Association between mediterranean diet and metal(loid) exposure in 4-5-year-old children living in Spain.

Even relatively low levels of metals exposure may impact health, particularly among vulnerable populations such as infants and young children. However, little is known about the interplay between simultaneous metal exposures, common in real-life scenarios, and their association with specific dietary patterns. In this study, we have evaluated the association between adherence to Mediterranean diet (MD) and urinary metal concentrations individually and as an exposure mixture in 713 children aged 4-5-years from the INMA cohort study. We used a validated food frequency questionnaire to calculate two MD indexes scores: aMED and rMED. These indexes gather information on various food groups within the MD and score differently. To measure urinary concentrations of cobalt, copper, zinc, molybdenum, selenium, lead, and cadmium as exposure biomarkers, we used inductively coupled plasma mass spectrometry (ICP-MS), coupled with an ion chromatography (IC) equipment for arsenic speciation analysis. We applied linear regression and quantile g-computation, adjusted for confounders, to analyse the association between MD adherence and exposure to the metal mixture. High adherence to MD such as the quintile (Q) 5 MD was associated with higher urinary arsenobetaine (AsB) levels than Q1, with ß values of 0.55 (confidence interval - CI 95% 0.01; 1.09) for aMED and 0.73 (CI 95% 0.13; 1.33) for rMED. Consumption of fish was associated with increased urinary AsB but reduced inorganic arsenic concentrations. In contrast, the aMED vegetables consumption increased urinary inorganic arsenic content. A moderate level of adherence to MD (Q2 and Q3) was associated with lower copper urinary concentrations than Q1, with ß values of -0.42 (CI 95% -0.72; -0.11) for Q2 and -0.33 (CI 95% -0.63; -0.02) for Q3, but only with aMED. Our study, conducted in Spain, revealed that adhering to the MD reduces exposure to certain metals while increasing exposure to others. Specifically, we observed increase in exposure to non-toxic AsB, highlighting the significance of consuming fish/seafood. However, it is crucial to emphasize the necessity for additional efforts in reducing early-life exposure to toxic metals, even when adhering to certain food components of the MD.

Secondary organic aerosol origin in an urban environment: influence of biogenic and fuel combustion precursors.

Source contributions of organic aerosol (OA) are still not fully understood, especially in terms of quantitative distinction between secondary OA formed from anthropogenic precursors vs. that formed from natural precursors. In order to investigate the OA origin, a field campaign was carried out in Barcelona in summer 2013, including two periods characterized by low and high traffic conditions. Volatile organic compound (VOC) concentrations were higher during the second period, especially aromatic hydrocarbons related to traffic emissions, which showed a marked daily cycle peaking during traffic rush hours, similarly to black carbon (BC) concentrations. Biogenic VOC (BVOC) concentrations showed only minor changes from the low to the high traffic period, and their intra-day variability was related to temperature and solar radiation cycles, although a decrease was observed for monoterpenes during the day. The organic carbon (OC) concentrations increased from the first to the second period, and the fraction of non-fossil OC as determined by (14)C analysis increased from 43% to 54% of the total OC. The combination of (14)C analysis and Aerosol Chemical Speciation Monitor (ACSM) OA source apportionment showed that the fossil OC was mainly secondary (>70%) except for the last sample, when the fossil secondary OC only represented 51% of the total fossil OC. The fraction of non-fossil secondary OC increased from 37% of total secondary OC for the first sample to 60% for the last sample. This enhanced formation of non-fossil secondary OA (SOA) could be attributed to the reaction of BVOC precursors with NOx emitted from road traffic (or from its nocturnal derivative nitrate that enhances night-time semi-volatile oxygenated OA (SV-OOA)), since NO2 concentrations increased from 19 to 42 µg m(-3) from the first to the last sample.

Candida tropicalis antifungal cross-resistance is related to different azole target (Erg11p) modifications.

