This study developed and validated a method for simultaneously determining DEP
and 11 PCPs in fish muscle and livers. Although the cleanup was not so effective on liver
samples, the method offered reproducible analytical results on all analytes with %RSD
below 20% and accurate analytical results on most of the analytes with quantitative biases
below 30% by using isotope dilution techniques. In addition, the LODs of most analytes
ranged from to sub-ng/g to tens of ng/g w.w., and some LODs were lower than those in
other previous reports, indicating that better sensitivity was acquired for some analytes.
Furthermore, the MSPD method consumed only small volumes of organic solvents and
did not need expensive devices for extraction. The developed method is able to be applied
to the determination of these compounds in wild fish samples to acquire more information
about the levels of these chemicals in fish tissues and possible health effects on fish.
Since the cleanup effect on liver samples was not ideal with silica gel, the protocol
for preparing liver samples was more complicated than that for muscle samples. Further
studies are desired to improve the cleanup, for example, elimination of lipids by freezing
them in, or tests of other adsorbents such as Enhanced Matrix Removal-Lipid
(EMR-Lipid).
Reference
1. Mankidy, R., Wiseman, S., Ma, H., and Giesy, J.P., Biological impact of phthalates. Toxicol Lett, 2013. 217(1): p. 50-58.
2. Brausch, J.M. and Rand, G.M., A review of personal care products in the aquatic environment: environmental concentrations and toxicity. Chemosphere, 2011.
82(11): p. 1518-1532.
3. Daughton, C.G. and Ternes, T.A., Pharmaceuticals and personal care products in the environment: Agents of subtle change? Environ Health Persp, 1999. 107: p.
906-938.
4. Jackson, J. and Sutton, R., Sources of endocrine-disrupting chemicals in urban wastewater, Oakland, CA. Sci Total Environ, 2008. 405(1-3): p. 153-160.
5. Ramirez, A.J., Brain, R.A., Usenko, S., Mottaleb, M.A., O'Donnell, J.G., Stahl, L.L., Wathen, J.B., Snyder, B.D., Pitt, J.L., Perez-Hurtado, P., Dobbins, L.L., Brooks, B.W., and Chambliss, C.K., Occurrence of pharmaceuticals and personal care products in fish: results of national pilot study in the United States. Environ Toxicol Chem, 2009. 28(12): p. 2587-2597.
6. Du, B., Haddad, S.P., Luek, A., Scott, W.C., Saari, G.N., Kristofco, L.A., Connors, K.A., Rash, C., Rasmussen, J.B., Chambliss, C.K., and Brooks, B.W., Bioaccumulation and trophic dilution of human pharmaceuticals across trophic positions of an effluent-dependent wadeable stream. Philos Trans R Soc Lond B Biol Sci, 2014. 369(1656): p. 10.
7. Feng, Y.L., Liao, X., Grenier, G., Nguyen, N., and Chan, P., Determination of 18 phthalate metabolites in human urine using a liquid chromatography-tandem mass spectrometer equipped with a core–shell column for rapid separation. Anal Methods-UK, 2015. 7(19): p. 8048-8059.
8. Schettler, T., Human exposure to phthalates via consumer products. Int J Androl, 2006. 29(1): p. 134-139.
9. Net, S., Sempere, R., Delmont, A., Paluselli, A., and Ouddane, B., Occurrence, fate, behavior and ecotoxicological state of phthalates in different environmental matrices. Environ Sci Technol, 2015. 49(7): p. 4019-4035.
10. Kong, M., Song, Y., Zhang, Y., Liu, R., Wei, J., and Zheng, L., Fate of phthalate esters in municipal wastewater treatment plant and their environmental impact.
Water Sci Technol, 2016. 73(6): p. 1395-400.
Adeniyi, A., Phthalate ester plasticizers in freshwater systems of Venda, South Africa and potential health effects. Water Sa, 2010. 36(1): p. 117-125.
12. Yuan, S.Y., Liu, C., Liao, C.S., and Chang, B.V., Occurrence and microbial degradation of phthalate esters in Taiwan river sediments. Chemosphere, 2002.
49(10): p. 1295-1299.
