Electron Capture Negative Ionization Mode Research Articles

Simple multi-residue analysis of persistent organic pollutants and molecular tracers in atmospheric samples

We present a simple, selective and sensitive analytical method to quantitatively determine a wide range of halogenated persistent organic pollutants and molecular tracers in atmospheric samples. Identification and quantification was carried out by high-resolution gas chromatography, hyphenated with low-resolution mass spectrometry operating in electron impact (EI) and electron capture negative ionization (ECNI) mode. Optimization on a number of instrumental parameters was conducted to obtain ultra-trace detection limits, in the range of few fg/m3 for organohalogen compounds. Repeatability and reproducibility of the method was thoroughly evaluated. The analysis was validated with standard reference materials and successfully applied to actual atmospheric samples. The proposed multi-residue method provides a precise, affordable and practical procedure of sample analysis for environmental research laboratories with conventional instrumentation on a routine basis.•A simple combination of alumina, florisil and silica gel adsorbents was applied to sufficiently isolate polychlorinated biphenyls, organochlorine pesticides, polycyclic aromatic hydrocarbons, long chain n-alkanes, hopanes and steranes.•Full elution was achieved in two successive fractions, using small volumes of n-hexane and n-hexane/dichloromethane to recover all target substances.•To maximize analytical response, optimization was applied for three operating parameters in ECNI mode: i) ion source temperature; ii) emission current; and iii) electron energy.

Better screening of non-target pollutants in complex samples using advanced chromatographic and mass spectrometric techniques

The number of priority and emerging contaminants nowadays exceeds several thousands. As a consequence, it is a daunting task to monitor thousands of compounds using classical gas chromatography–mass spectrometry (GC–MS). Preliminary non-targeted screening is thus usually performed to identify the most relevant contaminants. Here we analyzed complex environmental samples of snow, rain water and cloud water from the Arctic, France, Chile, and Russia by two-dimensional gas chromatography (GC × GC) with ionization methods including electron ionization (EI), positive chemical ionization (PCI), and electron capture negative ionization (ECNI) modes, combined with high-resolution mass spectrometry. This approach combines the separation capacity of GC × GC, detailed EI mass spectral libraries, the softness of PCI, and the selectivity of ECNI. Switching between ionization modes without any hardware change allowed to increase the information capacity and reliability of analysis. The structural elucidation becomes easier and more reliable due to the detection of molecular ions in PCI and ECNI modes with corresponding extensive fragmentation in EI, while the ECNI mode improves about 100 times the detection limits for environmentally relevant halogenated and nitro compounds. Overall, a notable enhancement of the analytical capabilities for both targeted and non-targeted purposes is achieved.

Simple and fast method for the measurement of legacy and novel brominated flame retardants in human serum

Recent and reliable human biomonitoring data on brominated flame retardants (BFRs), either legacy or new BFRs, are still needed to assess human exposure. The aim of this work was therefore to develop and validate an accurate, fast and user-friendly analytical strategy for the determination of 15 legacy and novel BFRs in human serum namely 8 polybrominated diphenylethers (BDE-28, -47, −99, −100, −153, −154, −183, and −209), 1 hexabromobiphenyl (PBB-153), and 6 novel BFRs (pentabromotoluene, hexabromobenzene, pentabromoethylbenzene, 2-ethylhexy-2,3,4,5-tetrabromobenzoate, 1,2-bis(2,4,6-tribromophenoxy)ethane, and decabromodiphenylethane). This analytical procedure consisted in a simple liquid-liquid extraction followed by elution on a PHREE cartridge avoiding further laborious purification steps. The final determination was performed by gas chromatography coupled to mass spectrometry in electron capture negative ionization mode (GC-ECNI-MS). The 15 m long RTX-1614 allowed the simultaneous measurement of the 15 BFRs including low and high brominated species within a single injection on a single column. Except for 2-ethylhexy-2,3,4,5-tetrabromobenzoate (EHTBB) which showed very high response variations resulting in poor linearity, trueness and precision, and decabromodiphenylethane for which very low sensitivity was achieved, the 13 other BFRs passed the validation process with recoveries varying between 56 and 82%, and limits of quantification (LOQs) ranging from 2.5 to 6.0 pg/ml (34.5 pg/ml for BDE-209). Within the validated range of concentrations, the relative bias from the introduced levels were below 20% while the intra and inter precisions were maintained below 15%. The reliability of the technique was confirmed by successfully analyzing interlaboratory test materials (AMAP ring test for POPs in human serum).

