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.

The impact of the spill from the mine in Aznalcollar (Seville, Spain) on waterfowl in the Doñana National Park is assessed. The concentrations of Cu, Pb, Cd, Zn nd As in the liver and eggs of 16 species of waterfowl found dead in the Park between April and November 1998 were determined. The highest levels were found for Zn, followed by Cu, Pb, Cd and As. The main parameters related to the accumulation of these elements in the waterfowl studied were species and trophic level. The other variables studied--distance from the spill, days of exposure, sex, size, and age--are important, although this depends on the element studied. Zn and Cu from the spill have entered the food chain of the aquatic birds studied, but Cd, Pb and As have not. There is currently no evidence to suggest that the trace element concentrations measured have reached toxic levels.

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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.

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This article presents the impact on waterbirds in Doñana National Park (Spain) of an accidental release of 5 million m3 acid waste produced by the processing of pyrite ore. Heavy metals (zinc, copper, cadmium, and lead) and arsenic were measured in several soft tissues (liver, kidney, and muscle) taken from 14 waterfowl species collected between April 1998 and May 2000. The main source of copper and zinc found in the waterfowl species examined was the spill waste, whereas cadmium, lead, and arsenic could also came from other sources. Kidney was the primary organ for cadmium and lead accumulation, whereas liver accumulated the most zinc and copper. Arsenic was concentrated in both muscle and liver tissue. The degree of contamination of the area where the birds lived, their age, their sex their size, and the time since the spill were found to have less influence than species and trophic level on the accumulation of metal in organs and tissues. Four species (Anser anser, Ciconia ciconia, Larus ridibundus, and Porphyrio porphyrio) were found to have the highest levels of the 5 elements.