Analytical determination of bisphenol A (BPA) and bisphenol analogues in paper products by LC-MS/MS

ABSTRACT

In this study a sensitive analytical method based on liquid chromatography-electrospray tandem mass spectrometry (LC-MS/MS) was developed for the simultaneous analysis of bisphenol A (BPA), bisphenol AF (BPAF), bisphenol B (BPB), bisphenol E (BPE), bisphenol F (BPF) and bisphenol S in different paper and board products, including virgin fibre samples and recycled samples. Analytes were extracted from the paper matrix using a simple solvent extraction and chromatographic separation was performed on a C18 core-shell (100 mm x 2.1 mm i.d.; 1.7 µm particle size) column. The developed method showed good linearity (R² > 0.9921) for all analytes. Absolute recoveries ranged from 71 to 115% and precision in terms of reproducibility and repeatability (intra- and inter-day) yielded in relative standard deviations (RSDs) of less than 15.0% and 17.4%, respectively. The limit of detection (LOD) and limit of quantification (LOQ) for the different analytes ranged from 0.29 to 0.40 µg kg^?1 paper and from 1.09 to 1.32 µg kg^?1 paper, being in the same range for all analytes. Quantitation of the analytes was performed using the internal standard procedure, with concentrations of < LOQ to 9599 µg kg^?1 for the different analytes. Furthermore, a calculation of the maximum migration, assuming the ‘worst case’ scenario of 100% migration was performed.     

Analytical determination of bisphenol A (BPA) and bisphenol analogues in paper products by GC-MS/MS

ABSTRACT

Bisphenol A (BPA; 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol), a suspected endocrine disruptor with a weak estrogenic activity, is used in a variety of consumer products, including food-contact materials made of paper and cardboard products. Due to restrictions on the use of BPA because of its potential health risks, BPA is gradually being replaced by other bisphenols because no limitations exist for these substances. This study presents a method for the simultaneous analysis of BPA, bisphenol AF (BPAF), bisphenol B (BPB), bisphenol E (BPE), bisphenol F (BPF) and bisphenol S (BPS) in paper and board products using gas chromatography-tandem mass spectrometry (GC-MS/MS). Paper samples were extracted by liquid extraction, as well as by Folch extraction, derivatised with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and the results compared. The developed method showed good linearity (R² > 0.9965) and precision, yielding relative standard deviations (RSDs) of less than 16.6% for reproducibility and 19.8% for repeatability. The limits of detection and limits of quantification for the different bisphenols ranged from 0.23 to 2.70 µg kg^–1 paper and from 0.78 to 9.10 µg kg^–1 paper, respectively. Analysis of different paper products (recycled, virgin fibre) showed that all the analysed bisphenols were present in the samples, except for BPAF and BPB. A calculation of the ‘worst-case’ scenario assuming a maximum potential migration of 100% of the analytes into food showed that the analysed products can be assumed to be safe regarding the migration of bisphenols.     

Determination of bisphenol A in canned fatty foods by coacervative microextraction,liquid chromatography and fluorimetry

Decanoic acid reverse micelle-based coacervates were used to provide simple, rapid and almost solventless extraction of bisphenol A (BPA) from canned fatty foods. The procedure involved the extraction of 200–400 mg of homogenised food sample with an aqueous solution containing 20% THF and 200 mg of decanoic acid, conditions under which the coacervate (around 550 µl) formed in situ and instantaneously. The overall sample treatment took about 30 min and several samples could be simultaneously treated using conventional laboratory equipment. No clean-up or solvent evaporation were required before determination of BPA by liquid chromatography and fluorescence detection. Recoveries in samples were between 90 and 99%, with relative standard deviations in the range 2–7%. The limit of quantification ranged 29–15 ng g^?1 for 200–400 mg of sample, being far below the current specific migration limit (SML) set by the European Commission (600 ng g^?1). The method was successfully applied to the determination of BPA in the solid content of canned fish (from 20 to 129 ng g^?1) and meat (from undetected to 37 ng g^?1).     

