Search

This work presents an optimized gas chromatography–electron ionization–high-resolution mass spectrometry (GC-EI-HRMS) screening method. Different method parameters affecting data processing with the Agilent Unknowns Analysis SureMass deconvolution software were optimized in order to achieve the best compromise between false positives and false negatives. To this end, an accurate-mass library of 26 model compounds was created. Then, five replicates of mussel extracts were spiked with a mixture of these 26 compounds at two concentration levels (10 and 100 ng/g dry weight in mussel, 50 and 500 ng/mL in extract) and injected in the GC-EI-HRMS system. The results of these experiments showed that accurate mass tolerance and pure weight factor (combination of reverse-forward library search) are the most critical factors. The validation of the developed method afforded screening detection limits in the 2.5–5 ng range for passive sampler extracts and 1–2 ng/g for mussel sample extracts, and limits of quantification in the 0.6–3.2 ng and 0.1–1.8 ng/g range, for the same type of samples, respectively, for 17 model analytes. Once the method was optimized, an accurate-mass HRMS library, containing retention indexes, with ca. 355 spectra of derivatized and non-derivatized compounds was generated. This library (freely available at https://doi.org/10.5281/zenodo.5647960), together with a modified Agilent Pesticides Library of over 800 compounds, was applied to the screening of passive samplers, both of polydimethylsiloxane and polar chemical integrative samplers (POCIS), and mussel samples collected in Galicia (NW Spain), where a total of 75 chemicals could be identified. [ABSTRACT FROM AUTHOR]

BACKGROUND: Newborns in neonatal intensive care units (NICUs) are in contact with a variety of medical products whose production might include synthetic chemicals with hormonal activity. OBJECTIVES: Our aim was to assess the content of bisphenol A (BPA) and parabens (PBs) and the hormone-like activities of a subset of medical products commonly used in NICUs in prolonged intimate contact with NICU newborns. METHODS: Fifty-two NICU items were analyzed, determining the concentrations of BPA and PBs [methyl- (MeP), ethyl- (EtP), propyl- (PrP), and butylparaben (BuP)] and using the E-Screen and PALM-luciferase assays to measure the in vitro (anti-)estrogenic and (anti-)androgenic activity, respectively, of the extracts. Items found to have elevated BPA/PB content or hormone-like activities were further extracted using leaching methodologies. RESULTS: BPA was found in three-fifths and PBs in four-fifths of tested NICU items, and ~25% and ~10% of extracts evidenced estrogenic and anti-androgenic activity, respectively. The highest BPA content was found in the three-way stopcock (>7.000 ng/g), followed by patterned transparent film dressing, gastro-duodenal feeding tubes, sterile gloves, single-lumen umbilical catheters, and intravenous (IV) infusion extension sets (concentrations ranged from 100 to 700 ng/g BPA). A total PB concentration (?PPBs) >100 ng/g was observed in several items, including light therapy protection glasses, patterned transparent film dressing, winged IV catheters, IV infusion extension sets, and textile tape. The highest estrogenic activity [>450 pM estradiol equivalent (E2eq)] was found in small dummy nipples, three-way stopcocks, and patterned transparent film dressing and the highest anti-androgenic activity [>5 mM procymidone equivalent units per gram (Proceq/g)] in small dummy nipples and three-way stopcocks. DISCUSSION: According to these findings, neonates might be exposed to multiple sources of BPA and PBs in NICUs via inhalation, dermal, oral, and IV/parenteral routes. There is a need to address the future health implications for these extremely vulnerable patients and to adopt precautionary preventive measures as a matter of urgency. [ABSTRACT FROM AUTHOR]

Copyright of Revista de Toxicología is the property of Asociacion Espanola de Toxicologia and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Perfluorinated compounds (PFCs) are persistent and bioaccumulative organic compounds used as additives in many industrial products. After use, these compounds enter wastewater treatment plants (WWTP) and long-chain PFCs are primarily accumulated in sludge. The aim of this study was to determine the occurrence and behavior of five PFCs in sludge from 15 WWTP from Spain and Germany that receive both urban and industrial wastes. The PFCs studied were perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate (PFHxS), perfluorobutanesulfonate (PFBS), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA). One gram of freeze-dried, sieved, and homogenized sludge was extracted using an ultrasonic bath with methanol and glacial acetic acid. After that, the extract was recovered and evaporated to dryness with a TurboVap and then 1 mL of acetonitrile was added and the extract was cleaned up with black carbon. Liquid chromatography coupled to mass spectrometry operated in selected reaction monitoring was used to determine target compounds. Quality parameters are provided for the set of compounds studied. PFCs were detected in all samples. In Spanish sludge, ∑PFC ranged from 0.28 to 5.20 ng/g dry weight (dw) with prevalence of PFOS, while in German sludge, ∑PFC ranged from 20.7 to 38.6 ng/g dw and PFBS was the dominant compound. As a next step, the evolution of PFC concentrations within the sludge treatment steps (primary sludge, anaerobic digested sludge, and centrifuged sludge) was evaluated and differences among levels and patterns were observed and were attributed to the influent water quality and treatment used. Finally, we estimated the amount of PFCs discharged via sludge in order to determine the potential impact to the environment according to different sludge usage practices in the two regions investigated. This manuscript provided an intra-European overview of PFC distribution in sludge. Levels and compound distribution depend on the WWTP sampled. This study demonstrates that PFCs are persistent to sludge treatment and the loads in sludge may pose a future environmental risk, if not controlled. [ABSTRACT FROM AUTHOR]

Purpose: Solid waste incineration has recently attracted much attention because the combustion process involved produces highly toxic organohalogen contaminants such as dioxin-like polychlorinated biphenyls (DL-PCBs) present in fly ash. This has raised the need for simple, rapid, accurate methods for monitoring PCBs in ash samples. Methods: A method for the simultaneous quantitative determination of indicator, non-ortho and mono-ortho PCBs based on ultrasound-assisted extraction with 50:50 ( v/ v) n-hexane/acetone was developed, validated, and subsequently applied to real samples from a mussel shell incinerator facility in Galicia. The overall method quantification limits range from 0.35 to 1.5 ng/g in fly ash waste, from 0.30 to 1.0 ng/g in bottom ashes, and from 1.0 to 2.0 ng/g in sludge samples. Mean recoveries between 70% and 105% are achieved. Results: DL-PCBs were identified in ash and in sludge samples collected from the wastewater treatment plant of the waste incineration facility. The enrichment factors for fly ash ranged from 3.3 to 3.7. Sewage sludge was also found to contain some polychlorinated biphenyls such as PCB 77 (29 ± 5.0 ng/g; n = 4) and PCB 169 (6.9 ± 0.89 ng/g; n = 4), as well as three of the seven PCB-like indicators, namely: PCB 138 (14 ± 4.4 ng/g), PCB 153 (6.1 ± 1.4 ng/g), and PCB 180 (7.7 ± 3.0 ng/g). Toxicity equivalent concentrations were 0.0054 ng/g for bottom ash, 0.0264 ng/g for fly ash, and 3.6 ng/g for sewage sludge; these values are well below the limit for DL-PCBs in wastes recently set by the European Union. Conclusions: All samples studied contained PCBs at levels below the maximum tolerated limit established by European legislation. Based on their PCB content, the studied sewage sludge can be used as a soil amendment with no health risk. Also, fly ash and sewage sludge can be deemed stable PCB reservoirs releasing PCBs at concentrations below the regulatory cutoff to runoff water. [ABSTRACT FROM AUTHOR]

