Total mercury (Hg), monomethylmercury (MeHg), and selenium (Se) were determined in blood of 11 bird species living in Doñana National Park (DNP, Southwestern Spain) and the surrounding area in 1999 and 2000 after a mine spill accident. The total Hg contents found varied from 1.00 to 587 ng/mL, with an MeHg percentage higher than 80 \%, except in mallard species. In all the cases, the concentrations found were below the threshold of high risk for the bird populations. The parameters which most affected the accumulation of Hg and MeHg in the birds studied were, first, species, or trophic position, and second sampling area. Age does not seem to have a great influence on the content of Hg in the blood of these birds. The levels of Se found ranged from 108 to 873 ng/mL, and they were not affected by species, trophic level, age, or sampling area. The blood Hg concentrations of birds living in the area directly affected by the toxic mud, outside the park, were higher than those found in the other birds, and this could be explained by the mine spill accident happened in 1998. © 2013 Springer-Verlag Berlin Heidelberg.

[No abstract available]

[No abstract available]

Phthalates are chemicals that have been used for over 80 years in large quantities due to their wide range of applications, mainly in the plastic industry. For many years, these compounds were not considered dangerous for humans due to their low toxicity shown in the preliminary studies and their low persistence. However, research conducted in recent years has evidenced their activity as endocrine disruptors, and they are now considered as emerging contaminants and included in the priority list of dangerous substances in the legislation of many countries. This chapter provides an overview on the properties, major uses, emission sources, environmental and human levels, current legislation, behavior and fate of phthalates, and their metabolites, with special emphasis on their toxicity and human exposure. © Springer-Verlag Berlin Heidelberg 2011.

Introduction Concentrations and congener profiles of polychlorinated biphenyls (PCBs) and their hydroxylated metabolites (OH-PCBs) in placenta samples from a Madrid population (Spain) are reported. Structure dependent retentions of OH-PCBs are known to occur in both humans and wildlife, making it of interest to assess placental transfer of both parent compounds and their metabolites to the developing foetus. Results The ΣPCB concentrations found in placenta samples were in the range 943-4,331 pg/g fresh weight (f. w.), and their hydroxylated metabolites showed a 20-time lower concentration level (53-261 pg/g f. w.). The PCB profiles were surprisingly dominated by CB-52 and CB-101 accounting for more than 44\% of the total PCB concentration. This is indicating a source of exposure that is not yet identified. The OH-PCB profiles were dominated by 4-OH-CB187 and 4-OH-CB146, representing >50\% of the ΣOH-PCB concentration of the placenta samples. Statistical analysis of the data revealed strong correlations between the PCB congeners, among some OH-PCBs, and between OH-PCB metabolites with a meta- and para- substitution pattern. Both PCB and OH-PCB concentrations presented homogeneous distribution, what allowed the establishment of a partial least squares model that correlated the concentrations of OH-PCB with those of PCBs in placenta samples. In addition, causal correlations were observed between the concentrations of OH-PCBs and those of their corresponding PCB precursors. © 2011 Springer-Verlag.

The potential of three capillary columns based on b-cyclodextrin (i.e., Chirasil-Dex, BGB-172, and BGB-176SE) has been studied for the simultaneous enantiomeric separation of polychlorinated biphenyls (PCBs) andmethylsulfonylmetabolites of PCBs (MeSO2-PCBs) employing a heart-cut multidimensional gas chromatographic system (heart-cut MDGC). Among the columns studied, the BGB-176SE capillary column provided the best results, allowing the simultaneous enantioselective resolution of six MeSO 2-PCBs and six chiral PCBs; the Chirasil-Dex column did not resolve any of the studied MeSO2-PCBs; and a poor resolution was obtained for three MeSO2-PCBs when the BGB-172 column was employed. The developed method was successfully applied to two fish oil and one cow liver samples commercially available, which showed different enantioselective pattern. PCBs 91 and 176 presented a clear enrichment of the second eluted atropisomer in codfish oil, whereas in fish oil sample, slight enrichment of the first eluted atropisomer of CB45 and the second eluted atropisomer of CB136 were observed. © 2012 Wiley Periodicals, Inc.

