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PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry
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PerkinElmer: The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil Using Headspace Extraction and Gas Chromatography-Mass Spectrometry

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Levels of benzene, toluene, ethylbenzene, xylenes and styrene (BTEXS) find their way into olive trees and hence into the olives and olive oil mainly as a result of the presence of vehicle exhaust in …

Levels of benzene, toluene, ethylbenzene, xylenes and styrene (BTEXS) find their way into olive trees and hence into the olives and olive oil mainly as a result of the presence of vehicle exhaust in ambient air. Although there is widespread concern about the presence of these carcinogenic compounds in olive oil, no definitive methods or limits have yet been prescribed.

Various methods have been developed to detect and quantify these compounds down to levels of 5ng/g (5 ppb w/w). In this work, we have developed a simple method to determine these components in olive oil using headspace (HS) extraction and gas chromatography/mass spectrometry (GC/MS).

Sample preparation simply comprises dispensing and sealing 10g of olive into a standard 22-mL headspace vial and sampling the headspace vapor after being equilibrated at 90°C. The vapor is introduced into a Carbowax capillary column for chromatographic separation. Detection, identification and quantification is performed using a quadrupole MS system with a novel ionizer and detection system that enables detection limits, in single ion monitoring (SIM) mode, down to below 0.5ng/g without the need for headspace vapor preconcentration. The analysis is fully automated and takes just 10.5 minutes for the chromatography and an additional 3.5 minutes for cool-down and equilibration between analyses.
Excellent quantitative performance has been demonstrated and the system is easily able to see concentrations of these compounds in the range 0.9ng/g to 126.1ng/g in olive oil bought from a local supermarket.

Examples of the chromatography and quantitative performance will be presented.