Most organochlorine (OC) use has been banned in Spain, but these compounds are persistent and may still adversely affect predatory birds. Data generally are lacking, however. Residues of hexachlorobenzene, α-hexachlorocyclohexane, lindane, hexachloro-octahydro-epoxy-dimethanonaphthalene, DDT, dichlorodiphenyldichloroethane, dichlorodiphenyldichloroethylene (DDE), and polychlorinated biphenyls (PCBs) were measured in 22 failed eggs of booted eagles (Hieraaetus pennatus) and goshawks (Accipiter gentilis) from southeastern Spain; both species are declining in this region. Hexachloro-octahydro-epoxy-dimethanonaphthalene, DDE, and sum PCB congener concentrations were significantly higher in booted eagle than in goshawk eggs, and an inverse relationship was found between shell thickness and DDE concentrations in booted eagles. Organochlorides may have been associated with the failure of some booted eagle eggs, but concentrations in booted eagle and goshawk eggs decreased over the period during which populations have dwindled. Thus, although OCs may be a contributory factor, they are unlikely to be the primary cause of the recent population declines in southeastern Spain. [ABSTRACT FROM AUTHOR]

The occurrence of furan in commercial baby food samples from the Spanish market was evaluated using an automated headspace solid-phase microextraction method coupled to gas chromatography-mass spectrometry (HS-SPME-GC-MS). A total of 76 baby food samples including infant formula, baby cereals, fruit in cans and/or jars, vegetables, meat, and fish, were surveyed for furan content. The lowest concentration of this compound was found in infant formula (<0.02–0.33 ng ml−1), and cereal-based food (0.15–2.1 ng g−1) while baby food containing fish showed the highest concentrations (19–84 ng g−1). Following recommendation of the European Food Safety Authority (EFSA), the effect on furan content was evaluated of consumer home preparation of foods, heating and handling. Furan concentrations were reduced by up to 35% when samples were heated in a dish using microwave oven and by up to 53% when a hot water bath was used. Finally, we estimated the furan intake from baby food consumption (0.002–1.18 µg kg−1body weight day−1) and we calculated the margin of exposure (MOE) from samples as purchased and also after home preparation of the food. For infant formula and cereal baby foods, the MOEs (26,278–412,776) indicated no infant health concern or priority, while for meat and fish-based baby foods the values pointed to a potential public health risk, even considering the furan losses during preparation at home. [ABSTRACT FROM AUTHOR]

Spain is a relevant producer of oats (Avena sativa), but to date there has been no study on the occurrence/co-occurrence of mycotoxins in oats marketed in Spain. The present study is addressed to overcome this lack of knowledge. One hundred oat kernel samples were acquired across different Spanish geographic regions during the years 2015–2019 and analyzed for mycotoxin content using an ultra-high performance liquid chromatography electrospray ionization tandem mass spectrometry (UPLC–ESI–MS/MS) method and matrix-matched calibration. The focus was on the regulated mycotoxins although other relevant mycotoxins were considered. The percentage of incidence (levels ≥ limit of detection), mean and range (ng/g) of mycotoxins were as follows: zearalenone (66%, mean 39.1, range 28.1–153), HT-2 toxin (47%, mean 37.1, range 4.98–439), deoxynivalenol, (34%, mean 81.4, range 19.1–736), fumonisin B1 (29%, mean 157.5, range 63.2–217.4), and T-2 toxin, (24%, mean 49.9, range 12.3–321). Fumonisin B2, 3-acetyldeoxynivalenol, aflatoxins B1, B2, and G2, and ochratoxin A were also detected at low levels, but aflatoxin G1 was not. The maximum limits established by the European Commission for unprocessed oats were not exceeded, except for zearalenone (in one sample), and the sum of aflatoxins (in two samples). Mycotoxin co-occurrence at quantifiable levels in the same sample (two to five combinations) was found in 31% of samples. The most common mixtures were those of HT-2 + T-2 toxins alone or together with deoxynivalenol and/or zearalenone. [ABSTRACT FROM AUTHOR]

The northwest coast of Spain is characterized by an irregular coastline rich in marine life and with the highest mussel production in Europe. Taking this into account, the characterization of the pollution levels and the sources involved appear necessary. Not only were parent Polycyclic Aromatic Hydrocarbons (PAHs) analysed but also their alkylated homologues. In total, 35 compounds were analyzed in 5 sediment cores. Sediments were collected using a box core dredge and extracted by (Pressurized Liquid Extraction) whilst the quantification of PAHs was performed using gas chromatography coupled to mass spectrometry (GC-MS). The total concentration detected varied from 49.6 to 2489 ng g dry weight (d.w.) of which parent PAHs ranged from 44.5 to 2254 ng g d.w. and alkylated PAHs varied from 5.04 to 317 ng g d.w. Temporal and spatial evolution were outlined and pollution sources were identified along with a possible correlation between this pollution and local history and industry. Most of the PAHs from the superficial samples have a biomass and coal combustion profile, and some specific, localized events are reflected in the total PAH concentration evolution. Moreover, the study of the deepest layers of the sampled cores provides a baseline to develop background concentration values that will help in future sediment quality assessment. [ABSTRACT FROM AUTHOR]

Copyright of Revista de Toxicología is the property of Asociacion Espanola de Toxicologia and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

