Fluorescent kinetics combined with fourth-order calibration for the determination of diclofenac sodium in environmental water
A method that combines five-way fluorescence kinetics with fourth-order calibration for interference-free quantification of diclofenac sodium in river water was proposed and tested. Traditional fluorescence methods may not be suitable for such measurements since the fluorescence properties of the analyte are highly dependent on both pH and irradiation time in situ. In the method considered here, a five-way emission-excitation-time-pH data array was obtained from the samples by introducing the pH level and irradiation time as two extra modes. Then the data array was resolved by three fourth-order calibration algorithms: alternating fitting weighted residue quinquelinear decomposition (AFWRQQLD), five-way parallel factor analysis (five-PARAFAC), and alternating quinquelinear decomposition (AQQLD). The average recoveries and detection limits calculated for diclofenac sodium in a set of analyte-spiked river water samples using AFWRQQLD, five-PARAFAC, and AQQLD were 97.2 ± 3.2% and 1.9 ng mL−1, 96.8 ± 3.0% and 4.0 ng mL−1, and 92.6 ± 2.7% and 2.5 ng mL−1, respectively. A study of other figures of merit, statistical analysis, an elliptical joint confidence region test, and a t-test were additionally carried out to validate the analytical performance of the proposed method in detail. The results demonstrated that this new method required only two steps (fluorescence measurement and algorithm analysis) to determine the analyte concentration. It could therefore provide the basis for developing novel reliable and sensitive approaches for the accurate detection of pharmaceutical pollutants with unstable fluorescence properties in real complex matrices such as environmental water samples.
KeywordsEnvironmental monitoring Drug analysis Fluorescence kinetics High-order calibration Diclofenac sodium
The authors would like to acknowledge financial support from the National Natural Science Foundation of China (nos. 21765007, 21665002, and 21565012), Guangxi Key Research and Development Project (no. GuikeAB17129003), and Project of High Level Innovation Team/Outstanding Scholar and Key Laboratory of Food Safety and Detection in Guangxi Colleges and Universities (no. 2015GXNSFFA139005). They are also grateful to Dr. Amit Fischer of the Hebrew University of Jerusalem for helping to revise the manuscript, especially the grammar.
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflicts of interest.
- 1.Hofmann J, Freier U, Wecks M, Hohmann S. Degradation of diclofenac in water by heterogeneous catalytic oxidation with H2O2. Appl Catal B Environ. 2007;70(1):447–51. https://doi.org/10.1016/j.apcatb.2005.11.023.
- 2.Schwarzenbach RP, Escher BI, Fenner K, Hofstetter TB, Johnson CA, Gunten U, et al. The challenge of micropollutants in aquatic systems. Science. 2006;313(5790):1072–7. https://doi.org/10.1126/science.1127291.
- 3.Ma L, Liu Y, Zhang J, Yang Q, Li G, Zhang D. Impacts of irrigation water sources and geochemical conditions on vertical distribution of pharmaceutical and personal care products (PPCPs) in the vadose zone soils. Sci Total Environ. 2018;626:1148–56. https://doi.org/10.1016/j.scitotenv.2018.01.168.CrossRefGoogle Scholar
- 6.Tamura I, Yasuda Y, Kagota KI, Yoneda S, Nakada N, Kumar V, et al. Contribution of pharmaceuticals and personal care products (PPCPs) to whole toxicity of water samples collected in effluent-dominated urban streams. Ecotox Environ Safe. 2017;144:338–50. https://doi.org/10.1016/j.ecoenv.2017.06.032.
- 8.Roberts J, Kumar A, Du J, Hepplewhite C, Ellis DJ, Christy AG, et al. Pharmaceuticals and personal care products (PPCPs) in Australia’s largest inland sewage treatment plant, and its contribution to a major Australian river during high and low flow. Sci Total Environ. 2016;541(3):1625–37. https://doi.org/10.1016/j.scitotenv.2015.03.145.
- 9.Kallenborn R, Brorström-Lundén E, Reiersen LO, Wilson S. Pharmaceuticals and personal care products (PPCPs) in Arctic environments: indicator contaminants for assessing local and remote anthropogenic sources in a pristine ecosystem in change. Environ Sci Pollut Res Int. 2018;25(33):33001–13. https://doi.org/10.1007/s11356-017-9726-6.
