Environmental analysis of higher brominated diphenyl ethers and decabromodiphenyl ethane (original) (raw)
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Methods for determination of polybrominated diphenyl ethers in environmental samples - review
Journal of Separation Science, 2012
Polybrominated diphenyl ethers (PBDEs) are a group of persistent organic pollutants. They are used as flame retardants in plastics, paints, varnishes and textile materials. PBDEs pose great risk to the environment because of their high persistence and ability to get into the environment easily due to the lack of chemical bonds with the matrix of materials, to which they are added. Global research studies confirmed the occurrence of those compounds in the majority of elements of water and land environment. Analysis of PBDEs in environmental samples is one of the specific analytical methods of criteria that comprise low detection limits and high selectivity. The analysis of PBDEs in environmental samples is one of the specific analytical methods, in which the main criteria are low detection limits and high selectivity. In this article, a literature review of methods for environmental sample preparation and analysis of the PBDE content was presented. The article discusses the potential of modern extraction techniques such as: solid-phase microextraction, single-drop microextraction, dispersive liquid-liquid microextraction, microwave-assisted extraction, cloud point extraction, hollow fibre-liquid phase microextraction and others for the separation of PBDEs from environmental samples with a complex matrix. Among the methods for qualitative and quantitative determination of PBDEs, a particular focus was put on gas chromatography/mass spectrometry with various injection techniques and different types of sample ionisation.
Environmental Health Perspectives, 2007
Polybrominated diphenyl ethers (PBDEs) are ubiquitous environmental contaminants that are found in both abiotic and biotic environmental samples (Hites 2004; Streets et al. 2006). PBDEs are used as flame retardants; the three main commercial types of PBDE are penta-BDE, octa-BDE, and deca-BDE. DE-71, a widely used commercial penta-BDE product, is generally composed of 50-60% penta-BDE congeners, 24-38% tetra-BDE congeners, and 4-8% hexa-BDE congeners (Birnbaum and Staskal 2003). Since the 1970s, penta-BDE has been used as a flame retardant in polyurethane foam-containing consumer goods such as carpet padding, sofas, and mattresses; this flame retardant can account for up to 30% by weight of the foam (Hale et al. 2002). DE-71 also has minor uses in phenolic resins, polyesters, and epoxy. Despite its relatively small global production and usage compared with deca-BDE, the congeners in penta-BDE, such as 2,2´,4,4´-tetrabromodiphenyl ether (BDE-47), 2,2´,4,4´,5pentabromodiphenyl ether (BDE-99), and 2,2´,4,4´,5,5´-hexabromodiphenyl ether (BDE-153), are the most common PBDE congeners found in environmental samples, Materials and Methods Chemicals. We obtained commercial DE-71 from the Great Lakes Chemical Corporation (West Lafayette, IN). Dimethyl sulfoxide and β-estradiol-3-benzoate were purchased from Sigma Chemical Co. (St. Louis, MO), and corn oil was purchased from ICN Biomedicals (Aurora, OH). We purchased all of the neutral standards (
The difficulties in polybrominated diphenyl ethers (PBDEs) identification by GC-EI-MS technique
Proceedings of the 12th ISC Modern Analytical Chemistry, 2016
Awareness about the harmful effects of brominated flame retardants on living organisms increases mainly due to link their presence in the human environment with health disorders. Therefore is a need to conduct research aimed at content control of these chemicals in the environment. Recent improvements in injection techniques and mass spectrometer ionization methods have led to a variety of options to determine PBDEs in environmental samples. Some difficulties in qualitative and quantitative analysis still make dekaBDE congener (BDE-209). Modeling studies aimed at selecting the optimal conditions for the separation and identification of selected PBDEs patterns have been carried out. The results are an introduction to the study of real environmental samples. Using technique was gas chromatography with electronionization-mass spectrometry.
