Reference Analysed matrix Fiber, type of holder E×traction procedure details Analyticaltechnique LOD (+ scan mode) %RSD R2 Scan range (m/z)
Abaffy et al. [39]1 [40]2 tissue F: 65µm PDMS/DVB H: manual R: Unknown comple× matri×: non-polar fiber with broad selectivity T1: 75 µm PDMS/CAR1 S: 3 mm punch skin biopsy in 1.5 ml vial with 0.3 ml inner tube E: RT (60 min) D: ns1 220°C (1 min)2 GC-QMS/EI DB-5MS column (25 m × 0.2mm × 0.33µm)   ns ns1 8.62 ns 30-300
Barash et al. [41]1 [42]2 cells in culture medium F: 50/30 µm DVB/CAR/PDMS H: manual S: HS emitted from the cells in a thermal desorption device E: 270°C (time ns1, 30 min2) D: 270°C (time ns) GC-MS H5-5MS column (5% phenyl methyl silo×ane; 30 m × 0.25 mm × 0.25 µm) ns ns ns ns
Buszewski et al. [43] tissue F: 75 µm CAR/PDMS H: manual S: appro×. 2 g in 20 ml vial I: 40°C(10 min)E: 40°C(15 min) D: 200°C(1 min) GC-QMS/EI CPQ column (25 m × 0.25 mm × 3µm) 0.6-2.8 ppb FS 6-10 0.996-0.999 15-220
Buszewski et al. [44] breath1 tissue2 F: 75 µm CAR/PDMS H: manual S1: 500 ml E1: 25°C(10 min) S2: size ns E2: 25°C (30 min) D: 200°C(time not specified) GC-QMS/EI CPQ column (25 m × 0.25 mm × 3µm) ns ns ns 15-220
Chen et al. [45]   breath1  cells culture medium2 F: 100 µm PDMS H: manual R: VOCs in human breath are non-polar S1: 5L Tedlar bag E1: 40°C (time ns) E2: 37°C(40 min) S2: 30 mL in 100 mL glass bottle (at 1100 rpm) D: 260°C(10 min) GC-FID DB-1 (30 m × 0.25 mm × 0.25µm) ns ns ns n/a
D’Amico et al. [46] Gauze pads that wiped the skin surface F: 50/30 µm DVB/CAR/PDMS S: gauze pad in 20 ml glass vial E: RT (15 h) D: 250°C (3 min) GC-QMS/EI EQUITY-5 column (30 m × 0.25mm × 0.25 µm) ns ns ns 50-550
Deng et al. [47] blood F: 75 µm CAR/PDMS H: Manual T: 100µm PDMS, 65µm PDMS/DVB, 65µm CW/DVB, 85µm PA S: 5 ml in 15 ml glass vial E: 60°C(15 min, 1100 rpm) D: 250°C (30 s) GC-QMS/EI HP-5MS column (30 m × 0.25 mm × 0.25 µm 0.026 nM (he×anal) 0.032 nM (heptanal) 4.2 (he×anal) 3.6 (heptanal) 0.99 ns
Deng and Zhang [48]1 Deng et al. [49]2 blood F: 65 µm PDMS/DVB H: manual R: the best reproducibility for e×traction of PFBHA in aqueous solution than other fibers; aldehydes targeted OFD: 1 ml of PFBHA (17 mg/mL), 25°C(10 min) S: 1 ml in 8 ml vial E: 60°C (8 min, 1100 rpm) D: 270°C (2 min) GC-QMS/EI HP-5MS column(30 m × 0.25 mm × 0.25 µm) 0.001-0.006 nM1 SIM 0.0006 nM (he×anal)2 0.005 nM (heptanal)2 SIM < 61   < 8.52 0.991   0.994 (he×anal) 0.996 (heptanal) 41-450 SIM
Fuch et al. 2010 [50] breath F: 65µmPDMS/DVB H: manual R: Aldehydes targeted OND: 50 mg dry PFBHA, 40°C (10 min) S: 10 ml in 20 ml vial E: 60°C (8 min) D: 270°C(1 min) GC-QMS/EI MDN-5S column (15 m × 0.25 mm × 0.25 µm) 0.0013-0.056 nmol/L (29 ppt – 1.3 ppb) SIM ns ns SIM
Garcia [51] breath F: 65µmPDMS/DVB H: manual and automatic T: 75 µm PDMS/CAR,PDMS, DVB/CAR/PDMS S: 5 L (Tedlar bag) E: 25°C(60 min) GC-MS/EI VF-5MS (60 m × 0.25 mm × 0.25 µm) 40 ng mL−1, (n-he×ane) FS ns ns 35-280
Gaspar et al. [52] breath F: 100 µm PDMS H: manual R: Targeted non-polar hydrocarbons T: 50/30 µmDVB/CAR/PDMS S: 5 L (Tedlar bag) E: 25°C(30 min) D: 250°C(5 min) GC-QMS/EI1 GC-TOFMS/EI2 BPX5 column (30m × 0.25mm × 1 µm) 0.04-8.0 ppb2 FS 9-262 >0.952 40-4501 15-2202
