Occurrence and congener specific profiles of polybrominated diphenyl ethers and their hydroxylated and methoxylated derivatives in breast milk from Catalonia

The presence of polybrominated diphenyl ethers (PBDEs) from mono to hepta brominated and 11 hydroxylated (OH-) and methoxylated (MeO-) PBDEs was examined in 37 breast milk samples collected from 11 mothers living in Barcelona. An extraction method based on accelerated solvent extraction followed by gas chromatography coupled to high resolution mass spectrometry was used to inequivocally identify all target compounds at the low pg g(-1) lw level. Data obtained were examined for absolute and relative concentrations and specific PBDE, OH- and MeO-PBDE congener patterns. Sigma PBDE concentration ranged between 1,161 and 1,372,797 pg g(-1) lw and BDEs 47, 99, 100, 153 and 183 accounted for more than 80% of the total PBDEs. All tri and tetra OH- and MeO-PBDEs compounds were detected at levels between 6 and 14,984 pg g(-1)lw. The median ratio OH/PBDE and MeO-PBDEs/PBDEs was from 2.9% to 1.6%, respectively, suggesting either that PBDE metabolism to OH- and MeO- derivatives is not an important degradation route in humans or either OH- and MeO-PBDEs are rapidly excreted. No significant correlation was observed between PBDEs and OH- and MeO-PBDE, although OH- and OMe-PBDEs co-occurred in mothers' milk (R(2)=0.5349). According to the daily intake of PBDEs and OH- and MeO-PBDEs, which was between 0.47 and 363 ng d(-1) (excluding a smoking donor), potential health risks associated with these compounds are assessed.     

Polybrominated diphenyl ethers in South China maternal and fetal blood and breast milk

Twenty-one-paired human fetal and maternal serum and 27 breast milk samples at South China were analyzed for concentrations of polybrominated diphenyl ethers (PBDEs). Seven PBDE congeners (BDE-28, -47, -99, -100, -153, -154, and -183) were quantified using gas chromatography/mass spectrometry (GC/MS). This is the first report to present the residue levels of PBDEs in human samples of China. The concentrations of total PBDEs ranged from 1.5 to 17 ng/g in the samples and were within the range reported in European samples for a similar population, but lower than human tissue levels in North America. BDE-47 and -153 were the dominant PBDE congeners in all samples and accounted for 60% of the total PBDEs. Further research is needed to determine the exposure route of PBDEs and their health effects.     

Determination of dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) in paper pulp mill defoamer additives and in paper pulp samples

An analytical procedure has been developed for quantitatively measuring dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) present at part-per-billion levels in paper mill defoamers and paper pulp using gas chromatography coupled with either low resolution mass spectrometry (GC-LRMS) or high resolution mass spectrometry (GC-HRMS).     

Validation of a pressurized solvent extraction and GC-NCI-MS method for the low level determination of 40 polybrominated diphenyl ethers in mothers' milk

This study reports an efficient method for the determination of 40 PBDEs from mono- to hepta-brominated in human milk. Pressurized liquid extraction (PLE) was optimized to recover PBDEs in a quantitative way using 1g of freeze dried milk. Due to the great amount of coextracted compounds, the clean-up step was optimized using alumina SPE disposable cartridges of 2 and 5g. Whereas 2g alumina SPE failed in providing good extraction yields, all PBDEs were satisfactorily recovered using 5g alumina SPE cartridges. Detection was performed with gas chromatography coupled to mass spectrometry with negative chemical ionization and method detection limits ranged from 0.01 to 0.05mugkg(-1) wet weight (ww) with a good intra and inter-day variation (coefficient of variation lower than 13.4%). This method was validated by participating in an interlaboratory exercise from Quasimeme (United Kingdom), where a standard solution containing seven congeners and a certified unspiked mothers' milk were analyzed. In the standard mixture, levels between 96.915 and 570.172mugl(-1) were quantified, whereas in certified mothers' milk, BDEs 47, 99, 100 and 154 were detected at levels from 0.010 and 0.061mugkg(-1) ww, with an error <30%. The applicability of the method was tested experimentally in five mothers' milk samples, where only BDE 47 was detected at a maximum concentration of 10.45mugkg(-1) lipid weight (lw). PLE succeeded in extracting all PBDEs from the sample with good reproducibility although the clean-up step had to be severely performed to eliminate sample interferences such as milk lipids and proteins.     

