Skip to main content
Log in

Simultaneous determination of fourteen pharmaceuticals in sewage sludge using online solid-phase extraction-liquid chromatography-tandem mass spectrometry combined with accelerated solvent extraction

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

Abstract

An online solid-phase extraction (SPE) liquid chromatography tandem mass spectrometry method (HPLC-MS/MS) combined with accelerated solvent extraction (ASE) was developed for simultaneous determination of 14 pharmaceuticals in sludge. In the online SPE procedures, ultrapure water with no additives was used as the loading solvent. In addition, low molecular weight targets such as atenolol were difficult to retain on SPE column after acetone was added to the washing solvent. The response signal of analytes can be greatly improved by adding 0.2% formic acid to the mobile phase. Under the optimized conditions, the recoveries of all the analytes ranged between 75.1 and 112%. Moreover, the limit of detections ranged from 1.8 to 7.9 ug/kg. The precision of analytical data was determined with relative standard deviation (RSD) ≤ 4.87%. This method was successfully applied to determine the concentration of pharmaceuticals in sludge.

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

Access this article

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

Instant access to the full article PDF.

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

Similar content being viewed by others

Data availability

The manuscript has data included as electronic supplementary material.

References

  • Badawy MEI, El-Nouby MAM, Kimani PK, Lim LW, Rabea EI (2022) A review of the modern principles and applications of solid-phase extraction techniques in chromatographic analysis. Anal Sci 38(12):1457–1487

    Article  CAS  Google Scholar 

  • Bean TG, Chadwick EA, Herrero-Villar M, Mateo R, Naidoo V, Ratter B (2022) Do pharmaceuticals in the environment pose a risk to wildlife? Environ Toxicol Chem, Article 20221118.

  • Belay MH, Precht U, Mortensen P, Marengo E, Robotti E (2022) A fully automated online SPE-LC-MS/MS method for the determination of 10 pharmaceuticals in wastewater samples. Toxics 10(3), 103.

  • Boix C, Ibanez M, Sancho JV, Rambla J, Aranda JL, Ballester S, Hernandez F (2015) Fast determination of 40 drugs in water using large volume direct injection liquid chromatography-tandem mass spectrometry. Talanta 131:719–727

    Article  CAS  Google Scholar 

  • Canadas R, Garcinuno Martinez RM, Paniagua Gonzalez G, Fernandez Hernando P (2022) Development of a molecularly imprinted polymeric membrane for determination of macrolide antibiotics from cow milk. Polymer 249, 124843.

  • Carretero V, Blasco C, Pico Y (2008) Multi-class determination of antimicrobials in meat by pressurized liquid extraction and liquid chromatography-tandem mass spectrometry. J Chromatogr A 1209(1–2):162–173

    Article  CAS  Google Scholar 

  • Chan CL, Wai HKF, Wu P, Lai SW, Chan OSK, Tun HM (2022) A universal LC-MS/MS method for simultaneous detection of antibiotic residues in animal and environmental samples. Antibiotics-Basel 11(7):845

    Article  CAS  Google Scholar 

  • Chen LG, Wang H, Zeng QL, Xu Y, Sun L, Xu HY, Ding L (2009) On-line coupling of solid-phase extraction to liquid chromatography-a review. J Chromatogr Sci 47(8):614–623

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Dagot C (2018) Pharmaceuticals in the environment and their treatment in wastewater treatment plants. Environ Risque & Sante 17:47–58

    Google Scholar 

  • De Mastro F, Cacace C, Traversa A, Pallara M, Cocozza C, Mottola F, Brunetti G (2022) Influence of chemical and mineralogical soil properties on the adsorption of sulfamethoxazole and diclofenac in Mediterranean soils. Chem Biol Technol Agricult 9(1):34

    Article  Google Scholar 

  • Demirhan BE, Demirhan B (2022) Detection of antibiotic residues in blossom honeys from different regions in Turkey by LC-MS/MS method. Antibiotics-Basel 11(3):357

    Article  Google Scholar 

  • Diaz-Cruz MS, Lopez de Alda MJ, Barcelo D (2006) Determination of antimicrobials in sludge from infiltration basins at two artificial recharge plants by pressurized liquid extraction-liquid chromatography-tandem mass spectrometry. J Chromatogr A 1130(1):72–82

