Recent advances in MSPD for the extraction of pesticide residues, PPCPs, inorganic and organometallic compounds

Caldas, Sergiane Souza; Rombaldi, Caroline; Cerqueira, Maristela Barnes R.; Soares, Bruno Meira; Primel, Ednei Gilberto

Palavras-chave: Sample preparation, complex samples, organic compounds, inorganic compounds, MSPD.

Resumo Determination of pesticides, Pharmaceuticals and Personal Care Products (PPCPs), inorganic compounds and organometalic species in solid, semi-solid and viscous samples have been carried out using a wide number of sample preparation techniques. Low cost, high efficiency, low consumption of solvent, besides the possibility of automation have been the target. The Matrix Solid Phase Dispersion (MSPD) technique seems to be an interesting alternative for the sample preparation. MSPD is based on the sample homogenization with a solid support, which acts as an abrasive, and promotes the disruption of the physical structure of the sample. MSPD shows as the main advantages the low consumption of solvent and the high extraction efficiency. Besides, there is the possibility to carry the clean-up and the extraction in only one step. This review presents the fundamentals and applications of MSPD for the determination of pesticides, PPCPs, inorganic and organometalics contaminants in different complex samples.

Referências Bibliográficas

1. Environmental Protection Agency – EPA. Pharmaceuticals and Personal Care Products as Pollutants (PPCPs). [cited 2013 Oct]. Available from:
2. Lanças FM. Avanços Recentes e Tendências Futuras das Técnicas de Separação: uma visão pessoal. Scientia Chromatographica 2008; 17-44.
3. Capriotti AL, Cavaliere C, Laganà A, Piovesana S, Samperi R. Recent trends in matrix solid-phase dispersion. TrAC Trends in Analytical Chemistry 2013.; 43(1):53-66. trac.2012.09.021
4. Barker SA, Long AR, Short CR. Isolation of drug residues from tissues by solid phase dispersion. Journal of Chromatography A 1989; 475(2):353-361.
5. Barker SA. Matrix solid-phase dispersion. Journal of Chromatography A 2000; 885(1-2):115-127. http://
6. Barker SA. Matrix solid phase dispersion (MSPD). Journal of Biochemical and Biophysical Methods 2007.; 70(2):151-162. PMid:17107714. http://dx.doi. org/10.1016/j.jbbm.2006.06.005
7. Kristenson EM, Ramos L, Brinkman UAT. Recent advances in matrix solid-phase dispersion. TrAC Trends in Analytical Chemistry 2006; 25(2):96-111.
8. Capriotti AL, Cavaliere C, Giansanti P, Gubbiotti R, Samperi R, Laganà A. Recent developments in matrix solid-phase dispersion extraction. Journal of Chromatography A 2010; 1217(16):2521-2532. PMid:20116066. chroma.2010.01.030
9. Qiao F, Du J. Rapid screening of clenbuterol hydrochloride in chicken samples by molecularly imprinted matrix solid-phase dispersion coupled with liquid chromatography. Journal of Chromatography B 2013.; 923-924:136-140. PMid:23500358. http://dx.doi. org/10.1016/j.jchromb.2013.02.016
10. Su R, Wang X, Xu X, Wang Z, Li D, Zhao X, et al. Application of multiwall carbon nanotubesbased matrix solid phase dispersion extraction for determination of hormones in butter by gas chromatography mass spectrometry. Journal of Chromatography A 2011; 1218(31):5047-5054. PMid:21676404. chroma.2011.05.088
11. Casado J, Rodríguez I, Carpinteiro I, Ramil M, Cela R. Gas chromatography quadrupole time-of-flight mass spectrometry determination of benzotriazole ultraviolet stabilizers in sludge samples. Journal of Chromatography A 2013; 126-132. PMid:23608406.
12. Bogialli S, D’Ascenzo G, Di Corcia A, Lagana A, Nicolardi S. A simple and rapid assay based on hot water extraction and liquid chromatography–tandem mass spectrometry for monitoring quinolone residues in bovine milk. Food Chemistry 2008; 108(1):354-360.