Seasonal variability of polychlorinated biphenyls (PCBs) and polychlorinated diphenyl ethers (PBDEs) congener profiles in butter in Poland: Dietary risk evaluation

Various statistical methods have been employed to analyse in details seasonal diversification of polychlorinated biphenyl (PCB)/polybrominated diphenyl ether (PBDE) congener profiles found in butter fat. The variability of the PCB/PBDE congener profiles indicates the presence of various sources of the milk fat contamination. The obtained results suggest that the environmental chemical background has the highest share in the contamination sources pattern. Ion trap mass spectrometry coupled to high-resolution gas chromatography with semi-permeable membrane dialysis sample cleanup was used for determination of PCBs and PBDEs in milk fat. Determined butter fat PCB profiles were similar to the profiles characteristic for Aroclor 1254 technical mixture. Our data indicate that dietary intake of PCB/PBDE with milk and milk products may be estimated to be about 717.5 pg kg b.w.^?1 day^?1 for six-indicator PCBs, 0.329 (equivalent toxicity, TEQ) pg kg b.w.^?1 day^?1 for 12 DL PCBs and 50 pg kg b.w.^?1 day^?1 for PBDEs (sum of 14 congeners).     

A gas chromatography/high-resolution mass spectrometry (GC/HRMS) method for determination of polybrominated diphenyl ethers in fish

A method for the determination of polybrominated diphenyl ethers (PBDEs) in biota for routine analysis is described. The mass spectroscopic (MS) evaluation of 23 brominated diphenyl ethers, under electron ionization and electron capture negative ion conditions using magnetic sector and quadrupole mass spectrometers, showed that high-resolution mass spectrometry (HRMS) under electron ionization conditions was the most reliable technique, with high selectivity and adequate sensitivity. The instrument detection limit for this method ranged for individual congeners between 4.8 and 0.1 pg for 3-bromodiphenyl ether (BDE-2) and 2,3',4,4'-tetrabromodiphenyl ether (BDE-66), respectively, and method detection limit for each homologue group ranged between 5 pg/g for salmon certified reference material (CRM) and 93 pg/g for lake trout CRM. The effectiveness of this method was evaluated by analyzing the occurrence of PBDEs in commercially available CRMs comprising Lake Ontario lake trout, Pacific herring, and sockeye salmon. The average coefficients of variation for the replicate analyses of PDBEs in several tissue samples were: 25% for lake trout, 36% for Pacific herring, and 34% for sockeye salmon. The average deviations in the inter-laboratory study were: 14% for lake trout, 15% for Pacific herring, and 37% for sockeye salmon. Results indicated that the described method, based on gas chromatography/high-resolution mass spectrometry, is reliable for determining PBDE concentrations in biological tissues.     

Comparison of polybrominated diphenyl ethers in fish, vegetables, and meats and levels in human milk of nursing women in Japan

