The impact of baking on chlorinated paraffins: Characterization of C10–C17 chlorinated paraffins in oven-baked pastry products and unprocessed pastry dough by HPLC–ESI–Q–TOF–MS
Abstract This study presents an HPLC–ESI–Q–TOF method for simultaneous quantification of short-chain chlorinated paraffins (SCCPs, C10–13) and an additional characterization of medium-chain chlorinated paraffins (MCCPs, C14–17) in oven-baked pastry products (n = 38) and unprocessed pastry dough material (n = 15). Almost 2 times higher SCCP levels were found in the dough material. ΣSCCP concentrations in products ranged from 0.3 ng g−1 to 23.0 ng g−1 (mean: 6.3 ng g−1), while the results for dough ranged from 5.8 ng g−1 to 22.8 ng g−1 (mean: 12.9 ng g−1). Regardless of the sample matrix, the most abundant CP homologue groups were hepta- and octa-chlorinated undecanes and dodecanes. The avera…
The occurrence of Dechlorane Plus and related norbornene-based flame retardants in Baltic wild salmon (Salmo salar)
Twenty five Baltic wild salmon (Salmo salar) specimens were analysed for the content of Dechlorane-related compounds (DRCs). Out of the ten analysed DRCs, seven compounds were detected in the muscle tissues of salmon, including Dechlorane (Dec) 602, Dec 603, syn- and anti-stereoisomers of Dechlorane Plus (DP), Dechlorane Plus monoadduct (1,3-DPMA), hexachlorocyclopentadienyl-dibromocyclooctane (DBHCTD), and Mirex. The concentrations of Dec 604 and two DP dechlorinated compounds - decachloropentacyclooctadecadiene (Cl10DP) and undecachloropentacyclooctadecadiene (Cl11DP) - were below the limit of detection in all samples. The aggregated concentrations of DRCs (ΣDRC) were in the range of 551-…
Ultra high performance liquid chromatography-time-of-flight high resolution mass spectrometry in the analysis of hexabromocyclododecane diastereomers: method development and comparative evaluation versus ultra high performance liquid chromatography coupled to Orbitrap high resolution mass spectrometry and triple quadrupole tandem mass spectrometry.
An efficient ultra high performance liquid chromatography (UHPLC)-time-of-flight high resolution mass spectrometry (TOF-HRMS) method was elaborated for the determination of hexabromocyclododecane (HBCD) diastereomers in fish samples and compared against UHPLC-Orbitrap-HRMS and UHPLC-triple quadrupole (QqQ) tandem MS (MS/MS) techniques. The TOF-HRMS analyzer was operated at high resolution (>10000 full width at half maximum (FWHM)) with scanning the m/z range from 600 to 700, to achieve picogram quantitation limits. The effects of various operational parameters on the instrumental response were systematically investigated. Evaluation of the influence of sample clean-up procedure steps on sig…
Liquid chromatography and characterization of ether-functionalized imidazolium ionic liquids on mixed-mode reversed-phase/cation exchange stationary phase
Abstract A new series [CnOmmim]Cl of imidazolium cation-based ionic liquids (ILs), with an ether functional group on the alkyl side-chain, has been prepared. The possibility of analyzing the ionic liquids by high performance liquid chromatography (HPLC) was investigated on mixed-mode reversed/cation exchange stationary phase with the aqueous-acetonitrile mobile phase. Elution parameters, such as retention factor, selectivity and column efficiency, were studied as functions of mobile phase composition and pH. The ILs were characterized by elemental analysis, and infrared, UV and 1H, 13C NMR spectroscopy.
Evaluation of analytical performance of gas chromatography coupled with atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS) in the target and non-targeted analysis of brominated and chlorinated flame retardants in food.
