In Vivo SPME for Bioanalysis in Environmental Monitoring and Toxicology

  • Anna RoszkowskaEmail author
  • Miao Yu
  • Janusz Pawliszyn


Solid-phase microextraction (SPME) is a well-established sample preparation technique in the field of environmental and toxicological studies. The application of SPME has extended from the headspace extraction of volatile compounds to the capturing of short-lived and unstable components of the ecosystem extracted from the living organism via direct immersion of SPME probes into the tissue (in vivo SPME). The development of biocompatible coatings and availability of different calibration approaches enables in vivo sampling of exogenous and endogenous compounds from the living plants and animals without the need for tissue collection. In addition, new geometry designs such as thin-film coatings, needle trap devices, recession needles, coated tips or blades has increased the sensitivity and robustness of in vivo sampling. Here, we present the fundamentals of in vivo SPME technique, including the types of extraction mode, geometry design of the coatings, calibration methods and data analysis methods used in untargeted in vivo SPME. We also discuss recent applications of in vivo SPME in environmental studies and in the analysis of pollutants in plant and animal tissues in addition to in vivo human saliva, breath and skin analysis. In summary, in vivo SPME technique shows great potential for both targeted and untargeted screening of small molecules in the living organisms exposed to the surrounding environment.


SPME In vivo sampling Environment Toxicology Contaminants Calibration Bioanalysis 



This monograph was developed within the framework of the Environment Canada through the Environmental Damages Fund (grant EC-129114).