At present, little is known about the occurrence of polybrominated diphenyl ethers (PBDEs) in fish and food products sold in Japan. To investigate whether human exposure to PBDEs through the diet is significant, the concentrations of PBDEs were determined in fish and in meat and vegetables sold in two food markets in the city of Hirakata, Osaka prefecture. The concentrations of PBDEs in the breast milk of 12 primiparae nursing women at one month after delivery also were determined to ascertain the relationship between the levels found in the diet and levels in humans. sigma PBDE concentrations ranged between 21 and 1650 pg/g fresh weight in the edible tissues of five species of fish and one shellfish species. The highest concentrations were measured in yellow-fin tuna, followed by short-necked clam, salmon, yellowtail, mackerel and young yellowtail. Interestingly, sigma PBDE concentrations were not statistically significantly different in two cultured mackerel samples from Japan and mackerel collected from northern European waters. sigma PBDE concentrations in beef, pork and chicken meat (ranging between 6.25 and 63.6 pg/g fresh weight) and in three different vegetables (ranging between 38.4 and 134 pg/g fresh weight) were significantly lower than the concentrations in fish. In human milk, sigma PBDE concentrations ranged between 668 and 2840 pg/g lipid basis, which is comparable to the levels in populations of nursing women reported in Sweden and elsewhere. There was a strong positive relationship between PBDE concentrations in human milk and dietary intake of fish and shellfish, which was established in the women from responses to a questionaire on food consumption habits. The results of this study of food products commonly consumed in Japan and the levels found in nursing women raise a concern about low level PBDE contamination of fish and other foods intended for human consumption.     

Development of an analytical strategy based on liquid chromatography-high resolution mass spectrometry for measuring perfluorinated compounds in human breast milk: application to the generation of preliminary data regarding perinatal exposure in France

Perfluorinated compounds (PFCs) are man-made chemicals for which endocrine disrupting properties and related possible side effects on human health have been reported, particularly in the case of an exposure during the early stages of development, (notably the perinatal period). Existing analytical methods dedicated to PFCs monitoring in food and/or human fluids are currently based on liquid chromatography coupled to tandem mass spectrometry, and were recently demonstrated to present some limitations in terms of sensitivity and/or specificity. An alternative strategy dedicated to the analysis of fourteen PFCs in human breast milk was proposed, based on an effective sample preparation followed by a liquid chromatography coupled to high resolution mass spectrometry measurement (LC-HRMS). This methodology confirmed the high interest for HRMS after negative ionization for such halogenated substances, and finally permitted to reach detection limits around the pg mL(-1) range with an outstanding signal specificity compared to LC-MS/MS. The proposed method was applied to a first set of 30 breast milk samples from French women. The main PFCs detected in all these samples were PFOS and PFOA with respective median values of 74 (range from 24 to 171) and 57 (range from 18 to 102) pg mL(-1), respectively. These exposure data appeared in the same range as other reported values for European countries.     

Monitoring of PBDEs concentration in umbilical cord blood and breast milk from Korean population and estimating the effects of various parameters on accumulation in humans

In this study, we investigated concentration, congener distribution pattern, and effects of potential environmental factors that affect PBDE accumulation. We also estimated correlation between PBDE concentration and health status or thyroid function by analyzing 90 cord blood and 21 breast milk samples obtained from Korean population. Seven from tri- to hepta-BDEs were analyzed by solid phase extraction-high-resolution gas chromatography/high-resolution mass spectrometry (SPE-HRGC/HRMS). The total concentration of 7 PBDEs in cord blood was 2.786-94.64 ng g(-1) lipid and that in breast milk was 1.076-8.664 ng g(-1) lipid. Tetra-BDE (#47) was the predominant type of PBDE and was present at concentrations of over 40% in both sample types. A weak correlation was observed between the concentration of BDE28 and 153 and thyroid hormone concentration only in the breast milk samples. In children, a weak negative correlation was observed between free thyroxine (FT4) concentration and BDE28 concentration (0.302, p<0.05), while in mothers, a weak positive correlation was observed between thyroid hormone concentration and BDE153 concentration (0.403, p<0.05). No significant correlations between PBDE concentration and work and residential environments were found in this study, but a weak correlation between BDE concentration in cord blood and potential PBDE sources was confirmed by investigating the frequency of oil paint usage (0.510, p<0.001). A weak correlation was also found between PBDE concentration in breast milk during pregnancy and dietary habits such as green tea drinking (0.541, p=0.025) and Trichiuridae intake (0.565, p=0.015).     