Migration of bisphenol A from polycarbonate baby bottles under real use conditions

Migration of the potential endocrine disrupter, bisphenol A (BPA), from 31 polycarbonate (PC) baby bottles into aqueous food simulants was studied under real repetitive use, using a sensitive and fully validated liquid chromatographic method with fluorescence detection. Confirmation of the presence of BPA was performed by liquid chromatography–mass spectrometry (LC–MS). The effects of cleaning in a dishwasher or with a brush, sterilization with boiling water and the temperature of migration were examined. It was shown that temperature was the crucial factor for the migration of BPA from the plastic bottles to water. All samples released BPA in the concentration range 2.4–14.3 µg kg^?1 when filled with boiled water and left at ambient temperature for 45 min. The decrease of BPA release in the sterilization water and in the food simulant over 12 cycles of use indicated that the hypothesis of polymer degradation in water is dubious. Estimated infantile dietary exposure, regarding the use of PC baby bottles, ranged between 0.2 and 2.2 µg kg^?1 bw day^?1, which is below the Tolerable Daily Intake of 50 µg kg^?1 bw recently established by EFSA.     

Simultaneous determination of bisphenol A and bisphenol B in beverages and powdered infant formula by dispersive liquid–liquid micro-extraction and heart-cutting multidimensional gas chromatography-mass spectrometry

The purpose of this study was to establish a reliable, cost-effective, fast and simple method to quantify simultaneously both bisphenol A (BPA) and bisphenol B (BPB) in liquid food matrixes such as canned beverages (soft drinks and beers) and powdered infant formula using dispersive liquid–liquid micro-extraction (DLLME) with in-situ derivatisation coupled with heart-cutting gas chromatography-mass spectrometry (GC-MS). For the optimisation of the DLLME procedure different amounts of various extractive and dispersive solvents as well as different amounts of the derivative reagent were compared for their effects on extraction efficiency and yields. The optimised procedure consisted of the injection of a mixture containing tetrachloroethylene (extractant), acetonitrile (dispersant) and acetic anhydride (derivatising reagent) directly into an aliquot of beverage samples or into an aqueous extract of powdered milk samples obtained after a pretreatment of the samples. Given the compatibility of the solvents used, and the low volumes involved, the procedure was easily associated with GC-MS end-point determination, which was accomplished by means of an accurate GC dual column (heart-cutting) technique. Careful optimisation of heart-cutting GC-MS conditions, namely pressure of front and auxiliary inlets, have resulted in a good analytical performance. The linearity of the matrix-matched calibration curves was acceptable, with coefficients of determination (r2) always higher than 0.99. Average recoveries of the BPA and BPB spiked at two concentration levels into beverages and powdered infant formula ranged from 68% to 114% and the relative standard deviation (RSD) was <15%. The limits of detection (LOD) in canned beverages were 5.0 and 2.0?ng?l^–1 for BPA and BPB, respectively, whereas LOD in powdered infant formula were 60.0 and 30.0?ng?l^–1, respectively. The limits of quantification (LOQ) in canned beverages were 10.0 and 7.0?ng?l–1 for BPA and BPB, respectively, whereas LOQ in powdered infant formula were 200.0 and 100.0?ng?l^–1, respectively. BPA was detected in 21 of 30 canned beverages (ranging from 0.03 to 4.70?µg?l^–1) and in two of seven powdered infant formula samples (0.23 and 0.40?µg?l^–1) collected in Portugal. BPB was only detected in canned beverages being positive in 15 of 30 samples analysed (ranging from 0.06 to 0.17?µg?l^–1). This is the first report about the presence of BPA and BPB in canned beverages and powdered infant formula in the Portuguese market.     