  1. Alam MN, Ricardez-Sandoval L, Pawliszyn J (2015) Numerical modeling of solid-phase microextraction: binding matrix effect on equilibrium time. Anal Chem 87:9846–9854. Scholar
  2. Arthur CL, Pawliszyn J (1990) Solid phase microextraction with thermal desorption using fused silica optical fibers. Anal Chem 62:2145–2148. Scholar
  3. Augusto Gomez-Rios G, Vasiljevic T, Gionfriddo E, Yu M, Pawliszyn J (2017) Towards on-site analysis of complex matrices by solid-phase microextraction-transmission mode coupled to a portable mass spectrometer via direct analysis in real time. Analyst. Scholar
  4. Bai Z, Pilote A, Sarker PK, Vandenberg G, Pawliszyn J (2013) In vivo solid-phase microextraction with in vitro calibration: determination of off-flavor components in live fish. Anal Chem 85:2328–2332. Scholar
  5. Bessonneau V, Bojko B, Pawliszyn J (2013) Analysis of human saliva metabolome by direct immersion solid-phase microextraction LC and benchtop orbitrap MS. Bioanalysis 5:783–792. Scholar
  6. Bessonneau V, Boyaci E, Maciazek-Jurczyk M, Pawliszyn J (2015) In vivo solid phase microextraction sampling of human saliva for non-invasive and on-site monitoring. Anal Chim Acta 856:35–45. Scholar
  7. Bojko B, Pawliszyn J (2014) In vivo and ex vivo SPME: a low invasive sampling and sample preparation tool in clinical bioanalysis. Bioanalysis 6:1227–1239. Scholar
  8. Boyacı E, Bojko B, Reyes-Garcés N, Poole JJ, Gómez-Ríos GA, Teixeira A, Nicol B, Pawliszyn J (2018) High-throughput analysis using non-depletive SPME: challenges and applications to the determination of free and total concentrations in small sample volumes. Sci Rep 8.
  9. Domingo-Almenara X, Montenegro-Burke JR, Benton HP, Siuzdak G (2018) Annotation: a computational solution for streamlining metabolomics analysis. Anal Chem 90:480–489. Scholar
  10. Duffy E, Jacobs MR, Kirby B, Morrin A (2017) Probing skin physiology through the volatile footprint: discriminating volatile emissions before and after acute barrier disruption. Exp Dermatol 10:919–925. Scholar
  11. Ghiasvand AR, Hosseinzadeh S, Pawliszyn J (2006) New cold-fiber headspace solid-phase microextraction device for quantitative extraction of polycyclic aromatic hydrocarbons in sediment. J Chromatogr A ExTech 2006 (1124):35–42. Scholar
  12. Gionfriddo E, Boyacı E, Pawliszyn J (2017) New generation of solid-phase microextraction coatings for complementary separation approaches: a step toward comprehensive metabolomics and multiresidue analyses in complex matrices. Anal Chem 89:4046–4054. Scholar
  13. Godage NH, Gionfriddo E (2019) A critical outlook on recent developments and applications of matrix compatible coatings for solid phase microextraction. TrAC Trends Anal Chem 111:220–228. Scholar
  14. Gómez-Ríos GA, Tascon M, Pawliszyn J (2018) Coated blade spray: shifting the paradigm of direct sample introduction to MS. Bioanalysis 10:257–271. Scholar
  15. Grote C, Pawliszyn J (1997) Solid-phase microextraction for the analysis of human breath. Anal Chem 69:587–596. Scholar
  16. Huq M, Tascon M, Nazdrajic E, Roszkowska A, Pawliszyn J (2019) Measurement of free drug concentration from biological tissue by solid-phase microextraction: in Silico and experimental study. Anal Chem. Scholar
  17. Jiang R, Cudjoe E, Bojko B, Abaffy T, Pawliszyn J (2013) A non-invasive method for in vivo skin volatile compounds sampling. Anal Chim Acta 804:111–119. Scholar
  18. Jiang R, Pawliszyn J (2014) Cooled membrane for high sensitivity gas sampling. J Chromatogr A 1338:17–23. Scholar
  19. Jiang R, Pawliszyn J (2012) Thin-film microextraction offers another geometry for solid-phase microextraction. TrAC Trends Anal Chem 39:245–253. Scholar
  20. Kleeblatt J, Schubert JK, Zimmermann R (2015) Detection of gaseous compounds by needle trap sampling and direct thermal-desorption photoionization mass spectrometry: concept and demonstrative application to breath gas analysis. Anal Chem 87:1773–1781. Scholar
  21. Llompart M, Celeiro M, García-Jares C, Dagnac T (2019) Environmental applications of solid-phase microextraction. TrAC Trends Anal Chem 112:1–12. Scholar