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  • 1µL of 0.01% std into empty vial
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    1. The Determination of Benzene, Toluene, Ethyl Benzene, Xylenes and Styrene in Olive Oil using HS Extraction and GC/MS Andrew Tipler Chromatography R&D Manager PerkinElmer Inc., Shelton, CT© 2009 PerkinElmer 2012
    2. Olive Oil Olive oil is produced by grinding olives and extracting the oil by mechanical (pressing) or chemical (solvent extraction) means. Olive oil is composed mainly of the mixed triglyceride esters of oleic acid and palmitic acid and of other fatty acids, along with traces of squalene and sterols. It is commonly used in cooking, cosmetics, pharmaceuticals, and soaps and as a fuel.
    3. Olive Oil Production Annual per Production in Production % Consumption capita Country tons (2009) (2009) (2005) consumption (kg) World 2,907,985 100% 100% 0.4 Spain 1,199,200 41.2% 20% 13.6 Italy 587,700 20.2% 30% 12.4 Greece 332,600 11.4% 9% 23.7 Syria 168,163 5.8% 3% 7.0 Tunisia 150,000 5.2% 2% 11.1 Turkey 143,600 4.9% 2% 1.2 Morocco 95,300 3.3% 2% 1.8 Portugal 53,300 1.8% 2% 7.1 France 6,300 0.2% 4% 1.3 United States 2,700 0.1% 8% 0.6 Others 169,122 5.8% 18% 1.2 Source: Wikipedia.com
    4. Effects of Air Pollution Olive trees are good at absorbing air pollutants and passing them on to the olives and thus into the oil
    5. Acceptable limits for BTEXS in olive oil “Concentrations in olive oil were found to be around several tens of µg/kg for benzene; a few hundred µg/kg for toluene and many hundreds of µg/kg for the sum of ethyl benzene and xylenes. Substantial concentrations of styrene were found which however was probably of natural origin. The situation was considered to be sufficiently serious that a definition of provisional limits for these components was proposed (benzene: 50µg/kg; toluene: 180µg/kg; ethyl benzene: 50µg/kg; xylenes: 280µg/kg). However, these were not imposed as a consequence of disagreement in the European Union” . Maurus Biedermann, Konrad Krob, Gianni Morchio, Z Lebensm Unters Forsch (1995) 200; 266-272. Despite the strong concerns, even today, there still appears to be no agreement on the acceptable limits of BTEXS in olive oil. On 10 June 2011, the US National Toxicology Program has described styrene as "reasonably anticipated to be a human carcinogen".
    6. BTEXS (~0.6ng) separation using GC/MS Styrene 30m x 0.25mm x 1.0µm Elite-Wax o-Xylene Scan EI+ 9.92 TIC100 35(1)-10-130(0) Ethylbenzene 1.17e8 p-Xylene m-Xylene Toluene 8.85 7.94 8.07 Benzene 6.63 5.24 % 4.92 5.00 4.62 4.72 6.49 0 Time 5.05 5.55 6.05 6.55 7.05 7.55 8.05 8.55 9.05 9.55 10.05
    7. Sampling Olive Oil Olive oil is a heavy sample matrix and is not very GC- friendly. Direct injection will cause problems with breakdown and Don’t do this in your lab! contamination. Some form of extraction technique is required to separate the BTEXS from the sample matrix prior to introduction into the GC.
    8. Headspace Sampling Headspace sampling provides a very easy way to extract the volatile BTEXS compounds from the olive oil matrix. 10g of sample are placed in a vial which is then sealed with a cap and maintained at 90°C for 20 minutes. The volatile components (including BTEXS) will partition into the vapor phase 0.15mL of the vapor phase is transferred to the GC column for analysis.
    9. Analytical System Clarus SQ8 GC/MS TurboMatrix HS Sampler
    10. Pressure-Balanced Headspace Sampling Equilibration Pressurization Sampling V2 V1 V1 V1 PHS Valve closed for just a few secondsOlive oilsample
    11. Total Ion Chromatogram from Spiked Olive Oil 1: Scan EI+ Ethanol100 TIC 10g olive oil spiked with 17ng/g BTEXS 1.17e8 30m x 0.25mm x 1.0µm Elite-Wax 35(1)-10-130(0) Ethylbenzene p-Xylene Toluene m-Xylene Benzene o-Xylene Styrene % 6.57 7.21 4.62 4.63 4.91 5.70 7.97 8.34 5.91 6.29 10.43 8.21 6.06 8.91 0 Time 5.05 5.55 6.05 6.55 7.05 7.55 8.05 8.55 9.05 9.55 10.05
    12. Single Ion Monitoring Improves Selectivity and Detectability 9.93 100 2.61e4 Styrene SIM @ 104 Daltons % 0 Ethylbenzene p-Xylene 8.17 m-Xylene 100 9.38e3 SIM @ 106 Daltons o-Xylene 7.94 8.07 8.86 % 0 6.62 Toluene 100 4.80e4 SIM @ 92 Daltons % 0 5.24 100 Benzene 6.95e4 SIM @ 78 Daltons % 0 Time 5.10 5.60 6.10 6.60 7.10 7.60 8.10 8.60 9.10 9.60 10.10
    13. SiFi Enables ‘Simultaneous’ Full and Single Ion Data collection
    14. 0 % 1005.10 OliveOilAStd_060 Benzene @ 78 Da5.606.106.60 Toluene @ 92 Da7.107.60 Ethylbenzene @ 106 Da8.10 p-Xylene @ 106 Da m-Xylene @ 106 Da8.60 o-Xylene @ 106 Da9.10 SIM of Olive oil spiked with 17ng/g BTEXS9.60 9.95 Styrene @ 104 Da10.10 Time
    15. Extracted Calibration Plot for Benzene 18000 y = 178.38x - 60.006 16000 R² = 0.9998 14000 12000 Peak Area (Counts) 10000 8000 6000 4000 2000 0 0 10 20 30 40 50 60 70 80 90 100 Concentration (ppb w/w)
    16. Extracted Calibration Plot for Styrene 1200 y = 12.021x - 3.8872 R² = 0.9997 1000 800 Peak Area (Counts) 600 400 200 0 0 10 20 30 40 50 60 70 80 90 100 Concentration (ppb w/w)
    17. Quantitative Performance RSD r2 Limit of Detection Compound (% at 45ng/g, n=10) (from 4.5 to 90ng/g) (ng/g)Benzene 1.7 0.9998 0.1Toluene 3.8 0.9986 0.2Ethylbenzene 2.3 0.9995 0.3p-Xylene 3.5 0.9997 0.3m-Xylene 3.7 0.9998 0.3o-Xylene 3.3 0.9995 0.3Styrene 3.5 0.9997 0.3Standard mixtures prepared in 10g ‘clean’ olive oil
    18. Low-Level Determination of BTEXS in Olive Oil S/N:RMS=23.81 TIC100 1.84e3 Styrene, 3.1ng/g 10.03 9.71 9.80 10.17 % 0 S/N:RMS=39.67 TIC100 2.47e3 m-Xylene, 5.4ng/g 8.85 % 8.34 7.93 8.06 8.57 8.93 9.05 7.73 7.80 0 S/N:RMS=71.15 TIC100 1.10e4 Toluene, 5.9ng/g % 0 S/N:RMS=14.84 TIC100 3.90e3 Benzene, 0.9ng/g 5.01 5.42 % 0 Time 5.10 5.60 6.10 6.60 7.10 7.60 8.10 8.60 9.10 9.60 10.10
    19. Background from ‘Clean’ Olive Oil Toluene @ 92 Da Benzene @ 78 Da ‘Clean’ Olive Oil spiked with 17ng/g BTEXSOliveOilAStd_060100 Ethylbenzene @ 106 Da m-Xylene @ 106 Da Styrene @ 104 Da p-Xylene @ 106 Da o-Xylene @ 106 Da % 9.95 0 5.10 5.60 6.10 6.60 7.10 7.60 8.10 8.60 9.10 9.60 10.10 Time ‘Clean’ Olive OilOliveOilA_061100 % 0 Time 5.10 5.60 6.10 6.60 7.10 7.60 8.10 8.60 9.10 9.60 10.10
    20. BTEXS in Olive Oil from Local Supermarket (ng/g) Ethylbenzene Sample Source m-Xylene p-Xylene o-Xylene Benzene Toluene StyreneCalifornia 0.89 5.86 1.66 1.45 5.24 3.77 3.07Italy, Greece, Spain Tunisia 2.86 27.55 6.12 5.86 16.73 8.75 41.34Italy, Spain, Greece, Tunisia 3.07 24.22 13.47 7.85 23.64 13.97 39.59Italy, Spain, Tunisia, Turkey, 2.99 17.03 3.74 3.44 9.35 6.14 40.09ArgentinaSpain, Argentina 2.43 34.99 7.22 7.42 18.97 10.65 126.11Italy, Spain, Greece, Tunisia, 4.09 35.71 19.13 17.10 59.31 28.10 61.05Morocco, Syria, TurkeyItaly, Greece, Spain, Tunisia 1.25 2.79 ND 1.80 3.74 3.17 7.39
    21. Conclusions The sensitivity of the MS detector in SIM mode enables detection of low levels of BTEXS with standard headspace sampling. Detection limits of 0.1 to 0.3ng/g have been demonstrated which compare favorably against those in other published papers (~5ng/g). The HS sampling system simplifies sample preparation and eliminates the effects from a heavy sample matrix entering the chromatographic column and the MS detector. Good quantitative performance has been shown. Significant levels of BTEXS were found in olive oils purchased at a local (Connecticut) supermarket.

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