The occurrence of polar pesticides in sediments has not been extensively investigated because of their relatively poor hydrophobicity and apparently less persistence in the environment. However, their continuous release into the aquatic systems calls for the evaluation of their potential accumulation in sediments and the role of this matrix as a potential source of these compounds. Considering this, a method based on pressurized liquid extraction (PLE), extract clean-up by solid phase extraction (SPE), and analyte determination by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was developed and validated to analyze 50 relevant (frequently used and/or regulated or found in water) medium to highly polar pesticides in sediments. The method showed good performance regarding accuracy (relative recoveries between 76 and 124%), precision (relative standard deviation values < 20%), sensitivity (LODs in the low nanogram per gram for most compounds), linearity (coefficients of determination > 0.99), and matrix effects (negligible for all analytes). The use of an isotope dilution approach for quantification ensures result reliability. As a part of the validation process, the method was applied to the analysis of the target pesticides in sediments from the Llobregat River (NE Spain) showing the presence of five of them, namely, terbutryn, dichlorvos, terbuthylazine, diazinon, and irgarol. All 5 pesticides, due to both the concentrations found and their physical-chemical characteristics, demonstrate high potential for bioaccumulation and risk to aquatic organisms. Additional multi-disciplinary studies that investigate pesticide occurrence in different aquatic compartments and evaluate the potential risks for aquatic ecosystems are required to assess the environmental impact and significance of the presence of pesticides in sediments. [ABSTRACT FROM AUTHOR]

Copyright of Revista de Toxicología is the property of Asociacion Espanola de Toxicologia and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Given the widespread use of bisphenols and parabens in consumer products, the assessment of their intake is crucial and represents the first step towards the assessment of the potential risks that these compounds may pose to human health. In the present study, a total of 98 samples of food items commonly consumed by the Spanish population were collected from different national supermarkets and grocery stores for the determination of parabens and bisphenols. Our analysis demonstrated that 56 of the 98 food samples contained detectable levels of parabens with limits of quantification (LOQ) between 0.4 and 0.9 ng g−1. The total concentration of parabens (sum of four parabens: ∑parabens) ranged from below the LOQ to 281.7 ng g−1, with a mean value of 73.86 ng g−1. A total of 52% of the samples showed detectable concentrations of bisphenols. Bisphenol A (BPA) was the most frequently detected bisphenol in the food samples analysed, followed by bisphenol S (BPS) and bisphenol E (BPE). Bisphenol AF (BPAF), bisphenol B (BPB) and bisphenol P (BPP) were not found in any of the analysed samples. LOQ for these bisphenols were between 0.4 and 4.0 ng g−1. [ABSTRACT FROM AUTHOR]

Purpose: Perfluorinated compounds (PFCs) are widely distributed from industrialized to remote locations throughout the world. This study demonstrates the spatial distributions of PFCs in water and sediments from the L'Albufera Natural Park (Valencia, Spain). Methods: Grab water and sediment samples were collected. PFCs were extracted from sediments with acidified acetonitrile by ultrasonication and cleaned up by solid-phase extraction (SPE) and from water by SPE. Determination was carried out by liquid chromatography-tandem mass spectrometry. Results: In 100% of the samples (both water and sediments), perfluorooctane sulfonate (PFOS) and perfluoroctanoic acid (PFOA) were the predominant PFCs. Among the 12 sampling sites, PFOS concentrations in sediments ranged from 0.10 to 4.80 ng/g dry weight and in water from 0.94 to 58.1 ng/L. PFOA concentrations in sediment were from 0.004 to 1.24 ng/g and in water from 0.99 to 120 ng/L. Other perfluorocarboxylic acids (C5, C6, C7, C9, and C10) and perfluorosulfonates (C4 and C10) were also identified in several locations. The sum of all 10 compounds (ΣPFCs) concentration range from 0.99 to 120 ng/L in water and from 0.25 to 17.4 ng/g in sediments. Sediment-water distribution coefficients (log K) were in the range 2.31-4.51 and positively correlated with perfluoroalkyl chain length. Conclusions: PFC concentrations in water and sediment were both less than those able to cause acute toxicity; low but detectable PFCs pollution in the L'Albufera Natural Park in Valencia was demonstrated. These compounds are bioaccumulative; thus, the risk associated with these exposures requires a deeper evaluation of long-term chronic toxicity. [ABSTRACT FROM AUTHOR]

Levels and profiles of 10 individual congeners of polychlorinated biphenyls (PCBs) were studied in 3 species of commercial scallops ( Pecten maximus, Chlamys varia, and Chlamys opercularis) from several Rías in Galician littoral (NW, Spain). ΣPCBs levels ranged from 2.21 to 41.0 ng/g wet weight for P. maximus, from 13.9 to 24.9 ng/g wet weight for C. varia, and from 1.58 to 24.3 ng/g wet weight for C. opercularis. The possible influence between biometric parameters (lipid content, condition index, and shell size) and PCBs levels were studied using statistical analysis (ANOVA). No relationship between biometric parameters could be established in the studied samples. Multivariate analysis showed there were differences in bioaccumulation of some PCBs congeners. Principal component analysis classifies clearly the 3 studied Rías (Ría de Ferrol, Ría de Arousa, and Ría de Vigo) taking into account PCBs levels found in the shellfish. Practical Applications: We investigated levels and profiles of 10 congeners of PCBs in 3 commercial scallop species from the Galician littoral zone. The influence of 3 biometric parameters on polychlorinated biphenyls (PCBs) levels was also studied in order to assess results from the monitoring programs of production areas. According to PCBs levels, geographical differences were observed in commercial scallops from the 3 studied estuarine bays (Ría de Ferrol, Ría de Arousa, and Ría de Vigo). [ABSTRACT FROM AUTHOR]

The main objective of this work was to assess and compare the levels, patterns, and sources of contamination of 16 polycyclic aromatic hydrocarbons (PAHs) between Portugal, Spain, and Greece (in the island of Crete). A total of 9 sampling sites were chosen (4 in urban and 5 in non-urban areas) in each country and pine needles from the Pinus pinea L. species were collected. Although the mean total PAH levels was similar in the three countries (279 ± 236 ng g−1 for Portugal, 294 ± 258 ng g−1 for Spain, 301 ± 253 ng g−1 for Greece, all dry weight) and, in general, 3-ring and 4-ring PAHs were predominant (being phenanthrene consistently the most abundant), there were some visible differences in the aromatic ring patterns and possible sources between the three regions. Source apportionment was done using PAH ratios (Phen/Ant and Flt/Pyr crossplots) and reflected mixed petrogenic and pyrogenic sources. Furthermore, Principal Component Analysis (PCA) clearly separated the urban and the non-urban sites and all three countries, which reinforces that the sources of contaminations vary in each case and the suitability of pine needles for trans-boundary biomonitoring of PAHs. [ABSTRACT FROM AUTHOR]