13. Zeng, F., Cui, K., Xie, Z., Liu, M., Li, Y., Lin, Y., Zeng, Z., and Li, F., Occurrence of phthalate esters in water and sediment of urban lakes in a subtropical city, Guangzhou, South China. Environ Int, 2008. 34(3): p. 372-380.
14. Huang, P.C., Tien, C.J., Sun, Y.M., Hsieh, C.Y., and Lee, C.C., Occurrence of phthalates in sediment and biota: relationship to aquatic factors and the biota-sediment accumulation factor. Chemosphere, 2008. 73(4): p. 539-544.
15. Valton, A.S., Serre-Dargnat, C., Blanchard, M., Alliot, F., Chevreuil, M., and Teil, M.J., Determination of phthalates and their by-products in tissues of roach (Rutilus rutilus) from the Orge river (France). Environ Sci Pollut Res Int, 2014.
21(22): p. 12723-12730.
16. Chen, X., Xu, S., Tan, T., Lee, S.T., Cheng, S.H., Lee, F.W., Xu, S.J., and Ho, K.C., Toxicity and estrogenic endocrine disrupting activity of phthalates and their mixtures. Int J Environ Res Public Health, 2014. 11(3): p. 3156-3168.
17. Staples, C.A., Peterson, D.R., Parkerton, T.F., and Adams, W.J., The environmental fate of phthalate esters: A literature review. Chemosphere, 1997.
35(4): p. 667-749.
18. Arnot, J.A. and Gobas, F.A.P.C., A review of bioconcentration factor (BCF) and bioaccumulation factor (BAF) assessments for organic chemicals in aquatic organisms. Environ Rev, 2006. 14(4): p. 257-297.
19. Miege, C., Choubert, J.M., Ribeiro, L., Eusebe, M., and Coquery, M., Fate of pharmaceuticals and personal care products in wastewater treatment plants--conception of a database and first results. Environ Pollut, 2009. 157(5): p. 1721-1726.
20. Oulton, R.L., Kohn, T., and Cwiertny, D.M., Pharmaceuticals and personal care products in effluent matrices: A survey of transformation and removal during wastewater treatment and implications for wastewater management. J Environ Monit, 2010. 12(11): p. 1956-1978.
21. Verlicchi, P., Al Aukidy, M., and Zambello, E., Occurrence of pharmaceutical compounds in urban wastewater: removal, mass load and environmental risk after
22. Blair, B.D., Crago, J.P., Hedman, C.J., Treguer, R.J., Magruder, C., Royer, L.S., and Klaper, R.D., Evaluation of a model for the removal of pharmaceuticals, personal care products, and hormones from wastewater. Sci Total Environ, 2013.
444: p. 515-521.
23. Blair, B.D., Crago, J.P., Hedman, C.J., and Klaper, R.D., Pharmaceuticals and personal care products found in the Great Lakes above concentrations of environmental concern. Chemosphere, 2013. 93(9): p. 2116-2123.
24. Subedi, B., Du, B., Chambliss, C.K., Koschorreck, J., Rudel, H., Quack, M., Brooks, B.W., and Usenko, S., Occurrence of pharmaceuticals and personal care products in German fish tissue: A national study. Environ Sci Technol, 2012.
46(16): p. 9047-9054.
25. Yang, Y., Ok, Y.S., Kim, K.H., Kwon, E.E., and Tsang, Y.F., Occurrences and removal of pharmaceuticals and personal care products (PPCPs) in drinking water and water/sewage treatment plants: A review. Sci Total Environ, 2017. 596-597:
p. 303-320.
26. Xie, Z., Lu, G., Liu, J., Yan, Z., Ma, B., Zhang, Z., and Chen, W., Occurrence, bioaccumulation, and trophic magnification of pharmaceutically active compounds in Taihu Lake, China. Chemosphere, 2015. 138: p. 140-147.
27. Moreno-Gonzalez, R., Rodriguez-Mozaz, S., Huerta, B., Barcelo, D., and Leon, V.M., Do pharmaceuticals bioaccumulate in marine molluscs and fish from a coastal lagoon? Environ Res, 2016. 146: p. 282-298.