Comparing different gas chromatographic methods for the quantification of bisphenol A (BPA) trace levels in paper and cardboard products from the market

Bisphenol A (BPA; 4,4?-(propane-2,2-diyl)diphenol), a suspected endocrine disruptor with weak estrogenic activity, is used in a variety of consumer products, including paper and cardboard products used as food contact materials. The present study compared four different gas chromatographic methods for the analysis of BPA in paper and cardboard food packages. Eighteen different food packages were extracted and BPA was determined using two different derivatisation reactions – trimethylsilylation with N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) and halide alkylation with pentafluorobenzoyl chloride (PFBOCl) – and four different separation and detection techniques. The BSTFA derivatives were quantified with (1) GC-MS in single-ion monitoring (SIM) mode with electron ionisation (EI-GC-MS) and (2) GC-MS/MS in multiple reaction monitoring (MRM) mode using electron ionisation (EI-GC-MS/MS); while the PFBOCl derivatives were quantified with (3) GC-MS using electron ionisation (EI-GC-MS) as well as (4) GC-MS with negative chemical ionisation (NCI-GC-MS). All developed methods showed good linearity (R² > 0.9938), precision (CV < 4.5% for reproducibility; CV < 2.2% for repeatability) and sensitivity, with limits of detection (LODs) between 0.02 µg kg^?1 for the pentafluorobenzoyl derivatives measured with the NCI-GC-MS method and 6 µg kg^?1 for the pentafluorobenzoyl derivatives determined with EI-GC-MS. Levels of BPA in the samples were in agreement for all methods, ranging from values below the limit of quantitation (LOQ) to 11.9 mg kg^?1 paper. In a last step, the maximum potential migration into food products was calculated for all tested paper and cardboard samples, assuming a ‘worst case’ scenario of 100% migration.     

Migration of bisphenol A from plastic baby bottles,baby bottle liners and reusable polycarbonate drinking bottles

Human exposure to bisphenol A (BPA) has recently received special attention. It has been shown that exposure to BPA may occur through the consumption of beverages or foods that have been in contact with polycarbonate (PC) plastic containers or epoxy resins in food packaging. A BPA migration study was conducted using a variety of plastic containers, including polycarbonate baby bottles, non-PC baby bottles, baby bottle liners, and reusable PC drinking bottles. Water was used to simulate migration into aqueous and acidic foods; 10% ethanol solution to simulate migration to low- and high-alcoholic foods; and 50% ethanol solution to simulate migration to fatty foods. By combining solid-phase extraction, BPA derivatization and analysis by GC-EI/MS/MS, a very low detection limit at the ng l^?1 level was obtained. Migration of BPA at 40°C ranged from 0.11 µg l^?1 in water incubated for 8 h to 2.39 µg l^?1 in 50% ethanol incubated for 240 h. Residual BPA leaching from PC bottles increased with temperature and incubation time. In comparison with the migration observed from PC bottles, non-PC baby bottles and baby bottle liners showed only trace levels of BPA. Tests for leachable lead and cadmium were also conducted on glass baby bottles since these represent a potential alternative to plastic bottles. No detectable lead or cadmium was found to leach from the glass. This study indicated that non-PC plastic baby bottles, baby bottle liners and glass baby bottles might be good alternatives for polycarbonate bottles.     

A survey of bisphenol A and other bisphenol analogues in foodstuffs from nine cities in China

Bisphenol A (BPA) is a high-production-volume chemical that is widely used in polycarbonate plastics and epoxy food-can coatings. Following several studies that have reported adverse effects of BPA over the past decade, other bisphenol analogues, such as bisphenol F (BPF), bisphenol S (BPS), bisphenol AF (BPAF), and bisphenol B (BPB), have been gradually developed as substitutes for BPA in several applications. Nevertheless, few studies have reported on the occurrence of compounds other than BPA in foodstuffs. In this study, 289 food samples (13 categories: cereals and cereal products, meat and meat products, fish and seafood, eggs, milk and milk products, bean products, fruits, vegetables, cookies/snacks, beverages, cooking oils, condiments, and others), collected from nine cities in China, were analysed for eight bisphenol analogues using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). BPA and BPF were found widely in foodstuffs at concentrations ranging from below the limit of quantitation (LOQ) to 299 ng g^–1 (mean = 4.94 ng g^–1) and from below the LOQ to 623 ng g^–1 (mean = 2.50 ng g^–1), fresh weight, respectively. The highest total concentrations of bisphenols (∑BPs: sum of eight bisphenols) were found in the category of vegetables that included canned products (mean = 27.0 ng g^–1), followed by fish and seafood (16.5 ng g^–1) and beverages (15.6 ng g^–1). ∑BP concentrations (mean = 2–3 ng g^–1) in milk and milk products, cooking oils, and eggs were low. Food samples sold in metallic cans contained higher mean ∑BP concentrations (56.9 ng g^–1) in comparison with those packaged in glass (0.43 ng g^–1), paper (11.9 ng g^–1), or plastic (6.40 ng g^–1). The daily dietary intakes of bisphenols were estimated, based on the mean concentrations measured and daily consumption rates of foods, to be 646 and 664 ng kg^–1 bw day^–1 for men and women, respectively.     