Introduction: The content of 16 polycyclic aromatic hydrocarbons (PAHs) was determined in 60 samples from three environmental matrices (soils, sediments, and pine needles) in an effort to assess their distribution on a river basin scale. Methods: A sampling campaign was carried out in 2006, selecting urban, industrial, and agricultural sampling sites along the northeast of Spain. Techniques used included pressurized liquid extraction and solid-liquid ultrasonic extraction followed by gas chromatography-electron impact ionization mass spectrometry. Results: The mean total PAHs concentrations were 290 < 613 < 1,628 ng/g (dry weight) in pine needles, soil, and sediments, respectively. There is a good correspondence between the total concentration of soils and pine needles, as opposed to the levels between sediments and pine needles. The high concentrations found in some Pinus halepensis samples may reflect a superior uptake potential of this species in comparison to the others studied. The three matrices present a very different PAH distribution pattern, with pine needles showing a predominance of the lighter (2-, 3-, and 4-ring) PAHs, whereas 5- and 6-ring PAHs are the most abundant in soils. Sediments display a more heterogeneous pattern, with contributions of all the PAHs but different distribution depending on the site, suggesting a wider range of input sources. Established PAH molecular ratios and principal component analysis were used to identify the origins and profiles of PAHs. While sediments showed a wide range attributed to historical inputs, soils and pine needles confirmed the compartmentalization of the PAHs, with lighter airborne PAHs accumulated in pine needles and heavier ones in soils. Conclusions: It can be suggested that the monitoring of several matrices is a strong tool to elucidate the contamination sources and accumulation patterns of PAHs. However, given the influence of the matrix type on this assessment, the information should be considered complementary, yet allowing a more comprehensive depiction of the area in question. [ABSTRACT FROM AUTHOR]

Individual parent polycyclic aromatic hydrocarbons (PAHs) were identified and quantified in samples of recent sediments at 32 stations in the Ria de Vigo (NW Spain) and its adjacent shelf by high-performance liquid chromatography and a fluorescence detector. This area suffers the pressure of nearly 500,000 inhabitants and includes a number of important marine organisms. The total concentration for the sum of the 13 PAHs quantified were in the range 28–3203 ng/g. The highest concentrations were found near the city of Vigo, where marinas and dockyards as well as highways with a high traffic flow are established. Low PAH concentrations were determined in the outermost part of the estuary, far from the anthropogenic influence. PAH isomers concentration ratios were assessed, indicating that the main source of these compounds in the whole area is pyrolysis. When compared with the EACs, threshold effect level, and probable effect level values, only the samples from the inner part of the ría can occasionally present adverse biological effects due to the PAH concentrations. [ABSTRACT FROM AUTHOR]

Mussels (Mytilus galloprovincialis) were sampled in March 1996 from five stations along the Western Mediterranean coast (Barcelona, Ebro Delta, Alboraya, Cullera, Denia) corresponding to urban, industrial and agricultural areas. Different biochemical and cellular markers were determined in the mussels in order to assess the effects and/or exposure to pollutants. The cytochrome P450 system, acetylcholinesterase and metallothioneins were among the biochemical markers selected for the study. Histochemical analysis of ß-glucuronidase and catalase activity were performed as marker enzymes for lysosomes and peroxisomes. Chemical analyses indicated that mussels from Barcelona and Denia as highly exposed to polycyclic aromatic hydrocarbons (PAHs)(1.8-2.7 µg g[sup -1] w.w. against 0.02-0.10 µg g[sup -1] w.w.), and polychlorinated biphenyls (PCBs)(132-260 ng g[sup -1] w.w. against 8-24 ng g[sup -1] w.w.). This was in agreement with changes in lysosome structure and higher number of peroxisomes in those organisms. High levels of metals (particularly Cr and Cu) were recorded in the digestive gland of Alboraya mussels, which also had elevated metallothionein content (28 nmol g[sup -1] w.w.) in comparison with the other stations (15-20 nmol g[sup -1] w.w.). Benzo(a)pyrene hydroxylase (BPH) activity indicated Cullera and Barcelona as possibly polluted sites. The results support the usefulness of the biomarker approach to assess and diagnose environmental pollution. The use of a battery of biomarkers at different levels of biological organization coupled with chemical analysis is highlighted. [ABSTRACT FROM AUTHOR]

The article presents a study which investigates the levels of hexachlorobenzene (HCB) in cheeses, which were produced in Spain to evaluate its repercussions on human health. The study used a Hewlett-Packard gas chromatograph with a 63 electron capture detector (ECD). Results show that all Spanish cheese samples contained HCB residues with 9.26 ng/g fat basis.

The article presents a study which estimates the organochlorine pollutants level in human milk samples taken from Madrid, Spain, and investigates the significant alterations of contaminants levels. The study uses the gas chromatography analysis on Hewlett-Packard 5890 with nickel (Ni) 63 electron capture detection. Results show that the levels on fat are measured as appropriate for the organochlorine pollutants concentrations in human milk.

The environmental exposure to trace metal(loid)s (As, Cd, Cu, Fe, Mn, Pb, and Zn) was assessed near a ferromanganese alloy plant using filters from personal particulate matter (PM) samplers (bioaccessible and non-bioaccessible fine and coarse fractions) and whole blood as short-term exposure markers, and scalp hair and fingernails as long-term biomarkers, collected from volunteers (n = 130) living in Santander Bay (northern Spain). Bioaccessible and non-bioaccessible metal(loid) concentrations in coarse and fine PM from personal samplers were determined by ICP-MS after extraction/digestion. Metal(loid) concentration in biomarkers was measured after alkaline dilution (whole blood) and acid digestion (fingernails and scalp hair) by ICP-MS as well. Results were discussed in terms of exposure, considering the distance to the main Mn source, and sex. In terms of exposure, significant differences were found for Mn in all the studied fractions of PM, As in whole blood, Mn and Cu in scalp hair and Mn and Pb in fingernails, with all concentrations being higher for those living closer to the Mn source, with the exception of Cu in scalp hair. Furthermore, the analysis of the correlation between Mn levels in the studied biomarkers and the wind-weighted distance to the main source of Mn allows us to conclude that scalp hair and mainly fingernails are appropriate biomarkers of long-term airborne Mn exposure. This was also confirmed by the significant positive correlations between scalp hair Mn and bioaccessible Mn in coarse and fine fractions, and between fingernails Mn and all PM fractions. This implies that people living closer to a ferromanganese alloy plant are exposed to higher levels of airborne metal(loid)s, mainly Mn, leading to higher levels of this metal in scalp hair and fingernails, which according to the literature, might affect some neurological outcomes. According to sex, significant differences were observed for Fe, Cu and Pb in whole blood, with higher concentrations of Fe and Pb in males, and higher levels of Cu in females; and for Mn, Cu, Zn, Cd and Pb in scalp hair, with higher concentrations in males for all metal(loid)s except Cu. [ABSTRACT FROM AUTHOR]