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Dugheri S, Mucci N, Bonari A, Marrubini G, Cappelli G, Ubiali D, Campagna M, Montalti M, Arcangeli G (2020) Solid phase microextraction techniques used for gas chromatography: a review. Acta Chromatogr 32(1):1–9

    Article  Google Scholar 

  • Hennion MC (1999) Solid-phase extraction: method development, sorbents, and coupling with liquid chromatography. J Chromatogr A 856(1–2):3–54

    Article  CAS  Google Scholar 

  • Hyotylainen T (2007) Principles, developments and applications of on-line coupling of extraction with chromatography. J Chromatogr A 1153(1–2):14–28

    Article  Google Scholar 

  • Idder S, Ley L, Mazellier P, Budzinski H (2013) Quantitative on-line preconcentration-liquid chromatography coupled with tandem mass spectrometry method for the determination of pharmaceutical compounds in water. Anal Chim Acta 805:107–115

    Article  CAS  Google Scholar 

  • Jacobsen AM, Halling-Sorensen B (2006) Multi-component analysis of tetracyclines, sulfonamides and tylosin in swine manure by liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem 384(5):1164–1174

    Article  CAS  Google Scholar 

  • Johnson GR (2022) PFAS in soil and groundwater following historical land application of biosolids. Water Res 211, 118035.

  • Khan GA, Lindberg R, Grabic R, Fick J (2012) The development and application of a system for simultaneously determining anti-infectives and nasal decongestants using on-line solid-phase extraction and liquid chromatography-tandem mass spectrometry. J Pharm Biomed Anal 66:24–32

    Article  CAS  Google Scholar 

  • Khasawneh OFS, Palaniandy P (2021) Occurrence and removal of pharmaceuticals in wastewater treatment plants. Process Saf Environ Prot 150:532–556

    Article  CAS  Google Scholar 

  • Kinney CA, Furlong ET, Zaugg SD, Burkhardt MR, Werner SL, Cahill JD, Jorgensen GR (2006) Survey of organic wastewater contaminants in biosolids destined for land application. Environ Sci Technol 40(23):7207–7215

    Article  CAS  Google Scholar 

  • Kumar M, Sridharan S, Sawarkar AD, Shakeel A, Anerao P, Mannina G, Sharma P, Pandey A (2023) Current research trends on emerging contaminants pharmaceutical and personal care products (PPCPs): a comprehensive review. Sci Total Environ 859(Pt 1):160031–160031

    Article  CAS  Google Scholar 

  • Kunene P, Mahlambi P (2022) Assessment of antiretroviral drugs in vegetables: evaluation of microwave-assisted extraction performance with and without solid-phase extraction cleanup. Separation Science Plus 6(2), Article 20221216

  • Li F, Luo JW, Zhu BQ, Liu Z (2022) Pretreatment methods for the determination of antibiotics residues in food samples and detected by liquid chromatography coupled with mass spectrometry detectors: a review. J Chromatogr Sci 60(10):991–1003

    Article  CAS  Google Scholar 

  • Liang YS, Liu JQ, Zhong QS, Yu DB, Yao JT, Huang TH, Zhu MJ, Zhou T (2019) A fully automatic cross used solid-phase extraction online coupled with ultra-high performance liquid chromatography-tandem mass spectrometry system for the trace analysis of multi-class pharmaceuticals in water samples. J Pharm Biomed Anal 174:330–339

    Article  CAS  Google Scholar 

  • Licul-Kucera V, Ladanyi M, Hizsnyik G, Zaray G, Mihucz VG (2019) A filtration optimized on-line SPE-HPLC-MS/MS method for determination of three macrolide antibiotics dissolved and bound to suspended solids in surface water. Microchem J 148:480–492

    Article  CAS  Google Scholar 

  • Liu JL, Wong MH (2013) Pharmaceuticals and personal care products (PPCPs): a review on environmental contamination in China. Environ Int 59:208–224

    Article  CAS  Google Scholar 

  • Lu XF, Zhou Y, Zhang J, Ren YP (2019) Determination of multi-class antibiotic residues in compost by microwave-enhanced accelerated solvent extraction and ultra performance convergence chromatography with tandem mass spectrometry. J Sep Sci 42(6):1281–1288