Determination of 2,6-diisopropylnaphthalene (DIPN) and n-dibutylphthalate (DBP) in food and paper packaging materials from US marketplaces

A gas chromatography-ion-trap tandem mass spectrometry procedure was developed for the determination of 2,6-diisopropylnaphthalene (DIPN) and n-dibutylphthalate (DBP) in domestic and imported paper packages and food sold in US marketplaces. The procedure involved ultrasonic extraction with dichloromethane, followed by analysis with the gas chromatography-ion-trap tandem mass spectrometry. Calibration curves for DIPN and DBP were achieved with concentrations ranging from 0.01 to 10 µg ml^?1 and the corresponding r ² values were 0.9976 and 0.9956, respectively. In most of the fortified samples the recoveries were higher than 80% with a relative standard deviation (RSD) <10%. Using this procedure, it was found that less than 20% of the tested domestic packages and more than 60% of the tested imported food packages contained both DIPN and DBP. The concentrations of DIPN and DBP ranged from 0.09 to 20 mg kg^?1 and 0.14 to 55 mg kg^?1, respectively, with most of the DINP and DBP levels lower than 20 mg kg^?1. DIPN was not detected (<0.01 mg kg^?1) in 41 food samples and DBP was only detected in two domestic and four imported food samples with concentrations ranging from <0.01 to 0.81 mg kg^?1.     

A sensitive determination method for carbendazim and thiabendazole in apples by solid-phase microextraction−high performance liquid chromatography with fluorescence detection

A new analytical method for the determination of carbendazim (MBC) and thiabendazole (TBZ) in apples is reported, based on solid-phase microextraction (SPME) coupling HPLC with fluorescence detection. The main SPME and HPLC experimental conditions were optimized. The apples were first blended and centrifuged. Then, an aliquot of the resulting solution was subjected to SPME on a 60 µm polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibre for 35 min at room temperature with the solution being stirred at 1100 rev min^–1. The extracted pesticides on the SPME fibre were desorbed in the mobile phase into the SPME/HPLC interface for HPLC analysis. The method was linear over the range 0.01–1 mg kg^–1 in apples for both MBC and TBZ, with detection limits of 0.005 and 0.003 mg kg^–1 and correlation coefficients of 0.9995 and 0.9998, respectively. The average recoveries for MBC and TBZ were 91.5 and 92.3% with the relative standard deviations (RSD) of 4.7 and 4.1% at the 0.1 mg kg^–1 level, and 94.6 and 96.1% with RSD of 3.3 and 3.8% at the 0.5 mg kg^–1 level, respectively. The method is simple, sensitive, organic solvent-free and is suitable for the determination of MBC and TBZ in apples.     