13. Caldas SS, Bolzan CM, Menezes EJD, Escarrone ALV, Martins CDMG, Bianchini A, et al. A vortexassisted MSPD method for the extraction of pesticide residues from fish liver and crab hepatopancreas with determination by GC–MS. Talanta 2013; 112:63- 68.. PMid:23708538. talanta.2013.03.054
14. Rodrigues SA, Caldas SS, Primel EG. A simple; efficient and environmentally friendly method for the extraction of pesticides from onion by matrix solidphase dispersion with liquid chromatography–tandem mass spectrometric detection. Analytica Chimica Acta 2010.; 678(1):82-89. PMid:20869508. http://dx.doi. org/10.1016/j.aca.2010.08.026
15. Cheng J, Liu M, Yu Y, Wang X, Zhang H, Ding L, et al. Determination of pyrethroids in porcine tissues by matrix solid-phase dispersion extraction and highperformance liquid chromatography. Meat Science 2009.; 82(4):407-412. PMid:20416606. http://dx.doi. org/10.1016/j.meatsci.2008.09.011
16. Fernandez-Alvarez M, Llompart M, Lamas JP, Lores M, Garcia-Jares C, Cela R, et al. Development of a matrix solid-phase dispersion method for the simultaneous determination of pyrethroid and organochlorinated pesticides in cattle feed. Journal of Chromatography A 2009; 1216(14):2832-2842. PMid:18952214. http://
17. Chen L, Li B. Determination of imidacloprid in rice by molecularly imprinted-matrix solid-phase dispersion with liquid chromatography tandem mass spectrometry. Journal of Chromatography B 2012.; 897:32-36. PMid:22534657. http://dx.doi. org/10.1016/j.jchromb.2012.04.004
18. Bogialli S, D’Ascenzo G, Di Corcia A, Laganà A, Tramontana G. Simple assay for monitoring seven quinolone antibacterials in eggs: Extraction with hot water and liquid chromatography coupled to tandem mass spectrometry: Laboratory validation in line with the European Union Commission Decision 657/2002/ EC. Journal of Chromatography A 2009; 1216(5):794- 800.. PMid:19095237. chroma.2008.11.070
19. Wang H, Yan H, Qiao J. Miniaturized matrix solid-phase dispersion combined with ultrasoundassisted dispersive liquid–liquid microextraction for the determination of three pyrethroids in soil. Journal of Separation Science 2012; 35(2):292- 298.. PMid:22162219. jssc.201100753
20. González-Mariño I, Rodríguez I, Quintana J, Cela R. Matrix solid-phase dispersion followed by gas chromatography-mass spectrometry for the determination of triclosan and methyl triclosan in sludge and sediments. Analytical and Bioanalytical Chemistry 2010; 398(5):2289-2297. PMid:20809191.
21. García-Rodríguez D, Cela-Torrijos R, Lorenzo-Ferreira RA, Carro-Díaz AM. Analysis of pesticide residues in seaweeds using matrix solid-phase dispersion and gas chromatography–mass spectrometry detection. Food Chemistry 2012; 135(1):259-267. http://dx.doi. org/10.1016/j.foodchem.2012.04.088
22. Sánchez-Brunete C, Miguel E, Tadeo JL. Determination of organochlorine pesticides in sewage sludge by matrix solid-phase dispersion and gas chromatography–mass spectrometry. Talanta 2008; 74.(5):1211-1217. PMid:18371771. http://dx.doi. org/10.1016/j.talanta.2007.08.025
23. Wang S, Mu H, Bai Y, Zhang Y, Liu H. Multiresidue determination of fluoroquinolones, organophosphorus and N-methyl carbamates simultaneously in porcine tissue using MSPD and HPLC–DAD. Journal of Chromatography B 2009; 877.(27):2961-2966. PMid:19646932. http://dx.doi. org/10.1016/j.jchromb.2009.07.011
24. Gutiérrez Valencia TM, García de Llasera MP. Determination of organophosphorus pesticides in bovine tissue by an on-line coupled matrix solidphase dispersion–solid phase extraction–high performance liquid chromatography with diode array detection method. Journal of Chromatography A 2011; 1218.(39):6869-6877. PMid:21872255. http://dx.doi. org/10.1016/j.chroma.2011.08.011
25. Abhilash PC, Singh V, Singh N. Simplified determination of combined residues of lindane and other HCH isomers in vegetables, fruits, wheat, pulses and medicinal plants by matrix solid-phase dispersion (MSPD) followed by GC–ECD. Food Chemistry 2009.; 113(1):267-271. foodchem.2008.07.004