Abstract A new analytical method was established and validated for the analysis of eighteen halogenated flame retardants (HFRs)in food products. Gas chromatography (GC) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) employing atmospheric pressure chemical ionization (APCI) was used for the identification and quantitation of contaminants. Intra-laboratory validation of the method was performed with respect to recovery, repeatability, linear calibration ranges, instrumental and method limits of quantitation (i-LOQ and m-LOQ), and trueness was verified where possible by analysis of reference materials (RMs). The validation results indicated recoveries of ana…
The development and validation of a rapid method for the determination of antimicrobial agent residues in milk and meat using ultra performance liquid chromatography coupled to quadrupole – Orbitrap mass spectrometry
Abstract A new multi-class method has been developed for the identification and quantification of the residues of 26 antibiotics from different classes (sulfonamides, macrolides, tetracyclines, penicillins, and quinolones) in milk and meat by ultra performance liquid chromatography coupled to hybrid quadrupole – high resolution Orbitrap mass spectrometry (UPLC–qOrbitrap). The sample preparation included extraction of two analytical portions with acetonitrile and 5% trichloroacetic acid, respectively, followed by centrifugation and filtration. The method was validated over three days at 50% of MRL (maximum residue limit) set in the European Union. Experiments on spiked meat and milk samples …
Occurrence of Brominated Persistent Organic Pollutants (PBDD/DFs, PXDD/DFs, and PBDEs) in Baltic Wild Salmon (Salmo salar) and Correlation with PCDD/DFs and PCBs
The contamination profiles of polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs), diphenyl ethers (PBDEs), and mixed monobromo/chloro dibenzo-p-dioxins (PXDDs) and dibenzofurans (PXDFs) were determined in the tissue of Baltic wild salmon and compared with those of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs). Out of the analyzed PXDD/DFs, only the 3-B-2,7,8-triCDF was detected (in the concentration range of 0.039-0.075 pg g(-1) fresh weight (f.w.)). The toxic equivalents (TEQs) for analyzed PBDD/DFs (0.074-0.142 pg TEQ g(-1) f.w.) were found to contribute on average 2.1% to the total PCDD/DF-PBDD/DF-TEQ. The total concentrations of 27 P…
Multi-analyte method for the analysis of legacy and alternative brominated and chlorinated flame retardants in food products of animal origin using gas chromatography - magnetic sector high resolution mass spectrometry
Abstract An analytical method was developed and validated for the analysis of 32 halogenated flame retardants (HFRs), including 13 polybrominated diphenyl ethers (PBDEs), 9 dechlorane-related compounds (DRCs) and 10 of the so-called alternative BFRs in food samples of animal origin. Gas chromatography (GC) coupled with magnetic sector high resolution mass spectrometry (HRMS) was used for the instrumental analysis. Intralaboratory validation of the developed method was performed in terms of recovery, repeatability, linear calibration ranges, instrumental and method limits of quantitation (i-LOQ and m-LOQ). Where possible, trueness was verified by the analysis of reference materials (RMs). Fo…
Development and optimization of gas chromatography coupled to high resolution mass spectrometry based method for the sensitive determination of Dechlorane plus and related norbornene-based flame retardants in food of animal origin
An analytical method has been developed for the trace determination of 10 dechlorane-related compounds (DRCs) in food products by gas chromatography - high resolution mass spectrometry (GC-HRMS). The highest sensitivity of this instrumental analysis method was achieved by selection of the GC column type, optimization of the heated zones within the instrument, and adjusting the electron impact energy. The efficiency of solid phase extraction as clean-up procedure was also optimized. Two different types of cartridges - neutral silica gel and Florisil®, as well as seven organic solvents or their mixtures - n-hexane, cyclohexane, acetone, toluene, n-hexane/ethyl acetate, n-hexane/acetone, and n…
New perspectives on diastereoselective determination of hexabromocyclododecane traces in fish by ultra high performance liquid chromatography-high resolution orbitrap mass spectrometry.
a b s t r a c t A new analytical method is presented for diastereoisomer-specific identification and quantitation of hexabromocyclododecanes (HBCD) in fish samples. The method is based on extraction of the target analytes from samples with a mixture of organic solvents, with further three-stage clean-up includ- ing destructive removal of matrix components with sulphuric acid and acid-impregnated silica gel, and Florisil adsorption column chromatography. Ultra high performance liquid chromatography (UPLC) cou- pled with high resolution (HR) Orbitrap mass spectrometry featuring heated electrospray ionization (HESI-II) interface operated in negative ion mode was employed for the identification…
Brominated flame retardants and toxic elements in the meat and liver of red deer (Cervus elaphus), wild boar (Sus scrofa), and moose (Alces alces) from Latvian wildlife.