28. Beydoun, M.A., Gamaldo, A.A., Beydoun, H.A., Tanaka, T., Tucker, K.L., Talegawkar, S.A., Ferrucci, L., and Zonderman, A.B., Caffeine and alcohol intakes and overall nutrient adequacy are associated with longitudinal cognitive performance among U.S. adults. J Nutr, 2014. 144(6): p. 890-901.
29. Alvarez-Munoz, D., Rodriguez-Mozaz, S., Maulvault, A.L., Tediosi, A., Fernandez-Tejedor, M., Van den Heuvel, F., Kotterman, M., Marques, A., and Barcelo, D., Occurrence of pharmaceuticals and endocrine disrupting compounds in macroalgaes, bivalves, and fish from coastal areas in Europe. Environ Res, 2015.
143(Pt B): p. 56-64.
30. Wang, J. and Gardinali, P.R., Analysis of selected pharmaceuticals in fish and the fresh water bodies directly affected by reclaimed water using liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem, 2012. 404(9): p.
2711-2720.
M.W., Is there a risk associated with the insect repellent DEET (N,N-diethyl-m-toluamide) commonly found in aquatic environments? Sci Total Environ, 2007.
384(1-3): p. 214-220.
32. Swale, D.R., Sun, B., Tong, F., and Bloomquist, J.R., Neurotoxicity and mode of action of N, N-diethyl-meta-toluamide (DEET). PLoS One, 2014. 9(8): p.
e103713.
33. Tanoue, R., Nomiyama, K., Nakamura, H., Kim, J.W., Isobe, T., Shinohara, R., Kunisue, T., and Tanabe, S., Uptake and tissue distribution of pharmaceuticals and personal care products in wild fish from treated-wastewater-impacted streams.
Environ Sci Technol, 2015. 49(19): p. 11649-11658.
34. Giokas, D.L., Salvador, A., and Chisvert, A., UV filters: From sunscreens to human body and the environment. TrAC-Trend Anal Chem, 2007. 26(5): p. 360-374.
35. Gago-Ferrero, P., Diaz-Cruz, M.S., and Barcelo, D., An overview of UV-absorbing compounds (organic UV filters) in aquatic biota. Anal Bioanal Chem, 2012. 404(9): p. 2597-2610.
36. Schlumpf, M., Cotton, B., Conscience, M., Haller, V., Steinmann, B., and Lichtensteiger, W., In vitro and in vivo estrogenicity of UV screens. Environ Health Persp, 2001. 109: p. 239-244.
37. Langford, K.H., Reid, M.J., Fjeld, E., Oxnevad, S., and Thomas, K.V., Environmental occurrence and risk of organic UV filters and stabilizers in multiple matrices in Norway. Environ Int, 2015. 80: p. 1-7.
38. Peng, X., Jin, J., Wang, C., Ou, W., and Tang, C., Multi-target determination of organic ultraviolet absorbents in organism tissues by ultrasonic assisted extraction and ultra-high performance liquid chromatography-tandem mass spectrometry. J Chromatogr A, 2015. 1384: p. 97-106.
39. Soni, M.G., Carabin, I.G., and Burdock, G.A., Safety assessment of esters of p-hydroxybenzoic acid (parabens). Food Chem Toxicol, 2005. 43(7): p. 985-1015.
40. Chen, J., Ahn, K.C., Gee, N.A., Gee, S.J., Hammock, B.D., and Lasley, B.L., Antiandrogenic properties of parabens and other phenolic containing small molecules in personal care products. Toxicol Appl Pharmacol, 2007. 221(3): p.
278-284.
41. Djatmika, R., Hsieh, C.C., Chen, J.M., and Ding, W.H., Determination of paraben preservatives in seafood using matrix solid-phase dispersion and on-line
1037: p. 93-99.
42. Teil, M.J., Tlili, K., Blanchard, M., Chevreuil, M., Alliot, F., and Labadie, P., Occurrence of polybrominated diphenyl ethers, polychlorinated biphenyls, and phthalates in freshwater fish from the Orge river (Ile-de France). Arch Environ Contam Toxicol, 2012. 63(1): p. 101-113.