Migration of bisphenol A into water from polycarbonate baby bottles during microwave heating

A comprehensive migration database was established for bisphenol A from polycarbonate baby bottles into water during exposure to microwave heating. Eighteen different brands of polycarbonate baby bottles sold in Europe were collected. Initial residual content of bisphenol A and migration after microwave heating were determined. Residual content of bisphenol A in the polycarbonate baby bottles ranged from 1.4 to 35.3 mg kg^?1. Migration of bisphenol A was determined by placing a polycarbonate bottle filled with water in a microwave oven and heating to 100°C; the level of bisphenol A in the water was analysed by GC–MS. The procedure of microwave heating and analysis was repeated twice for the same bottle and, thus, three migration extracts were prepared for each test specimen. Migration of bisphenol A into water ranged from <0.1 to 0.7 µg l^?1. There was no correlation between the amount of residual content of bisphenol A in the bottles and the migration of bisphenol A into water. Furthermore, there was no correlation between the amounts of bisphenol A in consecutive migration extracts. Data show that during three microwave-heating cycles of a baby bottle made from polycarbonate, microwave radiation had no effect on the migration of bisphenol A into water from polycarbonate. All levels found were well below the specific migration limit of 0.6 mg kg^?1 specified for bisphenol A in Commission Directive 2004/19/EC.     

Ionic Liquid-Immobilized Expanded Perlite Solid-Phase Extraction for Separation/Analysis of Bisphenol A in Food Packaging Material

The ionic liquid-immobilized expanded perlite (IL-EP) as a novel solid phase extraction adsorbent coupled with fluorescence spectroscopy for the separation/analysis of bisphenol A (BPA) was established. The results showed that BPA was rapidly adsorbed on IL-EP and separated/recycled from aqueous solution without centrifugation. It was worth mentioning that methanol as eluent could give a significant enhancement to the fluorescence of BPA. Moreover, the pseudo-second-order model fitted the adsorption kinetics data well, which indicated that chemisorption controlled the adsorption of BPA on IL-EP. The linear calibration curve for BPA was obtained over the concentration ranges of 0.01–10.0 μg mL^?1 with the detection limits (LOD) of 0.3 ng mL^?1. This method was applied to determinate BPA in food packaging material with reasonable results.     

Comparison of four analytical techniques based on atomic spectrometry for the determination of total tin in canned foodstuffs

Different techniques for the determination of total tin in beverages and canned foods by atomic spectrometry were compared. The performance characteristics of inductively coupled plasma-mass spectrometry (ICP-MS), hydride generation-inductively coupled plasma-atomic emission spectrometry (HG-ICP-AES), electrothermal atomisation-atomic absorption spectrometry (ETA-AAS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) were determined in terms of linearity, precision, recovery, limit of detection, decision limit (CCα) and detection capability (CCβ) (Decision 2002/657/EC). Calibration ranges were covered from ng?l^?1 to mg?l^?1 level. Limits of detection that ranged from 0.01, 0.05, 2.0 to 200?µg?l^?1 were reached for ICP-MS; HG-ICP-AES; ETA-AAS and ICP-AES, respectively. Precision, calculated according to ISO 5725-2 for repeatability and within-laboratory reproducibility and expressed as relative standard deviation (RSD), ranged from 1.6% to 4.9%; and recovery, based on Decision 2002/657/EC, was found to be between 95% and 110%. Procedures for the mineralisation or extraction of total tin were compared. Wet digestion, sequentially, with nitric acid and hydrogen peroxide provided the best results. The influence of possible interferences present in canned food and beverage was studied, but no interference in the determination of tin was observed. Since maximum levels for tin established by European Union legislation vary from 50?mg?kg^?1 in canned baby foods and infant foods up to 200?mg?kg^?1 in canned food, ICP-AES was chosen as the preferred technique for routine analysis thanks to its good precision, reliability and ease of use. The accuracy of this routine method was confirmed by participation in six proficiency test schemes with z-scores ranging from ?1.9 to 0.6. Several canned foodstuffs and beverage samples from a local market were analysed with this technique.     