Candida tropicalis ranks between third and fourth among Candida species most commonly isolated from clinical specimens. Invasive candidiasis and candidemia are treated with amphotericin B or echinocandins as first-line therapy, with extended-spectrum triazoles as acceptable alternatives. Candida tropicalis is usually susceptible to all antifungal agents, although several azole drug-resistant clinical isolates are being reported. However, C. tropicalis resistant to amphotericin B is uncommon, and only a few strains have reliably demonstrated a high level of resistance to this agent. The resistance mechanisms operating in C. tropicalis strains isolated from clinical samples showing resistance to azole drugs alone or with amphotericin B cross-resistance were elucidated. Antifungal drug resistance was related to mutations of the azole target (Erg11p) with or without alterations of the ergosterol biosynthesis pathway. The antifungal drug resistance shown in vitro correlated very well with the results obtained in vivo using the model host Galleria mellonella. Using this panel of strains, the G. mellonella model system was validated as a simple, nonmammalian minihost model that can be used to study in vitro-in vivo correlation of antifungals in C. tropicalis. The development in C. tropicalis of antifungal drug resistance with different mechanisms during antifungal treatment has potential clinical impact and deserves specific prospective studies.

Effects of PCBs, p,p'-DDT, p,p'-DDE, HCB and beta-HCH on thyroid function in preschool children.

OBJECTIVE: Several studies have shown that some organochlorine compounds (OCs) can interfere with the thyroid system. As thyroid hormones (THs) are essential for normal brain development, it is important to study the association between THs and OCs during pregnancy and childhood. We have evaluated the relationship between thyroid function and OCs in preschool children. METHODS: Children from a general population birth cohort in Menorca (n = 259), Spain were assessed at the age of 4 years. Concentrations of THs (free T4 and total T3), thyrotropin (TSH) and a range of OCs were measured in peripheral blood. RESULTS: Blood levels of dichlorodiphenyl trichloroethane (p,p'-DDT), beta-hexachlorocylcohexane (beta-HCH), polychlorinated biphenyls (congeners PCB-138, PCB-153 and PCB-118) were related to lower total T3 levels (p<0.05). In addition, free T4 was inversely associated with PCB-118, while no relationship was found between TSH and any of the measured OCs. CONCLUSIONS: This study suggests that even at background levels of exposure, OCs may affect the thyroid system, particularly total T3 levels.

Assessment of the environmental and physiological processes determining the accumulation of organochlorine compounds in European mountain lake fish through multivariate analysis (PCA and PLS).

The presence of organochlorine compounds (OCs)-namely hexachlorobenzene (HCB), hexachlorocyclohexanes (HCH), polychlorobiphenyls (PCBs #28, 52, 101, 118, 138, 153 and 180), dichlorodiphenyltrichloroethane (DDT) and dichlorodiphenyldichloroethane (DDE)-was examined in various fish tissues (muscle and liver) sampled in 23 mountain lakes in Europe. The dependence of these organochlorine compounds on geographical parameters (altitude, longitude, latitude and temperature) and physiological parameters (lipid content, age, weight and size) was assessed. Principal components analysis (PCA) and partial least squares (PLS) models were used for the analyses. PCA results showed that organochlorine compound concentrations in fish tissues increased with increasing altitude and decreasing temperatures. This trend appeared to be more marked for the less volatile compounds. Some differences were found between the muscle and liver in the effects of the percentage of lipids on the accumulation of organochlorine compounds and the behaviour of HCB. Moreover, PCBs tended to accumulate more in liver rather than in muscle. PCA scores clearly differentiated samples according to the lake of origin. PLS models confirmed that temperature and altitude were the main factors influencing the accumulation of most organochlorine compounds in the lipids of the fish tissue.

Particle-related exposure, dose and lung cancer risk of primary school children in two European countries.

