POPs and PAHs in fish oil-based food supplements at the Czech market.

The objectives of this study were to assess concentrations of three groups of persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs) in 44 fish oil-based food supplements, to estimate their daily intake by consumers and, to evaluate the compliance of the oil samples with the oil origin declarations (cod liver oil or fish oil). The concentrations of ∑PCBs (7 congeners), OCPs (19 compounds, represented mainly by ∑DDTs), ∑PBDEs (10 congeners), and ∑PAHs (16 compounds) found in samples ranged between 0.15-55.7 µg kg-1, 0.93-72.8 µg kg-1, 0.28-27.5 µg kg-1, and 0.32-51.9 µg kg-1, respectively. Besides, the authenticity of the oils was assessed based on the fingerprints obtained by DART-HRMS, an ambient mass spectrometry technique. Four samples declared as fish oil were probably prepared from cod liver oil, which is much cheaper. Furthermore, these samples contained elevated concentrations of halogenated POPs when compared to supplements produced from fish oil.

Are fish oil-based dietary supplements a significant source of exposure to chlorinated paraffins?

Chlorinated paraffins (CPs) are an emerging group of environmental pollutants associated with adverse effects on human health (such as endocrine disruption and possible carcinogenicity). CPs are classified into several groups: short- (SCCPs), medium- (MCCPs) and long-chain chlorinated paraffins (LCCPs). In this study, CPs were determined in fish oil-based omega-3 dietary supplements (DS) representing widely consumed products that might be contaminated with various lipophilic contaminants including CPs. The CPs were isolated from DS (n = 85) by solid phase extraction. The SCCPs and MCCPs were determined by gas chromatography coupled with high-resolution mass spectrometry operated in a negative chemical ionisation mode. The LCCPs (up to C21) were screened using supercritical fluid chromatography coupled with high-resolution mass spectrometry with electrospray ionisation operated in negative mode. The CP concentrations varied from <0.01 to 56.48 µg/g fat for SCCPs (median 0.12 µg/g fat; limit of quantification, LOQ, for SCCPs was exceeded in 51 out of 85 samples) and from <0.03-89.08 µg/g fat for MCCPs (median 0.26 µg/g fat; LOQ for MCCPs was exceeded in 66 out of 85 samples), respectively. The LCCPs were not quantified in this study, nevertheless their limit of detection (0.5 µg/g fat) was exceeded in 7 out of 85 samples. Due to high levels of CPs, DS might pose as a significant source of CPs exposure to some population groups.

Application of the GC-HRMS based method for monitoring of short- and medium-chain chlorinated paraffins in vegetable oils and fish.

The aim of this study was to develop methods for the determination of short- and medium-chain chlorinated paraffins (SCCPs; MCCPs) in vegetable oils and fish employing gas chromatography coupled with high-resolution mass spectrometry because of a lack of information on the presence of chlorinated paraffins in food consumed in Europe. For isolation of CPs from fish, an ethyl acetate extraction followed by a clean-up of the extract by gel permeation chromatography was performed. The same purification step was used for the isolation of CPs from the vegetable oils. The concentration range for SCCPs was <10-389 ng/g lipid weight (lw, mean 36 ng/g lw for the oils and 28 ng/g lw for the fish) and that for MCCPs was <20-543 ng/g lw (mean 55 ng/g lw for the oils and 59 ng/g lw for the fish). There was found a high variability in concentrations of CPs influenced by area of origin.

Multiclass analytical method for the determination of natural/synthetic steroid hormones, phytoestrogens, and mycoestrogens in milk and yogurt.

Within this study, a new method enabling monitoring of various estrogenic substances potentially occurring in milk and dairy products was proposed. Groups of compounds fairly differing in physico-chemical properties and biological activity were analyzed: four natural estrogens, four synthetic estrogens, five mycoestrogens, and nine phytoestrogens. Since they may pass into milk mainly in glucuronated and sulfated forms, an enzymatic hydrolysis was involved prior to the extraction based on the QuEChERS methodology. For the purification of the organic extract, a dispersive solid-phase extraction (d-SPE) with sorbent C18 was applied. The final analysis was performed by ultra-high-performance liquid chromatography (UHPLC) coupled with triple quadrupole tandem mass spectrometry (MS/MS). Method recovery ranged from 70 to 120% with a relative standard deviation (RSD) value lower than 20% and limits of quantification (LOQs) in the range of 0.02-0.60 µg/L (0.2-6.0 µg/kg dry weight) and 0.02-0.90 µg/kg (0.2-6.0 µg/kg dry weight) for milk and yogurt, respectively. The new procedure was applied for the investigation of estrogenic compounds in 11 milk samples and 13 yogurt samples from a Czech retail market. Mainly phytoestrogens were found in the studied samples. The most abundant compounds were equol and enterolactone representing 40-90% of all estrogens. The total content of phytoestrogens (free and bound) was in the range of 149-3870 µg/kg dry weight. This amount is approximately 20 times higher compared to non-bound estrogens.