Pine needles as passive bio-samplers to determine polybrominated diphenyl ethers

Eight polybrominated diphenyl ethers (PBDEs) were determined in pine needles of three species (Pinus halepensis, Pinus pinea and Pinus nigra) collected in the NE Spain in an attempt to use this matrix for the biomonitoring of airborne PBDEs. The method used was based in ultrasonic extraction followed by alumina and Florisil clean-up and determination by gas chromatography coupled to mass spectrometry in negative chemical ionization. Recoveries were between 99% and 138%, limits of detection between 0.011 and 0.070 ng g⁻¹-dw (0.232 ng g⁻¹-dw for BDE 209) and repeatability lower than 13%. PBDE levels ranged between 0.027 ng g⁻¹-dw and 13.04 ng g⁻¹-dw, with predominance of BDE 209, followed by BDEs 47. P. halepensis was the species with the highest PBDE levels and P. nigra, the least, according to their widespread and remote distribution, respectively. The presence of PBDEs in pine needles was attributed to the release of in-use PBDEs, transport through atmosphere and adsorption upon lipid rich pine needles. Given the easy collection of pine needles, its ample distribution and its potential to accumulate airborne contaminants, this matrix is proposed as passive bio-sampler to be used in PBDE monitoring programs.

Capsule

Pine needles can be used to biomonitor airborne PBDEs.     

Large-scale evaluation of the current level of polybrominated diphenyl ethers (PBDEs) in breast milk from 13 regions of Japan

Polybrominated diphenyl ethers (PBDEs) were measured in 2004 in 105 breast milk samples collected from 13 regions of Japan (Hokkaido, Akita, Miyagi, Tokyo, Gifu, Fukui, Kyoto, Hyogo, Wakayama, Shimane, Yamaguchi, Kochi and Okinawa). Six congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154) were determined by gas chromatography /mass spectrometry (GC/MS). Total PBDE levels ranged from 0.01 to 23.0 ng/g lipid (geometric mean (GM), 1.34 ng/g lipid). BDE-47 (GM, 0.66 ng/g lipid, 59% of sigmaPBDE) was the most abundant congener present in breast milk and was detected in 99% of the samples. Total PBDE levels were higher in northern Japan than in other regions. We analyzed the effects of occupation, age, smoking status, alcohol consumption and number of deliveries on total PBDE levels. None of these factors were significantly associated with the level of PBDEs. The present study revealed that the current level of exposure to PBDEs in Japan is lower than that in the USA or Sweden. GMs (ng/g lipid) (GSD, geometric standard deviation) and medians (ng/g lipid) of PBDE levels in each district are as follows: Hokkaido 2.70 (1.70), 2.74; Akita 4.49 (2.19), 5.44; Miyagi 1.77 (4.37), 1.11; Tokyo 1.39 (2.09), 1.63, Gifu 2.83 (4.79), 2.23; Fukui 1.05 (2.34), 1.18; Kyoto 1.31 (2.95), 1.33; Hyogo 1.02 (2.69), 0.88; Wakayama 1.33 (3.80), 1.70; Shimane 0.83 (2.51), 0.66; Yamaguchi 1.74 (2.82), 1.76; Kochi 0.50 (2.69), 0.74 and Okinawa 1.91 (2.75), 1.22. This is the first large-scale study of current PBDE levels in breast milk in Japan.     