26. Vazquez-Quintal P, Muñoz-Rodríguez D, Medina- Peralta S, Moguel-Ordóñez Y. Extraction of Organochlorine Pesticides from Bee Pollen by Matrix Solid-Phase Dispersion: Recovery Evaluation by GC– MS and Method Validation. Chromatographia 2012; 75.(15-16):923-930. 012.-2272-y
27. Rallis GN, Sakkas VA, Boumba VA, Vougiouklakis T, Albanis TA. Determination of organochlorine pesticides and polychlorinated biphenyls in postmortem human lung by matrix solid-phase dispersion with the aid of response surface methodology and desirability function. Journal of Chromatography A 2012; 1227:1-9. PMid:22265777. http://dx.doi. org/10.1016/j.chroma.2011.12.083
28. Totti S, Fernández M, Ghini S, Picó Y, Fini F, Mañes J, et al. Application of matrix solid phase dispersion to the determination of imidacloprid, carbaryl, aldicarb, and their main metabolites in honeybees by liquid chromatography–mass spectrometry detection. Talanta 2006; 69(3):724-729. PMid:18970629. http://
29. Yu H, Mu H, Hu YM. Determination of fluoroquinolones, sulfonamides, and tetracyclines multiresidues simultaneously in porcine tissue by MSPD and HPLC–DAD. Journal of Pharmaceutical Analysis 2012; 2(1):76-81. jpha.2011.09.007
30. Lu Y, Shen Q, Dai Z, Zhang H, Wang H. Development of an on-line matrix solid-phase dispersion/fast liquid chromatography/tandem mass spectrometry system for the rapid and simultaneous determination of 13 sulfonamides in grass carp tissues. Journal of Chromatography A 2011; 1218(7):929-937. PMid:21215404. chroma.2010.12.064
31. Souza MRR, Moreira CO, De Lima TG, Aquino A, Dórea HS. Validation of a matrix solid phase dispersion (MSPD) technique for determination of pesticides in lyophilized eggs of the chicken Gallus gallus domesticus. Microchemical Journal 2013; 110:395-401.
32. Míguez-Framil M, Moreda-Piñeiro A, Bermejo- Barrera P, Álvarez-Freire I, Tabernero MJ, Bermejo AM. Matrix solid-phase dispersion on column clean-up/pre-concentration as a novel approach for fast isolation of abuse drugs from human hair. Journal of Chromatography A 2010; 1217(41):6342- 6349.. PMid:20817166. chroma.2010.08.034
33. Martín-Esteban A. Molecularly-imprinted polymers as a versatile, highly selective tool in sample preparation. TrAC Trends in Analytical Chemistry 2013; 45:169- 181..
34. Qiao F, Sun H. Simultaneous extraction of enrofloxacin and ciprofloxacin from chicken tissue by molecularly imprinted matrix solid-phase dispersion. Journal of Pharmaceutical and Biomedical Analysis 2010.; 53(3):795-798. PMid:20619993. http://dx.doi. org/10.1016/j.jpba.2010.06.008
35. Qiao F, Yan H. Simultaneous analysis of fluoroquinolones and xanthine derivatives in serum by molecularly imprinted matrix solid-phase dispersion coupled with liquid chromatography. Journal of Chromatography B 2011; 879(30):3551- 3555.. PMid:21978534. jchromb.2011.09.040
36. Sun H, Qiao F, Liu G, Liang S. Simultaneous isolation of six fluoroquinolones in serum samples by selective molecularly imprinted matrix solid-phase dispersion. Analytica Chimica Acta 2008; 625(2):154- 159.. PMid:18724989. aca.2008.07.025
37. Carro AM, Lorenzo RA, Fernández F, Rodil R, Cela R. Multi-residue screening of chlorinated and brominated compounds from aquaculture samples using matrix solid-phase dispersion—gas chromatography–mass spectrometry. Journal of Chromatography A 2005; 1071.(1-2):93-98. PMid:15865179. http://dx.doi. org/10.1016/j.chroma.2004.12.005
38. Moliner-Martinez Y, Campíns-Falcó P, Molins- Legua C, Segovia-Martínez L, Seco-Torrecillas A. Miniaturized matrix solid phase dispersion procedure and solid phase microextraction for the analysis of organochlorinated pesticides and polybrominated diphenylethers in biota samples by gas chromatography electron capture detection. Journal of Chromatography A 2009; 1216(39). PMid:19709665. http://dx.doi. org/10.1016/j.chroma.2009.08.021
39. Barriada-Pereira M, Gonzlez-Castro MJ, Muniategui- Lorenzo S, Lpez-Maha P, Prada-Rodrguez D. Sample preparation based on matrix solid-phase dispersion and solid-phase extraction cleanup for the determination of organochlorine pesticides in fish. Journal of AOAC International 2010; 93(3):992-998. PMid:20629405.