In order to evaluate the contamination status of terrestrial biota in Latvia, muscle and liver tissues of red deer (Cervus elaphus), wild boar (Sus scrofa), and moose (Alces alces) were analyzed for the content of polybrominated diphenyl ethers (PBDE), hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA), as well as cadmium and lead. The highest mean concentrations of PBDEs (46.6pgg-1 wet weight (w.w.)), cadmium (0.95mgkg-1 w.w.), and lead (0.22mgkg-1 w.w.) were observed in the tissues of moose, while the wild boar samples contained the highest levels of HBCD, with the mean concentration equal to 264pgg-1 w.w. in muscle tissues. Generally low mean concentrations of TBBPA from 0.52 t…
Occurrence of selected per- and polyfluorinated alkyl substances (PFASs) in food available on the European market - A review on levels and human exposure assessment.
Abstract Per- and polyfluorinated alkyl substances (PFASs) are considered emerging persistent organic pollutants, which are chemically, thermally, and biologically stable, or degrade to persistent end products. Dietary intake is considered as one of the main human exposure pathways of these chemicals and, having entered the human body, PFASs are not metabolised and accumulate in tissues, while their toxicological properties may cause various health problems. Several studies on the occurrence of PFASs in various food types have been conducted, including the assessment of dietary exposure. The most important sources were fish, meat, eggs, fruits, and vegetables. Fruits and vegetables recently…
Rapid determination of pharmaceuticals in wastewater by direct infusion HRMS using target and suspect screening analysis
Abstract A wide-scope screening of active pharmaceutical ingredients (APIs) and their transformation products (TPs) in wastewater can yield valuable insights and pinpoint emerging contaminants that have not been previously reported. Such information is relevant to investigate their occurrence and fate in various environmental compartments. In this study, we explored the applicability of direct infusion high resolution mass spectrometry (DI-HRMS) for comprehensive and rapid detection of APIs and their TPs in wastewater samples. The method was developed using a Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) system and incorporated both wide-scope suspect screening and…
Emerging brominated flame retardants and dechlorane-related compounds in European eels (Anguilla anguilla) from Latvian lakes
Abstract Fifteen halogenated flame retardants (HFRs) including seven emerging brominated flame retardants (EBFRs) and eight dechlorane-related compounds (DRCs) were analyzed in eels (Anguilla anguilla) sampled from five Latvian lakes. Out of the seven EBFRs, hexabromocyclododecane (HBCD) and decabromodiphenyl ethane (DBDPE) were found in eels in quantifiable concentrations, up to 6.58 and 33.0 ng g−1 lipid weight (l.w.), respectively. The mean total concentration of DRCs (∑DRC) in the samples was 0.62 ng g−1 l.w. and the geographical distribution of DRC contamination was nearly uniform among the selected lakes. Dechlorane 602 (Dec 602) was the predominant component, whereas the composition …
Brominated, chlorinated and mixed brominated/chlorinated persistent organic pollutants in European eels (Anquilla anquilla) from Latvian lakes
Fifty-eight European eel (Anquilla anquilla) specimens collected from five Latvian lakes were investigated for six groups of persistent organic pollutants (POPs), including polychlorinated, polybrominated and mixed bromo-chloro dibenzo-p-dioxins and dibenzofurans (PCDD/DFs, PBDD/DFs and PXDD/DFs), polychlorinated and mixed bromo-chloro biphenyls (PCBs and PXBs) and polybrominated diphenyl ethers (PBDEs). PCDD/DFs and PCBs were found to occur in the range 0.85–15.8 pg Total-WHO2005-TEQ g−1 f.w., and concentrations in most of the samples were below the maximum levels specified in European Commission Regulation (EU) No. 1259/2011. The summed concentrations of 27 PBDEs (∑PBDE) and 16 non-dioxin…
Application of Dopant-Assisted Atmospheric Pressure Photoionisation HPLC–MS Method for the Sensitive Determination of Polycyclic Aromatic Hydrocarbons in Dark Chocolate
