María José González

Conservation status and limiting factors in the endangered population of Egyptian vulture (Neophron percnopterus) in the Canary Islands

Egyptian vulture populations have decreased sharply in the Western Palearctic; island populations are almost extinct in the Mediterranean and the Macaronesian regions. In the Canary archipelago, the species only survives in the islands of Fuerteventura and Lanzarote. During 1998–2001 we examined population parameters and evaluated some potential limiting factors for this isolated and sedentary population. The total population (breeding and non-breeding birds) was monitored annually. In addition, 26 fledglings and 33 immatures ( 6 years old birds) and immature annual survival rates were similar, around 90%. Adult survival was lower than expected as territorial birds seem more susceptible to poisoning. Immature survival could be favoured by the existence of regular feeding places. Casualties from power lines was the main cause of mortality (12 cases during the study period). Blood sampling revealed high frequencies of lead poisoning: 13.5 and 2.7% of individuals showed sub-clinical and clinical intoxication levels, respectively, probably caused by the ingestion of lead shot. Priority conservation measures should be directed to reduce electrocution risks, illegal poisoning, and lead contamination. Population reinforcement with birds coming from other populations is not recommended as previous information reveals morphological and genetic differentiation of Canarian Egyptian vultures compared with continental populations. # 2002 Elsevier Science Ltd. All rights reserved.

Mercury, lead and cadmium in human milk in relation to diet, lifestyle habits and sociodemographic variables in Madrid (Spain)

BACKGROUND Although breastfeeding is the ideal way of nurturing infants, it can be a source of exposure to toxicants. This study reports the concentration of Hg, Pb and Cd in breast milk from a sample of women drawn from the general population of the Madrid Region, and explores the association between metal levels and socio-demographic factors, lifestyle habits, diet and environmental exposures, including tobacco smoke, exposure at home and occupational exposures. METHODS Breast milk was obtained from 100 women (20 mL) at around the third week postpartum. Pb, Cd and Hg levels were determined using Atomic Absorption Spectrometry. Metal levels were log-transformed due to non-normal distribution. Their association with the variables collected by questionnaire was assessed using linear regression models. Separate models were fitted for Hg, Pb and Cd, using univariate linear regression in a first step. Secondly, multivariate linear regression models were adjusted introducing potential confounders specific for each metal. Finally, a test for trend was performed in order to evaluate possible dose-response relationships between metal levels and changes in variables categories. RESULTS Geometric mean Hg, Pb and Cd content in milk were 0.53 μg L(-1), 15.56 μg L(-1), and 1.31 μg L(-1), respectively. Decreases in Hg levels in older women and in those with a previous history of pregnancies and lactations suggested clearance of this metal over lifetime, though differences were not statistically significant, probably due to limited sample size. Lead concentrations increased with greater exposure to motor vehicle traffic and higher potato consumption. Increased Cd levels were associated with type of lactation and tended to increase with tobacco smoking. CONCLUSIONS Surveillance for the presence of heavy metals in human milk is needed. Smoking and dietary habits are the main factors linked to heavy metal levels in breast milk. Our results reinforce the need to strengthen national food safety programs and to further promote avoidance of unhealthy behaviors such as smoking during pregnancy.

Distribution of Trace Metals in Sediments and the Relationship with their Accumulation in Earthworms

Abstract Concentrations of Cd, Pb, Cu and Zn and their speciation in river sediments (Guadalquivir River, Spain), were determined. Relationships between trace metal concentrations in sediments and earthworms were studied in order to estimate the rate at which metals accumulated in organisms living in sediments. The bioavailable fraction of Cd represented more than 50 % of the total Cd found in sediments, and this percentage was much greater than those of the other elements examined. Most of the Cu was present in the organic and residual fractions. Lead and Zn were mainly associated with the crystalline iron oxide fraction. The application of factorial analysis to the total heavy metal concentrations and some soil properties reduced the number of original variables to only three, namely factors, which explained the total variance of 94 %. Metals accumulated in earthworms were related by a second grade polynomial equation with fractions where the metals were mainly bound. Cd exhibited the highest accumulati...