Schools represent a critical microenvironment in terms of air quality due to the proximity to outdoor particle sources and the frequent lack of proper ventilation and filtering systems. Moreover, the population exposed in schools (i.e. children) represents a susceptible population due to their age. Air quality-based studies involving students' exposure at schools are still scarce and often limited to mass-based particle metrics and may thus underestimate the possible effect of sub-micron particles and particle toxicity. To this purpose, the present paper aims to evaluate the exposure to different airborne particle metrics (including both sub- and super-micron particles) and attached carcinogenic compounds. Measurements in terms of particle number, lung-deposited surface area, and PM fraction concentrations were measured inside and outside schools in Barcelona (Spain) and Cassino (Italy). Simultaneously, PM samples were collected and chemically analysed to obtain mass fractions of carcinogenic compounds. School time airborne particle doses received by students in classrooms were evaluated as well as their excess lung cancer risk due to a five-year primary school period. Median surface area dose received by students during school time in Barcelona and Cassino resulted equal to 110mm2 and 303mm2, respectively. The risk related to the five-year primary school period was estimated as about 2.9×10-5 and 1.4×10-4 for students of Barcelona and Cassino, respectively. The risk in Barcelona is slightly higher with respect to the maximum tolerable value (10-5, according to the U.S. Environmental Protection Agency), mainly due to toxic compounds on particles generated from anthropogenic emissions (mainly industry). On the other hand, the excess lung cancer risk in Cassino is cause of concern, being one order of magnitude higher than the above-mentioned threshold value due to the presence of biomass burning heating systems and winter thermal inversion that cause larger doses and great amount of toxic compounds on particles.

Enhanced climate instability in the North Atlantic and southern Europe during the Last Interglacial.

Considerable ambiguity remains over the extent and nature of millennial/centennial-scale climate instability during the Last Interglacial (LIG). Here we analyse marine and terrestrial proxies from a deep-sea sediment sequence on the Portuguese Margin and combine results with an intensively dated Italian speleothem record and climate-model experiments. The strongest expression of climate variability occurred during the transitions into and out of the LIG. Our records also document a series of multi-centennial intra-interglacial arid events in southern Europe, coherent with cold water-mass expansions in the North Atlantic. The spatial and temporal fingerprints of these changes indicate a reorganization of ocean surface circulation, consistent with low-intensity disruptions of the Atlantic meridional overturning circulation (AMOC). The amplitude of this LIG variability is greater than that observed in Holocene records. Episodic Greenland ice melt and runoff as a result of excess warmth may have contributed to AMOC weakening and increased climate instability throughout the LIG.

Assessment of lifetime exposure to trihalomethanes through different routes.

OBJECTIVES: To evaluate lifetime exposure to trihalomethanes (THM) through ingestion, inhalation, and dermal absorption in a hospital based case-control study of bladder cancer conducted between 1998 and 2001 in five areas of Spain. The study base was comprised of subjects living in the catchment areas of the participating hospitals. METHODS: Individual information on water related habits was obtained from personal interviews of 1219 cases and 1271 controls: residential and occupational history, drinking water source at each residence and job, amount of water consumption, frequency and duration of showering, bathing, and swimming pool attendance. THM levels, water source history, and year when chlorination started in study areas were ascertained through measurements in drinking water samples and questionnaires to water companies and local authorities. Estimates of THM levels covered 79% of the subjects' person-years of exposure. RESULTS: Current and historical average THM levels in water were correlated. Control subjects reported that drinking water source in the last residence was municipal for 63%, bottled for 22%, private well for 2%, and other sources for 13%. For the time window between age 15 and the time of interview, average residential THM level was 32.2 mug/l. THM exposure through ingestion was 23.7 mug/day on average, and was correlated with the ingestion THM level in the workplace. Overall, 79% usually took showers, 16% usually took baths, and 13% had ever attended a swimming pool. Between 21% and 45% of controls unexposed to THM through ingestion were evaluated as moderately or highly exposed through showering or bathing, and 5-10% were exposed through swimming in pools. CONCLUSION: The importance of evaluating different routes is underscored by findings from experimental studies showing substantial differences in THM uptake and internal distribution by route.

GC and GC-MS characterization of crude oil transformation in sediments and microbial mat samples after the 1991 oil spill in the Saudi Arabian Gulf coast.

