Ingrid Ericson Jogsten

Levels in food and beverages and daily intake of perfluorinated compounds in Norway

Perfluorinated compounds (PFCs) have been determined in 21 samples of selected food and beverages such as meat, fish, bread, vegetables, milk, drinking water and tea from the Norwegian marked. Up to 12 different PFCs were detected in the samples. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were found in concentrations similar to or lower than what has been observed in other studies world-wide. Differences in the relative proportion of PFOA and PFOS between samples of animal origin and samples of non-animal origin were observed and support findings that PFOS has a higher bioaccumulation potential in animals than PFOA. Based on these 21 measurements and consumption data for the general Norwegian population, a rough estimate of the total dietary intake of PFCs was found to be around 100 ng d(-1). PFOA and PFOS contributed to about 50% of the total intake. When dividing the population in gender and age groups, estimated intakes were decreasing with increasing age and were higher in males than females. The estimated intakes of PFOS and PFOA in the present study are lower than what has been reported in studies from Spain, Germany, United Kingdom, Canada and Japan. This study illustrates that by improving the analytical methods for determination of PFC in food samples, a broad range of compounds can be detected, which is important when assessing dietary exposure.

Exposure to perfluorinated compounds in Catalonia, Spain, through consumption of various raw and cooked foodstuffs, including packaged food.

In this study, the role that some food processing and packaging might play as a source of perfluorinated compounds (PFCs) through the diet was assessed. The levels of PFCs were determined in composite samples of veal steak (raw, grilled, and fried), pork loin (raw, grilled, and fried), chicken breast (raw, grilled, and fried), black pudding (uncooked), liver lamb (raw), marinated salmon (home-made and packaged), lettuce (fresh and packaged), pate of pork liver, foie gras of duck, frankfurt, sausages, chicken nuggets (fried), and common salt. Among the 11 PFCs analyzed, only PFHxS, PFOS, PFHxA, and PFOA were detected in at least one composite sample, while the levels of the remaining PFCs (PFBuS, PFHpA, PFNA, PFDA, PFUnDA, and PFDoDA) were under their respective detection limits. PFOS was the compound most frequently detected, being found in 8 of the 20 food items analyzed, while PFHxA was detected in samples of raw veal, chicken nuggets, frankfurt, sausages, and packaged lettuce. According to the results of the present study, it is not sufficiently clear if cooking with non-stick cookware, or packaging some foods, could contribute to a higher human exposure to PFCs.

Human dietary exposure to perfluoroalkyl substances in Catalonia, Spain. Temporal trend

In this study, we assessed the levels of 18 perfluoroalkyl substances (PFASs) in the most widely consumed foodstuffs in Catalonia, Spain, as well as the total dietary intake of these compounds. Forty food items were analysed. Only perfluoropentanoic acid (PFPeA), perfluorohexadecanoic acid (PFHxDA) and perfluorooctanoicdecanoic acid (PFOcDA) were not detected in any sample. Perfluorooctane sulfonate (PFOS) was the compound found in the highest number of samples (33 out of 80), followed by perfluorooctanoic acid (PFOA), perfluoroheptanoic acid (PFHpA), perfluorohexane sulfonic acid (PFHxS), perfluorodecanoic acid (PFDA) and perfluorodecane sulfonic acid (PFDS). Fish and shellfish was the food group in which more PFASs were detected and where the highest PFAS concentrations were found. The highest dietary intakes corresponded to children, followed by male seniors, with values of 1787 and 1466ng/day, respectively. For any of the age/gender groups of the population, the Tolerable Daily Intakes (TDIs) recommended by the EFSA were not exceeded. In general terms, PFAS levels found in the current study are lower than the concentrations recently reported in other countries.

Analysis of POPs in human samples reveal a contribution of brominated dioxin of up to 15% of the total dioxin TEQ

Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) were analyzed in both human adipose tissue and plasma from nine individuals, from the Swedish general population, using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). In addition, several other persistent organic pollutants (POPs) were determined in the same samples, including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and perfluorinated chemicals (PFCs). Polybrominated dibenzofurans were detected in all of the human adipose tissue samples confirming their presence in the Swedish population. The highest concentration was found for 2,3,7,8-TeBDF, ranging from 0.27 to 2.4 pg g(-1) lipid, followed by 1,2,3,7,8-PeBDF, 0.23-0.89pgg(-1) lipid, 2,3,4,7,8-PeBDF, 0.44-0.54 pg g(-1) lipid, and 2,7/2,8-DiBDF, 0.19-0.30 pg g(-1) lipid. No PBDDs could be detected above the limit of detection (<0.02-<0.21 pg g(-1) lipid) in any of the samples. The levels of PCDD/Fs were in the range 1.79-31.5pg toxic equivalents (TEQ)g(-1) lipid, and PBDEs were found in the 1.16-7.46 ng g(-1) lipid range. The measured chlorinated dioxins indicate decreasing human concentrations in Sweden. The toxicity equivalents (TEQ) for PBDD/Fs (0.2-0.8 pg TEQg(-1) lipid) were found to contribute 1-15% of the total dioxin TEQ of the chlorinated dioxins and furans (5-18 pg TEQg(-1) lipid) depending on the individual. Also PBDEs concentrations are decreasing compared to 1997-2000, but most noteworthy a shift in BDE pattern where BDE#47 is surpassed by BDE#153. The levels of PFCs are in the same range as the highest levels of the traditional POPs (sum of 60 PCBs) based on volume. These findings illustrate the importance of continuous monitoring of brominated compounds in both human and the environment.