  22. Lord HL, Zhan W, Pawliszyn J (2010) Fundamentals and applications of needle trap devices: a critical review. Anal Chim Acta 677(1):3–18. A selection of papers presented at the 11th International Symposium on Advances in Extraction Technologies (ExTech2009). Scholar
  23. Martendal E, Carasek E (2011) A new approach based on a combination of direct and headspace cold-fiber solid-phase microextraction modes in the same procedure for the determination of polycyclic aromatic hydrocarbons and phthalate esters in soil samples. J Chromatogr A 1218:1707–1714. Scholar
  24. Martos PA, Pawliszyn J (1998) Sampling and determination of formaldehyde using solid-phase microextraction with on-fiber derivatization. Anal Chem 70:2311–2320. Scholar
  25. Menezes HC, Paiva MJN, Santos RR, Sousa LP, Resende SF, Saturnino JA, Paulo BP, Cardeal ZL (2013) A sensitive GC/MS method using cold fiber SPME to determine polycyclic aromatic hydrocarbons in spring water. Microchem J 110:209–214. Scholar
  26. Miller TH, Bury NR, Owen SF, MacRae JI, Barron LP (2018) A review of the pharmaceutical exposome in aquatic fauna. Environ Pollut 239:129–146. Scholar
  27. Moliner-Martinez Y, Herráez-Hernández R, Verdú-Andrés J, Molins-Legua C, Campíns-Falcó P (2015) Recent advances of in-tube solid-phase microextraction. TrAC Trends Anal Chem 71:205–213. Scholar
  28. Musteata FM, Sandoval M, Ruiz-Macedo JC, Harrison K, McKenna D, Millington W (2016) Evaluation of in vivo solid phase microextraction for minimally invasive analysis of nonvolatile phytochemicals in Amazonian plants. Anal Chim Acta 933:124–133. Scholar
  29. Nakajima D, Tin-Tin-Win-Shwe Kakeyama M, Fujimaki H, Goto S (2006) Determination of toluene in brain of freely moving mice using solid-phase microextraction technique. Neuro Toxicol 27: 615–618. Scholar
  30. Niri VH, Eom I-Y, Kermani FR, Pawliszyn J (2009) Sampling free and particle-bound chemicals using solid-phase microextraction and needle trap device simultaneously. J Sep Sci 32:1075–1080. Scholar
  31. Ouyang G, Oakes KD, Bragg L, Wang S, Liu H, Cui S, Servos MR, Dixon DG, Pawliszyn J (2011a) Sampling-rate calibration for rapid and nonlethal monitoring of organic contaminants in fish muscle by solid-phase microextraction. Environ Sci Technol 45:7792–7798. Scholar
  32. Ouyang G, Vuckovic D, Pawliszyn J (2011b) Nondestructive sampling of living systems using in vivo solid-phase microextraction. Chem Rev 111:2784–2814. Scholar
  33. Ouyang G, Pawliszyn J (2008) A critical review in calibration methods for solid-phase microextraction. Anal Chim Acta 627:184–197. Scholar
  34. Pawliszyn J (2012) Handbook of solid phase microextraction. Elsevier.
  35. Piri-Moghadam H, Ahmadi F, Gómez-Ríos GA, Boyacı E, Reyes-Garcés N, Aghakhani A, Bojko B, Pawliszyn J (2016) Fast quantitation of target analytes in small volumes of complex samples by matrix-compatible solid-phase microextraction devices. Angew Chem Int Ed 55:7510–7514. Scholar
  36. Poole JJ, Grandy JJ, Yu M, Boyaci E, Gómez-Ríos GA, Reyes-Garcés N, Bojko B, Heide HV, Pawliszyn J (2017) Deposition of a sorbent into a recession on a solid support to provide a new, mechanically robust solid-phase microextraction device. Anal Chem. Scholar
  37. Qiu J, Chen G, Xu J, Luo E, Liu Yan, Wang F, Zhou H, Liu Yuan, Zhu F, Ouyang G (2016) In vivo tracing of organochloride and organophosphorus pesticides in different organs of hydroponically grown malabar spinach (Basella alba L.). J Hazard Mater 316:52–59. Scholar
  38. Reiche N, Mothes F, Fiedler P, Borsdorf H (2013) A solid-phase microextraction method for the in vivo sampling of MTBE in common reed (Phragmites Australis). Environ Monit Assess 185:7133–7144. Scholar
  39. Reyes-Garcés N, Gionfriddo E, Gómez-Ríos GA, Alam MN, Boyacı E, Bojko B, Singh V, Grandy J, Pawliszyn J (2018) Advances in solid phase microextraction and perspective on future directions. Anal Chem 90:302–360. Scholar
  40. Risticevic S, Souza-Silva EA, Gionfriddo E, DeEll JR, Cochran J, Hopkins WS, Pawliszyn J Application of in vivo solid phase microextraction (SPME) in capturing metabolome of apple (Malus × domestica Borkh.) fruit, under review (Frontiers in Plant Science)Google Scholar
