Sabrina Moret

Polycyclic aromatic hydrocarbons in edible fats and oils: occurrence and analytical methods

This review deals with analytical methods for polycyclic aromatic hydrocarbon (PAH) determination in oils and fats. The data reported in the introduction deal with PAH dietary intake from this group of food and contamination levels recently found by some authors in different vegetable oils, stressing the importance of establishing a method suitable for routine analyses. Traditional sample preparation relies on tedious, time-consuming procedures. They generally consist of an extraction step (liquid-liquid partition, caffeine complexation, saponification) followed by one or more purification procedures (column chromatography, thin-layer chromatography, solid-phase extraction). The analytical determination is usually carried out by HPLC and spectrofluorometric detection, or through high-resolution capillary GC coupled to flame ionisation detection or mass spectrometry. LC is a valid alternative to the traditional sample preparation, and off-line LC-LC allows performing an accurate PAH analysis in less than 2 h. Also supercritical fluid extraction, allowing performing both extraction and clean-up in one combined step, is a promising technique. Hyphenated techniques such as LC-GC and LC-LC-GC seem to be very promising. A completely on-line method for alkylated PAH determination in oils or lipidic extracts contaminated with mineral oil involves a two-dimensional LC-step with intermediate eluent evaporation and GC transfer through a vaporiser/overflow interface.

High-performance liquid chromatographic evaluation of biogenic amines in foods an analysis of different methods of sample preparation in relation to food characteristics

Biogenic amines are compounds formed by amino acid decarboxylation in fermented foods. Most of the methods for amine determination involve acid extraction followed by a liquid-liquid purification step. The different parameters which can influence amine recoveries are considered; experience with different foods such as cheese, fish and meat preserves are reported and for each of them the optimized analytical procedure is described. Data concerning recovery and repeatability of the method are also reported and the various factors that influence amine extraction are discussed. The possibility of applying direct derivatization without any other purification step is also considered.

A rapid method for polycyclic aromatic hydrocarbon determination in vegetable oils

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 μL 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%.

Overview on polycyclic aromatic hydrocarbons: Occurrence, legislation and innovative determination in foods

Polycyclic aromatic hydrocarbons are ubiquitous compounds, well-known to be carcinogenic, which can reach the food in different ways. Thus the analysis of such compounds has always been of great importance. The aim of the present review, is not only to give an overview of the most recent sample preparation and analytical approaches (such as pressurized liquid extraction, solid-phase microextraction, supercritical fluid extraction, etc.), but also to introduce such a topic to researchers who want to approach it for the first time; therefore, the most significant references related to general aspects, such as formation, toxicity, risk assessment, occurrence in food, are reported and briefly discussed.

Optimisation of microwave assisted extraction (MAE) for polycyclic aromatic hydrocarbon (PAH) determination in smoked meat.

A rapid extraction method involving microwave assisted extraction (MAE), followed by sample clean-up on a silica cartridge, reversed-phase high performance liquid chromatography (RP-HPLC) and spectrofluorimetric detection, was optimised for polycyclic aromatic hydrocarbon (PAH) determination in smoked meat. Compared to solvent extraction assisted by sonication, MAE, carried out with n-hexane on 2g of lyophilised sample at 115°C for 15min, allowed to obtain better extraction efficiencies. Limits of quantification (LOQ, s/n=10) lower than 0.2μg/kg wet weight were found for all PAHs, except for Fl (0.3μg/kg), P (0.6μg/kg) and IP (0.4μg/kg). The optimised procedure, that presented good analytical performances (with recoveries ranging from 77% to 103%, and precision within 10% for most of the PAHs), was applied to determine PAH content in different smoked meat products from the Italian market.