Atmospheric-Pressure Chemical Ionization Tandem Mass Spectrometry (APGC/MS/MS) an Alternative to High-Resolution Mass Spectrometry (HRGC/HRMS) for the Determination of Dioxins

The use of a new atmospheric-pressure chemical ionization source for gas chromatography (APGC) coupled with a tandem quadrupole mass spectrometry (MS/MS) system, as an alternative to high-resolution mass spectrometry (HRMS), for the determination of PCDDs/PCDFs is described. The potential of using atmospheric-pressure chemical ionization (APCI) coupled to a tandem quadrupole analyzer has been validated for the identification and quantification of dioxins and furans in different complex matrices. The main advantage of using the APCI source is the soft ionization at atmospheric pressure, which results in very limited fragmentation. APCI mass spectra are dominated by the molecular ion cluster, in contrast with the high energy ionization process under electron ionization (EI). The use of the molecular ion as the precursor ion in MS/MS enhances selectivity and, consequently, sensitivity by increasing the signal-to-noise ratios (S/N). For standard solutions of 2,3,7,8-TCDD, injections of 10 fg in the splitless mode on 30- or 60-m-length, 0.25 mm inner diameter (id), and 25 μm film thickness low-polarity capillary columns (DB5MS type), signal-to-noise (S/N) ratios of >10:1 were routinely obtained. Linearity was achieved in the region (correlation coefficient of r(2) > 0.998) for calibration curves ranging from 100 fg/μL to 1000 pg/μL. The results from a wide variety of complex samples, including certified and standard reference materials and samples from several QA/QC studies, which were previously analyzed by EI HRGC/HRMS, were compared with the results from the APGC/MS/MS system. Results between instruments showed good agreement both in individual congeners and toxic equivalence factors (TEQs). The data show that the use of APGC in combination with MS/MS for the analysis of dioxins has the same potential, in terms of sensitivity and selectivity, as the traditional HRMS instrumentation used for this analysis. However, the APCI/MS/MS system, as a benchtop system, is much easier to use.

Gas chromatography/atmospheric pressure chemical ionization/mass spectrometry for the analysis of organochlorine pesticides and polychlorinated biphenyls in human serum

A method using a novel atmospheric pressure chemical ionization source for coupling gas chromatography (GC/APCI) to triple quadrupole mass spectrometry (MS/MS) for the determination of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) regulated by the Stockholm Convention is presented. One microliter injection of a six-point calibration curve of native PCBs and OCPs, ranging from 0.04 to 300pg/μL, was performed. The relative standard deviation (RSD) of the relative response factors (RRFs) was less than 15% with a coefficient of determination (r(2))>0.995. Meanwhile, two calibration solutions (CS), CS 2 (0.4pg/μL) and CS 3 (4pg/μL) were analyzed to study the repeatability calculated for both area and RRFs. The RSD for RRF ranged from 3.1 to 16% and 3.6 to 5.5% for CS 2 and CS 3, respectively. The limits of detection (LOD) determined by peak-to-peak signal-to-noise ratio (S/N) of 3 were compared between the GC/APCI/MS/MS and a GC coupled to high resolution mass spectrometry (GC/HRMS) system. GC/APCI/MS/MS resulted in lower LOD for most of the compounds, except for PCB#74, cis-chlordane and trans-chlordane. GC/APCI/MS/MS and GC/HRMS were also compared by performing analysis on 75 human serum samples together with eight QA/QC serum samples. The comparison between GC/APCI/MS/MS system and GC/HRMS system for 16 of the targeted compounds was carried out. No statistically significant difference was discovered. Due to increased sensitivity and user friendly operation under atmospheric pressure, GC/APCI/MS/MS is a powerful alternative technique that can easily meet the specification of GC/HRMS.

Rapid separation of hexabromocyclododecane diastereomers using a novel method combining convergence chromatography and tandem mass spectrometry

Analysis of the brominated flame retardant hexabromocyclododecane (HBCDD) is characterized by the separation of its three predominant diastereomers. This analysis is typically performed using rever ...