Rapid determination of polycyclic aromatic hydrocarbons (PAHs) in tea using two-dimensional gas chromatography coupled with time of flight mass spectrometry.

A simple, fast, and cost effective sample preparation procedure has been developed and validated for the determination of 15+1 European Union Polycyclic Aromatic Hydrocarbons (15+1 EU PAHs) in dried tea leave samples. Based on a critical assessment of several sample extraction/clean-up approaches, the method based on the ethyl acetate extraction followed by the use of PAHs dedicated cartridges with molecularly imprinted polymers (MIPs) has been found as an optimal alternative in terms of time demands and obtained good extract purity. For the final identification/quantification of target PAHs, two dimensional gas chromatography coupled to a time-of-flight mass spectrometry (GC×GC-TOFMS) was used. The performance characteristics of the overall analytical method for individual PAHs determined at three spiking levels (0.5, 2.5 and 5 µg kg(-1)) were in following ranges: limits of quantitation (LOQs) 0.05-0.2 µg kg(-1), repeatabilities 2-9%, and recoveries 73-103%. The recoveries achieved by the newly developed sample preparation procedure when employed for naturally contaminated sample ("incurred" PAHs) were comparable to those obtained by other routinely used approaches employing sonication and/or pressurised liquid extraction for sample analytes isolation. The validated method was subsequently used for the determination of selected genotoxic PAHs in 36 samples of black and green tea obtained from the Czech retail market. The levels of ΣPAH4 (sum of benzo[a]anthracene (BaA), chrysene (CHR), benzo[b]fluoranthene (BbFA) and benzo[a]pyrene (BaP)) in black and green tea leaves ranged from 7.4 to 700 µg kg(-1) and from 4.5 to 102 µg kg(-1), respectively. Contamination of tested tea samples by BaP was in the range of 0.2-152 µg kg(-1).

Streamlining sample preparation and gas chromatography-tandem mass spectrometry analysis of multiple pesticide residues in tea.

In this work, a new rapid method for the determination of 135 pesticide residues in green and black dry tea leaves and stalks employing gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) with a triple quadrupole was developed and validated. A substantial simplification of sample processing prior to the quantification step was achieved: after addition of water to a homogenised sample, transfer of analytes into an acetonitrile layer was aided by the addition of inorganic salts. Bulk co-extracts, contained in the crude organic extract obtained by partition, were subsequently removed by liquid-liquid extraction using hexane with the assistance of added 20% (w/w) aqueous NaCl solution. The importance of matrix hydration prior to the extraction for achieving good recoveries was demonstrated on tea samples with incurred pesticide residues. For most of the analytes, recoveries in the acceptable range of 70-120% and repeatabilities (relative standard deviations, RSDs) ≤20% were achieved for both matrices at spiking levels of 0.01, 0.1 and 1 mg kg(-1). Under optimised GC-MS/MS conditions, most of the analytes gave lowest calibration level ≤0.01 mg kg(-1), permitting the control at the maximum residue levels (MRLs) laid down in Regulation (EC) No 396/2005. The developed method was successfully applied to the determination of pesticide residues in real tea samples.

Absorption and translocation of polybrominated diphenyl ethers (PBDEs) by plants from contaminated sewage sludge.

Polybrominated diphenyl ethers (PBDEs) are used as additive flame retardants. PBDEs are persistent, bioaccumulative and toxic compounds. They are often detected in sewage sludge which is applied on agricultural soils as fertilizer. The objective of this study was to find out whether plants are able to accumulate and translocate PBDEs. Tobacco (Nicotiana tabacum) and nightshade (Solanum nigrum) were planted in pots containing contaminated sewage sludge and uncontaminated substrate. After 6 months of plant cultivation in sewage sludge up to 15.4 ng g(-1) dw and 76.6 ng g(-1) dw of PBDE congeners--BDE 47, BDE 99 and BDE 100---were accumulated in the nightshade and tobacco tissue, respectively. Corresponding values in plants vegetated in the control garden substrate were 10 times lower. The bioconcentration factors (BCFs) of accumulated congeners were calculated. Tobacco exhibited higher BCFs values and for both plants BCFs values of BDE 47, BDE 99, BDE 100 and BDE 209 negatively correlated with their octanol-water partition coefficients (logK(ow)). The exception was decaBDE (BDE 209) which was accumulated only in tobacco tissue in the concentration of 116.8 ng g(-1) dw. The majority of PBDEs was detected in above-ground plant biomass indicating that both plants have the ability to translocate PBDEs. To our knowledge this is one of the first studies reporting the accumulation of both lower PBDEs and BDE 209 in plants. Our results suggest that absorption, accumulation and translocation of PBDEs by plants and their transfer to the food chain could represent another possible risk for human exposure.