43. Ji, Y., Wang, F., Zhang, L., Shan, C., Bai, Z., Sun, Z., Liu, L., and Shen, B., A comprehensive assessment of human exposure to phthalates from environmental media and food in Tianjin, China. J Hazard Mater, 2014. 279: p. 133-140.
44. Chen, C.L., Löfstrand, K., Adolfsson-Erici, M., and MacLeod, M., Determination of fragrance ingredients in fish by ultrasound-assisted extraction followed by purge & trap. Anal Methods-UK, 2017. 9(15): p. 2237-2245.
45. Gago-Ferrero, P., Diaz-Cruz, M.S., and Barcelo, D., Multi-residue method for trace level determination of UV filters in fish based on pressurized liquid extraction and liquid chromatography-quadrupole-linear ion trap-mass spectrometry. J Chromatogr A, 2013. 1286: p. 93-101.
46. Kannan, K., Reiner, J.L., Yun, S.H., Perrotta, E.E., Tao, L., Johnson-Restrepo, B., and Rodan, B.D., Polycyclic musk compounds in higher trophic level aquatic organisms and humans from the United States. Chemosphere, 2005. 61(5): p. 693-700.
47. Meinerling, M. and Daniels, M., A validated method for the determination of traces of UV filters in fish using LC-MS/MS. Anal Bioanal Chem, 2006. 386(5):
p. 1465-1473.
48. Cheng, Z., Nie, X.P., Wang, H.S., and Wong, M.H., Risk assessments of human exposure to bioaccessible phthalate esters through market fish consumption.
Environ Int, 2013. 57-58: p. 75-80.
49. Adeogun, A.O., Ibor, O.R., Omogbemi, E.D., Chukwuka, A.V., Adegbola, R.A., Adewuyi, G.A., and Arukwe, A., Environmental occurrence and biota concentration of phthalate esters in Epe and Lagos Lagoons, Nigeria. Mar Environ Res, 2015. 108: p. 24-32.
50. Sorensen, L.K., Determination of phthalates in milk and milk products by liquid chromatography/tandem mass spectrometry. Rapid Commun Mass Spectrom, 2006. 20(7): p. 1135-1143.
51. Xu, D., Deng, X., Fang, E., Zheng, X., Zhou, Y., Lin, L., Chen, L., Wu, M., and Huang, Z., Determination of 23 phthalic acid esters in food by liquid
56.
52. Carmona, E., Andreu, V., and Pico, Y., Multi-residue determination of 47 organic compounds in water, soil, sediment and fish-Turia River as case study. J Pharm Biomed Anal, 2017. 146: p. 117-125.
53. Liu, Y.Y., Hu, X.L., Bao, Y.F., and Yin, D.Q., Simultaneous determination of 29 pharmaceuticals in fish muscle and plasma by ultrasonic extraction followed by SPE-UHPLC-MS/MS. J Sep Sci, 2018. 41(10): p. 2139-2150.
54. Barker, S.A., Long, A.R., and Short, C.R., Isolation of drug residues from tissues by solid-phase dispersion J Chromatogr, 1989. 475: p. 353-361.
55. Barker, S.A., Matrix solid phase dispersion (MSPD). J Biochem Biophys Methods, 2007. 70(2): p. 151-162.
56. Capriotti, A.L., Cavaliere, C., Laganà, A., Piovesana, S., and Samperi, R., Recent trends in matrix solid-phase dispersion. TrAC-Trend Anal Chem, 2013. 43: p. 53-66.
57. Capriotti, A.L., Cavaliere, C., Foglia, P., Samperi, R., Stampachiacchiere, S., Ventura, S., and Laganà, A., Recent advances and developments in matrix solid-phase dispersion. TrAC-Trend Anal Chem, 2015. 71: p. 186-193.
58. Freitas, S., Serafim, F., and Lanças, F., Determination of target pesticide residues in tropical fruits employing matrix solid-phase dispersion (MSPD) extraction followed by high resolution gas chromatography. J Brazil Chem Soc, 2018. 29(5):
p. 1140-1148.
59. Ramirez, A.J., Mottaleb, M.A., Brooks, B.W., and Chambliss, C.K., Analysis of pharmaceuticals in fish using liquid chromatography-tandem mass spectrometry.