Occurrence of halogenated natural products in highly consumed fish from polluted and unpolluted tropical bays in SE Brazil

Natural compounds from the metabolism of marine organisms have been detected at high concentrations in environmental samples which are not the producers of these compounds. These natural substances are known as halogenated natural products (HNPs). HNPs are possibly toxic halogenated compounds analogous to POPs that may bioaccumulate and biomagnify along the food web and pose a further risk to human and environmental health. The present study analyzed the occurrence of HNPs in the edible muscle of the three most consumed commercial fish species in the state of Rio de Janeiro: sardine (Sardinella brasiliensis), whitemouth croaker (Micropogonias furnieri) and mullet (Mugil liza) from the highly polluted Guanabara Bay (GB) and the less polluted Ilha Grande Bay (IGB). The analytical steps included Soxhlet extraction, clean-up step and injection in a gas chromatography system coupled to a mass spectrometer operated in the electron-capture negative ion mode (GC/ECNI-MS). The compounds 2,4,6-TBP, 2,4,6-TBA, MHC-1, Q1, 6-MeO-BDE 47 and 2′-MeO-BDE 68 were found in the analyzed fish from both studied areas. Q1, 6-MeO-BDE 47 and 2′-MeO-BDE 68 showed the highest concentrations in samples. Q1 concentrations in the sardines from IGB were higher than the sardines from GB (p < 0.05) and higher than the other IGB species (p < 0.05). The differences found among the species may be related to their characteristic habitat and diet. It is noteworthy that most of these compounds do not have any toxicological reference value. Moreover, the HNPs are being detected in species of low trophic level and since this study has worked only with commercial species, these fish may be considered as a source for human exposure to these natural compounds.

Brominated flame retardants (BFRs) in eggs from birds of prey from Southern Germany, 2014

In Southern Germany, peregrine falcons (Falco peregrinus), which almost exclusively prey on other birds, are top predators of the terrestrial food chain. These animals accumulate persistent organic pollutants (POPs) and halogenated flame retardants (HFRs) with mothers transferring these lipophilic contaminants to their eggs. Here we analyzed unhatched eggs of eleven peregrine falcons and six of other species, and report concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), hexabromobenzene (HBB), 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) and its metabolites, pentabromoethylbenzene (PBEB), pentabromotoluene (PBT), and tribromophenol (TBP). The extract of one purified peregrine falcon egg sample was comprehensively analyzed in a non-target (NT) approach by gas chromatography with mass spectrometry in the electron capture negative ion mode. A total of ∼400 polyhalogenated compounds were detected, among them dechloranes and possibly transformation products, two tetrabrominated metabolites of PBT and several compounds unknown to us which could not be identified.

Simultaneous determination of dechloranes, polybrominated diphenyl ethers and novel brominated flame retardants in food and serum.

A sensitive method for the simultaneous quantification of dechloranes, polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs) has been developed for gas chromatography (GC) coupled to tandem mass spectrometry operating in electron capture negative ionization (ECNI) mode. The major advance has been achieved by combining selected ion monitoring (SIM) and multiple reaction monitoring (MRM) modes in well-defined time windows, to determine dechloranes, PBDEs and NBFRs at picogram per gram level in one single analysis in complex matrix biological samples. From the chromatographic point of view, efforts were devoted to study several injection modes using multimode inlet (MMI) in order to obtain low instrumental detection limits, necessary for trace compounds such as Dechlorane Plus (DP) isomers. Method performance was also evaluated: calibration curves were linear from 20fgμL-1 to 100pgμL-1 for the studied compounds, with method detection limits at levels of 50fgg-1 for DPs. Repeatability and reproducibility, expressed as relative standard deviation, were better than 5% even in solvent vent mode for the injection of standards. The application to a wide range of complex samples (including food, human and animal serum samples) indicated a sensitive and reliable way to quantify at the picogram per gram level 4 halogenated norbornenes (HNs), Dechlorane Plus (anti-DP and syn-DP) and 2 of their homologues (Dechlorane-602 and Dechlorane-603), 11 PBDE congeners (no. 28, 47, 49, 66, 85, 99, 100, 153, 154, 183 and 209) and 5 novel BFRs, i.e. decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), hexabromobenzene (HBB), 2,3,4,5-tetrabromo-ethylhexyl-benzoate (TBB) and tetrabromophthalate (TBPH). Graphical Abstract GC-ECNI-MS/MS chromatograms showing the most sensitive transition for DPs when injecting 2 μL of a 16 fg/μL standard solution of s-DP and a-DP at three different source temperatures.

