Determination of 3-Chloro-1,2-Propanediol in Foods and Food Ingredients by Gas Chromatography with Mass Spectrometric Detection: Collaborative Study

Abstract

The results of a collaborative study are reported for the determination of 3-chloro-1,2-propanediol (3-monochloropropane-1,2-diol; 3-MCPD) in a wide range of foods and food ingredients, using gas chromatography with mass spectrometric detection and incorporating the use of a deuterated internal standard. After a pretrial study, 12 laboratories (6 United Kingdom, 1 Switzerland, 1 Japan, 2 United States, 1 The Netherlands, and 1 from the European Commission) were asked to analyze 12 test materials (as known duplicates or split-level samples) by using a prescribed procedure. The test materials consisted of duplicate samples of acid-hydrolyzed vegetable protein (containing 3-MCPD at 0.029 mg/kg), malt extract (0.055 mg/kg), wholemeal bread crumbs (0.030 mg/kg), salami (0.016 mg/kg), cheese alternative (0.043 mg/kg), and soup powder (split levels at 0.045 and 0.041 mg/kg). Repeatability ranged from 0.005 to 0.013 mg/kg and reproducibility, from 0.010 to 0.027 mg/kg, for the samples tested. Precision values were well within statistically predicted levels (HORRAT values of <1 for 5 of the 6 matrixes tested) and within method criteria prepared by a joint working group composed of the United Kingdom Ministry of Agriculture, Fisheries and Food and industry representatives. The study demonstrated the satisfactory validation of the method for quantifying 3-MCPD at levels of ≥0.010 mg/kg. The limit of detection derived from separate in-house studies was estimated to be 0.005 mg/kg. The method was adopted First Action by AOAC INTERNATIONAL.

Risks for human health related to the presence of 3‐ and 2‐monochloropropanediol (MCPD), and their fatty acid esters, and glycidyl fatty acid esters in food

“…Reference materials containing 3-MCPD are commercially available only for soy sauce. The HFBI method has been validated for 3-MCPD in acid-HVP, stocks and soups, soy sauce, salami, fish, cheese, cereals and bread by an international collaborative trial (Brereton et al, 2001). The PBA method has been validated in-house for 3-and 2-MCPD using samples of biscuits, potato crisps, cereals, bread, meat and fish (Wenzl et al, 2015) and found to have good agreement with results obtained with HFBI.…”

“…Domestic cooking procedures have been shown to increase the levels of 3-MCPD in a limited number of foods studied. The effect is particularly observed in the toasting of bread (Crews et al, 2001;Breitling-Utzmann et al, 2003Hamlet and Sadd, 2004). The increase in the level of 3-MCPD content of bread is greater in brown and wholemeal types.…”

“…The increase in the level of 3-MCPD content of bread is greater in brown and wholemeal types. It has been shown that domestic grilling can increase 3-MCPD levels in cheeses, and microwave cooking produces a lesser increase (Crews et al, 2001). The frying or grilling of meat in the form of beef burgers produces low levels of 3-MCPD, and a significant increase in 3-MCPD can occurs on frying batter, depending on the ingredient composition.…”

“…The diethyl ether extract was concentrated to low volume and the 3-MCPD derivatised to the di-(HFB) prior to GC-MS. Deuterated internal standards were also introduced. Food samples were also analysed in this way (after removal of fat) by Hamlet (1998) who used GC with tandem mass spectrometric determination (GC-MS/MS), and by Brereton et al (2001) who used GC-MS in selected ion monitoring (SIM) mode. The latter method was validated by collaborative trial and was accepted as official methods by the Association of Official Analytical Chemists (AOAC) and by the European Committee for Standardization (CEN, 2004) and has found widespread use (Nyman et al, 2003;Le on et al, 2008).…”

Cyclohexanone/sulfonated polymer catalyst: a new simple derivatizing procedure for GC‐MS determination of 2‐ and 3‐monochloropropanediols

“…These methods suffer from various drawbacks associated with current derivatization schemes. Derivatization with HFBI requires strictly anhydrous conditions (Brereton et al 2001), an excess of PBA is deleterious to the chromatographic system or has to be removed after the reaction (Weisshaar 2008), and aliphatic ketone derivatives lack characteristic molecular ions of the derivatives (Dayrit and Ninonuevo 2004). This last derivatization is usually accomplished using p-toluenesulfonic acid as a catalyst which must be removed from the reaction medium through additional steps.…”