First study of congener group patterns and concentrations of short- and medium-chain chlorinated paraffins in fish from the North and Baltic Sea

This study presents the first investigation of concentrations and congener group patterns of short- (SCCPs) and medium-chain chlorinated paraffins (MCCPs) in fish from the North and Baltic Sea. North Sea dab, cod and flounder were studied. High resolution gas chromatography (HRGC) coupled to low resolution mass spectrometry (LRMS) in the electron capture negative ionization mode (ECNI) was employed. Good linearity (R2>0.993, 7 measuring points) was achieved between 1 and 100 ng/g of CP mixtures for SCCPs and MCCPs. The limits of detection were 0.5-1 ng/microl of CP mixture for the major congener groups of SCCPs and MCCPs. A clean-up comprising fat extraction, adsorption chromatography on silicagel impregnated with concentrated sulphuric acid and adsorption chromatography on Florisil was employed to avoid interferences from other polychlorinated compounds. Recoveries of CPs in spiked samples ranged between 80% and 100%. Accuracy was controlled with spiked samples and deviated not more than 10% from the expected values. Quantification was performed with standards of an average chlorine content as close as possible to that of the samples (SCCPs: 59-62%, MCCPs: 53-58%). SCCP concentrations ranged between 19 and 286 ng/g liver wet weight (ww), MCCP concentrations were comparable with a range of 25-260 ng/gww. Congener group patterns were also determined and discussed. In samples from the Baltic Sea the SCCP congener pattern was similar to that of commercial SCCP mixtures or C13 congeners were most abundant. In samples from the North Sea a higher relative abundance of C10 congeners was observed.     

Time-trend (1973-2000) of polybrominated diphenyl ethers in Japanese mother's milk

The time-trend and recent concentrations of polybrominated diphenyl ethers (PBDEs) in Japanese mother's milk were investigated. The time-trend of 16 PBDEs (BDE-28, 37, 47, 66, 71, 75, 77, 85, 99, 100, 119, 153, 154, 138, 183, and 190) in pooled milk samples from mothers living in Osaka between 1973 and 2000 was analyzed. Additionally, PBDE concentrations in individual milk samples collected from 13 mothers living in Kanagawa and Okayama in 1999 were measured. The total concentration of all PBDE congeners (SigmaPBDEs) measured in the pooled samples increased during the period between 1973 (<0.01 ng/g lipid) and 1988 (1.64 ng/g lipid), and remained low afterwards while showing remarkable changes in PBDE congener profiles. The SigmaPBDEs in the 1999 individual milk samples were also low (0.56-3.97 ng/g lipid), except for a single sample (291 ng/g lipid). The source of this exposure could not be identified.     

Concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk of women from Catalonia, Spain

In this study, the concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk from women living in the vicinity of a new hazardous waste incinerator (HWI) in Catalonia, Spain, were determined. The study was performed after 4 years of regular operations in the facility and the present PCB levels were compared with baseline concentrations obtained in a pre-operational program. PCBs and PBDEs levels were determined by HRGC/HRMS in 15 samples. In the present study planar PCBs ranged from 1.3 to 6.3 pg WHO-TEQ/g fat with a mean value of 3.8 pg WHO-TEQ/g fat. After adding dioxin-like mono-ortho-PCBs the total PCB-TEQ concentrations ranged from 3.8 to 13.3 pg WHO-TEQ/g fat (mean value: 8.7 pg WHO-TEQ/g fat). A comparison of the current data with those obtained in the baseline study showed significant decreases for both planar and total WHO-TEQ of PCBs: 47.9% and 44.6%, respectively. PCB concentrations in milk of women living in urban zones were higher than those living near industrial areas (10.1 and 7.4 pg WHO-TEQ/g fat, respectively). Mean PBDE concentrations were 2.2 and 2.5 ng/g fat for women living in urban and industrial zones, respectively. Dietary intake of PCBs and PBDEs for a standard adult woman samples were 898 and 843 ng/day for PCBs, and 72 and 63 ng/day for PBDEs, for residents in urban and industrials areas, respectively. This study suggests that dietary intake is more relevant for human exposure to PCBs and PBDEs than living near the HWI.     

