HPLC-FLD simultaneous determination of 13 polycyclic aromatic hydrocarbons: validation of an analytical procedure for soybean oils (original) (raw)
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Food Analytical Methods, 2016
The aim of this work was to determine the level of contamination of different groups of vegetable oils available on the Polish market with polycyclic aromatic hydrocarbons, i.e. benzo(a)pyrene and sum of benzo(a)pyrene, benz(a)anthracene, benzo(b)fluoranthene and chrysene, the content of which in foodstuffs is limited by Commission Regulation (EU) 2015/1125 of 10 July 2015. The research materials were refined rapeseed oils, sunflower oils, olive pomace oil, rapeseed oils with olive oil and unrefined soybean and coconut oils. The research methods included process of saponification of the vegetable oils, extraction of the polycyclic aromatic hydrocarbons fraction, clean-up by use a column packed with aluminum oxide and elution by petroleum ether, and then quantitative and qualitative determination of by high performance liquid chromatography with fluorescence detection method. Values of limit of detection and limit of quantification obtained during validation of the method were 0.18 and 0.25 μg/kg, respectively, and were significantly lower than the respective maximum values given in Commission Regulation (EU) 836/2011. The highest polyaromatic hydrocarbons content was found in unrefined coconut and soybean oils. The benzo(a)pyrene content and sum of benzo(a)pyrene, benz(a)anthracene, benzo(b)fluoranthene and chrysene in all the tested sample did not exceed the maximum levels given in Commission Regulation (EU) 2015/1125.
A rapid method for polycyclic aromatic hydrocarbon determination in vegetable oils
Journal of Separation Science, 2002
Despite the carcinogenic properties of some PAHs, and although edible oils are particularly prone to PAH contamination, no international legal limits for PAH in edible oils have been yet established. However, a number of methods for such analyses have been published, most of which are time consuming and unsuitable for routine analysis, as they do not permit analysis of a large number of samples per day. Since sample preparation is the most time-consuming part of analysis, research to find fast sample preparation methods is of topical interest. In this paper, solid phase extraction with silica cartridges is applied as sole sample preparation step. A 250-mg sample of oil in n-hexane is loaded onto a 5 g silica cartridge and the PAH fraction is eluted with 8 mL of n-hexane/dichloromethane 70/30. After solvent evaporation, the volume was adjusted to 100 lL and injected into a HPLC equipped with a C18 reverse phase column and a spectrofluorometric detector. Results show a relatively low recovery for the more volatile PAHs (Na and Ac) and good recovery for heavy PAHs. Repeatability is quite satisfactory, as coefficients of variation range between 5.0 and 13.0%.
Analytical and Bioanalytical Chemistry, 2008
A collaborative study on the analysis for 15+1 EU priority PAHs in edible oils was organised to investigate the state-of-the-art of respective analytical methods. Three spiked vegetable oils, one contaminated native sunflower oil, and one standard solution were investigated in this study. The results of 52 laboratories using either high-performance liquid chromatography with fluorescence detection or gas chromatography with massselective detectors were evaluated by application of robust statistics. About 95% of the laboratories were able to quantify benzo[a]pyrene together with five other PAHs included in the commonly known list of 16 US-EPA PAHs. About 80% of the participants also quantified seven additional PAHs in most samples, two of which were benzo[b]fluoranthene and benzo[k]fluoranthene, which were also known from the EPA list. Only about 50% of the participants quantified cyclopenta[cd]pyrene, benzo [j] fluoranthene, and benzo[c]fluorene. The robust relative standard deviations of the submitted results without discrimination between the methods applied ranged between 100% for 5-methylchrysene in spiked olive oil and 11% for the same analyte in spiked sunflower oil. The results clearly showed that for these analytes the methods of analysis are not yet well established in European laboratories, and more collaborative trials are needed to promote further development and to improve the performances of the respective methods.
Journal of Separation Science, 2003
An off-line high-performance normal-phase liquid chromatography procedure with a silica column followed by reversed-phase high-performance liquid chromatography (HPLC) with fluorescence detection for the determination of polycyclic aromatic hydrocarbons (PAHs) in edible oils is reported. The method was validated using certified reference materials and compared with a standardized method widely used in the food industry, consisting in low pressure column chromatography with alumina as stationary phase followed by reversed phase HPLC determination. The limits of detection were lower than 1 ng/g and good selectivity was achieved for both methods. There were no significant differences in accuracies and precisions obtained for each approach. The advantages and disadvantages of the two methods are discussed.
Acta Chromatographica
An HPLC method with fluorescence detection has been developed for determination of eight polycyclic aromatic hydrocarbons (PAH) with four to six condensed aromatic carbon rings in edible oils and smoked products. The method employs preparative size-exclusion chromatography for efficient one-step lipid removal without saponification; benzo[b]chrysene is used as internal standard for quantification. Two other methods (liquid-liquid extraction and solid-phase extraction) were tested for onestep clean-up and sample enrichment but it was found that one-step procedures did not remove lipids completely. Linearity of calibration plots was good for all PAH in the concentration range from the detection limit (approx. 0.1 ppb) to 100 ppb. The repeatability (RSD, n = 6) for different PAH ranged from 0.5 to 5%. Analysis of standard reference materials from the National Institute of Standards and Technology (mussel tissue, SRM 2978), the Community Bureau of Reference (coconut oil, CRM 458), and the Central Science Laboratory (olive oils, FAPAS 0615, 0618, and 0621) resulted in a good agreement between measured and certified concentrations. The method described has been used for determination of the PAH content of twelve samples of edible oil, rape seed, milk powder, hens' egg white and yolk, smoked sausage, white cottage cheese, and sprats. The PAH were identified from their fluorescence spectra.