EVALUATION OF GENOTOXIC EFFECTS OF HEAVY METALS AND ARSENIC IN WILD NESTLING WHITE STORKS (CICONIA CICONIA) AND BLACK KITES (MILVUS MIGRANS) FROM SOUTHWESTERN SPAIN AFTER A MINING ACCIDENT

Studies of birds from Doñana (southwestern Spain) after the Aznalcóllar mining accident (April 1998) have reported high levels of genetic damage when compared to conspecifics from reference areas. However, potential relationships between DNA damage and metal pollution have not yet been reported. The aim of the present study was to investigate the current levels of Zn, Pb, As, Cu, and Cd and to determine if they were associated with the genetic damage observed in free-living, nestling white storks (Ciconia ciconia) and black kites (Milvus migrans) born in the Doñana area after the mining spill. Blood concentrations of heavy metals and of As were quantified and DNA damage (comet assay) was determined in 258 storks and 132 kites monitored during a four-year period (1999-2002). Correlations between these elements and genetic damage varied between species and throughout years within species. Some elements did not show any relationship with DNA damage (e.g., Pb), whereas others had a significant correlation (e.g., As in storks, and Cu and Cd in kites) or only marginal statistical effects (e.g., Zn and Cd in storks, and As in kites) in some years but not in others. These results suggest that nestling white storks and black kites were affected, in part, by the elements studied, but they alone do not satisfactorily explain the observed DNA damage. Moreover, our results show that species-specific differences should be carefully considered when planning schemes for pollution monitoring, and highlight the need for including the temporal scale into the study of the pollutants effects in the wild.

Enantiomeric separation of chiral polycyclic musks by capillary electrophoresis: Application to the analysis of cosmetic samples.

The enantiomeric separation of four chiral polycyclic musks (Galaxolide, Tonalide, Traseolide and Phantolide) using CE was achieved for the first time in this work. Two chiral methodologies were developed by CD-MEKC using SDS as surfactant in a CHES buffer (pH 9.0). One methodology enabled the fast enantiomeric separation of individual polycyclic musks with analysis times lower than 10min for Tonalide, 13min for Traseolide and Phantolide, and 17min for Galaxolide. Enantiomeric resolutions obtained were higher than 1.5 using different separation media for each compound. A second methodology was also developed enabling the simultaneous enantioseparation of the four musks. In this case, the use of a dual CD system containing two neutral CDs was necessary to achieve the separation of all enantiomers from three out of four musks in 45min. Although a coelution between Galaxolide and Phantolide was observed, the use of different UV absorption wavelengths allowed the simultaneous analysis of both musks. In addition, a sweeping strategy was performed in order to increase the sensitivity of the method. Appropriate analytical characteristics (linearity, LOD and LOQ, precision and absence of matrix interferences) were obtained for conventional and sweeping methodologies. Finally, the usefulness of the method was demonstrated in the determination of the enantiomers of the polycyclic musks in personal care products as perfumes.

Cytogenetic status in newborns and their parents in Madrid: the BioMadrid study.