The massive oil discharge in the Saudi Arabian coast at the end of the 1991 Gulf War is used here as a natural experiment to study the ability of microbial mats to transform oil residues after major spills. The degree of oil transformation has been evaluated from the analysis of the aliphatic and aromatic hydrocarbons by gas chromatography (GC) and GC coupled to mass spectrometry (GC-MS). The oil-polluted microbial mat samples from coastal environments exhibited an intermediate degree of transformation between that observed in superficial and deep sediments. Evaporation, photo-oxidation and water-washing seemed to lead to more effective and rapid elimination of hydrocarbons than cyanobacteria and its associated microorganisms. Furthermore, comparison of some compounds (e.g. regular isoprenoid hydrocarbons or alkylnaphthalenes) in the oil collected in the area after the spill or in the mixtures retained by cyanobacterial growth gave rise to an apparent effect of hydrocarbon preservation in the microbial mat ecosystems.

Age dependence of the accumulation of organochlorine pollutants in brown trout (Salmo trutta) from a remote high mountain lake (Redó, Pyrenees).

Polychlorobiphenyls (PCBs), hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB) and DDT were examined in the muscle of brown trout (Salmo trutta) from a high mountain lake located in the Pyrenees (Catalonia, Spain) that was used as a model of these lacustrine environments. Results indicate that fish age is the main factor of variability among specimens in this population that is subjected to atmospheric inputs of the organochlorine compounds (OC). Increases of 2- and 20-fold between fish aged 1 year and 15 years old are found. The observed pattern cannot be explained in terms of fish size, condition factor, or muscle lipid content. Higher molecular weight compounds (higher lipophilicity) are better correlated with fish age than low molecular weight compounds. A transformation from 4,4'-DDT to 4,4'-DDE occurs in fish after ingestion; this results in amplified age-dependent signals, especially in male specimens. In contrast, PCB congener #180 has lower age dependence than the general OC group, which could be due to its high hydrophobicity (log K(ow) > 7). In any case, selective accumulation of hydrophobic compounds is already observed among younger fish (age, 1 year). Due to this effect, the relative OC composition does not reflect the main OC pollutants in the lake waters.

Meta-analysis of studies on individual consumption of chlorinated drinking water and bladder cancer.

STUDY OBJECTIVE: To evaluate whether consumption of chlorinated drinking water is associated with bladder cancer. DESIGN: A bibliographic search was conducted and the authors selected studies evaluating individual consumption of chlorinated drinking water and bladder cancer. The authors extracted from each study risk estimates for intermediate and long term (>40 years) consumption of chlorinated water, stratified by sex when possible, and performed meta-analysis for the two exposure levels. A meta-analysis was also performed of the dose-response regression slopes. SETTING: Populations in Europe and North America. PARTICIPANTS: Those included in six case-control studies (6084 incident bladder cancer cases, 10,816 controls) and two cohort studies (124 incident bladder cancer cases) fulfilling the inclusion criteria. MAIN RESULTS: Ever consumption of chlorinated drinking water was associated with an increased risk of bladder cancer in men (combined OR=1.4, 95%CI 1.1 to 1.9) and women (combined OR=1.2, 95%CI 0.7 to 1.8). The combined OR for mid-term exposure in both genders was 1.1 (95% CI 1.0 to 1.2) and for long term exposure was 1.4 (95%CI 1.2 to 1.7). The combined estimate of the slope for a linear increase in risk was 1.13 (95% CI 1.08 to 1.20) for 20 years and 1.27 (95% CI 1.15 to 1.43) for 40 years of exposure in both sexes. CONCLUSIONS: This meta-analysis of the best available epidemiological evidence indicates that long term consumption of chlorinated drinking water is associated with bladder cancer, particularly in men. The observed relative risk is only moderately high, but the population attributable risk could be important as the vast majority of the population of industrialised countries is potentially exposed to chlorination byproducts for long time periods.

Assessment of the sample handling procedures in a labor-saving method for the analysis of organochlorine compounds in a large number of fish samples.