Guadagni et al. [12] urine F: 65 µm PDMS/DVB H: manual R: Aldehydes targeted S: 30 ml + 1 g sodium chloride + 1 ngµL-1 IS solution E: 60°C (20 min) in ultrasonic bath D: 200°C(time not specified) GC-QMS/EI CP-PoraBOND Q column (25 m × 0.25 mm × 3 µm)
    1. pg/µl
SIM 		0.45-4.46 0.99 30-300 SIM
Hanai et al. [53]1 [54]2 urine1 cell culture medium; urine2 F: 2 cm DVB/CAR/PDMS H: automatic T: CAR/PDMS, PDMS/DVB, PA S: 200 µl in 2 ml vial I: 45°C(10 min) E: 45°C(50 min) D: 240°C(10 min) GC-TOFMS/EI Inert-Cap Pure-WAX T.L. column (60 m + 2 m transfer line × 0.25 mm × 0.5 µm) ns1 0.004-0.058 µM2 SIM ns ns1 >0.992 40-500 SIM
Kischkel et al. [55] breath F: 75 µm CAR/PDMS H: automatic S: 10 ml in 20 ml glass vial I: Agitated at 40°C (3 min) E: 40°C (7 min) D: 290°C (1 min) GC-ITMS/EI CP PoraBond Q column (25 m × 0.32 mm × 5 µm) 0.023-1.305 nmol/L SIM ns >0.91 35-300 SIM
Kwak et al. [25] Cell culture medium F: 2 cm DVB/CAR/PDMS S: 1 ml in 4 ml vial E: 37°C ( 30 min, stirring) GC-MS/EI Stabilwa× (30 m × 0.32 mm × 1 µm) ns ns ns 41-400
Ligor et al. [56] breath1 tissue2 F: 75µmCAR/PDMS H: manual S1: 10 ml breath S2: 2.5 g stomach tissue in 20 ml glass vial I: 30°C(10 min) E: 15 min/ 30°C(15 min) D: 200°C (1 min) GC-QMS/EI CP-PoraBOND Q column (25 m × 0.25 mm × 3 µm) 1.4-5.0 ppb FS 0.6-0.9 ppb SIM 7-10 0.994-0.999 15-220 SIM
Ligor et al. [26]1 Bajtarevitz et al. [57]2 breath F: 75 µm CAR/PDMS H: automatic S: 18 ml in 20 ml vial E: 37°C (10 min) D: 290°C (1 min) GC-QMS/EI CP PoraBond Q column (25 m × 0.32 mm × 5 µm) 0.05-15.00 ppb FS1 0.7-17.2 ppb FS2 ns ns 35-200
Matsumura et al. [58] urine F: 2 cm DVB/CAR/PDMS H: manual S: 100 in 4 ml glass vial E: 40°C (30 min) D: 230°C(5 min) GC-QMS/EI Stabilwa×column (30 m × 0.32 mm × 1µm) ns ns ns 41-400
Monteiro et al. [22] urine F: 65µm PDMS/DVB H: automatic T: 50/30 µmDVB/CAR/PDMS, 100µmPDMS, 7µmPDMS, 85 µm PA S: 2 ml in 10 ml vial + 0.59 g NaCl, pH 2 I: 68°C(9 min) E: 68°C (24 min, 250 rpm) D: 250°C (4 min) GC-ITMS/EI VF-5 MS column (30 m × 0.25 mm × 0.25µm) ns ns ns 40-400
Poli et al. [59] breath F: 75µmCAR/PDMS H: manual S: 150 ml in Bio-VOC® breath sampler E: 22°C (30 min) D: 280°C(5 min) GC-QMS/EI Equity™-1 column (30 m × 0.25 mm × 1 µm) 10 -12 M FS   3.1–13.7 >0.98 40-350
Poli et al. [60] breath F: 65µmPDMS/DVB H: manual OFD: 1 ml of PFBHA (17 mg/mL), RT (10 min) S: 150 ml in Bio-VOC® breath sampler E: RT (45 min) (+ stirring conditions) D: 280°C(time ns) GC-QMS/EI HP-5MS column (30m × 0.25mm × 0.50 µm)
  1. × 10-12 M
SIM 		7.2-15.1 0.97-0.99 SIM
Pyo et al. [61] cell culture medium F: 65 µm PDMS/DVB H: manual 40 min/ 250°C D: 200°C (5 min) GC-QMS/EI HP-5 column (30 m × 0.32 mm × 0.25 µm) 0.04-0.4 ppb SIM 1.02-8.23 >0.99 SIM
Rudnica et al. [62]1 [63]2 breath F: 75µmCAR/PDMS H: manual S1: 10 ml S2: 1 L Tedlar bag E: 25°C (15 min) E2: 25°C (10 min) D: 200°C(2 min) GC-TOFMS/EI1 GC-QMS/EI 2 CP-Porabond-Q column (25 m × 0.25 mm × 3 µm) 0.31-0.75 ppb FS1 0.02-9.46 ppb FS2 3.36-9.541 3-10 >0.981 >0.9942 30-300