Determination of halogenated flame retardants in food: Optimization and validation of a method based on a two-step clean-up and gas chromatography–mass spectrometry

In this work, a new simple method based on a two-step clean-up and gas chromatography–mass spectrometry analysis for the determination of emerging halogenated flame retardants (HFRs), such as dechlorane plus (DP) and brominated phthalates, and polybrominated diphenyl ethers (PBDEs) in different food items was optimized and validated. Several types of food items, i.e. fish (smoked salmon and cod fillet), meat (chicken breast), chicken eggs, cow milk, and extra virgin olive oil, were chosen as representative matrices of the main food categories. After lyophilisation, the food samples were extracted using acetonitrile:toluene (9:1, v/v). As interferences, such as lipids and pigments, were co-extracted, a two-step clean-up (including Florisil and acid silica) was performed to efficiently remove them prior to GC–MS analysis in electron capture negative ionization mode (GC–ECNI/MS). The performance criteria established by the European Commission (2014/118/EU) were achieved with this method for all target analytes, except for the LOQ achieved for BDE-209 (0.1 ng/g wet weight, ww). The trueness ranged between 75 and 125% for most compounds and the matrices analyzed and the repeatability (expressed as RSD%) was <20%, within the set performance criteria. The method was then used for the determination of PBDEs and emerging HFRs in 20 different food items purchased from Antwerp supermarkets, revealing a prevalent contamination with PBDEs (up to 2.02 ng/g ww) and tribromoanisole (up to 6.6 ng/g ww) in the fish/seafood category.

Multi-residue determination of polyhalogenated carbazoles in aquatic sediments

Recent studies have discovered a number of polyhalogenated carbazoles (PHCZs) in aquatic sediments and soil. These substances are attracting emerging concern due to their environmental presence, persistence, and potential dioxin-like activities. In response to the increasing interests in these chemicals, the present study aimed to develop an efficient and sensitive analytical methodology for quantitative determination of environmentally relevant PHCZs in aquatic sediments. The developed method employed time- and solvent-saving extraction and cleanup procedures and utilized gas chromatogram–mass spectrometry (GC–MS) for separation and determination of PHCZ analytes. PHCZs substituted with bromine atom(s) (except for 3-bromocarbazole) or a combination of bromine and chlorine atoms were analyzed by GC–MS in the electron-capture negative ionization (ECNI) mode, whereas congeners substituted with chlorine atoms as well as 3-bromocarbazole were analyzed in electron impact (EI) ionization mode. The developed method demonstrated negligible matrix effects, satisfactory and stable recoveries, and low method limits of quantification (0.11–0.53ng/g dry weight (dw)) of target analytes. Using this method, we successfully determined a number of PHCZs in surface sediments from the Saginaw River system (Michigan, USA) and the Saginaw Bay of Lake Huron, with the summed concentrations of PHCZ congeners ranging up to 46.3ng/gdw. Given that further investigations are needed to better elucidate the sources, environmental behavior, fate, and toxicity of PHCZs, highly sensitive and efficient analytical methodologies would be essentially needed to fill in these knowledge gaps.

Selective pressurized liquid extraction technique for halogenated organic pollutants in marine mammal blubber: A lipid-rich matrix

Analytical methods for unique and rare samples, such as marine mammal tissue, strive to reduce opportunities for analyte loss and contamination. Historically, analytical methodologies for marine mammal tissues required an extraction followed by multiple cleanup and concentration steps. These steps increase the opportunity for analyte loss and sample contamination. Selective pressurized liquid extractions (SPLE; an analytical technique that combines PLE with in-cell adsorbent cleanup) have the potential to reduce and/or eliminate the number of steps. A SPLE method was developed for the simultaneous extraction of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) from bowhead whale blubber. This SPLE utilized acidic silica with a fat-to-fat retainer ratio of 0.02 as well as eliminated post-extraction cleanup steps, such as size-exclusion chromatography step. In addition, neutral silica was placed beneath the acidic silica as an acid buffer, thereby preventing acid from contaminating the extraction system. Analysis was performed using gas chromatography/mass spectrometry in electron capture negative ionization mode. PBDE, PCB and OCP triplicate recoveries averaged 84±1%, 83±3%, and 76±11%, respectively. Overall, measurements of NIST Whale Blubber SRM 1945 were within±30% of certified values. PBDEs were measured for the first time in bowhead whale blubber; average concentrations ranged from 0.2 to 1.4ngg−1 wet weight (ww). Average OCPs and PCBs concentrations ranged from 0.4 to 37ngg−1ww and 0.1 to 3.0ngg−1ww, respectively, which were within one order of magnitude lower than those previously reported in bowhead whale blubber.