Multiple food research studies have shown that the polycyclic aromatic hydrocarbon (PAHs) are frequently found in processed cocoa products and chocolate. In a present study a method based on dopant-assisted atmospheric pressure photoionisation (DA-APPI) combined with a liquid chromatography/high-resolution mass spectrometer (HPLC-HRMS) for high-sensitivity analysis of four EU marker PAHs in dark chocolate samples was developed and fully validated according to the performance criteria set in EU guidelines. PAHs detection was achieved by HRMS in positive electrospray ionization mode with toluene used as a dopant to enhance the ionization efficiency of non-polar PAHs. The on-column instrument …
Development and optimization of confirmatory liquid chromatography—Orbitrap mass spectrometry method for the determination of 17 anticoccidials in poultry and eggs
A new sensitive and selective multi-residue method based on liquid chromatography - Orbitrap high resolution mass spectrometry (LC-Orbitrap-HRMS) was developed and validated for the determination of 17 anticoccidials in poultry and eggs. Instrumental parameters were optimized by the means of statistical experimental designs to improve the sensitivity, precision, and repeatability of the method. Further optimization of auto-tuned MS parameters led to an increase of signal intensity by 10% to 99% for 16 out of 17 analytes. The sample preparation procedure included extraction from muscle tissue and egg samples with acetonitrile, followed by preconcentration, reconstitution, and filtration. Val…
Analytical capabilities of high performance liquid chromatography – Atmospheric pressure photoionization – Orbitrap mass spectrometry (HPLC-APPI-Orbitrap-MS) for the trace determination of novel and emerging flame retardants in fish
A new analytical method was established and validated for the analysis of 27 brominated flame retardants (BFRs), including so called "emerging" and "novel" BFRs (EBFRs and NBFRs) in fish samples. High performance liquid chromatography (HPLC) coupled to Orbitrap mass spectrometry (Orbitrap-MS) employing atmospheric pressure photoionization (APPI) interface operated in negative mode was used for the identification/quantitation of contaminants. HPLC-Orbitrap-MS analysis provided a fast separation of selected analytes within 14 min, thus demonstrating a high throughput processing of samples. The developed methodology was tested by intralaboratory validation in terms of recovery, repeatability, …
Method development for the simultaneous determination of polybrominated, polychlorinated, mixed polybrominated/chlorinated dibenzo-p-dioxins and dibenzofurans, polychlorinated biphenyls and polybrominated diphenyl ethers in fish.
An analytical methodology was developed for simultaneous determination of five groups of persistent organic pollutants (POPs) including polybrominated, polychlorinated and mixed brominated-chlorinated dibenzo-p-dioxins and dibenzofurans (PBDD/DFs, PCDD/DFs and PXDD/DFs, respectively), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in fish samples. The presented analytical approach was based on well established and robust method for determination of PCDD/DFs and PCBs, which was augmented with gas chromatography coupled to high resolution mass spectrometry (GC-HRMS) to include PBDEs, as well as poorly investigated PBDD/DFs and PXDD/DFs at toxicologically significa…
Content of polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls in fish from Latvian lakes
Seventeen polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDFs) of the highest priority as well as twelve dioxin-like polychlorinated biphenyls (dl-PCBs) were analyzed in the muscle tissues of the following freshwater fish species sampled from eleven Latvian freshwater lakes: perch (Perca flavescens), carp (Cyprinus carpio), eel (Anguilla rostrata), bream (Abramis brama), chub (Leuciscus cephalus), pike (Esox lucius), sheatfish (Silurus glanis) and roach (Rutilus). To analyze the selected persistent organic pollutants in fish matrices, an optimization of EPA-1613 and EPA-1668A clean-up procedures was carried out, followed by validation of the analytical procedure …