- 10.Dai G, Wang B, Fu C, Dong R, Huang J, Deng S, et al. Pharmaceuticals and personal care products (PPCPs) in urban and suburban rivers of Beijing, China: occurrence, source apportionment and potential ecological risk. Environ Sci Process Impacts. 2016;18(4):445–55. https://doi.org/10.1039/c6em00018e.
- 13.Rolando B, Lazzarato L, Donnola M, Marini E, Joseph S, Morini G. Pozzoli. C, Fruttero R, Gasco A. Water-soluble nitric-oxide-releasing acetylsalicylic acid (ASA) prodrugs. ChemMedChem. 2013;8(7):1199–209. https://doi.org/10.1002/cmdc.201300105.
- 17.Johnson AC, Dumont E, Williams RJ, Oldenkamp R, Cisowska I, Sumpter JP. Do concentrations of ethinylestradiol, estradiol, and diclofenac in European rivers exceed proposed EU environmental quality standards? Environ Sci Technol. 2013;47(21):12297–304. https://doi.org/10.1021/es4030035.CrossRefGoogle Scholar
- 18.Pimenta AM, Araújo AN, Montenegro MCBSM. Simultaneous potentiometric and fluorimetric determination of diclofenac in a sequential injection analysis system. Anal Chim Acta. 2002;470(2):185–94. https://doi.org/10.1016/S0003-2670(02)00669-4.
- 19.Blom N, Sygusch J. Energetically favorable binding site determination between two molecules. USP 5866343. 1999.Google Scholar
- 20.Deng A, Himmelsbach M, Zhu QZ, Frey S, Sengl M, Buchberger W, et al. Residue analysis of the pharmaceutical diclofenac in different water types using ELISA and GC−MS. Environ Sci Technol. 2003;37(15):3422–9. https://doi.org/10.1021/es0341945.
- 21.Agüera A, Mezcua M, Mochol F, Vargas-Berenguel A, Fernández-Alba AR. Application of gas chromatography-hybrid chemical ionization mass spectrometry to the analysis of diclofenac in wastewater samples. J Chromatogr A. 2006;1133(1):287–92. https://doi.org/10.1016/j.chroma.2006.08.017.
- 22.Osorio V, Imbertbouchard M, Zonja B, Abad JL, Pérez S, Barceló D. Simultaneous determination of diclofenac, its human metabolites and microbial nitration/nitrosation transformation products in wastewaters by liquid chromatography/quadrupole-linear ion trap mass spectrometry. J Chromatogr A. 2014;1347(15):63–71. https://doi.org/10.1016/j.chroma.2014.04.058.CrossRefGoogle Scholar
- 24.Manzo V, Ulisse K, Rodríguez I, Pereira E, Richter P. A molecularly imprinted polymer as the sorptive phase immobilized in a rotating disk extraction device for the determination of diclofenac and mefenamic acid in wastewater. Anal Chim Acta. 2015;889:130–7. https://doi.org/10.1016/j.aca.2015.07.038.CrossRefGoogle Scholar
- 26.Lonappan L, Publicharla R, Rouissi T, Brar SK, Verma M, Surampalli RY, et al. Diclofenac in municipal wastewater treatment plant: quantification using laser diode thermal desorption--atmospheric pressure chemical ionization--tandem mass spectrometry approach in comparison with an established liquid chromatography-electrospray ionization-tandem mass spectrometry method. J Chromatogr A. 2016;1433:106–13. https://doi.org/10.1016/j.chroma.2016.01.030.
- 34.Bro R. Review on multiway analysis in chemistry: 2000–2005. Anal Chem. 2006;36(3–4):279–93. https://doi.org/10.1080/10408340600969965.
- 35.Bro R. Multi-way analysis in the food industry: models, algorithms, and applications. Doctoral thesis. Amsterdam: Universiteit van Amsterdam; 1998.Google Scholar
- 38.Maggio RM, Peña AMDL, Olivieri AC. Unfolded partial least-squares with residual quadrilinearization: a new multivariate algorithm for processing five-way data achieving the second-order advantage. Application to fourth-order excitation-emission-kinetic-pH fluorescence analytical data. Chemometr Intell Lab Syst. 2011;109(2):178–85. https://doi.org/10.1016/j.chemolab.2011.09.002.CrossRefGoogle Scholar
- 39.Zhu SH, Wu HL, Xia AL, Nie JF, Bian YC, Cai CB, et al. Excitation-emission-kinetic fluorescence coupled with third-order calibration for quantifying carbaryl and investigating the hydrolysis in effluent water. Talanta. 2009;77(5):1640–6. https://doi.org/10.1016/j.talanta.2008.09.052.