Anal Chem, 2007. 79(8): p. 3155-3163.
60. Mottaleb, M.A., Usenko, S., O'Donnell, J.G., Ramirez, A.J., Brooks, B.W., and Chambliss, C.K., Gas chromatography-mass spectrometry screening methods for select UV filters, synthetic musks, alkylphenols, an antimicrobial agent, and an insect repellent in fish. J Chromatogr A, 2009. 1216(5): p. 815-823.
61. Cao, X.L., Zhao, W., Churchill, R., and Hilts, C., Occurrence of Di-(2-ethylhexyl) adipate and phthalate plasticizers in samples of meat, fish, and cheese and their packaging films. J Food Prot, 2014. 77(4): p. 610-620.
62. Guerranti, C., Cau, A., Renzi, M., Badini, S., Grazioli, E., Perra, G., and Focardi, S.E., Phthalates and perfluorinated alkylated substances in Atlantic bluefin tuna (Thunnus thynnus) specimens from Mediterranean Sea (Sardinia, Italy): Levels
667.
63. 陳家揚、龍世俊。生活污水中個人保健品殘留化學物質之檢測技術建立研究
（2/4）。2008。行政院環保署報告編號 EPA-97-E3S4-02-02。
64. 陳家揚、龍世俊。生活污水中個人保健品殘留化學物質之檢測技術建立研究
（3/4）。2009。行政院環保署報告編號 EPA-98-E3-S4-02-03。
65. 陳家揚。生活污水中個人保健品殘留化學物質之檢測技術建立研究（4/4）。
2010。行政院環保署報告編號 EPA-99-E3-S4-02-02。
66. Tang, T.C., Determination of nitrated/oxygenated polycyclic aromatic hydrocarbons and personal care products in river water, sediment, fish muscle and liver with ultra-performance liquid chromatography/tandem mass spectrometry.
2015, Nationl Taiwan University.
67. 陳家揚。土壤底泥中農藥多環芳香烴酚類塑化劑有機錫調查計畫(2/2)。
2014。行政院環保署報告編號 EPA-103-1604-02-02。
68. Guo, Y. and Kannan, K., Challenges encountered in the analysis of phthalate esters in foodstuffs and other biological matrices. Anal Bioanal Chem, 2012.
404(9): p. 2539-2554.
69. Kwon, J.W., Armbrust, K.L., Vidal-Dorsch, D., Bay, S.M., and Xia, K., Determination of 17 alpha-ethynylestradiol, carbamazepine, diazepam, simvastatin, and oxybenzone in fish livers. J AOAC Int, 2009. 92(1): p. 359-369.
70. Guo, Y., Zhang, Z., Liu, L., Li, Y., Ren, N., and Kannan, K., Occurrence and profiles of phthalates in foodstuffs from China and their implications for human exposure. J Agric Food Chem, 2012. 60(27): p. 6913-6919.
Figures
Figure 1. Chromatograms of ESI+ of a chemical standard solution (0.5 µg/mL in methanol standard solution, injection 4 µL)
Acetaminophen Caffeine
DEET DEP Benzophenone
Oxybenzone
Figure 2. Chromatograms of ESI- of a chemical standard solution (0.5 µg/mL in methanol standard solution, injection 4 µ L)
In matrix blank In a spiked sample
Figure 3. Chromatograms of the first and second product ions of acetaminophen in liver Methyl paraben
Ethyl paraben
Propyl paraben Ketoprofen Butyl paraben
Ibuprofen
The first product ion
The second product ion
Figure 4. Signal intensities of DEP and basic PCPs with different organic mobile phases (0.25 µg/mL in methanol standard solution, injection 4 µL, n = 3)
Figure 5. Chromatograms of benzophenone with different organic mobile phases (0.25 0.00E+00