Monitoring cytogenetic damage is frequently used to assess population exposure to environmental mutagens. The cytokinesis‐block micronucleus assay is one of the most widely used methods employed in these studies. In the present study we used this assay to assess the baseline frequency of micronuclei in a healthy population of father‐pregnant woman‐newborn trios drawn from two Madrid areas. We also investigated the association between micronucleus frequency and specific socioeconomic, environmental, and demographic factors collected by questionnaire. Mercury, arsenic, lead, and cadmium blood levels were measured by atomic absorption spectrometry. The association between micronucleated cell frequency and the variables collected by questionnaire, as well as, the risk associated with the presence of elevated levels of metals in blood, was estimated using Poisson models, taking the number of micronucleated cells in 1,000 binucleated cells (MNBCs) as the dependent variable. Separate analyses were conducted for the 110 newborns, 136 pregnant women, and 134 fathers in whom micronuclei could be assessed. The mean number of micronucleated cells per 1,000 binucleated cells was 3.9, 6.5, and 6.1 respectively. Our results show a statistically significant correlation in MNBC frequency between fathers and mothers, and between parents and newborns. Elevated blood mercury levels in fathers were associated with significantly higher MNBC frequency, compared with fathers who had normal mercury levels (RR:1.21; 95%CI:1.02–1.43). This last result suggests the need to implement greater control over populations which, by reason of their occupation or life style, are among those most exposed to this metal. Environ. Mol. Mutagen., 2010.

Novel analytical approach for brominated flame retardants based on the use of gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry with emphasis in highly brominated congeners

The analysis of brominated flame retardants (BFRs) commonly relies on the use of gas chromatography coupled to mass spectrometry (GC-MS) operating in electron ionization (EI) and electron capture negative ionization (ECNI) modes using quadrupole, triple quadrupole, ion trap, and magnetic sector analyzers. However, these brominated contaminants are examples of compounds for which a soft and robust ionization technique might be favorable since they show high fragmentation in EI and low specificity in ECNI. In addition, the low limits of quantification (0.01 ng/g) required by European Commission Recommendation 2014/118/EU on the monitoring of traces of BFRs in food put stress on the use of highly sensitive techniques/methods. In this work, a new approach for the extremely sensitive determination of BFRs taking profit of the potential of atmospheric pressure chemical ionization (APCI) combined with GC and triple quadrupole (QqQ) mass analyzer is proposed. The objective was to explore the potential of this approach for the BFRs determination in samples at pg/g levels, taking marine samples and a cream sample as a model. Ionization and fragmentation behavior of 14 PBDEs (congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two novel BFRs, decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), in the GC-APCI-MS system has been investigated. The formation of highly abundant (quasi) molecular ion was the main advantage observed in relation to EI. Thus, a notable improvement in sensitivity and specificity was observed when using it as precursor ion in tandem MS. The improved detectability (LODs < 10 fg) achieved when using APCI compared to EI has been demonstrated, which is especially relevant for highly brominated congeners. Analysis of samples from an intercomparison exercise and samples from the marine field showed the potential of this approach for the reliable identification and quantification at very low concentration levels.

Miniaturized selective pressurized liquid extraction of polychlorinated biphenyls and polybrominated diphenyl ethers from feedstuffs

A new miniaturized pressurized liquid extraction (PLE) with in-cell purification method has been developed for the simultaneous extraction of endogenous prioritary and toxic polychlorinated biphenyls (PCBs) and environmentally relevant tri- to deca-brominated diphenyl ether (PBDE) congeners from different feed matrices. Parameters affecting the efficiency of the selective PLE process, such as sorbent:matrix ratio, volume and nature of the extraction solvent, PLE working mode, extraction time and temperature, and amount of co-sorbents, were optimized. n-Hexane and n-hexane:dichloromethane (1:1, v/v) were used as extraction solvents. 8-mL of organic solvents and 3.5 g of sorbents sufficed for complete sample treatment. Only 0.25 g of feed sample were required for accurate determination of the endogenous PCBs studied using gas chromatography with a micro-electron capture detector (GC-μECD) during method development, and for PBDE analysis using either GC-μECD or gas chromatography with negative chemical ionization-quadrupole mass spectrometry (GC-NCI-qMS). Gas chromatography coupled to ion trap detection working in tandem mode, GC-ITD (MS/MS), was used for final PCB confirmation. Additional purification of the sample extracts was not required. The performance of the complete PLE-based method was evaluated at two spiking levels, 0.4 and 4 ng/g wet weight. Recoveries in the range 60-120% were obtained for PCBs, while those of PBDEs ranged from 86% to 114% for most of the target analytes. The relative standard deviations were in general lower than 20%. The optimized procedure was applied to the determination of the investigated PCBs and PBDEs in a variety of feed samples.