40. García de Llasera MP, Reyes-Reyes ML. A validated matrix solid-phase dispersion method for the extraction of organophosphorus pesticides from bovine samples. Food Chemistry 2009; 114(4):1510-1516. http://dx.doi. org/10.1016/j.foodchem.2008.11.006
41. Chen WL, Wang GS, Gwo JC, Chen CY. Ultra-high performance liquid chromatography/tandem mass spectrometry determination of feminizing chemicals in river water, sediment and tissue pretreated using disk-type solid-phase extraction and matrix solid-phase dispersion. Talanta 2012; 89:237- 245.. PMid:22284486. talanta.2011.12.020
42. Zuloaga O, Navarro P, Bizkarguenaga E, Iparraguirre A, Vallejo A, Olivares M, et al. Overview of extraction, clean-up and detection techniques for the determination of organic pollutants in sewage sludge: A review. Analytica Chimica Acta 2012; 736:7- 29.. PMid:22769001. aca.2012.05.016
43. Blanco E, Casais MC, Mejuto MC, Cela R. Approaches for the Simultaneous Extraction of Tetrabromobisphenol A, Tetrachlorobisphenol A, and Related Phenolic Compounds from Sewage Sludge and Sediment Samples Based on Matrix Solid-Phase Dispersion. Analytical Chemistry 2006; 78(8):2772- 2778.. PMid:16615792. ac0522512
44. Li ZY, Zhang ZC, Zhou QL, Gao RY, Wang QS. Fast and precise determination of phenthoate and its enantiomeric ratio in soil by the matrix solid-phase dispersion method and liquid chromatography. Journal of Chromatography A 2002; 977(1):17-25.
45. Shen X, Cai J, Gao Y, Su Q. Determination of Organophosphorus Pesticides in Soil by MMSPD-GC-NPD and Confirmation by GC-MS. Chromatographia 2006; 64(1-2):71-77. http://dx.doi. org/10.1365/s10337-006-0813-y
46. Albero B, Sánchez-Brunete C, Miguel E, Pérez RA, Tadeo JL. Analysis of natural-occurring and synthetic sexual hormones in sludge-amended soils by matrix solid-phase dispersion and isotope dilution gas chromatography–tandem mass spectrometry. Journal of Chromatography A 2013; 1283:39- 45.. PMid:23465128. chroma.2013.01.113
47. Ettiene G, Bauza R, Plata MR, Contento AM, Ríos Á. Determination of neonicotinoid insecticides in environmental samples by micellar electrokinetic chromatography using solid-phase treatments. Eletrophoresis 2012; 33(19-20):2969- 2977.. PMid:22997021. elps.201200241
48. Pavlović DM, Pinušić T, Periša M, Babić S. Optimization of matrix solid-phase dispersion for liquid chromatography tandem mass spectrometry analysis of 12 pharmaceuticals in sediments. Journal of Chromatography A 2012; 1-15. PMid:22939206. http://
49. Pérez R, Albero B, Miguel E, Sánchez-Brunete C. Determination of parabens and endocrine-disrupting alkylphenols in soil by gas chromatography–mass spectrometry following matrix solid-phase dispersion or in-column microwave-assisted extraction: a comparative study. Analytical and Bioanalytical Chemistry 2012; 402(7):2347-2357. PMid:21792551.