1.00E+06 2.00E+06 3.00E+06 4.00E+06 5.00E+06 6.00E+06 7.00E+06
Signal intensity
ACN Methanol
In acetonitrile
In methanol
Figure 6. Chromatograms of acetaminophen with different initial organic mobile phase proportions (0.25 µg/mL in methanol standard solution, injection 4 µL)
Figure 7. Signal intensities of acidic PCPs under different chromatographic conditions (1 0.00E+00
Figure 8. Chromatograms of ESI- with different chromatographic conditions (1 µg/mL in methanol standard solution, injection 4 µL)
Figure 9. Signal intensities of DEP and basic PCPs with different ionization source
Figure 10. Elution efficiencies (%) of analytes with different combinations of elution solvents on C18 non-endcapped adsorbent (n = 4)
Figure 11. Elution efficiencies (%) of analytes with different elution volumes at each
Figure 12. Elution efficiencies (%) of analytes with different combinations of elution solvents on alumina cartridge (n = 4)
0 20 40 60 80 100 120
Elution efficiency (%)
Methanol/acetone Methanol/DCM
0 20 40 60 80 100 120
Elution efficiency (%)
C18 C8
Figure 14. Elution efficiency (%) of analytes from different cleanup adsorbents (n = 4)
Figure 15. Background levels of DEP and benzophenone using the silica gel with and 0
Figure 16. Peak areas of analytes using the silica gel with and without pre-wash step (n = 4)
1 g of silica gel 2 g of silica gel
Figure 17. Appearance of eluents of liver samples using different amount of silica gel for 0.00E+00
5.00E+04 1.00E+05 1.50E+05 2.00E+05 2.50E+05
Peak areas
Not washed Washed
Figure 18. Peak areas of analytes in the 500-μL final residues of liver samples (original samples) and their two-fold dilution samples (n = 4) ((A): the analytes with areas over 50,000; (B): the analytes with areas below 50,000)
0.00E+00
Figure 19. Matrix effect factors (%) of analytes in matrices(n = 4)
Tables
Table 1. Chemical structures and molecular weights of analytes Compounds Molecular
weight
Structure
Diethyl phthalate 222.2
Acetaminophen 151.16
Caffeine 194.19
DEET 191.27
Benzophenone 182.22
Oxybenzone 228.24
Methyl paraben 152.15
Ethyl paraben 166.17
Propyl paraben 180.2
Butyl paraben 194.23
Ketoprofen 254.28
Ibuprofen 206.28
Table 2. The LC conditions of separating analytes
Table 3. Tandem mass parameters
Compounds
Cone voltages (V)
Precursor ion > product ion I (collision energy, V), product ion II (collision energy, V)
Table 4. Different chromatographic conditions for ESI-
Table 5. Matrix effect factors (%) of analytes in matrices (mean ± SD, n = 4)
Table 6. Extraction efficiencies (%) of analytes in matrices (n = 4)
Compounds Muscle Liver
Table 7. IDLs, IQLs, linear ranges and r2 of calibration curves
Compounds IDL (pg) IQL (pg) Linear range
(ng/mL) r2
DEP 4.04 10.6 5-4000 0.998