In this study, for the first time, levels and accumulation profiles of eight currently available polybrominated/chlorinated biphenyl congeners (PXBs; XB-77, -105, -118, -126A, -126B, -126C, -156 and -169, named according to IUPAC nomenclature) in human breast milk collected form Spanish women in 2005 were reported. Concentrations and congener specific profiles of polychlorinated biphenyls (PCBs), including co-planar PCBs, (co-PCBs) and polybrominated diphenyl ethers (PBDEs) were also reported.A concentration of 0.45pgg-1 lipid weight was found for total PXBs, and arithmetic mean concentrations of 125, 25 and 5.5ngg-1 lipid weight were determined for total PCBs, co-PCBs and total PBDEs respectively. Detectable levels of all congeners investigated, except CB-123 and XB-169 were found. Levels of PCBs were similar to those found in Spanish samples collected after 2000, and lower than those obtained before 2000. CB-138, -153 and -180 were the predominant PCB congeners. PBDE levels, dominated by BDE-47, -99, -100 and -209, were lower than PCB levels. PXB concentrations were the lowest, with XB-156 being the most abundant. The concentration levels of PCBs and PBDEs found in this study were in the same range as those from other European countries. Levels of PXBs were much lower than published values determined in Japan which were the only data found in the literature. © 2011 Elsevier Ltd.

Traditionally, the determination of hydroxylated polychlorinated biphenyls (OH-PCBs) has been carried out by gas chromatography (GC). However, the gas chromatographic behavior and sensitivity of this type of hydroxylated compounds are not always satisfactory, hence a prior derivatization of the OH-PCBs must be performed. Therefore, the development of liquid chromatographic methods should prove to be a very interesting task aimed at dealing with the instrumental determination of OH-PCBs. Taking into account that octadecylsilane stationary phases are not the most adequate for the separation of isobaric compounds, an amide-type column has been tested. For the development of the method, the Response Surface Methodology was used, based on a Box-Wilson Central Composite experimental design. The initial content of methanol in the mobile phase, the gradient time, and the concentration and the pH value of the buffer were chosen as relevant experimental parameters. A global optimum was obtained by selecting the elution time, the sensitivity and the overall resolution as responses to optimize. The developed method for liquid chromatography presented a very good resolution and sensitivity, and a reasonably short analysis time. In addition, a retention study was conducted in order to survey the different interactions that take place in the separation process, showing that hydrogen bonding is the main interaction between OH-PCBs and the amide-type stationary phase. However, a substantial contribution of dispersion forces was present in methanol contents in the mobile phase below 65\%. Besides, the pH value of the mobile phase was found to be the most important parameter to control the hydrogen bond forces and therefore, to regulate the OH-PCBs separation. © 2010 Elsevier B.V.

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), two groups of Persistent Organic Pollutants (POPs), are structurally related chlorinated aromatic hydrocarbons which are generally referred to as “dioxins.” They are of great concern due to the extreme toxicity of the 2,3,7,8 chlorine substituted congeners and their presence in all compartments of the environment. PCDD/Fs are formed as by-products of a wide variety of chemical industry and combustion processes that contain chlorine and chlorinated aromatic hydrocarbon sources [1]. Due to their low water solubility, hydrophobicity, and resistance to degradation, these substances are found in a wide range of biological samples, and tend to accumulate in animal and human adipose tissues through the food web [2]. Among the 210 possible congeners, seven 2,3,7,8-substituted PCDDs and 10 PCDFs are generally considered the most persistent and toxic PCDD/F congeners, since they have toxic properties similar to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), which is the most toxic congener of these compounds [3-5]. © 2010 by Taylor and Francis Group, LLC.

It is well documented and experimentally confirmed that hexabromocyclododecanes (HBCDs) tend to associate with several anions forming different adducts that can affect the sensitivity and the accuracy of the determinations. In the present work, two different approaches for HBCD determination have been optimised and characterised based on their repeatability and intermediate precision, linear calibration ranges, sensitivity, limits of detection and quantification and application to commercial food samples. Both methods involve the use of a triple quadrupole mass spectrometer coupled to a liquid chromatograph and the addition of different ammonium salts to the mobile phase, i.e. ammonium chloride or ammonium acetate, in order to encourage (Cl method) or try to inhibit (Ac method), respectively, the formation of the chlorine adducts of the molecular ion. Precision of the two methods investigated was similar and both approaches presented a comparable behaviour for the analysis of food samples. However, the Cl method showed higher sensitivity and the limits of detection (0.23-0.41 pg on column) and quantification (0.77-1.35 pg on column) were up to 14 times lower than those obtained applying the Ac method. All these facts make the Cl method the best choice for the quantification of HBCDs in food samples with low concentration levels. © 2009 Elsevier B.V. All rights reserved.