Effectiveness of intensive group and individual interventions for smoking cessation in primary health care settings: a randomized trial

ObjectivesPrimary: To compare the effectiveness of intensive group and individual interventions for smoking cessation in a primary health care setting; secondary: to identify the variables associated with smoking cessation.MethodsThree-pronged clinical trial with randomisation at the individual level. We performed the following: an intensive individual intervention (III), an intensive group intervention (IGI) and a minimal intervention (MI). Included in the study were smokers who were prepared to quit smoking. Excluded from the study were individuals aged less than 18 years or with severe mental conditions or terminal illnesses. The outcome measure was continued abstinence at 12 months confirmed through CO-oximetry (CO). The analysis was based on intention to treat.ResultsIn total, 287 smokers were recruited: 81 in the III, 111 in the IGI, and 95 in the MI. Continued abstinence at 12 months confirmed through CO was 7.4% in the III, 5.4% in the IGI, and 1% in the MI. No significant differences were noted between III and MI on the one hand, and between IGI and MI on the other [RR 7.04 (0.9-7.2) and RR 5.1 (0.6-41.9), respectively]. No differences were noted between IGI and III [RR 0.7 (0.2-2.2)]. In multivariate analysis, only overall visit length showed a statistically significant association with smoking cessation.ConclusionsThe effectiveness of intensive smoking interventions in this study was lower than expected. No statistically significant differences were found between the results of individual and group interventions.Trial registration numberISRCTN32323770

Triple quadrupole tandem mass spectrometry: A real alternative to high resolution magnetic sector instrument for the analysis of polychlorinated dibenzo-p-dioxins, furans and dioxin-like polychlorinated biphenyls.

This paper reports on the optimisation, characterisation, validation and applicability of gas chromatography coupled to triple quadrupole mass spectrometry in its tandem operation mode (GC-QqQ(MS/MS) for the quantification of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs, dioxins) and dioxin-like polychlorinated biphenyls (DL-PCBs) in environmental and food matrices. MS/MS parameters were selected to achieve the high sensitivity and selectivity required for the analysis of this type of compounds and samples. Good repeatability for areas (RSD = 1-10%, for PCDD/Fs and DL-PCBs) and for ion transition ratios (RSD = 0.3-10%, for PCDD/Fs, and 0.2-15%, for DL-PCBs) and low instrumental limits of detection, 0.07-0.75 pg μL(-1) (for dioxins) and 0.05-0.63 pg μL(-1) (for DL-PCBs), were obtained. A comparative study of the congener specific determination using both GC-QqQ(MS/MS) and gas chromatography-high resolution mass spectrometry (GC-HRMS) was also performed by analysing several fortified samples and certified reference materials (CRMs) with low (feed and foodstuffs), median (sewage sludge) and high (fly ash) toxic equivalency (TEQ) concentration levels, i.e. 0.60, 1.83, 72.9 and 3609 pg WHO-TEQ(PCDD/Fs) g(-1). The agreement between the results obtained for the total TEQs (dioxins) on GC-QqQ(MS/MS) and GC-HRMS in all the investigated samples were within the range of ±4%, and that of DL-PCBs at concentration levels of 0.84 pg WHO-TEQs (DL-PCBs) g(-1), in the case of feedstuffs, was 0.11%. Both instrumental methods have similar and comparable linearity, precision and accuracy. The GC-QqQ(MS/MS) sensitivity, lower than that of GC-HRMS, is good enough (iLODs in the down to low pg levels) to detect the normal concentrations of these compounds in food and environmental samples. These results make GC-QqQ(MS/MS) suitable for the quantitative analysis of dioxins and DL-PCBs and a real alternative tool to the reference sector HRMS instruments.