Median concentration of total PBDEs in maternal serum, paternal serum, umbilical cord serum, and breast milk samples were 12, 12, 17, and 6.1 ng/g lipid weight (lw) in Vallecas and 9.7, 12, 15, and 5.5 ng/g lw in Getafe. The median value found in placentas was 1.9 ng/g lw (in Vallecas). BDE 47 was the predominant congener in serum samples (maternal, paternal, and umbilical cord), while BDE 209 was predominant in placenta and breast milk samples. BDEs 196 and 197 were detected in most of the placenta and breast milk samples. The results show that PBDEs, like other POPs, can cross the placenta barrier, although the speed of the process seems to differ for each PBDE congeners. The total PBDE concentrations found in this study are consistent with research reported elsewhere. They are in the same range as those recently reported by other European and Asian studies and lower than those conducted in the U.S.A. No significant differences were found (p > 0.05) between regions, sexes, and ages, while statistically significant differences (p < 0.05) were found between maternal serum, umbilical cord serum, and breast milk samples. The presence of PBDEs in cord blood and placenta samples indicates that there is prenatal exposure of PBDEs, which could continue after birth via breast milk.

Concentrations of 15 BDEs flame retardants have been determined in a large variety of food samples purchased in different markets across Spain. This is the first time that BDEs 184, 191, 196, and 197; impurities from BDEs formulations; and/or degradation products of BDE 209, have been detected in foodstuffs. Values ranged from <0.01 to 2482 pg/g fresh weight. The highest total BDE concentrations were found in fish samples (median of 189, range of 24-880 pg/g f.w.), followed by oils (median of 119, range of 14.8-2958 pg/g f.w.), meats (median of 75.9, range of 6.82-2518 pg/g f.w.), shellfish (median of 75.7, range of 3.29-677 pg/g f.w.), eggs (median of 73.5, range of 12.8-557 pg/g f.w.), and dairy products (median of 66.1, range of 3.24-1588 pg/g f.w.). The total BDE values found in this study are consistent with research reported elsewhere. They are in the same range as those recently reported by other European and Asian studies and lower than those conducted in the U.S. BDE 47 was the predominant congener in fish, shellfish, dairy products (except butter), and meats, while BDE 209 was the predominant in oil and egg samples. The most remarkable findings in this study were the large contribution of the highest brominated BDEs (hepta- to deca-BDE), and principally BDE 209, to the total BDE concentration found in Spanish foods, except fish and shellfish, and the presence of BDE 184, 191, 196, and 197 in many of the samples. The calculated intake of 38.5 ng/day of BDEs was comparable to intake assessment from other UE countries.

A method based on gas chromatography (GC) separation followed by ion trap tandem mass spectrometry detection in EI mode (ITD-MS/MS), using isotope dilution, was developed for the determination of ten native polybrominated diphenyl ethers (PBDEs) and four (13)C(12)-labeled congeners in biological (fat tissue and human serum) and food samples. The highest-mass fragment ions were used as precursor ions for those congeners with molecular ions with m/z values higher than the maximum of the instrument. In these cases (hepta-BDEs and (13)C(12)-hexa-BDEs) no fragmentation was achieved under the experimental conditions employed. Repeatability (lower than 9%) and reproducibility (lower than 13%), expressed as relative standard deviation (RSD, n = 3 and 4, respectively), were satisfactory. Similarly, the coefficient of variation (n = 4) of the isotopic ratio between the two most abundant product ions was lower than 10 and 6% for native and labeled congeners, respectively. To evaluate the feasibility of the method, the optimized isotope dilution GC/ITD-MS/MS method was used for the quantitation of selected PBDE congeners in different samples including adipose tissue, human serum and foodstuff samples, from three inter-laboratory comparative exercises, covering a wide range of concentrations. A solid-phase extraction procedure, previously developed for PCB determination in small-size bird serum samples, was successfully applied to quantification of PBDEs in 1 mL samples of human serum.

The polychlorinated dibenzo-p-dioxin (PCDD), dibenzofuran (PCDF), and polychlorinated biphenyl (PCB) contents of 123 Spanish commercial salmon, tuna fish, sardine, oyster, mussel, and clam samples from 1995 to 2003 were investigated. A significant decrease of dioxin and non-ortho PCB concentrations in the studied species was found over the years. The decrease was greater in the case of dioxins than in that of non-ortho PCBs, especially during the early years of the study. PCB and PCDD/F concentrations in the years 2001-2003 were comparable to those reported in the literature for similar species collected after 1999. Mean PCB concentrations ranged from 3.46 ng/g of fresh weight (fw) in clams to 100 ng/g of fw in tuna fish. PCDD/F mean current levels ranged from 0.62 pg/g of fw in clams to 2.89 pg/g of fw in oysters. Toxic equivalent quantities (WHO-TEQ) ranged from 0.05 pg of WHO-TEQ(PCDD/Fs)/g of fw in clams to 0.5 pg of WHO-TEQ(PCDD/Fs)/g of fw in salmon (in the upper bound determination levels). When coplanar PCBs were included, the WHO-TEQ(PCDD/Fs+cop) (PCBs) values increased by a range of 1.7 times in oysters to 14.1 times in tuna fish. The decrease in dioxin concentrations suggests that efforts to control dioxin emissions and to reduce human exposure through foodstuffs are succeeding. The high contribution of PCBs to total WHO-TEQs in the fish and shellfish species investigated suggests that it is important to determine PCBs in foodstuffs, and especially in fish products, and they should be included in further research and future legislation.