ENVIRONMENTAL FATE OF THREE NOVEL BROMINATED FLAME RETARDANTS IN AQUATIC MESOCOSMS

Currently, little is known about the environmental fate and persistence of novel brominated flame retardants (NBFRs). The recent detection of NBFRs in sediment cores and air samples provides insight into their persistence and potential for transport. Limited numbers of laboratory studies have examined the fate and behavior of these compounds, but field-based fate studies have been especially lacking. The authors conducted an aquatic mesocosm experiment to assess the behavior of three NBFRs: bis(tribromophenoxy)ethane (BTBPE), tetrabromobisphenol A bis(2,3-dibromopropyl ether; TBBPA-DBPE), and Firemaster BZ-54, a commercial mixture containing bis(2-ethylhexyl)tetrabromophthalate (BEHTBP) and 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTeBB) in a ratio of 1:4. Analysis by gas chromatography-mass spectrometry, operated in the electron capture negative ionization mode, revealed partitioning between the particulate and sediment phases, with BTBPE, TBBPA-DBPE, and BEHTBP identified as being environmentally persistent in both the particulate and the sediment compartments. The median dissipation times (DT50) differed in each compartment, with more rapid disappearance in the particulate (9-30 d) compared with the sediment compartment (>100 d) for each compound. The degradation products were more concentrated in the particulate compartment and corresponded to known photodegradation products. The ratio of EHTeBB to BEHTBP differed in the mesocosm compartments compared with the technical product used for treatment, indicating increased degradation of EHTeBB relative to BETHBP.

Stable isotope gas chromatography–tandem mass spectrometry determination of aminoethylcysteine ketimine decarboxylated dimer in biological samples

Aminoethylcysteine ketimine decarboxylated dimer (AECK–DD; systematic name: 1,2-3,4-5,6-7,8-octahydro-1,8a-diaza-4,6-dithiafluoren-9(8aH)-one) is a previously described metabolite of cysteamine that has been reported to be present in mammalian brain, urine, plasma, and cells in culture and vegetables and to possess potent antioxidative properties. Here, we describe a stable isotope gas chromatography–tandem mass spectrometry (GC–MS/MS) method for specific and sensitive determination of AECK–DD in biological samples. 13C2-labeled AECK–DD was synthesized and used as the internal standard. Derivatization was carried out by N-pentafluorobenzylation with pentafluorobenzyl bromide in acetonitrile. Quantification was performed by selected reaction monitoring of the mass transitions m/z 328 to 268 for AECK–DD and m/z 330 to 270 for [13C2]AECK–DD in the electron capture negative ion chemical ionization mode. The procedure was systematically validated for human plasma and urine samples. AECK–DD was not detectable in human plasma above approximately 4nM but was present in urine samples of healthy humans at a maximal concentration of 46nM. AECK–DD was detectable in rat brain at very low levels of approximately 8pmol/g wet weight. Higher levels of AECK–DD were detected in mouse brain (∼1nmol/g wet weight). Among nine dietary vegetables evaluated, only shallots were found to contain trace amounts of AECK–DD (∼6.8pmol/g fresh tissue).

Thorough analysis of polyhalogenated compounds in ray liver samples off the coast of Rio de Janeiro, Brazil