Analytica Chimica Acta, 2009
High performance liquid chromatography coupled to an ultraviolet, diode array or fluorescence detector (HPLC/UV-FLD) has been used to set up a method to detect the 15(+1) EU priority polycyclic aromatic hydrocarbons (PAHs) in food supplements covering the categories of dried plants and plant extracts excluding oily products. A mini validation was performed and the following parameters have been determined: limit of detection, limit of quantification, precision, recovery and linearity. They were in close agreement with quality criteria described in the Commission Regulation (EC) No 333/2007 concerning the PAH benzo[a]pyrene in foodstuffs, except the not fluorescent cyclopenta [c,d]pyrene for which the UV detection leads to a higher limit of detection. Analysis of twenty commercial food supplements covering mainly the class of dried plants was performed to evaluate their PAHs contamination levels and to test the applicability of the method to various plant matrices. Fifty percent of analyzed samples showed concentration exceeding 2 g kg −1 for one or more PAHs.
Food Additives and Contaminants, 2007
A protocol for the measurement of 27 polycyclic aromatic hydrocarbons (PAHs) in vegetable oils by GC/MS has undergone single-laboratory validation. PAHs were measured in three oils (olive pomace, sunflower and coconut oil). Five samples of each oil (one unfortified, and four fortified at concentrations between 2 µg/kg and 50 µg/kg) were analysed in replicate (four times in separate runs). Two samples (one unfortified and one fortified at 2 µg/kg) of five oils (virgin olive oil, grapeseed oil, toasted sesame oil, olive margarine and palm oil) were also analysed. The validation included an assessment of measurement bias from the results of 120 measurements of a certified reference material (coconut oil BCR CRM458 certified for 6 PAHs).
Chromatographia, 1991
An on-line combination of liquid chromatography, gas chromatography and mass spectrometry has been realized by coupling a quadrupole mass spectrometer to an LC-GC apparatus. Liquid chromatography was used for sample Pretreatment of oil samples of different origin. The apPropriate LC fraction, containing polycyelic aromatic hydrocarbons, was transferred to the gas chromatograph Using a loop-type interface. After solvent evaporation through the solvent vapour exit and subsequent GC separation, the compounds were introduced into the mass Spectrometer for detection and identification. The GC Column was connected to a short piece of deactivated fused silica that protruded into the ion source. The total analytical setup allowed the direct analysis of oil samples after dilution in n-pentane without any sample clean-up. Detection limits arc about 40 pg in the full scan mode and about 1 pg with selective ion monitoring, i.e. 20 ppb and 0.5 ppb respectively.
Twenty-eight different tea samples sold in the United States were evaluated using high-performance liquid chromatography (HPLC) with fluorescence detection (FLD) for their contamination with polycyclic aromatic hydrocarbons (PAHs). Many PAHs exhibit carcinogenic, mutagenic, and teratogenic properties and have been related to several kinds of cancer in man and experimental animals. The presence of PAHs in environmental samples such as water, sediments, and particulate air has been extensively studied, but food samples have received little attention. Eighteen PAHs congeners were analyzed, with percentage recovery higher than 85%. Contamination expressed as the sum of the 18 analyzed PAHs was between 101 and 1337 mg/kg on dry mass and the average contents in all of the 28 examined samples was 300 mg/kg on dry mass. Seven of the congeners were found in all samples with wide ranges of concentrations as follows: fluorene (7-48 mg/kg), anthracene (1-31 mg/kg), pyrene (1-970 mg/kg), benzo(a)anthracene (1-18 mg/kg) chrysene (17-365 mg/kg), benzo(a)pyrene (1-29 mg/kg), and indeno(1,2,3-cd)pyrene (4-119 mg/kg). The two most toxic congeners benzo(a)pyrene and dibenzo(a,h)anthracene
Journal of Separation Science, 2008
Polycyclic aromatic hydrocarbons (PAHs) are a large class of organic compounds. It has been established that the main source of exposure to these compounds for human beings is through food, particularly fats and oils, due to the lipophilic nature of these polycyclic compounds. The aim of this work was to optimise and validate a method involving SPE and HPLC for rapid determination of the 16 European Union (EU) priority PAHs (required by the Recommendation 2005/108/EC) in vegetable oils. Two spectrofluorometric detectors and a UV-Visible detector in series were used to identify and quantify the target compounds. Linearity, recoveries, LOD, and LOQ were found to be in agreement with the performance criteria for benzo[a]pyrene (BaP) analysis as required by the Commission Directive 2005/10/EC, and satisfactory for all the compounds of interest, except for cyclopenta [c,d]pyrene, which presented a very low signal in the UV. Optimised chromatographic conditions for the separation of 25 PAHs, comprising both EPA and EU priority PAHs plus benzo[e]pyrene and benzo[b]chrysene, have been also proposed.