Polychlorinated biphenyls in contaminated soil samples evaluated by GC-ECD with dual-column and GC-HRMS

We present and compare results obtained from the analysis of polychlorinated biphenyls (PCBs) of a limited number of contaminated soil samples collected in three areas of Basilicata region (south of Italy). The levels of PCBs were evaluated by using two analytical methods: (i) parallel dual-column gas-chromatography with dual electron capture detectors (GC-ECD) and (ii) gas-chromatography coupled to high-resolution mass spectrometry (GC-HRMS) via electron impact ionization (EI) in the multiple ion monitoring mode (MIM, two ions per compound). Two extraction methods prior to sample cleanup were also examined: microwave-assisted extraction (MAE) and ultrasonic-assisted extraction (UAE). The MAE was the extraction procedure adopted using acetone/n-hexane (1:1, v/v) as it is mainly characterized by higher sample throughput and allowed reduced consumption of organic solvents. While extraction and analysis of spiked soil samples showed the applicability of both methods, systematic differences between the results were obtained for the sum of PCBs as a result of some non-detected congeners by GC-ECD compared with GC-HRMS. Indeed, high resolution MS using EI mode (electron energy 40eV) with a resolving power of 10,000 provides additional information about the contamination pattern. The GC-ECD screening of 11 soil samples led to just one sample non-compliant to as it was close to the guide value for soils fixed by the Italian legislation (i.e., 60ppb for private or urban soil). Using GC-HRMS, the amount of all PCBs found ranged from 5.4 to 127ppb with five soil samples non-compliant to the guide value. The number of identified congeners ranged from 1 to 9 and 9 to 18 using dual-column GC-ECD and GC-HRMS, respectively.     

Synthesis, isolation and purification of C10-C13 polychloro-n-alkanes for use as standards in environmental analysis

Short chain (C10-C13) polychloro-n-alkanes (sPCAs) mixtures were synthesized by refluxing pure n-alkane (> 99%) with sulfuryl chloride (SO2Cl2) in the presence of UV-light (550 W). The free radical initiated reactions produced analogs containing approximately 4-9 chlorine atoms on each carbon chain. Purification of reaction products was achieved by adsorption chromatography on Florisil. The products were characterized by high-resolution gas chromatography/mass spectrometry (HRGC/MS) operated in the electron capture negative ionization (ECNI) and in electron ionization (EI) modes. Individual standards can now be combined to create standards whose profiles resemble that of environmental samples. Quantification of a known amount of the newly synthesized sPCAs mixture, using an industrial formulation as an external standard, resulted in an overestimation (approximately 28%) in its true value.     

Brominated flame retardants in the Australian population: 1993-2009

Brominated flame retardants, including hexabromocyclododecane (HBCD) and polybrominated diphenyl ethers (PBDEs) are used to reduce the flammability of a multitude of electrical and electronic products, textiles and foams. The use of selected PBDEs has ceased, however, use of decaBDE and HBCD continues. While elevated concentrations of PBDEs in humans have been observed in Australia, no data is available on other BFRs such as HBCD. This study aimed to provide background HBCD concentrations from a representative sample of the Australian population and to assess temporal trends of HBCD and compare with PBDE concentrations over a 16 year period. Samples of human milk collected in Australia from 1993 to 2009, primarily from primiparae mothers were combined into 12 pools from 1993 (2 pools); 2001; 2002/2003 (4 pools); 2003/2004; 2006; 2007/2008 (2 pools); and 2009. Concentrations of ∑HBCD ranged from not quantified (nq) to 19 ng g(-1)lipid while α-HBCD and γ-HBCD ranged from nq to 10 ng g(-1)lipid and nq to 9.2 ng g(-1)lipid. β-HBCD was detected in only one sample at 3.6 ng g(-1)lipid while ∑(4)PBDE ranged from 2.5 to 15.8 ng g(-1)lipid. No temporal trend was apparent in HBCD concentrations in human milk collected in Australia from 1993 to 2009. In comparison, PBDE concentrations in human milk show a peak around 2002/03 (mean ∑(4)PBDEs=9.6 ng g(-1)lipid) and 2003/04 (12.4 ng g(-1)lipid) followed by a decrease in 2007/08 (2.7 ng g(-1)lipid) and 2009 (2.6 ng g(-1)lipid). In human blood serum samples collected from the Australian population, PBDE concentrations did not vary greatly (p=0.441) from 2002/03 to 2008/09. Continued monitoring including both human milk and serum for HBCD and PBDEs is required to observe trends in human body burden of HBCD and PBDEs body burden following changes to usage.     