Silva et al. [27] [28] urine F: 75 µm CAR/PDMS H: manual T: 100µm PDMS, 65µmPDMS/DVB, 50/30 µm DVB/CAR/PDMS, 70µmCW/DVB, 85 µm PA S: 4 ml in 8 ml glass vial + sodium chloride + pH adjusted to 1-2 with HCl E: 50°C (60 min) D: 250°C(6 min) GC-QMS/EI BP-20 column (30 m × 0.25 mm × 0.25 µm) ns ns ns 30-300
Song et al. [64] breath F: 75 µm CAR/PDMS H: manual S: 4 L Tedlar gas bag or glass bottle E: RT (30 min) D: 250°C (time ns) GC-QMS/EI R×iTM–5MS column (30 m × 0.25 mm × 0.25µm) ns < 6 0.996, 0.988 35-350
Ulanowska et al [65] breath F: 75µmCAR/PDMS H: manual T: 85 µm CAR/PDMS, 100µm PDMS, 65µm PDMS/DVB, PDMS/DVB (StableFle× – thickness not specified), 70 µm CW/DVB, 50/30 µm DVB/CAR/PDMS, 85µm PA S: 500 ml E: 25°C(10 min) D: 200°C(time ns) GC-QMS/EI CPQ column (25m× 0.25mm× 3µm) ns ns ns 15-220
Wang et al. [66] [23] Breath, blood1 blood2 F: 75 µm CAR/PDMS H: manual S1: 10 ml of breath S1: 2 ml in 20 ml vial S2: 2 ml, vial size ns E: 40°C(40 min) D: 200°C(2 min) GC-QMS/EI DB-5MS column (30 m × 0.25 mm × 0.25µm) ns ns ns 35-200
Xue et al. [67] blood     F: 75 µm CAR/PDMS H: manual T: 100µm PDMS, 65µm PDMS/DVB, CW/DVB, 85µm PA S: 5 ml in 15 ml vial E: 60°C(40 min, 1100 rpm) D: 250°C (30 s) GC-QMS/EI HP-5MS column (30 m × 0.25 mm × 0.25µm) ns 5.2 % ns ns
Yu et al. [68]   breath F: 100µmPDMS H: manual R: Non-polar hydrocarbons targeted, thick phase more suitable for VOCs S: 5 L Tedlar bag E: 26°C(20 min) D: 320°C (10 min) GC-FID DB-1 column (30 m × 0.25 mm × 0.25µm) 1.2 × 10-2– 1.26 ng/ml n/a 3.7-9.8 >0.98 n/a
Yu et al. [20]   breath1 cells in culture medium2 F: ns H: manual E1: 37°C(50 min) E2: RT (100 min) GC-MS (column ns) ns ns ns ns
Zhang et al. [21] cell culture medium F: 75 µm CAR/PDMS H: manual I: 38°C (10 min) E: 38°C(44 min, agitation) D: 280°C (2 min) GC-QMS/EI R×-5MS column (30 m × 0.25 mm × 0.25µm) ns ns ns 42-400
Zimmermann et al [24] cell culture medium F: 65µmCAR/DVB H: manual R: E×pected alcohols, esters and ketones E: 37°C(40 min) D: 200°C (20 s) GC-QMS/EI SB-11 column (60 m × 0.32 mm × 0.2 µm) ns ns ns ns
CAR: Carbo×en; D: Desorption; DVB: Divinylbenzene; E: E×traction; EI: Electron Ionization, F: SPME Fiber type Used; FID: Flame Ionization Detector, FS: Full Scan; GC: Gas - Chromatography; H: Holder type used; I: Incubation, IT: Ion Trap, LOD: Limit of Detection; M: Matri×; MS: Mass - Spectrometry; n/a: not applicable; ns: not specified; OFD: on-Fiber Derivatization; PA: Polyacrylate; PDMS: Polydimethylsilo×ane; PEG: Carbowa×-Polyethylene Glycol; PFBHA: O-(2,3,4,5,6-Pentafluorophenyl) Methylhydro×ylamine Hydrochloride; RSD: Relative Standard Deviation; RT: Room Temperature; Q: Quadupole, R2: Coefficient of Determination; R: Reason for the SPME Fiber Selection; S: Sample; SIM: Selected Ion Monitoring; T: SPME fibers that were tested, TOF: Time-Of-Flight; 1 = parameter or result used/obtained in the study or with the use of the matri× with the superscript 1; 2 = Parameter or result used/obtained in the study or with the use of the matrix with the superscript 2.
Table 1: Demonstrates the analysed matri×, the type of fiber and holder used, the e×traction conditions, the applied separation and the detection system, and the achieved methodvalidation parameters in the studies investigating potential biomarkers of cancer performed to date.