Levels of dechloranes and polybrominated diphenyl ethers (PBDEs) in human serum from France
Environment International, 2014
Human exposure to dechloraneshas been evaluated in Western Europe (France) with the analysis of Dechlorane Plus (DP), Dechloranes (Dec) 602, 603, 604, Chlordene Plus (CP) and Mirex in 48 serum samples collected between 2003 and 2005. While no production source has been identified in Europe until now, detection frequencies for all investigated dechloranes were high, except for Dec 604 whichwas below detection limit for all samples.The mean DP concentration was 1.40 ± 1.40 ng/g lipid weight (lw), lower than levels reported in serum from Chinese population, but higher than levels reported in Canadian human milk.To the best of our knowledge, this is the first time ∑ 5 dechloranelevels are reported for human serum. A specific pattern of contamination was found (Dec 603 > DP > Mirex > Dec 602 > CP)compared to other biota samples that have been analyzed from Europe,with Dec 603 as the most abundant dechlorane (meanlevel: 2.61 ± 2.63 ng/g lw). Dec 603 and CP levels were correlated with age and with levels of some bioaccumulative organochlorine pesticides (OCPs). These results indicate that bioaccumulation properties should be further investigated and taken in consideration when assessing human exposure to dechloranes.For comparison purposes, polybrominated diphenyl ether(PBDE) levels were also measuredfor BDE-47,-99,-100,-153 and-154 in the serum samples. As expected, BDE-47 and BDE-153 were the major congeners with mean levels of 2.06 ± 1.80 ng/g lw and 1.39 ± 0.97 ng/g lw, respectively. The mean ∑ 5 PBDE levels (4.32 ± 2.99 ng/g lw) was in the range typical ofWestern Europe levels, but lower than the mean ∑ 5 dechlorane levels (6.24 ± 4.16 ng/g lw).These results indicate that the attention to dechloranes should be continued if research indicates toxicological concerns.
Analytical Chemistry, 2009
A total of 14 tetra-to deca-PBDE congeners were separated on a C 18 reversed phase liquid chromatographic column. PBDEs 47, 85, 99, 100, 153, 154, 183, 196, 197, 203, 206, 207, 208, and 209 were eluted using a gradient methanol/water/toluene mobile phase system at a flow rate of 0.5 mL min -1 . 13 C-BDE-47, 13 C-BDE-99, 13 C-BDE-153, BDE-128, and 13 C-BDE-209 were used as internal standards, while 13 C-BDE-100 was used as a syringe standard. Separated analytes were ionized using an atmospheric pressure photoionization (APPI) source equipped with a 10 eV krypton lamp and operated in negative ion mode. [M-Br + O]ions were monitored as precursor ions for all studied PBDEs, except for BDE-208 and BDE-209 which produced higher intensity at the [C 6 Br 5 O]ion cluster.
2004
Standard reference materials (SRMs) are valuable tools in developing and validating analytical methods to improve quality assurance standards. The National Institute of Standards and Technology (NIST) has a long history of providing environmental SRMs with certified concentrations of organic and inorganic contaminants. Here we report on new certified and reference concentrations for 27 polybrominated diphenyl ether (PBDE) congeners in seven different SRMs: cod-liver oil, whale blubber, fish tissue (two materials), mussel tissue and sediment (two materials). PBDEs were measured in these SRMs, with the lowest concentrations measured in mussel tissue (SRM 1974b) and the highest in sediment collected from the New York/New Jersey Waterway (SRM 1944). Comparing the relative PBDE congener concentrations within the samples, we found the biota SRMs contained primarily tetrabrominated and pentabrominated diphenyl ethers, whereas the sediment SRMs contained primarily decabromodiphenyl ether (BDE 209). The cod-liver oil (SRM 1588b) and whale blubber (SRM 1945) materials were also found to contain measurable concentrations of two methoxylated PBDEs (MeO-BDEs). Certified and reference concentrations are reported for 12 PBDE congeners measured in the biota SRMs and reference values are available for two MeO-BDEs. Results from a sediment interlaboratory comparison PBDE exercise are available for the two sediment SRMs (1941b and 1944).