  41. Roszkowska A, Yu M, Bessonneau V, Ings J, McMaster M, Smith R, Bragg L, Servos M, Pawliszyn J (2019) In vivo solid-phase microextraction sampling combined with metabolomics and toxicological studies for the non-lethal monitoring of the exposome in fish tissue. Environ Pollut 249:109–115. Scholar
  42. Shigeyama H, Wang T, Ichinose M, Ansai T, Lee S-W (2019) Identification of volatile metabolites in human saliva from patients with oral squamous cell carcinoma via zeolite-based thin-film microextraction coupled with GC–MS. J Chromatogr B 1104:49–58. Scholar
  43. Souza-Silva ÉA, Gionfriddo E, Pawliszyn J (2015) A critical review of the state of the art of solid-phase microextraction of complex matrices II. Food analysis. TrAC Trends Anal Chem 71:236–248. Scholar
  44. Togunde OP, Lord H, Oakes KD, Servos MR, Pawliszyn J (2013) Development and evaluation of a new in vivo solid-phase microextraction sampler. J Sep Sci 36:219–223. Scholar
  45. Vasiljevic T, Singh V, Pawliszyn J (2019) Miniaturized SPME tips directly coupled to mass spectrometry for targeted determination and untargeted profiling of small samples. Talanta 199:689–697. Scholar
  46. Vereb H, Dietrich AM, Alfeeli B, Agah M (2011) The possibilities will take your breath away: breath analysis for assessing environmental exposure. Environ Sci Technol 45:8167–8175. Scholar
  47. Vuckovic D (2013) High-throughput solid-phase microextraction in multi-well-plate format. TrAC Trends Anal Chem 45:136–153. Scholar
  48. Vuckovic D, de Lannoy I, Gien B, Shirey RE, Sidisky LM, Dutta S, Pawliszyn J (2011) In Vivo Solid-Phase Microextraction: Capturing the Elusive Portion of Metabolome. Angew Chem Int Ed 50:5344–5348. Scholar
  49. Vuckovic D, Zhang X, Cudjoe E, Pawliszyn J (2010) Solid-phase microextraction in bioanalysis: new devices and directions. J Chromatogr Mass Spectrom Innov Appl Part VI 1217:4041–4060. Scholar
  50. Wang S, Oakes KD, Bragg LM, Pawliszyn J, Dixon G, Servos MR (2011) Validation and use of in vivo solid phase micro-extraction (SPME) for the detection of emerging contaminants in fish. Chemosphere 85:1472–1480. Scholar
  51. Wang Y, Zhang J, Ding Y, Zhou J, Ni L, Sun C (2009) Quantitative determination of 16 polycyclic aromatic hydrocarbons in soil samples using solid-phase microextraction. J Sep Sci 32:3951–3957. Scholar
  52. Win-Shwe T-T, Mitsushima D, Nakajima D, Ahmed S, Yamamoto S, Tsukahara S, Kakeyama M, Goto S, Fujimaki H (2007) Toluene induces rapid and reversible rise of hippocampal glutamate and taurine neurotransmitter levels in mice. Toxicol Lett 168:75–82. Scholar
  53. Xu J, Chen G, Huang S, Qiu J, Jiang R, Zhu F, Ouyang G (2016) Application of in vivo solid-phase microextraction in environmental analysis. TrAC Trends Anal Chem 85:26–35. Scholar
  54. Yu M, Olkowicz M, Pawliszyn J (2019) Structure/reaction directed analysis for LC-MS based untargeted analysis. Anal Chim Acta 1050:16–24. Scholar
  55. Zhang L, Gionfriddo E, Acquaro V, Pawliszyn J (2018) Direct immersion solid-phase microextraction analysis of multi-class contaminants in edible seaweeds by gas chromatography-mass spectrometry. Anal Chim Acta 1031:83–97. Scholar
  56. Zhang Q-H, Zhou L-D, Chen H, Wang C-Z, Xia Z-N, Yuan C-S (2016) Solid-phase microextraction technology for in vitro and in vivo metabolite analysis. TrAC Trends Anal Chem 80:57–65. Scholar
  57. Zhu F, Xu J, Ke Y, Huang S, Zeng F, Luan T, Ouyang G (2013) Applications of in vivo and in vitro solid-phase microextraction techniques in plant analysis: a review. Anal Chim Acta 794:1–14. Scholar

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© Springer Nature Singapore Pte Ltd. 2020

Authors and Affiliations

  1. 1.Department of ChemistryUniversity of WaterlooWaterlooCanada
  2. 2.Department of Pharmaceutical ChemistryMedical University of GdanskGdanskPoland
  3. 3.Department of Environmental Medicine and Public Health, Icahn School of Medicine at Mount SinaiNew YorkUSA

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