    Article  CAS  Google Scholar 

  • Martin-Pozo L, de Alarcon-Gomez B, Rodriguez-Gomez R, Teresa Garcia-Corcoles M, Cipa M, Zafra-Gomez A (2019) Analytical methods for the determination of emerging contaminants in sewage sludge samples. A review. Talanta 192:508–533

    Article  CAS  Google Scholar 

  • Mohapatra S, Huang C-H, Mukherji S, Padhye LP (2016) Occurrence and fate of pharmaceuticals in WWTPs in India and comparison with a similar study in the United States. Chemosphere 159:526–535

    Article  CAS  Google Scholar 

  • Montemurro N, Postigo C, Chiron S, Barcelo D, Perez S (2019) Analysis and fate of 14 relevant wastewater-derived organic pollutants in long-term exposed soil. Anal Bioanal Chem 411(12):2687–2696

    Article  CAS  Google Scholar 

  • Morales S, Canosa P, Rodriguez I, Rubi E, Cela R (2005) Microwave assisted extraction followed by gas chromatography with tandem mass spectrometry for the determination of triclosan and two related chlorophenols in sludge and sediments. J Chromatogr A 1082(2):128–135

    Article  CAS  Google Scholar 

  • Panditi VR, Batchu SR, Gardinali PR (2013) Online solid-phase extraction-liquid chromatography-electrospray-tandem mass spectrometry determination of multiple classes of antibiotics in environmental and treated waters. Anal Bioanal Chem 405(18):5953–5964

    Article  CAS  Google Scholar 

  • Pang XY, Li HY, Yu H, Zhan MM, Ba LG, Ya HY (2019) A metal organic framework polymer monolithic column as a novel adsorbent for on-line solid phase extraction and determination of ursolic acid in Chinese herbal medicine. J Chromatogr B Analyt Technol Biomed Life Sci 1125, 121715.

  • Perez-Lemus N, Lopez-Serna R, Perez-Elvira SI, Barrado E (2022) Analysis of 60 pharmaceuticals and personal care products in sewage sludge by ultra-high performance liquid chromatography and tandem mass spectroscopy. Microchem J 175, 107148.

  • Ramos L (2012) Critical overview of selected contemporary sample preparation techniques. J Chromatogr A 1221:84–98

    Article  CAS  Google Scholar 

  • Richter BE, Jones BA, Ezzell JL, Porter NL, Avdalovic N, Pohl C (1996) Accelerated solvent extraction: a technique for sample preparation. Anal Chem 68(6):1033–1039

    Article  CAS  Google Scholar 

  • Santos T, Sommaggio LRD, Marin-Morales MA (2022) Phyto-genotoxicity assessment of different associations between sludges from water and sewage treatment plants, before and after the bioremediation process. Environ Sci Pollut Res 29(26):40029–40040

    Article  CAS  Google Scholar 

  • Seifrtova M, Novakova L, Lino C, Pena A, Solich P (2009) An overview of analytical methodologies for the determination of antibiotics in environmental waters. Anal Chim Acta 649(2):158–179

    Article  CAS  Google Scholar 

  • Sellier A, Khaska S, Salle CLGL (2022) Assessment of the occurrence of 455 pharmaceutical compounds in sludge according to their physical and chemical properties: a review. J Hazard Mater 426, 128104.

  • Sharma UK, Sharma N, Gupta AP, Kumar V, Sinha AK (2007) RP-HPTLC densitometric determination and validation of vanillin and related phenolic compounds in accelerated solvent extract of Vanilla planifolia. J Sep Sci 30(18):3174–3180

    Article  CAS  Google Scholar 

  • Sun SJ, Zhao ZB, Li B, Ma LX, Fu DL, Sun XZ, Thapa S, Shen JM, Qi H, Wu YN (2019) Occurrence, composition profiles and risk assessment of polycyclic aromatic hydrocarbons in municipal sewage sludge in China. Environ Pollut 245:764–770

    Article  CAS  Google Scholar 

  • Swiacka K, Maculewicz J, Kowalska D, Caban M, Smolarz K, Swiezak J (2022) Presence of pharmaceuticals and their metabolites in wild-living aquatic organisms - current state of knowledge. J Hazard Mater 424, 127350.