50. Carpinteiro I, Abuin B, Ramil M, Rodriguez I, Cela R. Matrix solid-phase dispersion followed by gas chromatography tandem mass spectrometry for the determination of benzotriazole UV absorbers in sediments. Analytical and Bioanalytical Chemistry 2012.; 402(1):519-527. PMid:21910012. http://dx.doi. org/10.1007/s00216-011-5386-4
51. Wang T, Tong J, Sun M, Chen L. Fast and selective extraction of chloramphenicol from soil by matrix solid-phase dispersion using molecularly imprinted polymer as dispersant. Journal of Separation Science 2011.; 34(15):1886-1892. PMid:21674791. http://
52. Wen Y, Chen L, Li J, Ma Y, Xu S, Zhang Z, et al. Molecularly imprinted matrix solid-phase dispersion coupled to micellar electrokinetic chromatography for simultaneous determination of triazines in soil, fruit, and vegetable samples. Electrophoresis 2012; 33.(15):2454-2463. PMid:22887168. http://dx.doi. org/10.1002/elps.201100612
53. Albero B, Pérez RA, Sánchez-Brunete C, Tadeo JL. Occurrence and analysis of parabens in municipal sewage sludge from wastewater treatment plants in Madrid (Spain). Journal of Hazardous Materials 2012.; 239:48-55. jhazmat.2012.05.017
54. Santos LFS, Souza NRS, Ferreira J.A, Navickiene S. A reversed-phase high-performance liquid chromatography method combined with matrix solidphase dispersion extraction for the determination of teflubenzuron, lufenuron and bifenthrin residues in lyophilized coconut water. Journal of Food Composition and Analysis 2012; 26(1-2):183-188. http://dx.doi. org/10.1016/j.jfca.2012.03.007
55. Gilbert-López B, García-Reyes JF, Lozano A, Fernández-Alba AR, Molina-Díaz A. Large-scale pesticide testing in olives by liquid chromatography– electrospray tandem mass spectrometry using two sample preparation methods based on matrix solid-phase dispersion and QuEChERS. Journal of Chromatography A 2010; 1217(39):6022-6035. PMid:20728894. chroma.2010.07.062
56. Boti VI, Sakkas VA, Albanis TA. An experimental design approach employing artificial neural networks for the determination of potential endocrine disruptors in food using matrix solid-phase dispersion. Journal of Chromatography A 2009; 1216(9):1296- 1304.. PMid:19144345. chroma.2008.12.070
57. Ramos JJ, Rial-Otero R, Ramos L, Capelo JL. Ultrasonic-assisted matrix solid-phase dispersion as an improved methodology for the determination of pesticides in fruits. Journal of Chromatography A 2008.; 1212(1-2):145-149. PMid:18952216. http://
58. Silva MGD, Aquino A, Dórea HS, Navickiene S. Simultaneous determination of eight pesticide residues in coconut using MSPD and GC/MS. Talanta 2008; 76.(3).
59. Radišić M, Vasiljević T, Dujaković N, Laušević M. Application of Matrix Solid-Phase Dispersion and Liquid Chromatography–Ion Trap Mass Spectrometry for the Analysis of Pesticide Residues in Fruits. Food Analytical Methods 2013; 6(2):648-657. http://dx.doi. org/10.1007/s12161-012-9448-9
60. Guan SX, Yu Z-G, Yu HN, Song CH, Song ZQ, Qin Z. Multi-Walled Carbon Nanotubes as Matrix Solid-Phase Dispersion Extraction Adsorbent for Simultaneous Analysis of Residues of Nine Organophosphorus Pesticides in Fruit and Vegetables by Rapid Resolution LC–MS–MS. Chromatographia 2011; 73(1-2):33-41.
61. Navickiene S, Aquino A, Bezerra DSS. A Matrix Solid-Phase Dispersion Method for the Extraction of Seven Pesticides from Mango and Papaya. Journal of Chromatographic Science 2010; 48(9):750- 754.. PMid:20875237. chromsci/48.9.750
62. Aquino A, Navickiene S. MSPD Procedure for Determination of Carbofuran, Pyrimethanil and Tetraconazole Residues in Banana by GC–MS. Chromatographia 2009; 70(7-8):1265-1269. http://
63. Caetano J, Machado SA. Determination of carbaryl in tomato “in natura” using an amperometric biosensor based on the inhibition of acetylcholinesterase activity. Sensors and Actuators B: Chemical 2008; 129(1):40-46.