A rapid single step clean-up procedure with sulphuric acid oxidation for lipid removal has been assessed by a step-by-step recovery approach for its performance in the analysis of organochlorinated compounds in large numbers of fish samples (muscle). Recovery decreases are essentially due to losses by evaporation but their effect is compensated by correction of the recovery factor of tetrabromobenzene that is used as surrogate. Sample grounding with sodium sulphate provides significant higher concentrations than freeze-drying. Soxhlet extraction for 18 h is sufficient to draw most organochlorine compounds from the samples. Repeatability and reproducibility is smaller than the dispersion between fish of similar length and age from the same lake for all compounds except alpha-hexachlorocyclohexane.

Non-linear effects in the determination of paleotemperature U37(k') alkenone ratios by chemical ionization mass spectrometry.

The performance of gas chromatography coupled to mass spectrometry in the positive chemical ionization mode using ammonia as reagent gas (GC-PCI-MS) in the analysis of C37 alkenones for paleotemperature estimation has been re-evaluated. In some conditions, the discrepancies observed in the measurement of the U37(k') index with this technique as compared with GC equipped with flame ionization detection (GC-FID) cannot be explained by differences in sensitivity between the tri- and diunsaturated alkenones. Thus, at low (currently <0.3) or high (currently >0.4) U37(k') values the GC-PCI-MS determinations may be observed to be lower or higher, respectively, than those measured with GC-FID. As shown by analysis of a series of synthetic C37 alkenone standards these discrepant results can be explained by non linear effects in the GC-PCI-MS response factors. Second-order polynomial functions provide equations that describe better the signal to amount of analyte ratios. Users of GC-PCI-MS should calibrate their instruments with standards of known C37 alkenone composition in order to minimize non-linear effects.

Hexachlorocyclohexanes in human blood serum.

A simplified method allowing the determination of trace concentrations (ng/ml) of hexachlorocyclohexanes in human sera suitable for the analysis of large numbers of samples has been developed. Comparison of acid (conc. H2SO4,) and basic (5 M KOH) digestion has shown that good recoveries are obtained with the former when an internal standard, 1,2,4,5-tetrabromobenzene (TBB), is used to correct for volatilization losses. Good separation between alpha-, beta- and gamma-HCH isomers, TBB, hexachlorobenzene and some interfering compounds is obtained with DB-5 columns. The use of electron-capture detection (ECD) or negative ion chemical ionization mass spectrometry (NICI-MS) in the selected ion monitoring mode (m/z 71) provides sufficient sensitivity for quantitative determination. ECD is the most sensitive method for beta-HCH and NICI-MS for the other isomers. GC-NICI-MS is needed for the unambiguous determination of delta-HCH due to the coelution with one interfering compound. The method has been successfully applied to the analysis of a series of 625 samples collected in a population situated near the effluents of an organochlorinated solvent factory. The results have shown that beta-HCH is selectively accumulated in human sera and prompt to the preferential investigation of the toxic effects of this isomer in humans and mammals.

Bile acids and sterols in urban sewage treatment plants.

The composition of bile acids, sterols and sterones in water and sludge from an urban sewage treatment plant has been examined for assessment of the possible use of these compounds as pollution biomarkers. Samples were solvent-extracted, hydrolysed, and fractionated by column chromatography to separate acids, hydrocarbons, sterones and sterols. These fractions, except hydrocarbons, were methylated (acids only) and silylated for instrumental analysis. Gas chromatographic-mass spectrometric analysis was performed in the electron-impact mode, using a non-polar capillary column. Lithocholic acids (3alpha- and 3beta-epimers), coprostanone, coprostanol, cholesterol, cholestenone, and cholestanone were found in sludge and all waters. However, the waters after secondary plant treatment contained mainly lithocholic acids epimers and coprostanone, pointing to these compounds as potential markers for urban treatment plant effluents in natural waters courses.

Enhanced sensitivity in the analysis of trace organochlorine compounds by negative-ion mass spectrometry with ammonia as reagent gas.