Determination of furan levels in commercial samples of baby food from Brazil and preliminary risk assessment

Commercial baby food samples available on the Brazilian market (n = 31) were analysed for furan content using a gas chromatography-mass spectrometry method preceded by solid-phase microextraction. A limit of detection of 0.7 µg kg^?1, a limit of quantitation of 2.4 µg kg^?1, mean recoveries varying from 80% to 107%, and coefficients of variation ranging from 5.6% to 9.4% for repeatability and from 7.4% to 12.4% for within-laboratory reproducibility were obtained during an in-house validation. The levels of furan found in the samples were from not detected to 95.5 µg kg^?1. Samples containing vegetables and meat showed higher furan levels as compared with those containing only fruits. An exposure assessment showed furan intakes up to 2.4 µg kg^?1 body weight day^?1 (99th percentile) for babies fed exclusively with commercial baby foods. Margins of exposure obtained from intakes estimated in this work indicated a potential public health concern.     

Intake of bisphenol A from canned beverages and foods on the Belgian market

Bisphenol A (BPA), a contaminant which may be present in the coating of cans, was determined in 45 canned beverages and 21 canned food items from the Belgian market. Beverages had an average BPA concentration of 1.0 ng/ml, while canned foods had a higher average concentration of 40.3 ng/g. The amount of BPA present in food items was dependent on the type of can and sterilisation conditions rather than the type of food. For example, BPA was not detected in non-canned beverages (<0.02 ng/ml), while non-canned food items had a very low average concentration of 0.46 ng/g. Using detailed information from the Belgian food consumption survey, the BPA intake of adults through canned foods and beverages was estimated to be 1.05 µg/day or 0.015 µg/kg body weight/day (assuming an average adult weight of 70 kg). Intake assessments, based on urinary metabolite concentrations from the literature, resulted in slightly higher BPA intakes (range 0.028–0.059 µg/kg body weight/day). This suggests that sources other than canned foods and beverages contribute to BPA exposure in humans.     

Survey of fumonisins B1, B2 and B3 in conventional and organic retail corn products in Spain and Italy and estimated dietary exposure

A survey was conducted to determine the occurrence of fumonisin B₁, B₂ and B₃ during 2007 in 186 samples of organic and conventional locally available corn products. Samples included baby food (n = 62), corn flour (11), cornflakes (23), pasta (14), cookies (17) and other corn products (59) were obtained from popular markets of Valencia (Spain) and Perugia (Italy). The analytical method used pressurized liquid extraction and liquid chromatography/electrospray ionization tandem mass spectrometry with a triple quadrupole (QqQ) analyser. Of the 104 Spanish samples, 22% contained levels in the range of 2–449 µg kg^?1, 2–229 µg kg^?1 and 6–105 µg kg^?1 for FB₁, FB₂ and FB₃, respectively, while 19 (23%) of the 82 Italian samples were positive with quantifiable levels between 2–235 µg kg^?1, 3–187 µg kg^?1, and 4–40 µg kg^?1 for fumonisins B₁, B₂ and B₃, respectively. Overall, none of the Italian samples and only one organic baby food sample from a Spanish market was above the maximum permitted levels established by European legislation. Fumonisins were found mostly in corn flour followed by cookies and cornflakes. Eleven samples from Spain and nine samples from Italy were organic products, being contaminated the 72% and 77% of the samples, respectively. Analysis of the results showed that levels of fumonisins in corn products were similar in Italy and Spain. The safety of fumonisin intake through corn products was demonstrated by the calculation of the estimated daily intake of both populations considering organic and conventional products separately, which ranged from 1.7 × 10^?3 to 0.72 µg kg^?1 bw day^?1 and comparing them with the provisional maximum total daily intake (PMTDI) of 2 µg kg^?1 bw day^?1 established by the European Union.     

Effect of sterilisation and storage conditions on the migration of bisphenol A from tinplate cans of the Lebanese market

The use of bisphenol A (BPA) in lacquer coating of food cans has been restricted by different authorities in many countries, such as in Europe. However, such regulation does not exist in many other countries including Lebanon. Due to the lack of data on the quality of Lebanese can production; this study investigates the migration of BPA from two types of tinplate cans manufactured in Lebanon, before and after sterilisation. Cans were analysed under different storage conditions (time and temperature) and filled with an aqueous simulant. The determination of BPA was carried out using UPLC with fluorescence detection, and further confirmed by MS detection. After sterilisation BPA levels drastically increased from an average of 0.15 to 109 µg/kg, giving a BPA migration around 10.5 µg/dm² for both types of cans. Storage temperature and time had no significant influence on BPA levels in sterilised cans (p-value > 0.05); however, these factors significantly affected BPA levels in non-sterilised cans.     