Improvement of extraction procedure for biogenic amines in foods and their high-performance liquid chromatographic determination

A high-performance liquid chromatography method is described for the simultaneous determination of the biogenic amines tryptamine, 2-phenylethylamine, putrescine, cadaverine, histamine, tyramine, spermidine, and spermine in cheese. The optimization of the procedure for the extraction of amines from the matrix is described. The separation of dansyl derivatives of the amines was achieved by reversed-phase liquid chromatography with gradient elution, followed by UV detection at 254 nm. The mobile phase was acetonitrile-0.01 M phosphate buffer (pH 7)-water. Under these conditions, rapid elution of the amines in less than 13 min was obtained. Validation of the method included calibration experiments, addition of standard amines for the determination of amine recoveries and repeatability tests.

Determination of polycyclic aromatic hydrocarbons (PAHs) in commonly consumed Nigerian smoked/grilled fish and meat

Smoking and/or grilling, when carried out with traditional methods involving direct contact with wood combustion fumes, is responsible for high contamination levels with carcinogenic polycyclic aromatic hydrocarbons (PAHs). The aim of this work was to investigate the PAH content of different smoked or grilled meat and fish products commonly consumed in Nigeria. A rapid method involving microwave-assisted saponification and simultaneous extraction followed by solid-phase extraction (SPE), high-performance liquid chromatography (HPLC) separation and spectrofluorometric detection was employed. Samples that were smoked or grilled using traditional systems, which use a wood fire, were heavily contaminated with benzo[a]pyrene (BaP) at levels ranging from 2.4 to 31.2 µg kg−1 wet weight. Considerably lower contamination levels were found in samples smoked or grilled in the laboratory using a charcoal fire (BaP from 0.7 to 2.8 µg kg−1 wet weight). The health risk associated with a daily consumption of 100 g of these products was also evaluated using the margin of exposure (MOE) approach. MOE values lower than 10,000 were obtained for all smoked/grilled commercial samples, indicating a potential concern for consumer health.

Rapid SPE-HPLC determination of the 16 European priority polycyclic aromatic hydrocarbons in olive oils.

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.

Occurrence of C15-C45 mineral paraffins in olives and olive oils.

Different classes of olive oils and other olive samples (olives, olive paste and olive pomace) collected during their production were analysed for mineral paraffins in the range of C15–C45. None of the 22 extra virgin olive oils contained mineral paraffins above the detection limit of 1 mg kg−1. Also, lampante virgin olive oil from the olive mill showed no detectable amounts, but olive oil from the market contained 6–30 mg kg−1. This contamination cannot be attributed to the refining step, which, on the contrary, partially removes the more volatile hydrocarbons, but could result from transport. Olive-pomace oils obtained by second centrifugation contained 16–145 mg kg−1 mineral paraffins, presumably because of contamination during storage of the pomace. All olive-pomace oils from solvent extraction contained more than 100 mg kg−1 mineral paraffins, also mainly from storage. Deposition of particulate matter from the air, vehicle exhaust emissions and direct contamination from the bulldozers used to move the pomace were identified as potential sources.

Polycyclic aromatic hydrocarbons in frying oils and snacks.

The high incidence of lung cancer observed among Chinese women has been associated with exposure to fumes from cooking oil. Polycyclic aromatic hydrocarbons (PAHs) are a class of potentially mutagenic substances emitted from cooking oils heated at high temperatures. The objective of this study was to investigate whether deep frying with different oils under different conditions leads to the development of PAHs either in the oil or in the fried product (snacks). PAH analysis was carried out with solid-phase extraction followed by reverse-phase high-performance liquid chromatography and spectrofluorometric detection. Different oils were used to fry chips and extruded snacks in different industrial plants (continuous frying) at temperatures between 170 and 205 degrees C, and peanut oil was used to fry French fries and fish (discontinuous frying) at temperatures between 160 and 185 degrees C. No appreciable differences in PAH load was observed in the same oil before and after frying. Both before and after frying, the benzo[a]pyrene concentration in oils ranged from trace to 0.7 ppb. All the analyzed samples, including oils from fried snacks, had benzo[a]pyrene concentrations well below the 2 ppb limit recently proposed by the European Community.