This work presents an analytical methodology based on a "Quick, easy, cheap, effective, rugged, and safe" (QuEChERS) extraction and liquid chromatography-tandem mass spectrometry detection (LC-MS/MS) for the simultaneous determination of 35 psychoactive substances in fresh mussel samples. The compounds investigated include illicit drugs, new psychoactive substances, commonly prescribed psychiatric pharmaceuticals, and caffeine. The methodology was validated in terms of recovery (relative recoveries 77–118%), repeatability (relative standard deviation values <20%), and sensitivity (limits of detection and quantification <2 ng/g fresh weight (f.w.) and <6.7 ng/g f.w., respectively, for most compounds). The method was applied to the analysis of 15 samples, covering both commercially available mussels purchased from local food markets and wild fresh mussels collected in the Northeast coast of Spain in the Mediterranean Sea. Only one sample corresponding to wild mussels was found to contain 2 of the target analytes, namely, sertraline (1.5 ng/g f.w.) and caffeine, (12.8 ng/g f.w.). Unlabelled Image • Analysis of 35 psychoactive drugs in fresh mussels with QuEChERS and LC-MS/MS • Rapid, inexpensive, and simple sample preparation • The use of isotopically labeled surrogate standards assures results reliability. • Method detection limits were below 10 ng/g f.w. for all compounds. • Caffeine (12.8 ng/g f.w.) and sertraline (1.5 ng/g f.w.) found in wild mussels. [ABSTRACT FROM AUTHOR]

The occurrence of classical and emerging halogenated flame retardants in bird samples collected between 2010–17 from the Castrejón reservoir (central Spain) was studied. Different wetland bird samples were analysed, including unhatched bird eggs and liver of dead nestlings. Polybrominated diphenylethers (PBDEs) were detected in all the samples at high concentration values, with levels up to 5167 ng/g lw. Dechloranes were found in 78% of analysed samples, but at lower concentration levels, between not detected (nd) and 2153 ng/g lw. The time trend evaluation over the sampling period showed an approximately 50% decline in mean concentrations of PBDEs. However, the most recent data for PBDEs (2016–17) still indicate that, in some cases, and based on reported LOECs, wetland birds were exposed to PBDE concentrations that are associated with possible ecological hazards. • PBDEs were detected at high concentrations, with levels up to 5167 ng/g lw. • Dechloranes were found in 78% of samples, at concentrations up to 2153 ng/g lw. • Time trend evaluation for PBDEs along 2010–2017 showed a level decline. • Based on reported LOECs, birds were still exposed to PBDEs associated to ecological hazards. [ABSTRACT FROM AUTHOR]

Little information is available on the content of bisphenol A (BPA) and other endocrine-disrupting chemicals (EDCs) such as parabens in infant textiles and clothes. 1) To determine the concentrations of BPA and parabens in socks for infants and young children purchased in Spain, 2) to assess the (anti-)estrogenicity and (anti-)androgenicity of extracts from the socks, and 3) to estimate dermal exposure doses to these chemicals. Thirty-two pairs of socks for infants and young children (1–48 months) were purchased from 3 stores in Granada (Spain). Textile material was cut from the foot, toe, and leg of each sock (n = 96 samples) for chemical analysis. Hormone-like activities were determined in foot sections (n = 32 samples) by using the E-Screen assay for (anti-)estrogenicity and PALM luciferase assay for (anti-)androgenicity. BPA was present in 90.6% of samples at concentrations ranging from <0.70 to 3736 ng/g. BPA levels were around 25-fold higher in socks from store 1, which had a higher cotton content compared to stores 2 and 3. Ethyl-paraben was found in 100% of samples, followed by methyl-paraben (81.0%), and propyl-paraben (43.7%). No butyl-paraben was detected in any sample. Estrogenic activity was detected in 83.3% of socks from store 1 (range = 48.2–6051 pM E 2 eq/g) but in only three socks from stores 2 and 3. Anti-androgenic activity was detected in six of the 32 socks studied (range = 94.4–2989 μM Proceq/g), all from store 1. Estimated dermal exposure to BPA was higher from socks for children aged 36–48 months (median = 17.6 pg/kg/day), and dermal exposure to parabens was higher from socks for children aged 24–36 months (median = 0.60 pg/kg/day). This is the first report in Europe on the wide presence of BPA and parabens in socks marketed for infants and children. BPA appears to contribute to the hormone-like activity observed in sock extracts. Unlabelled Image • BPA was present in 91% of socks at concentrations ranging from <0.70 to 3736 ng/g. • Ethyl-paraben was found in 100% of socks, followed by methyl- and propyl-paraben. • Around 41% of socks extracts were estrogenic and 19% were anti-androgenic. • Hormone-like activities were higher in socks with higher BPA content. • The median estimated dermal exposure dose to BPA was 19.6 pg/kg/day. [ABSTRACT FROM AUTHOR]

Objective: To examine the association of placental levels of arsenic (As), cadmium (Cd), mercury (Hg), lead (Pb), manganese (Mn), and chromium (Cr) with birth outcomes (birth weight, length, and head circumference, low birth weight [LBW], gestational age, preterm delivery, and small for gestational age [SGA]) in mother-child pairs from the Environment and Childhood (INMA) Project in Spain.Methods: Metal concentrations were measured in placenta tissue samples randomly selected from five INMA cohorts. Data on birth outcomes were obtained from medical records. Associations were assessed in a sub-sample of 327 mother-infant pairs by regression models adjusted for confounding factors and for all metals simultaneously. Effect modification by sex was also evaluated.Results: Elevated placental Cd levels (>5.79 vs. <3.30 ng/g) were associated with reduced birth weight (-111.8 g, 95%CI = -215.6; -8.06, p-trend = 0.01) and length (-0.62 cm, 95%CI = -1.20; -0.04, p-trend = 0.02), while a 10% increase in Cd was associated with 1.21-fold increased odds (95%CI = 1.01; 1.43) of LBW in the global sample but with 14% lower odds (95%CI = 0.78; 0.96) of preterm delivery in males (Pinteraction = 0.10). Detected (vs. undetected) Hg was associated with reduced head circumference (-0.49 cm, 95%CI = -1.00; 0.03) in females (Pinteraction = 0.03). A 10% increase in placental Mn was associated with slight increases in gestational age (0.04 weeks, 95%CI = 0.01; 0.07) in the global sample and in head circumference (0.05 cm, 95%CI = -0.01; 0.10) in females (Pinteraction = 0.03). Elevated Cr levels (>99.6 vs. <56.1 ng/g) were associated with reduced birth length (-0.68 cm, 95%CI = -1.33; -0.04, p-trend = 0.02) and slightly increased gestational age (0.35 weeks, 95%CI = -0.07; 0.77, p-trend = 0.08) in the global sample. As and Pb were detected in few placentas (27% and 13%, respectively) and were not associated with any studied birth outcome.Conclusions: Data suggest that in utero exposure to Cd, Hg, and Cr could adversely affect fetal growth, whereas Mn and Cr appear to have a positive effect on gestational age. Given the relatively small number of subjects, sex-specific associations should be interpreted with caution. [ABSTRACT FROM AUTHOR]