Organochlorine pesticides in canned tuna and sardines on the Serbian market

The aim of this study was to determine the level of organochlorine (OC) pesticides in 57 samples of canned tuna and 31 samples of canned sardines in vegetable oil, collected from supermarkets in Serbia. OC pesticides α-HCH, β-HCH, δ-HCH, dichlorodiphenyltrichloroethane (DDT), DDE, DDD, dielderin, endosulfane I, endosulfane II, endosulan sulfate, endrin, endrin ketone, heptachlor, heptachlor epoxide, lindane, aldrin, metoxichlor, cis-chlordane and trans-chlordane were determined using a GS-MS method. The highest concentrations (µg kg^?1, arithmetic means) in canned tuna were for δ-HCH (60.6 ± 97.0) and p, p´-DDT (55.0 ± 25.1), while the corresponding values in canned sardines were for δ-HCH (90.7 ± 102.7) and endosulfane II (78.0 ± 145.9). Mean level for the sum of endosulfans was above the maximum limit in canned sardines (85.0 µg kg^?1). Also, dieldrin (39.7 µg kg^?1) was measured above the ML.     

Rapid determination of ethyl carbamate in Chinese rice wine using headspace solid‐phase microextraction and gas chromatography–mass spectrometry

Ethyl carbamate (EC) is a naturally occurring toxic contaminant that may imply a risk to human health and is usually found in alcoholic beverages such as Chinese rice wine. An automated procedure for the rapid determination of EC in Chinese rice wine was developed by headspace solid‐phase microextraction (HS‐SPME) coupled to gas chromatography–mass spectrometry (GC‐MS). Using propyl carbamate as internal standard, the optimized HS‐SPME sampling with a polyacrylic fibre was 45 min at 70°C after applying 38.8% NaCl to saturate the sample. This method showed good linearity over a range of 25–600 µg L^?1 (R² = 0.997). The recovery, relative standard deviation and limit of detection were 90.21–97.35%, lower than 2.89% and 1.19 µg L^?1, respectively. Additionally, the ethanol concentration had no effect on the analysis of EC. The total analysis time of 57 min per sample in continuous determination was twice as fast as the widely used solid‐phase extraction–GC‐MS method. This solvent‐free HS‐SPME‐GC‐MS procedure is suitable for the rapid, automated, and therefore convenient, determination of EC in Chinese rice wine. Copyright © 2012 The Institute of Brewing & Distilling     

Polycyclic aromatic hydrocarbons and halogenated persistent organic pollutants in canned fish and seafood products: smoked versus non-smoked products

In this study, levels of several groups of environmental contaminants represented by PAHs, PCBs, organochlorine pesticides and polybrominated diphenyl ethers were determined in various types of canned smoked and non-smoked fish and seafood products (54 samples) obtained from the Czech market. PAHs were detected in all of the studied samples, and at least one of the target halogenated persistent organic pollutants was present above the LOQ in 85% of the samples. The levels of PAHs, PCBs, organochlorine pesticides (mainly DDTs) and polybrominated diphenyl ethers found in the canned products varied in the range of 1.4–116?µg?kg^?1, 0.6–59.6?µg?kg^?1, 0.6–82.7?µg?kg^?1 and 0.1–2.1?µg?kg^?1 can content, respectively. Smoked sprats were the most contaminated fish product (n?=?12) in which the highest levels of both PAHs and persistent organic pollutants were found. In 67% of the samples of smoked sprats in oil, the level of benzo[a]pyrene exceeded the maximum level of 5?µg?kg^?1 established for smoked fish by European Union legislation. The distribution of target analytes between oil and fish fractions was also assessed. Significantly higher levels of PAHs were measured in the oil fraction.