2010
During recent years, a marked increase in the levels of brominated flame retardants (BFRs), especially polybrominated diphenyl ethers (PBDEs), in human tissues all over the world have been observed (Scheter et al., 2000; Tomsen et al., 2002). It is mainly due to the following facts: their production and use have undergone a dramatic increase starting in the 1980s (Sjödin et al., 2004) and their persistence and lipophilic character which tend to concentrate in the food chain, and thus accumulate in the human body (de Wit, 2002). The consumption in European countries of the different PBDE commercial mixtures available was estimated to be 150 metric tons of Penta-, 400 metric tons of Octa-and 7000 metric tons of Deca-BDE technical products (BSEF, 2000), which made the higher brominated PBDEs, mainly the PBDE 209, a matter of special concern in European countries. However, the majority of the data available in the literature are focused on tetra-to hexa-BDE congeners while little information is available on PBDEs 183 and 209 (the major components of the commercial flame retardant mixture Octa-BDE and Deca-BDE, respectively). In the same way, the concentrations concerning impurities of technical formulations and/or degradation products of PBDE 209, such as PBDEs 184, 191, 196, and 197 (Dandenourd et al., 2001; Stapleton et al., 2003), are very scarce in the literature. This fact could be related to the determination difficulties for high brominated PBDEs mainly when gas chromatography coupled with low resolution mass spectrometry (GC-MS) is used. GC-MS is a more selective technique than GC coupled to electron capture detector (ECD) but electron impact-MS (EI-MS) ionisation mode is less sensitive than GC-ECD. In this direction, negative chemical ionisation-MS (NCI-MS) operating mode has emerged as a valuable and more sensitive technique than EI-MS for the determination of PBDEs, mainly those with high bromination degree. On the other hand, human serum, umbilical cord serum, breast milk, and placenta samples are non-destructive matrices adequate for monitoring human exposure to PBDEs indicating both parents and neonates body burden. Although there is a wide knowledge on organochlorine contaminants in human tissues like serum and breast milk (Costopoulou et al., 2006; Chen et al., 2006), information regarding PBDE concentrations, mainly those of high-brominated congeners, in this kind of samples, is still very scarce in the literature. We present here, for the first time, PBDE levels, including tri-to deca-substituted congeners, found in human samples from the Spanish population. The preliminary results of an extended study of PBDE concentrations in paternal, maternal and neonate serum, breast milk, and placenta samples from individuals living in the Community of Madrid (Spain) are shown. Material and Methods. A total of 10 maternal serum samples, 10 paternal serum samples, 10 umbilical cord serum samples, 10 placenta samples, and 10 breast milk samples were colleted in 2005-2006 from volunteers living in the Community of Madrid (Spain). Once at the laboratory, serum samples were frozen at-20ºC and breast milk and placenta samples were freeze-dried and stored at room temperature until analysis. Serum samples were extracted and purified using a semi-automated solid phase extraction and cleanup method previously described (Gómara et al., 2002). The method used for breast milk and placenta
Journal of Chromatography A, 2009
A novel and efficient analytical methodology is proposed for extracting and preconcentrating polybrominated diphenyl ethers (PBDEs) from samples of environmental interest prior gas chromatography-mass spectrometry (GC-MS) analysis. It is based on the induction of micellar organized medium by using a non-ionic surfactant (Triton X-114) to extract the target PBDEs. To enable coupling the efficient extracting technique with GC analysis, ultrasound-assisted back-extraction (UABE) into an organic solvent was required. Several factors, including surfactant type and concentration, equilibration temperature and time, ionic strength, pH and buffers nature and concentration were studied and optimized over the extraction efficiency of the proposed technique. Under optimal experimental conditions, the target analytes were quantitatively extracted achieving an enrichment factor of 250 when 10 mL aliquot of ultrapure water spiked with PBDE-standard mixture (10 pg mL −1 each PBDE) was extracted. Method detection limits (MDLs) calculated with aqueous PBDEs solutions as three times the signal-to-noise ratio (S/N), ranged from 1 to 2 pg mL −1 with RSDs values ≤8.5% (n = 5). The coefficients of estimation of the calibration curves obtained following the proposed methodology were ≥0.9987 and linear range of all PBDEs was 4-150 pg mL −1 . The proposed methodology was validated by carrying out a recovery study by spiking the samples at two different concentration levels of PBDEs (10 and 50 pg mL −1 for waters samples). Recoveries values in the range of 96-106% for water samples were obtained showing satisfactory robustness of the method for analyzing PBDEs in water samples. The proposed methodology was applied for the analysis of PBDEs: 2,2 ,4,4 -tetraBDE (BDE-47), 2,2 ,4,4,5-pentaBDE (BDE-99), 2,2 ,4,4,6-pentaBDE (BDE-100) and 2,2,4,4 ,5,5 -hexaBDE (BDE-153) in water samples, including drinking, lake, river water and soil samples. Significant quantities of PBDEs were not found in the analyzed samples.