This study provides information on the current status of contamination by organochlorines (DDTs, PCBs, PCDDs and PCDFs) in the declining red kite (Milvus milvus L.) population breeding in the Doñana National Park (DNP), south-western Spain. Analyses were performed in addled eggs collected between 1999 and 2001. DDE concentrations ranged from 0.1 to 33.5 μg/g ww, representing more than 86\% of the total DDTs. Of the samples studied, 50\% showed DDE levels above those associated with reproductive impairment in other raptor species. Concentrations of ortho PCBs (average 36.8 μg/g ww ± 37.7) in 50\% of the eggs were much higher than levels reported to cause reduced hatching success, embryo mortality, and deformities in birds (> 20 μg/g ww). It is remarkable that average ortho PCB and DDE concentrations showed an increase of one order of magnitude compared to previous data for the species during the 80s. Total PCDD/Fs showed levels in the low pg/g range (7.2-42 pg/g ww), having PCDDs and PCDFs similar contributions in most samples. Total mean TEQs were 238 pg/g (ww), being the range 7.02-667 pg/g (ww). Spatial variation within DNP was observed for PCBs, DDTs, as well as for TEQs. Since some eggs exceeded the NOEL (67\%) and LOEL (33\%) reported for other raptor species, we would expect the red kite to experience detrimental effects to dioxin-like toxicity. Our results suggest that organochlorine contaminants should be regarded as an element of concern in the population under study, in addition to other conservation problems already reported. Further investigations should be undertaken to identify potential sources of these chemicals in DNP, and to find out if organochlorine contamination is present in other predator species in the area, as well as their potential health effects on individuals and/or populations. © 2007 Elsevier Ltd. All rights reserved.

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 lowerthan 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. © 2007 American Chemical Society.

An alternative method for the enantiomer specific determination of hexabromocyclododecanes (HBCD) by LC-ESI-MS/MS using an ion trap analyser is proposed. The method is based on the formation of a chlorine adduct (m/z 676.6) of the (±)α-, (±)β-, and (±)γ-HBCD enantiomers and their further fragmentation into their stable quasi-molecular ion (m/z 640.6). In this way, problems related to the ion trap low mass cutoff and variable amounts of other adduct peaks in the samples are solved. Parameters affecting separation, ionisation and MS/MS detection were studied. Method performance was also evaluated: calibration curves were found linear from 20 to 400 pg μL-1 for each enantiomer; detection limits ranged between 1.5 and 4.3 pg μL-1; repeatability and reproducibility, expressed as relative standard deviation, were lower than 6\% and 13\%, respectively. The application to different types of spiked samples (pork meat, lean fish, and butter) pointed out the occurrence of matrix effects that could be solved by using labelled standards. © 2007 Elsevier B.V. All rights reserved.

The applicability of two different MS ionisation modes (EI and ECNI) for the determination of PBDEs at low-trace levels in small-size (up to 1 mL) human samples was compared. The instrumental precision, expressed as R.S.D., obtained for both ionisation modes was similar and lower than 6\% (repeatability) and 12\% (intermediate precision) for all congeners investigated, except PBDE 209. The LODs obtained when using the ECNI-MS operation mode (6-507 fg) were lower than those found in EI-MS experiments (9 and 10,909 fg), mainly for those congeners with a high bromination degree, i.e., hepta- to deca-BDEs. The selectivity of the ECNI-MS method proposed in the present work was improved by using two ions of the [M-HxBry]- cluster as both qualifier and quantifier ions. For the final validation of the methods, serum and breast milk samples from two different inter-laboratory exercises were analysed. A good agreement was found between the results obtained using the proposed methods and the results provided by the different inter-laboratory organisations, but only ECNI-MS provided the low-LODs necessary for the quantification of high brominated congeners (mainly, PBDEs 196, 197 and 209) at low concentration levels in small-size human samples. Finally, the ECNI-MS method was applied to real-life samples obtained from the Spanish population and the preliminary results obtained were in the same range as those found in other European and Asian regions and lower than the concentrations reported in USA populations. © 2007 Elsevier B.V. All rights reserved.