Objective: To assess the daily intake of polychlorinated biphenyls not similar to dioxins (NDL-PCB) derived from fish consumption in Spain and compare it with tolerance limits in order to establish a safe threshold so that the nutritional benefits derived from fish consumption may be optimized.Design: Analysis of NDL-PCB in fish samples and ecological study of the estimated intake of NDL-PCB from fish consumption in different Spanish population groups.Subjects: National representative sample of the Spanish population.Results: The intake of NDL-PCB was estimated in two different scenarios: upper bound (UB) and lower bound (LB). Estimating intake using the average concentration of NDL-PCB found in the fish samples, the intake for 'other children' is estimated as: 1·80 (UB) and 5·33 (LB) ng/kg per d at the 50th percentile (P50); 7·39 (UB) and 21·94 (LB) ng/kg per d at the 95th percentile (P95) of fish consumption. Estimated NDL-PCB intake shoots up in the toddler group, reaching values of 30·43 (UB) and 90·37 (LB) ng/kg per d at P95. Estimated intake values are lower than those previously estimated in Europe, something expected since in previous studies intake was estimated through total diet. In adults, our estimated values are 1·59 (UB) and 4·72 (LB) ng/kg per d at P50; 4·95 (UB) and 14·72 (LB) ng/kg per d at P95.Conclusions: NDL-PCB concentration in fish is under the tolerance limits in most samples. However, daily intake in consumers of large quantities of fish should be monitored and special attention should be given to the youngest age groups due to their special vulnerability and higher exposure. [ABSTRACT FROM AUTHOR]

Tarragona County (Spain) is home to the most important chemical/petrochemical industrial complex in Southern Europe, which raises concerns about the presence and effects of the numerous environmental contaminants. In order to assess the levels and patterns of five classes of semi-volatile organic compounds (SVOCs) - polycyclic aromatic hydrocarbons (PAHs), synthetic musks (SMs), polychlorinated biphenyls (PCBs), brominated flame retardants (BFRs) and one organochlorine pesticide, hexachlorobenzene (HCB), 27 samples of soil and vegetation ( Piptatherum L.) from different areas (petrochemical, chemical, urban/residential, and background) of Tarragona County were analysed. The results show that PAHs levels in soils ranged from 45.12 to 158.00 ng/g and the urban areas presented the highest concentrations, mainly associated with the presence of a nearby highway and several roads with heavy traffic. PAHs levels in vegetation samples ranged from 42.13 to 80.08 ng/g, where the greatest influence came from the urban and petrochemical areas. In the case of SMs, levels in soils and vegetation samples ranged from 5.42 to 10.04 ng/g and from 4.08 to 17.94 ng/g, respectively, and in both cases, background areas (at least 30 km away from the main SVOCs emission sources) showed the highest levels, suggesting an influence of the personal care products derived from beach-related tourism in the coast. PCBs (from 6.62 to 14.07 ng/g in soils; from 0.52 to 4.41 ng/g in vegetation) prevailed in the chemical area in both matrices, probably associated with the presence of two sub-electrical stations located in the vicinities. In general terms, BFRs and HCB values recorded in soil and vegetation samples were quite similar between matrices and sampling areas. [ABSTRACT FROM AUTHOR]

This study aimed to estimate airborne nicotine concentrations and nicotine, cotinine, and tobacco-specific nitrosamines (TSNAs) in settled dust from private cars in Spain and the UK. We measured vapor-phase nicotine concentrations in a convenience sample of 45 private cars from Spain (N = 30) and the UK (N = 15) in 2017–2018. We recruited non-smoking drivers (n = 20), smoking drivers who do not smoke inside the car (n = 15), and smoking drivers who smoke inside (n = 10). Nicotine, cotinine, and three TSNAs (NNK, NNN, NNA) were also measured in settled dust in a random subsample (n = 20). We computed medians and interquartile ranges (IQR) of secondhand smoke (SHS) and thirdhand smoke (THS) compounds according to the drivers' profile. 24-h samples yielded median airborne nicotine concentrations below the limit of quantification (LOQ) (IQR:

A quantitative method based on ultrasound-assisted toluene extraction followed by liquid chromatography-electrospray ionization-tandem mass spectrometry for the analysis of C and C fullerenes, N-methylfulleropyrrolidine, [6, 6]-phenyl C butyric acid methyl ester and [6, 6]-thienyl C butyric acid methyl ester has been developed. The method was validated using fortified blank river sediments according to the criteria of Commission Decision 2002/657/EC. The method limits of detection ranged from 14 to 290 pg/g, making it suitable for its application in environmental analysis. The method has been applied to investigate fullerene content in 58 soil samples collected from different urban and industrial areas in Saudi Arabia and in river sediment from six different sites in the Llobregat River Basin. In addition, in the case of the Llobregat River, superficial water samples from the same sites of the sediments were collected and analysed using a previous method. In soils from Saudi Arabia, C-fullerene was the only compound that was detected and quantified in 19 % of samples. In the sediments of the Llobregat River, C-fullerene was also the only one detected (33 % of the samples), while in river water, C-fullerene was the most frequent compound, and it was quantified in 67 % of the samples. However, C-fullerene was present in two of the six samples, but at higher concentrations than C-fullerene, ranging from 0.9 to 7.8 ng/L. [ABSTRACT FROM AUTHOR]

An assessment of mercury (Hg) accumulation in fish from the Tagus River aquatic system (central Spain), which has been influenced by pollution from industrial and urban development, was performed. Total Hg (THg), inorganic Hg (IHg), and monomethylmercury (MMHg) were determined in muscle and liver of different fish species, including Cyprinus carpio, Ameiurus melas, and Chondrostoma miegii, sampled from three locations. Although concentrations of THg and Hg species showed wide variability among the fish species, they were also found to be considerably dependent on location and fish tissue. Relative contents of MMHg to THg in muscle varied from 60 to 88%, whereas those found in liver ranged from 7 to 59%. Mean THg concentrations ranged from 126 to 810 ng/g (dry weight [dw]) in liver and from 159 to 1057 ng/g dw in muscle. Therefore, the mean THg concentration in all fish muscle samples was far lower than the maximum residue level recommended by the European Union for fishery products. Nevertheless, the concentrations of Hg in fish muscle reported in this study were somewhat increased compared with other areas geographically distant from most major anthropogenic Hg sources and, in some cases, even greater than those previously reported elsewhere in more polluted areas. In contrast, Hg contents in liver were lower than those found in Hg-contaminated areas, but they were within the range found in other areas exposed to diffuse sources of pollution by Hg. Thus, this article provides an overview of the concentration and distribution of Hg species in fish muscle and liver tissues samples taken from a freshwater system in the Mediterranean River basin. [ABSTRACT FROM AUTHOR]