Acetaminophen 8.52 9.57 5-4000 0.998
Caffeine 12.5 22.9 10-4000 0.999
DEET 0.43 1.03 5-4000 0.993
Benzophenone 17.3 37.1 10-4000 0.999
Oxybenzone 0.64 1.95 1-4000 0.999
Methyl paraben 7.63 7.63 5-4000 0.999
Ethyl paraben 2.54 2.54 1-4000 0.999
Propyl paraben 1.29 2.14 5-4000 0.999
Butyl paraben 5.07 5.07 1-4000 0.999
Ketoprofen 47.7 159 50-4000 0.996
Ibuprofen 2.86 9.53 5-4000 0.999
Table 8. The limits of detection (LODs) and limits of quantification (LOQs) (mean ± SD, ng/g w.w. (ng/g d.w.), n = 4)
Muscle Liver
LOD LOQ LOD LOQ
DEP 1.40 ± 0.59 (6.51 ± 2.73) 5.52 ± 0.71 (25.7 ± 3.30) 14.8 ± 4.13 (45.4 ± 12.6) 46.2 ± 7.49 (141 ± 22.9) Acetaminophen 15.0 ± 3.59 (69.9 ± 16.7) 34.9 ± 9.27 (163 ± 43.1) 20.8 ± 10.8 (63.6 ± 32.9) 108 ± 27.9 (331 ± 85.3)
Caffeine 1.22 ± 0.27 (5.68 ± 1.26) 2.18 ± 0.47 (10.1 ± 2.19) 14.7 ± 2.62 (45.0 ± 8.00) 21.1 ± 7.79 (64.6 ± 23.8) DEET 0.57 ± 0.17 (2.65 ± 0.79) 1.04 ± 0.04 (4.86 ± 0.17) 4.37 ± 1.43 (13.4 ± 4.37) 10.6 ± 3.08 (32.5 ± 9.43) Benzophenone 5.66 ± 1.45 (26.3 ± 6.75) 9.18 ± 3.23 (42.7 ± 15.0) 104 ± 19.1 (319 ± 58.3) 281 ± 104 (861 ± 318)
Oxybenzone 1.26 ± 0.74 (5.88 ± 3.45) 1.26 ± 0.58 (5.87 ± 2.71) 6.79 ± 1.73 (20.8 ± 5.29) 16.6 ± 5.78 (50.7 ± 17.7) Methyl paraben 1.24 ± 0.23 (5.79 ± 1.08) 1.57 ± 0.61 (7.29 ± 2.86) 8.18 ± 2.06 (25.0 ± 6.32) 10.6 ± 5.29 (32.4 ± 16.2) Ethyl paraben 0.85 ± 0.23 (3.94 ± 1.08) 2.58 ± 0.90 (12.0 ± 4.20) 25.2 ± 13.1 (77.0 ± 40.1) 38.4 ± 9.12 (118 ± 27.9) Propyl paraben 1.90 ± 0.63 (8.84 ± 2.91) 4.91 ± 0.45 (22.8 ± 2.10) 19.3 ± 12.5 (59.0 ± 38.2) 19.5 ± 7.42 (59.7 ± 22.7) Butyl paraben 1.63 ± 0.36 (7.60 ± 1.67) 3.55 ± 2.28 (16.5 ± 10.6) 43.0 ± 16.1 (132 ± 49.3) 43.0 ± 16.1 (132 ± 49.3) Ketoprofen 4.48 ± 0.61 (20.8 ± 2.86) 14.9 ± 2.05 (69.4 ± 9.54) 57.2 ± 20.9 (175 ± 64.0) 191 ± 69.7 (584 ± 213)
Ibuprofen 1.20 ± 0.14 (5.57 ± 0.67) 3.99 ± 0.48 (18.6 ± 2.25) 6.81 ± 2.29 (20.8 ± 7.00) 22.7 ± 7.63 (69.4 ± 23.3)
Table 9. Accuracy and precision in fish muscle and liver (n = 4)
Muscle Liver
Spiked level (ng/g) 62.5 200 500 1000
Compounds % RSD % Bias % RSD % Bias % RSD % Bias % RSD % Bias
DEP 16.9% 73.2% 5.69% -6.43% 3.91% -25.3% 3.00% -12.2%
Acetaminophen 2.80% -7.12% 1.33% -4.81% 2.31% -8.70% 6.98% 6.64%
Caffeine 4.30% -3.88% 2.38% -0.47% 3.12% -7.13% 2.82% 4.62%
DEET 3.60% 11.4% 0.86% 11.4% 3.64% 4.80% 1.05% 11.0%
Benzophenone 6.71% 99.8% 4.60% 27.2% 10.7% 0.78% 2.89% 4.98%
Oxybenzone 5.52% 4.75% 5.36% 2.64% 4.82% -6.29% 6.39% -13.3%
Methyl paraben 2.38% 33.6% 1.74% 37.1% 2.19% 27.1% 7.94% 1.12%
Ethyl paraben 4.46% 2.20% 2.36% -5.37% 2.27% -13.8% 2.34% -0.46%
Propyl paraben 6.87% -34.4% 3.13% -42.4% 3.72% -34.1% 4.97% 7.20%
Butyl paraben 12.2% -14.0% 3.84% -23.9% 2.05% -27.6% 5.10% -6.72%
Ketoprofen 4.82% 7.41% 5.22% 3.93% 3.90% 7.77% 14.8% -21.1%
Ibuprofen 2.75% -1.47% 1.93% -1.86% 1.44% -6.79% 1.84% -2.18%