This work presents the concentrations of twenty PCB congeners, p,p′-DDT, and its two main metabolites, p,p′-DDE, p,p′-TDE, As, Cd, Cu, Pb, and Zn found in common chameleon eggs from nine different nests located in Southwest Spain. Of the heavy metals and arsenic, Zn and Cu exhibited the highest concentrations in egg contents (ranging from 10 100 to 12 950 and from 567 to 706 ng g-1 wet weight basis [w.w.], respectively) and eggshells (ranging from 5605 to 13 290 ng g-1 w.w. for Zn and from 1487 to 4361 ng g-1 w.w. for Cu). Total PCB concentrations in egg contents ranged from 32 to 52 ng g-1 w.w. and were higher than total dichlorodiphenylethanes concentrations (ranging from 0.67 to 1.9 ng g-1 w.w., calculated as the sum of p,p′-DDT plus p,p′-DDE and p,p′-TDE). Comparison of the data from the present study with the data from a study conducted in 1997 revealed a large decrease in Pb concentration and a twofold increase in PCB concentrations. Taking into account all the pollutants investigated, the contamination level found in common chameleon eggs from Southwest Spain was generally lower than has been reported in the literature for eggs of different reptile species. However, it should be borne in mind that most of the data found in the literature refer to highly polluted areas. © 2006 Elsevier Ltd. All rights reserved.

The feasibility of heart-cut MDGC-ECD and GC × GC-μ ECD for the separation of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) has been evaluated. Among the different column combinations tested, the best results were obtained when using either a DB-5 type or an HT-8 column as the first dimension combined with a mid-polar stationary phase (50\% phenyl) as the second dimension. The coelutions between the target PCBs and PBDEs in the first dimension were satisfactorily resolved once transferred to the second column. Repeatability and intermediate precision were satisfactory in both systems, considering retention times in both dimensions. Nevertheless, peak area/volume precision was better for heart-cut MDGC since software for the data analysis in the case of GC x GC was still under development. The need for multiple injections of the same extract on the heart-cut MDGC system was the main drawback since the analysis time it increased. GC × GC becomes then a valuable alternative able to achieve the same performance in one injection. However, the GC × GC data analysis is still very time-consuming and needs further development. The applicability of both separation techniques was shown using a human breast milk sample with low concetrations of PCBs (0.2-227 pg/g fresh weight) and PBDEs (1.2-41 pg/g fresh weight). © 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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. © 2006 American Chemical Society.

A high-performance liquid chromatography (HPLC) method using a column of 2-(1-pyrenyl) ethyldimethylsilylated silica was developed in this work in order to achieve satisfactory and reproducible fractionation of polychlorinated biphenyls (PCBs) from brominated flame retardants (BFRs) (polybrominated diphenylethers, PBDEs; and polybrominated biphenyls, PBBs). After the study of different chromatographic parameters (mobile phase composition and separation temperature were the most important) an isocratic elution with isooctane:toluene (98:2, v/v) at a flow-rate of 1 mL/min, a temperature of 45 °C, and UV-detection at 225 nm was selected for fractionation of PCBs (time region, 4.0-5.8 min) from PBDEs (5.8-9.0 min) and from PBBs (5.8-11.0 min). The applicability of this method to food samples was demonstrated by fractionating PCBs from PBDEs in three food samples (cheese, milk, and fish). Interferences from PCBs (present in real samples at much higher concentrations than PBDEs) were removed in this way. In addition, by analysing these samples by gas chromatography-mass spectrometry (GC-MS) with and without previous fractionation we were able to observe an improvement in detection sensitivity for PBDEs after HPLC fractionation. © 2006 Elsevier B.V. All rights reserved.

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 13C12-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 mlz values higher than the maximum of the instrument. In these cases (hepta-BDEs and 13C12-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. Copyright © 2005 John Wiley & Sons, Ltd.

The content of 30 polychlorinated biphenyls (PCBs) and the enantiomeric fractions of 10 chiral PCBs were determined in 17 infertile eggs from three different predatory bird species collected in Doñana National Park (DNP, Spain) in the period 1999-2000. The highest PCB concentration was found in eggs from red kites (0.52-110 μg/g on a fresh weight basis, f.w.) followed by buzzard (0.08-13 μg/g f.w.) and booted eagle (0.10-1.5 μg/g f.w.). Seventy-five percent of the red kite eggs had PCB levels above 4.7 μg/g f.w., which is associated in the literature with reproductive failure. This could be related to the fact that red kite populations have decreased by more than 50\% in the last five years in DNP. PCBs # 138, 153, and 180 were the most abundant in all cases. This is the first time that atropisomers of 10 chiral PCBs (PCBs # 45, 84, 91, 95, 132, 135, 136, 149, 174, and 176) in predatory bird eggs have been performed. The enantiomeric fractions (EFs) for most PCBs investigated were non-racemic (EF ≠ 0.5), ranging from 0.05 to 0.95. The results suggested that predatory birds, mainly red kite species, are highly polluted by PCBs, and PCBs # 95, 132, 135, 136, and 174 strongly deviate from the racemic-mixture values. © 2005 Elsevier Ltd. All rights reserved.