  • Verlicchi P, Al Aukidy M, Zambello E (2012) 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 

  • Wang CJ, Liu HJ, Chou T-C, Lin CC, Pan WH, Chen PC, Hsu JF (2022) Simultaneous determination of eight beta-adrenergic agonists in human urine by an isotope dilution-online clean-up system coupled with liquid chromatography-tandem mass spectrometry. Chemosphere 301, 134778.

  • Xu, X.Y., Zhu, B.Q., Liu, Z., Wang, F., Liang, J.J. 2019. Simultaneous determination of eight microcystins in fish by PRiME pass-through cleanup and online solid phase extraction coupled to ultra high performance liquid chromatography-tandem mass spectrometry. J Chromatogr B Analyt Technol Biomed Life Sci 1125, 121709.

  • Zhang Y, Guo CL, Liu HM, Yang L, Ren CY, Li T, Liu JX (2023) Multiplex quantitation of 17 drug-derived components in human plasma after administration of a fixed herbal preparation of Sailuotong using combined online SPE-LC-MS/MS methods. J Ethnopharmacol 302, 115843.

  • Zhang YZ, Wang B, Cagnetta G, Duan L, Yang J, Deng SB, Huang J, Wang YJ, Yu G (2018) Typical pharmaceuticals in major WWTPs in Beijing, China: occurrence, load pattern and calculation reliability. Water Res 140:291–300

    Article  CAS  Google Scholar 

  • Zheng GD, Yu B, Wang YW, Ma C, Chen TB (2021) Fate and biodegradation characteristics of triclocarban in wastewater treatment plants and sewage sludge composting processes and risk assessment after entering the ecological environment. J Hazard Mater 412, 125270.

  • Zhong MM, Wang TL, Qi CD, Peng GL, Lu ML, Huang J, Blaney L, Yu G (2019) Automated online solid-phase extraction liquid chromatography tandem mass spectrometry investigation for simultaneous quantification of per- and polyfluoroalkyl substances, pharmaceuticals and personal care products, and organophosphorus flame retardants in environmental waters. J Chromatogr A 1602:350–358

    Article  CAS  Google Scholar 

  • Zhou JH, Xue XF, Li Y, Zhang JZ, Chen F, Wu LM, Chen LZ, Zhao J (2009) Multiresidue determination of tetracycline antibiotics in propolis by using HPLC-UV detection with ultrasonic-assisted extraction and two-step solid phase extraction. Food Chem 115(3):1074–1080

    Article  CAS  Google Scholar 

  • Zhou Q, Wang N, Zhu LH, Tang HQ (2015) A fully automatic HPLC-CAD-DAD method coupled with ASE and online SPE for simultaneous determination of seven antibiotics in bio-matrices. Chromatographia 78(23–24):1475–1484

    Article  CAS  Google Scholar 

  • Zou JM, Yao B, Yan SW, Song WH (2022) Determination of trace organic contaminants by a novel mixed-mode online solid-phase extraction coupled to liquid chromatography-tandem mass spectrometry. Environ Pollut 303, 119112.

  • Zuloaga O, Navarro P, Bizkarguenaga E, Iparraguirre A, Vallejo A, Olivares M, Prieto A (2012) Overview of extraction, clean-up and detection techniques for the determination of organic pollutants in sewage sludge: a review. Anal Chim Acta 736:7–29

    Article  CAS  Google Scholar 

Download references

Funding

This study was funded by the Natural National Science Foundation of China (51979066) and Open Project of State Key Laboratory of Urban Water Resource and Environment (Harbin Institute of Technology) (No. ES201804).

Author information

Authors and Affiliations

Authors

Contributions

Shaojing Sun: Conceptualization, methodology, writing—review and editing

Fan Meng: Validation

Hong Qi: Supervision, conceptualization

Corresponding author

Correspondence to Hong Qi.

Ethics declarations

Ethical approval

Not applicable

Consent to participate

Not applicable

Consent to publish

Not applicable

Competing interests

The authors declare no competing interests.

Additional information

Responsible Editor: Ester Heath

Publisher's note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 262 KB)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sun, S., Meng, F. & Qi, H. Simultaneous determination of fourteen pharmaceuticals in sewage sludge using online solid-phase extraction-liquid chromatography-tandem mass spectrometry combined with accelerated solvent extraction. Environ Sci Pollut Res 30, 62522–62531 (2023). https://doi.org/10.1007/s11356-023-26072-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-023-26072-8

Keywords

Navigation