006

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors thank the financial support from the German Federal Ministry of Economics and Technology within the agenda for the promotion of industrial cooperative research and development (IGF) based on a decision of the German Bundestag. The access was opened by member organization environmental technology and organized by the AiF, Arbeitsgemeinschaft industrieller Forschungsvereinigungen, Cologne (IGF-Project No. 16723 N).

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Authors and Affiliations

  1. Institut für Energie und Umwelttechnik e. V., Institute of Energy and Environmental Technology (IUTA), Bliersheimer Str. 58-60, 47229, Duisburg, Germany

    C. vom Eyser & J. Tuerk

  2. Instrumental Analytical Chemistry, University of Duisburg-Essen, Universitätsstr. 5, 45141, Essen, Germany

    C. vom Eyser & T. C. Schmidt

  3. Hamburg University of Technology (TUHH), Eißendorfer Str. 42, 21073, Hamburg, Germany

    K. Palmu & R. Otterpohl

  4. Centre for Water and Environmental Research (ZWU), University of Duisburg-Essen, Universitätsstraße 2, 45141, Essen, Germany

    T. C. Schmidt & J. Tuerk

Authors
  1. C. vom Eyser
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  4. T. C. Schmidt
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Correspondence to J. Tuerk.

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Published in the topical collection celebrating ABCs 13th Anniversary.

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vom Eyser, C., Palmu, K., Otterpohl, R. et al. Determination of pharmaceuticals in sewage sludge and biochar from hydrothermal carbonization using different quantification approaches and matrix effect studies. Anal Bioanal Chem 407, 821–830 (2015). https://doi.org/10.1007/s00216-014-8068-1

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  • DOI: https://doi.org/10.1007/s00216-014-8068-1

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