Analysis of brominated flame retardants and their derivatives by atmospheric pressure chemical ionization using gas chromatography coupled to tandem quadrupole mass spectrometry

A validated method using an atmospheric pressure chemical ionization source for coupling gas chromatography (GC-APCI) to tandem quadrupole mass spectrometry (MS/MS) for the determination of brominated flame retardants (BFRs) is presented. Polybrominated diphenyl ethers (PBDEs), their methoxylated derivatives (MeO-PBDEs) and other emerging BFRs were included in this study. The method showed good linearity and repeatability. The relative standard deviation (RSD) of the relative response factors (RRFs) of all compounds was below 16%. Repeatability for BFRs was tested on one or two concentration levels of calibration standards with RSDs for RRFs below 16%. The lowest calibration standards (0.075-0.1pg/µL for emerging BFRs, BDE 209 and MeO-PBDEs mixtures, 0.625-6.25pg/µL for Br1-9 PBDEs mixtures) were used as instrument detection limits (IDL). The method was applied on biotic samples, including fish, osprey, and seal. In general, BDE 209 and decabromodiphenyl ethane (DBDPE) were detected in 50% of the seal samples. A 100% detection rate was achieved for 6-MeO-BDE 47 in all the samples (72-580pg/g ww in osprey samples, 24,000-96,000pg/g ww in seal samples and 78-99pg/g ww in fish samples). All Br3-6 PBDEs (BDE 28, 47, 99, 100, 153, 154) were detected in all the samples (ranging from 12 to 20,000pg/g ww), while BDE 183 was detected in 60% of the osprey eggs, 20% of the seal samples and below MDL in all fish samples. The results presented indicate the capability of the GC-APCI-MS/MS system for the detection and quantification of BFRs.

Examination of technical mixtures of halogen-free phosphorus based flame retardants using multiple analytical techniques

The application of phosphorus based flame retardants as replacements for commonly used halogenated flame retardants has been gaining interest due to the possibility that these compounds may have a less significant impact on human and environmental health. Unfortunately, little is known about the chemical compositions of many of the technical products (which often are mixtures) and a single separation technique for concurrent analysis of these types of compounds has not been identified. This paper reports the results of an investigation into the constituents of three halogen free organophosphate flame retardants (OPFRs), resorcinol bis(diphenyl phosphate) (RDBPP), bisphenol A bis(diphenyl phosphate) (BPA-BDPP), and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The major components of commercial samples of RDBPP and BPA-BDPP were isolated by preparative TLC and characterized by NMR. A commercial sample of DOPO was found to be essentially pure, but its analysis is complicated by the fact that it can exist in ring-open and ring-closed forms. With the structures of the components confirmed by NMR, multiple analytical separation techniques (gas chromatography (GC), liquid chromatography (LC), and packed column supercritical fluid chromatography (pSFC)) were investigated for the analysis of these three technical products. Packed column supercritical fluid chromatography allows the separation of the components of all three OPFRs, including the two forms of DOPO, in a single run.

Comparative assessment of the chromatographic separation of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans using supercritical fluid chromatography and high resolution gas chromatography

The analysis of legacy environmental contaminants, such as polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), using high resolution gas chromatography (HRGC) is well established and universally accepted. The use of an alternative separation technique, such as packed column supercritical fluid chromatography (pSFC), may be of interest as a fast, green, and cost effective method of analyzing environmental samples. The technique is amenable to a broad range of chemical compounds and could facilitate the simultaneous analysis of multiple compound classes as well as the inclusion of thermally labile compounds in a single targeted analysis. The recent re-emergence of this technology due to the introduction of more robust and efficient instrumentation may result in an increased acceptance of pSFC analytical techniques in this area. Herein, the first reported analytical separation of PCDDs and PCDFs by pSFC is described and its separation capabilities are compared with established HRGC protocols. Elution profiles of 2,3,7,8-substituted PCDDs and PCDFs were examined and the separation of PCDD/PCDF homologue groups was found to be comparable to those accomplished using HRGC. Similarly, the resolution of tetrachlorodibenzo-p-dioxin (TCDD) congeners, as required by current regulatory methods utilizing HRGC, was demonstrated and the separation of possible co-eluting PCDD/PCDF congeners was examined and compared to that achieved using popular HRGC capillary columns. The possibility of concurrent analysis of toxic polychlorinated biphenyls (PCBs) with PCDDs and PCDFs using the developed pSFC method was also investigated. The effective separation of these environmental contaminants obtained using pSFC and subsequent detection utilizing atmospheric pressure photoionization tandem mass spectrometry at environmentally relevant levels demonstrates the promise associated with this technique for the analysis of environmental extracts.