- 40.Kang C, Wu HL, Yu YJ, Liu YJ, Zhang SR, Zhang XH, et al. An alternative quadrilinear decomposition algorithm for four-way calibration with application to analysis of four-way fluorescence excitation-emission-pH data array. Anal Chim Acta. 2013;758(1):45–57. https://doi.org/10.1016/j.aca.2012.10.056.
- 42.Wu HL, Shibukawa M, Oguma K. An alternating trilinear decomposition algorithm with application to calibration of HPLC–DAD for simultaneous determination of overlapped chlorinated aromatic hydrocarbons. J Chemom. 1998;12(1):1–26. https://doi.org/10.1002/(SICI)1099-128X(199801/02)12:1<1::AID-CEM492>3.0.CO;2-4.CrossRefGoogle Scholar
- 43.Xia AL, Wu HL, Fang DM, Ding YJ, Hu LQ, Yu RQ. Alternating penalty trilinear decomposition algorithm for second-order calibration with application to interference-free analysis of excitation–emission matrix fluorescence data. J Chemom. 2010;19(2):65–76. https://doi.org/10.1002/cem.911.CrossRefGoogle Scholar
- 45.Jiang JH, Wu HL, Li Y, Yu RQ. Alternating coupled vectors resolution (ACOVER) method for trilinear analysis of three-way data. J Chemom. 2015;13(6):557–78. https://doi.org/10.1002/(SICI)1099-128X(199911/12)13:6<557::AID-CEM563>3.0.CO;2-C.CrossRefGoogle Scholar
- 47.Fu HY, Wu HL, Yu YJ, Yu LL, Zhang SR, Nie JF, et al. A new third-order calibration method with application for analysis of four-way data arrays. J Chemom. 2011;25(8):408–29. https://doi.org/10.1002/cem.1386.
- 48.Nie JF, Li B, Zhang Y, Fan JL, Yi ZS, Cai ZR. High-order calibration for the spectrofluorimetric determination of pesticides based on photochemical derivatization. A solution of the problems of inner-filter effects and matrix interferences in complex environmental water. Chemometr Intell Lab Syst. 2016;156:36–53. https://doi.org/10.1016/j.chemolab.2016.05.004.
- 50.Qing XD, Wu HL, Zhang XH, Li Y, Gu HW, Yu RQ. A novel fourth-order calibration method based on alternating quinquelinear decomposition algorithm for processing high performance liquid chromatography-diode array detection- kinetic-pH data of naptalam hydrolysis. Anal Chim Acta. 2015;861:12–24. https://doi.org/10.1016/j.aca.2014.12.037.CrossRefGoogle Scholar
- 51.Tomic I, Vidis-Millward A, Mueller-Zsigmondy M, Cardot JM. Setting accelerated dissolution test for PLGA microspheres containing peptide, investigation of critical parameters affecting drug release rate and mechanism. Int J Pharm. 2016;505:42–51. https://doi.org/10.1016/j.ijpharm.2016.03.048.CrossRefGoogle Scholar
- 52.Nie JF, Wu HL, Zhu SH, Han QJ, Fu HY, Li SF, et al. Simultaneous determination of 6-methylcoumarin and 7-methoxycoumarin in cosmetics using three-dimensional excitation-emission matrix fluorescence coupled with second-order calibration methods. Talanta. 2008;75(5):1260–9. https://doi.org/10.1016/j.talanta.2008.01.026.
- 55.Kozlowska M, Rodziewicz P, Utesch T, Mroginski MA, Kaczmarekkedziera A. Solvation of diclofenac in water from atomistic molecular dynamics simulations—interplay between solute-solute and solute-solvent interactions. Phys Chem Chem Phys. 2018;20(13):8629–39. https://doi.org/10.1039/C7CP08468D.