A comparison of the performances of ammonia and methane as reagent gases for the analysis of trace organochlorine compounds by gas chromatography coupled to negative-ion chemical ionization mass spectrometry is performed in the present study. Examples of standard mixtures and human blood samples analyzed with both reagents in scan and selected-ion monitoring mode are shown. Important advantages are observed as a consequence of the use of ammonia. These concern detection and quantitation limits and the lower dependence of sensitivity on the degree of chlorine substitution of the compounds.

Haloacetic acids and trihalomethanes in finished drinking waters from heterogeneous sources.

Trihalomethanes (THM) and haloacetic acids (HAA) are the most frequent chlorination by-products (CBP) in finished drinking waters. Traditionally, THM have been used as surrogates for CBP although the quantitative association between THM and other CBP is not well established. This problem is addressed in the present study from the analysis of THM and HAA in drinking water samples from four Spanish regions, representing areas with very different CBP composition, e.g. between 86 and 8.0 microg/l of THM and 50-3.0 microg/l of HAA. The resulting dataset exhibit a statistically significant correlation between total THM and HAA (Pearson's correlation coefficient, r(p)=0.815,p<0.0005). Furthermore, specific HAA are highly correlated with specific THM or their combinations. Accordingly, multivariate linear regression analysis of the concentrations observed show that the levels in total and specific HAA can be predicted from the THM content. These results are relevant for epidemiological studies on health effects from CBP exposure since they usually involve comparison of populations consuming waters of very distinct quality.

Polycyclic aromatic hydrocarbons in remote mountain lake waters.

Polycyclic aromatic hydrocarbons (PAH), including alkylated and sulfur derivatives, were identified and measured in the waters from three European remote mountain lakes during both ice-free and ice covered periods. The measured concentrations were in the same order in all three lakes (700-1100 pg/l). The PAH patterns in both dissolved and particulate water phases were dominated by the low molecular weight compounds (i.e. phenanthrene, fluoranthene and pyrene) in Lakes Redó (Pyrenees) and Gossenkölle (Alps). In contrast, the high molecular weight (HMW) compounds (i.e. chrysene+triphenylene, benzofluoranthenes, benzo[e]pyrene) were very significant in lake Ovre Neådalsvatn (Caledonian). These HMW PAH correspond to mixtures originating from high temperature combustion processes which have been photodegraded during long range atmospheric transport and parallel the PAH mixtures encountered in the underlying lake sediments. In contrast, dissolved PAH exhibit temperature dependence with higher concentrations found at water temperatures below 6-7 degrees C reflecting higher condensation from the atmospheric gas phase reservoir.

The mine tailing accident in Aznalcollar.

Massive amounts of acidic waters and mud (pH approximately 3) containing toxic metals such as zinc, lead, arsenic, copper, antimony, cobalt, thallium, bismuth, cadmium, silver, mercury and selenium were released in the surroundings of Doñana Park as a consequence of the mine tailings spill accident in Aznalcollar (SW Spain). This introductory paper describes the main characteristics of Doñana Park, the mine activities developed in Aznalcollar and their related environmental risks. The tailing spill accident and the first package of urgent actions undertaken for preventive and mitigation purposes are also summarized.

Polychlorinated biphenyl partitioning in the waters of a remote mountain lake.

The dissolved-particulate phase distribution of polychlorobiphenyls (PCBs) in the waters of a high mountain lake (Redó Lake, Pyrenees) has been studied. The lake is oligotrophic and its water hydrology is dominated by atmospheric precipitation; inputs from catchment or other sources are not significant. Samples were collected in several periods encompassing the summer and winter seasons. The PCB congener concentrations were rather uniform both in terms of water depth and seasonality showing steady state conditions. Seventy percent of the variation of the PCB particulate-dissolved phase coefficient (Kd) was correlated with temperature and log octanol-water (Kow)). Lower temperatures and hydrophobicity involved a higher association with the particulate phase. This behavior is consistent with the predominance of plankton among suspended particles following a two compartment model. Thus, temperature dependence seems mainly related to a rapid phase transfer mechanism such as surface adsorption to the cell membranes and log Kow influence could reflect steric restrictions for the uptake of these compounds upon algal ingestion.