Five liver samples of two different ray species (Gymnura altavela and Zapteryx brevirostris) off the coast of Rio de Janeiro, Brazil, were analyzed for their pollution with anthropogenic and naturally occurring organohalogen compounds. The samples were extracted with accelerated solvent extraction, and after a clean-up procedure, organohalogen compounds were separated by a modified group separation on activated silica. Subsequent analyses were done by targeted and non-targeted gas chromatography-mass spectrometry in the electron capture negative ion mode. "Classic" organohalogen compounds such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and technical 1,1,1-trichloro-2,2-di(4-chlorophenyl)ethane (DDT) were detected and quantified. PCBs generally exceeded the parts per million level and represented up to 90% of the total contamination of the ray livers. High concentrations were also detected for p,p'-DDE. Non-targeted full scan investigations lead to the detection of an abundant trichlorinated compound which was identified as a new DDT metabolite in biota. Different PBDE congeners and several halogenated natural products were quantified as well. In addition, polychlorinated terphenyls were identified and analyzed in the two species. Moreover, both ray species showed different fatty acid patterns and stable carbon isotope signatures. The two ray species showed high concentrations of organohalogen compounds in their liver tissue. Varied δ (13)C values by up to 3.1‰ indicated that the two ray species were living in different habitats.

Identification of Monochloro-Nonabromodiphenyl Ethers in the Air and Soil Samples from South China

Several studies have indicated that mixed brominated/chlorinated organic compounds could be formed during the thermal process such as the incineration of municipal solid waste and open burning of unregulated e-waste at recycling areas. In this study, air particles and soils from e-waste recycling areas, as well as outdoor and indoor air particles from urban Guangzhou, were collected and pooled for the identification of mixed chlorinated/brominated diphenyl ethers (PXDEs). Three monochloro-nonabromo diphenyl ethers (Cl-nonaBDEs), including 6'-Cl-BDE-206, 5'-Cl-BDE-207, and/or 4'-Cl-BDE-208, were first structurally identified in these air and soil samples. The identification was done by comparison of retention times in chromatograms of pure reference compounds and environmental samples, as well as by comparison with full-scan mass spectra data in electron capture negative ionization mode. Because of their similar physical-chemical properties, 4'-Cl-BDE-208 and 5'-Cl-BDE-207 absolutely coeluted, even on a nonpolar DB-5 column. Further investigation is still needed to clarify these findings. Nevertheless, the results indicated that Cl-nonaBDEs would occur in various environmental matrices. Because the replacement of Br by Cl will change the physical-chemical properties of PBDE analogues, environmental occurrence, fate, and transport, the potential toxicity of PXDEs should be investigated.

Identification of Hydroxylated Octa- and Nona-Bromodiphenyl Ethers in Human Serum from Electronic Waste Dismantling Workers

Previous studies have reported high serum concentrations of polybrominated diphenyl ethers, especially decabromodiphenyl ether (BDE-209), in the residents of an electronic waste (e-waste) dismantling site in Guiyu town, South China. In the present study, human serum samples in this region were collected and pooled for the identification of hydroxylated diphenyl ethers (OH-PBDEs). Three OH-PBDEs, including two hydroxylated octabromodiphenyl ethers (OH-octaBDEs, 6-OH-BDE196 and 6-OH-BDE199) and one hydroxylated nonabromodiphenyl ether (OH-nonaBDE, 6'-OH-BDE206), were first structurally identified. Identification was done by coeluting a mixture of synthetic authentic standards with the methylated OH-PBDEs from the pooled samples using two gas chromatography columns with different polarities. The results were supported by full scan mass spectrometric data in electron capture negative ionization mode. All three OH-PBDE metabolites had hydroxy groups substituted in the ortho position. These results indicate that hydroxylated higher brominated diphenyl ethers such as OH-octaBDEs and OH-nonaBDEs can accumulate in human blood. The results suggest that higher brominated diphenyl ethers could be oxidatively metabolized into OH-PBDEs in humans. Because low brominated OH-PBDEs can also be detected in abiotic media, further investigations are needed to determine the presence of higher brominated OH-PBDEs in the environment in this region.

Application of the novel 5-chloro-2,2,3,3,4,4,5,5-octafluoro-1-pentyl chloroformate derivatizing agent for the direct determination of highly polar water disinfection byproducts