Congener group patterns of chloroparaffins in marine sediments obtained by chloride attachment chemical ionization and electron capture negative ionization

Congener group patterns of technical short chain and medium chain chloroparaffins (SCCP and MCCP) were determined by electron capture negative ionization (ECNI) and chloride attachment chemical ionization (CACI) mass spectrometry (MS). In contrast to CACI-MS, congener patterns obtained by ECNI showed always a shift to the next higher chlorinated congener and carbon chain length group. Consequently, the calculated molecular masses and chlorine contents were higher for ECNI (factor 1.10+/-0.03 and 1.09+/-0.03, respectively). ECNI/CACI ratios in sediment samples from the North and Baltic Sea were also slightly higher. However, a more pronounced shift of the congener pattern for a given carbon chain length to congeners with 2-3 more chlorine atoms was observed. SCCP and MCCP concentrations obtained by ECNI-MS were in the range of 8-63ngg(-1) (North Sea) and 22-149ngg(-1) dry weight (Baltic Sea). MCCP levels were highest in all samples (MCCP/SCCP factor 1.1-3.2).     

Polybrominated diphenyl ethers (PBDEs) in human milk from Australia

Polybrominated diphenyl ethers (PBDEs) are flame retardants added to a multitude of products to reduce flammability. PBDEs have been widely detected and quantified in biota and humans in many industrialised countries from the Northern Hemisphere. However data concerning the levels of these compounds in the Australian population and environment remain limited. The objectives of this study were to determine PBDE concentrations and congener profiles in Australian human milk and compare this to concentrations found in other countries. Pooled human milk samples obtained from mothers residing in 12 regions of Australia were analysed by HRGC/HRMS for 18 PBDE congeners. In total, 157 human milk samples collected in 2002 and 2003 were divided into 17 regional pools. PBDEs were detected in all pools of human milk from Australia. The mean+/-standard deviation and median summation operatorPBDE concentrations were 11.1+/-3.2 and 11.0 ng g(-1) lipid, respectively with a range of 6.1-18.7 ng g(-1) lipid. The congener profile was dominated by BDE-47 followed by BDE-99, -100, -153, -154 and -183. Regional differences were evaluated, but no trends were observed. The data suggest regional differences are likely to be small if they exist at all. The concentrations of PBDEs found in Australian human milk were lower than those reported from North America but higher than those reported from Europe and Asia. Our results suggest that the exposure pathways which contribute to the PBDE body burden in the Australian population require a better understanding in order to determine future policy regarding their use and disposal.     

Method optimization to measure polybrominated diphenyl ether (PBDE) concentrations in soils of Bratislava, Slovakia

We modified an analytical method to determine polybrominated diphenyl ethers (PBDEs) in urban soils of Bratislava (Slovakia). Gel permeation chromatography (GPC) introduced as a clean-up step for soil extracts substantially reduced matrix enhancements when PBDEs were measured with gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS). The resulting method proved to be accurate, precise, and showed low detection limits. The sum of 15 PBDE concentrations in surface horizons of Bratislava soils ranged from 87 to 627 pg g⁻¹. PBDE concentrations were mostly higher in surface than deeper horizons probably because of atmospheric deposition and lack of substantial vertical transport. Lower brominated PBDEs undergo more soil-atmosphere exchanges or are more scavenged and transferred with litter fall to the soil organic matter than higher brominated ones as suggested by the correlation between lower brominated PBDEs and soil organic C (C_org) concentrations.