This paper documents levels of organochlorine pesticides (OCs) in coastal surface sediments from selected reference sites on the northern Atlantic Spanish coast. One hundred eight samples covering three estuaries in the Cantabrian Coast were sampled in 2006 and analyzed in the finer fraction (<63 μm) for 19 OCs by gas chromatography with electron capture detector after confirmation by mass spectrometry. Detected organochlorine pesticides were endosulfan α, endosulfan β, endosulfan sulfate, hexachlorobenzene (HCB), aldrin, dieldrin, methoxychlor, 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (4,4′-DDE) and 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane (4,4′-DDD). Total OCs concentrations ranged from 1.8 ng g dry weight (dw) to 3.9 ng g dw, showing a uniform distribution along the studied area, and being consistent with recorded levels in the literature for coastal sediments in other reference sites with low levels of pollution by OCs along the Atlantic Ocean. Endosulfan, 4,4′-DDD, HCB, aldrin, and dieldrin seemed to be ubiquitous as the legacy of past uses and deposition. OCs concentrations were significantly correlated to organic matter content and particle size distribution. No adverse biological effects derived from these pollutants are expected to take place as it can be concluded from the comparison with the existent marine sediment quality guidelines. [ABSTRACT FROM AUTHOR]

The increase in children obesity worldwide has been of particular concern in recent decades. Environmental factors have been proposed as contributors to obesity, and there is a growing concern over obesogens, environmental chemicals with potential obesity‐related endocrine‐disrupting properties. In this regard, bisphenol A (BPA) and its analogues are suspected to have obesogenic properties. Current document report on the activities of the fellow, undertaken during the fourth, 2020–2021 cycle of the EU‐FORA programme at the University of Granada, Institute of Nutrition and Food Science, in Spain. The work programme offered by the hosting site was related to the extrapolation of bisphenols exposure following the determination of these compounds in food frequently consumed by children and in their biological samples. The fellow has participated in the recruitment of the study population in the health centres. In addition, she has participated in the collection of the children biological samples, anthropometric measurements and dietary surveys and in the optimisation of the laboratory methodology for the extraction of bisphenols in biological samples. All these activities also provided the fellow an opportunity to develop her data science related skills, which will benefit her professional development. In addition, the fellow gained an overview of various topics related to food safety risk assessment by attending the EU‐FORA dedicated training modules. [ABSTRACT FROM AUTHOR]

In the current study, the QuEChERS extraction method with slight modifications, followed by liquid and gas chromatography–tandem mass spectrometry, was applied for the determination of 399 pesticide residues in 91 raw honey samples from northeastern Spain. The quality control procedure established in Document No. SANTE/12682/2019 was successfully followed: the responses in reagent blank and blank honey samples were below 30% of the reporting limit (0.01 mg kg−1) for all analysed compounds, the correlation coefficients (R2) were higher than 0.99 in most calibration curves, the deviation of back-calculated concentration from the true concentration was below ±20% (using the standard of 50 μg L−1 concentration), and the recoveries of spiked samples on matrix were within the range of 70–120% for almost all analytes. Only chlorfenvinphos (2–7.8 ng/g) and coumaphos (8.8–37 ng/g) were detected in 13 samples, and neither were observed to exceed their maximum residue limits (MRLs). Dietary risk assessment for pesticide residues in honey above their lowest calibrated level (LCL) was performed, and two different age groups, adults and infants, were considered as populations at risk. The contribution of honey lay far below the acceptable daily intake (ADI) for both pesticide residues. Therefore, according to our results, honey is unlikely to pose concerns for consumer health in terms of its contribution to dietary long-term exposure. However, to maintain the level of compliance, pesticide residues in honey should be continuously monitored. [ABSTRACT FROM AUTHOR]

The extraction of bioactive compounds from wine lees involves a variety of methods, the selection of which is crucial to ensure optimal yields. This systematic review, following PRISMA guidelines and utilizing the Web of Science database, aimed to examine the current state of this field, providing insights for future investigations. The search employed strategies with truncation techniques and Boolean operators, followed by a three-step screening using well-defined eligibility criteria. A bibliometric analysis was conducted to identify authors, affiliations, countries/regions, and research trends. Thirty references were selected for analysis, with Spain standing out as the main source of research on the topic. The majority of studies (66%) focused on the extraction of bioactive compounds from alcoholic fermentation lees, while 33% were directed towards malolactic fermentation lees. Binary mixtures (ethanol–water) were the predominant solvents, with ultrasound being the most used extraction method (31.3%), providing the highest average yields (288.6%) for the various evaluated compounds, especially flavonoids. The potential of wine lees as a source of bioactive compounds is highlighted, along with the need for further research exploring alternative extraction technologies and the combination of methods. Additionally, the importance of "in vitro" and "in vivo" tests to assess the bioactive potential of lees, as well as the use of computational tools to optimize extraction and identify the molecules responsible for bioactive activity, is emphasized. [ABSTRACT FROM AUTHOR]

A general decline in foundation species at the rocky intertidal has been observed during the last decades all around the world and primarily related to climate change. In agreement with that trend, the mussel aquaculture sector in Galicia (NW Spain), the main production area in Europe, has warned over the last years about a decline in the availability of wild mussel seed from the rocky coast. Here we compile for the first time, mussel seed collection reports by mussel farmers in Galicia for the period 2006–2021. We employed that dataset as a proxy of mussel recruitment evolution in the rocky shore for the last 16 years. Temporal analysis of our data confirmed the reported decline (-148 t yr-1), particularly pronounced from 2012 onwards. The data base also allowed us to analyze inter-annual variability according to both, climatic variations and management scenarios. Since cultivated mussels conform a meta-population with wild mussels from the rocky shore, alterations on the market preferences towards smaller individuals at harvest, could also contribute to a reduction in reproductive output. Our results show a decrease in life-time egg production under certain scenarios. Nonetheless, coastal upwelling seems to be the largest factor conditioning recruitment abundance, explaining as much as 60% of the variability observed. Decline on recruitment abundance was highly modulated by the observed increment in frequency of intense upwelling events, exceeding 500 m3 km-1 s-1 between July and November. Meridional winds also determined the spatial recruitment patterns, pointing to the large role of wind forcing on mussel larval dispersal. Our results highlights how alterations on upwelling regimes related to climate change can interact with mussel population dynamics and also condition aquaculture sustainability and food security. [ABSTRACT FROM AUTHOR]