A novel derivatizing agent, 5-chloro-2,2,3,3,4,4,5,5-octafluoropentyl chloroformate (ClOFPCF), was synthesized and tested as a reagent for direct water derivatization of highly polar and hydrophilic analytes. Its analytical performance satisfactorily compared to a perfluorinated chloroformate previously described, namely 2,2,3,3,4,4,5,5-octafluoropentyl chloroformate (OFPCF). The chemical properties (reactivity, selectivity, derivatization products, and their chromatographic and spectral features) for ClOFPCF were investigated using a set of 39 highly polar standard analytes, including, among others, hydroxylamine, malic and succinic acids, resorcinol, hydroxybenzaldehyde, and dihydroxybenzoic acid. Upon derivatization, the analytes were extracted from the aqueous solvent and analyzed by gas chromatography (GC)-mass spectrometry (MS) in the electron-capture negative ionization (ECNI) mode. Positive chemical ionization (PCI)-MS was used for confirming the molecular ions, which were virtually absent in the ECNI mass spectra. ClOFPCF showed good reaction efficiency, good chromatographic and spectroscopic properties (better than with OFPCF), good linearity in calibration curves, and low detection limits (0.3-1 microg/L). A unique feature of the derivatizations with ClOFPCF, and, in general, highly fluorinated chloroformates, is their effectiveness in reacting with carboxylic, hydroxylic, and aminic groups at once, forming multiply-substituted non-polar derivatives that can be easily extracted from the aqueous phase and determined by GC-ECNI-MS. The entire procedure from raw aqueous sample to ready-to-inject hexane solution of the derivatives requires less than 10 min. Another benefit of this procedure is that it produced stable derivatives, with optimal volatility for GC separation, and high electron affinity, which allows their detection as negative ions at trace level. In addition, their mass spectra exhibits chlorine isotopic patterns that clearly indicate how many polar hydrogens of the analyte undergo derivatization. Finally, derivatization with ClOFPCF was used successfully to identify 13 unknown highly polar disinfection byproducts (DBPs) in ozonated fulvic and humic acid aqueous solutions and in real ozonated drinking water.

Polybrominated Diphenyl Ethers in Umbilical Cord Blood and Relevant Factors in Neonates from Guiyu, China

We aimed to evaluate the exposure of neonates to polybrominated diphenyl ethers (PBDEs) from a primitive e-waste (obsolete electrical and electronic devices) recycling area, in Guiyu, China, and a control area, Chaonan, China, through umbilical cord blood (UCB), the health effects, and relevant factors. Questionnaires were addressed, and UCB was collected shortly after birth from 153 pregnant women between May and July 2007. Blood samples were prepared by liquid-liquid extracting methods. PBDE concentration was determined by gas chromatography/mass spectrometry in the electron capture negative ionization mode. The total PBDE concentration was higher in UCB samples from Guiyu than in Chaonan samples (median 13.84, range 1.14-504.97 ng g(-1) lipid, vs 5.23, range 0.29-363.70 ng g(-1) lipid) (p < 0.05). BDE-209 was the dominant PBDE congener, followed by BDE-47, -153, and -99. Residence in Guiyu, which is a site for e-waste recycling, involvement in e-waste recycling, and the residence also being used as a family workshop were significant factors contributing to PBDE exposure. PBDE levels significantly differed in neonates by normal birth and adverse birth outcomes including stillbirth, low birth weight, and premature delivery (p < 0.05). The neonates from Guiyu are exposed to high levels of PBDEs. Prenatal exposure to PBDEs may affect neonates' health in Guiyu, which still needs to be evaluated in larger epidemiological studies.

Sensitive and selective method for the determination of bisphenol-A and triclosan in serum and urine as pentafluorobenzoate-derivatives using GC–ECNI/MS

The development and validation of an analytical method is presented for the determination of bisphenol-A (BPA) and triclosan (TCS), two ubiquitous contaminants, in serum and urine. The glucuronidated metabolites were first turned into their free forms to determine total BPA and TCS. The determination consisted of a solid-phase extraction on Oasis HLB cartridges followed by an extractive derivatization with pentafluorobenzoylchloride. The extract was then purified on 10% (w/w) acidified silica and analyzed by gas chromatography–mass spectrometry in electron-capture negative ionization mode. Monitored ions were m/ z 616 and 406 for BPA and m/ z 482 and 287 for TCS, respectively. Limits of quantification were 0.5 ng/mL in serum and 0.2 ng/mL in urine for BPA and 0.1 ng/mL in serum and 0.05 ng/mL in urine for TCS. Method recoveries were between 76 and 110%, while repeatability was below 20%. The method was applied on 20 serum and 20 urine samples. The detection frequency in serum was 10% and 55% for BPA and TCS, respectively. BPA and TCS could be detected in all urine samples with median concentrations of 1.25 ng BPA/mL (range 0.58–5.20 ng/mL) and 1.71 ng TCS/mL (0.18–672 ng/mL).