64. Miao Q, Kong W, Yang S, Yang M. Comparison of sample preparation methods combined with gas chromatography with electron-capture detection for the analysis of multipesticide residues in lotus seeds. Journal of Separation Science 2013; 36(12):2010- 2019.. PMid:23585417. jssc.201300032
65. Wang Y, Xiao L, Cheng M. Determination of phenylureas herbicides in food stuffs based on matrix solid-phase dispersion extraction and capillary electrophoresis with electrochemiluminescence detection. Journal of Chromatography A 2011; 1218.(50):9115-9119. PMid:22078235. http://dx.doi. org/10.1016/j.chroma.2011.10.048
66. Calderón-Preciado D, Jiménez-Cartagena C, Peñuela G, Bayona JM. Development of an analytical procedure for the determination of emerging and priority organic pollutants in leafy vegetables by pressurized solvent extraction followed by GC–MS determination. Analytical and Bioanalytical Chemistry 2009.; 394(5):1319-1327. PMid:19225765. http://
67. García-Mayor M, Gallego-Picó A, Garcinuño R, Fernández-Hernando P, Durand-Alegría J. Matrix solid-phase dispersion method for the determination of macrolide antibiotics in sheep’s milk. Food Chemistry 2012; 134(1):553-558. http://dx.doi. org/10.1016/j.foodchem.2012.02.120
68. Canosa P, Rodríguez I, Rubí E, Ramil M, Cela R. Simplified sample preparation method for triclosan and methyltriclosan determination in biota and foodstuff samples. Journal of Chromatography A 2008.; 1188(2):132-139. PMid:18329035. http://dx.doi. org/10.1016/j.chroma.2008.02.064
69. Bolaños PP, Frenich AG, Vidal J. Application of gas chromatography-triple quadrupole mass spectrometry in the quantification-confirmation of pesticides and polychlorinated biphenyls in eggs at trace levels. Journal of Chromatography A 2007.; 1167(1):9-17. PMid:17764679. http://dx.doi. org/10.1016/j.chroma.2007.08.019
70. Moreda-Piñeiro A, Peña-Vázquez E, Hermelo- Herbello P, Bermejo-Barrera P, Moreda-Piñeiro J, Alonso-Rodríguez E, et al. Analytical Chemistry 2008; 80.(23):9272-9278.
71. Moreda-Piñeiro J, Alonso-Rodríguez E, Romarís- Hortas V, Moreda-Piñeiro A, López-Mahía P, Muniategui-Lorenzo S, et al. Assessment of the bioavailability of toxic and non-toxic arsenic species in seafood samples. Food Chemistry 2012; 130.(3):552-560. foodchem.2011.07.071
72. Duarte FA, Soares BM, Vieira AA, Pereira ER, Maciel JV, Caldas SS, et al. Assessment of Modified Matrix Solid-Phase Dispersion as Sample Preparation for the Determination of CH3Hg+ and Hg2+ in Fish. Analytical Chemistry 2013; 85(10):5015-5022. PMid:23614538.
73. Santoyo MM, Figueroa JAL, Wrobel K, Wrobel K. Analytical speciation of mercury in fish tissues by reversed phase liquid chromatography–inductively coupled plasma mass spectrometry with Bi3+ as internal standard. Talanta 2009; 79(3):706-711. PMid:19576434. talanta.2009.04.057
74. Serafimovski I, Karadjova I, Stafilov T, Cvetković J. Determination of inorganic and methylmercury in fish by cold vapor atomic absorption spectrometry and inductively coupled plasma atomic emission spectrometry. Microchemical Journal 2008; 89(1):42- 47..
75. Martínez-Fernández M, Barciela-Alonso MC, Moreda- Piñeiro A, Bermejo-Barrera P. Matrix solid phase dispersion-assisted BCR sequential extraction method for metal partitioning in surface estuarine sediments. Talanta 2011; 83(3):840-849. PMid:21147327. http://