Polybrominated diphenyl ethers in aircraft cabins – A source of human exposure?

Commercial aircrafts need a high degree of fire protection for passenger safety. Brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs), may be used for this purpose. Because PBDEs readily absorb to dust particles, aircraft crew and passengers may receive significant PBDEs exposure via inhalation. The aims of this work were to assess whether PBDEs could be found in aircraft cabin dust and whether serum levels of PBDEs increased in passengers after long-distance flights. Hence nine subjects on intercontinental flights collected cabin dust samples, as well as donated blood samples before departure and after return to Sweden. Two subjects who were domestic frequent flyers were also investigated. The levels of PBDEs in dust and serum were determined by GC/MS in electron capture negative ionization (ECNI) mode. Authentic reference substances were used for identification and quantitation. PBDEs were found in all aircraft dust samples at high concentrations, higher than in common household dust. Congener patterns indicated that the technical products PentaBDE, OctaBDE and DecaBDE were used in the aircrafts. Serum concentrations in the travellers were similar to those observed in Swedish residents in general. Post-travel serum levels of BDE-28, BDE-99, BDE-100, BDE-153, and BDE-154 were significantly higher ( p < 0.05) than concentrations prior to travel. The findings from this pilot study call for investigations of occupational exposures to PBDEs in cabin and cockpit crews.

Occurrence of polychlorinated naphthalenes, polychlorinated biphenyls and short-chain chlorinated paraffins in marine sediments from Barcelona (Spain)

Polychlorinated naphthalenes (PCNs), short-chain chlorinated paraffins (SCCPs) and polychlorinated biphenyls (PCBs) were analysed in marine sediment samples collected from the coastal area of Barcelona (Spain) and near of a submarine emissary coming from a waste water treatment plant located at the mouth of the Besòs River (Barcelona). An integrated sample treatment based on Soxhlet extraction followed by a simple clean-up with Florisil and graphitized carbon cartridge was employed. Gas chromatography coupled to ion-trap tandem mass spectrometry (GC–MS/MS) and gas chromatography–mass spectrometry in electron capture negative ionization mode, were used for PCN and SCCP determinations, respectively, while for PCB analysis gas chromatography with electron capture detection (GC-ECD) was used. The method developed provided low limits of detection (0.001–0.003 ng g −1 dry weight (dw) for PCNs, 1.8 ng g −1 for SCCPs and 0.006–0.014 ng g −1 dw for PCBs) and good run-to-run precisions (lower than RSD 8%) for the analysis of sediment samples. Concentration levels ranging from 0.17 to 3.27 ng g −1 dw for PCNs, between 0.21 and 1.17 μg g −1 dw for SCCPs, and from 2.33 to 44.00 ng g −1 (dw) for PCBs, were found in the coastal sediments, while for samples collected near to the submarine emissary higher levels (from 2.02 to 6.56 ng g −1 dw for PCNs, between 1.25 and 2.09 μg g −1 dw for SCCPs and from 22.34 to 37.74 ng g −1 dw for PCBs) were obtained. The results obtained provide new data about the occurrence of PCN and SCCP in the coastal area of Barcelona.

Fast analysis of decabrominated diphenyl ether using low-pressure gas chromatography–electron-capture negative ionization mass spectrometry

This paper reports the applicability of low-pressure gas chromatography–mass spectrometry operated in electron-capture negative ionization mode (LP-GC–ECNI-MS) for the analysis of decabrominated diphenyl ether (BDE-209). Particular attention was paid to find optimal injector and oven conditions for minimal thermal degradation of BDE-209. The analytical characteristics were compared for LP-GC columns (10 m × 0.53 mm) with different film thicknesses ( d f 0.15 μm versus 0.25 μm) and for a conventional GC column (15 m × 0.25 mm, 0.10 μm d f). Short residence times (6.5 and 9.8 min) of BDE-209 were found for the LP-GC systems with 0.15 and 0.25 μm d f, respectively, resulting in a low elution temperature and minimal degradation. Additionally, baseline separation of 22 polybrominated diphenyl ether (PBDE) congeners (major components of PBDE technical mixtures) was possible in less than 12 min using the LP-GC–ECNI-MS system with 0.15 μm d f. The optimized method was applied for the determination of PBDEs in Belgian indoor dust samples. The obtained concentrations of BDE-209 (range 8–292 ng/g dry weight) were in the same range or lower than concentrations in dust from other European countries.