Analysis of 35 parental and alkylated homologues of PAHs (Polycyclic Aromatic Hydrocarbons) was carried out in eleven marine sediment samples collected along a central transect in the biggest Galician ría. The samples were collected using a box-core dredge and, after freeze-drying, were kept frozen until analysis. The sediments were extracted by PLE (Pressurized Liquid Extraction) procedure and the quantification of PAHs was performed using gas chromatography coupled to mass spectrometry (GC–MS) with the aid of deuterated PAH internal standards. The total concentration of studied PAHs (Σ 35 PAHs) ranged from 44.8 to 7901 ng g −1 dry weight (d.w.). The highest PAH concentrations were found in sediments collected near the harbour (7901 ng g −1 ) and the cleanest positions were located in the outer zone of the ría. To date, these results are the first data presented in the area so they could be used for regular monitoring and control of future pollution episodes. [ABSTRACT FROM AUTHOR]

Agricultural management influences the soil ecosystem by affecting its physicochemical properties, residues of pesticides and microbiome. As vineyards grow crops with the highest incidence of pesticides, the aim of this study was to evaluate the impact of conventional and sustainable management systems of vineyards from DOP Ribeiro on the soil's condition. Samples from soils under three different management systems were collected, and the main soil physicochemical properties were evaluated. A selection of 50 pesticides were investigated by liquid chromatography with tandem mass spectrometry. The bacterial and fungal microbiomes were characterized through amplicon sequencing. The results show that organic agriculture positively influences soil pH and the concentration of some nutrients compared to conventional management. Our microbiome analysis demonstrated that transitioning from conventional to organic management significantly improves several BeCrop® indexes related to key microbial metabolism and soil bio-sustainability. Such a transition does not affect soil alpha diversity, but leads to a higher interconnected microbial network structure. Moreover, differential core genera and species for each management system are observed. In addition, the correlation of the microbiome with geographical distance is evidence of the existence of different microbial terroirs within DOP Ribeiro. Indeed, sustainable management leads to higher nutrient availability and enhances soil health in the short term, while lowering pesticide usage. [ABSTRACT FROM AUTHOR]

BACKGROUND: There is increasing interest in the potential effects of polybrominated diphenyl ethers (PBDEs) on children's neuropsychological development, but only a few small studies have evaluated such effects. OBJECTIVES: Our goal was to examine the association between PBDE concentrations in colostrum and infant neuropsychological development and to assess the influence of other persistent organic pollutants (POPs) on such association. METHODS: We measured concentrations of PBDEs and other POPs in colostrum samples of 290 women recruited in a Spanish birth cohort. We tested children for mental and psychomotor development with the Bayley Scales of Infant Development at 12-18 months of age. We analyzed the sum of the seven most common PBDE congeners (BDEs 47, 99, 100, 153, 154, 183, 209) and each congener separately. RESULTS: Increasing Σ[sub 7]PBDEs concentrations showed an association of borderline statistical significance with decreasing mental development scores (Βper log ng/g lipid = -- 2.25; 95% CI: -4.75, 0.26). BDE-209, the congener present in highest concentrations, appeared to be the main congener responsible for this association (Β= -- 2.40, 95% CI: -4.79, -- 0.01). There was little evidence for an association with psychomotor development. After adjustment for other POPs, the BDE-209 association with mental development score became slightly weaker (Β= -- 2.10, 95% CI: -4.66, 0.46). CONCLUSIONS: Our findings suggest an association between increasing PBDE concentrations in colostrum and a worse infant mental development, particularly for BDE-209, but require confirmation in larger studies. The association, if causal, may be due to unmeasured BDE-209 metabolites, including OH-PBDEs (hydroxylated PBDEs), which are more toxic, more stable, and more likely to cross the placenta and to easily reach the brain than BDE-209. [ABSTRACT FROM AUTHOR]

Levels of organochlorine pesticides (OCPs), including ΣDDTs, γ-HCH, HCB, aldrin, isodrin, trans-nonachlor, heptachlor and dieldrin, were determined in the razor clam, Ensis siliqua, collected monthly from February 2003 to April 2004 from the Islas Cíes in Ría de Vigo (Galicia, Spain). The sum of DDTs ranged from 2.17 to 26.9 ng g dry weight (dw). Principal component analysis showed seasonal trends in the levels of some OCPs (γ-HCH and dieldrin). Pearson correlations ( p < 0.05) were observed between OCP levels and the biometric parameters of condition index and body lipids. [ABSTRACT FROM AUTHOR]

Needles of three pine species ( Pinus halepensis, Pinus pinea and Pinus nigra) were analysed to assess the occurrence of polycyclic aromatic hydrocarbons (PAHs) in 34 sites located throughout the Ebro River, in Northeast Spain. Overall, the concentration varied between 55 and 808 ng g (dry weight). The three- and four-ring PAHs were the most representative, with phenanthrene having 43% of the total PAH load and naphthalene showing a high incidence in rural areas. Despite matrix apparent similarities, P. halepensis needles revealed higher entrapment levels than P. nigra and P. pinea, the latter showing the lowest levels. The assessment of possible sources using PAH ratios (phenanthrene/anthracene and fluoranthene/pyrene) did not reveal a clear tendency regarding the distinction of petrogenic and pyrogenic sources in general, reflecting heterogeneous sources of PAHs in the Ebro area. [ABSTRACT FROM AUTHOR]

Abstract: In 2000 and 2006, we determined the dietary intake of hexachlorobenzene (HCB) by the population of Catalonia, Spain. In order to establish the temporal trend in the levels of HCB in foodstuffs, as well as in the dietary exposure to that environmental pollutant, the concentrations were again analyzed by HRGC/HRMS in 65 composite food samples widely consumed by the Catalan population. Food samples were randomly purchased in November–December 2008 in local markets, small stores, supermarkets, and large grocery stores from 12 representative cities from Catalonia. The daily intake of HCB associated with this consumption was estimated for four age groups of the population of Catalonia: children, teenagers, adults and seniors, which were in turn divided according to sex. The highest mean HCB levels in food were detected in oils and fats (0.297 ng/g fw), dairy products (0.225 ng/g fw), and fish and seafood (0.170 ng/g fw). In the 2000 and 2006 surveys, total dietary intakes of HCB were 166.2 and 71.6 ng/day, respectively (or 2.4 and 1.0 ng/kg of body weight per day). In the current study, it was 37.7 ng/day (or 0.54 ng/kg of body weight per day), which means considerable decreases with respect to the previous intakes. According to recommendations of international regulatory organisms, the current dietary intake of HCB should not mean any significant health risk (carcinogenic and non-carcinogenic) for any of the age/gender groups of population here assessed. [Copyright &y& Elsevier]

Levels of lead (Pb) were analyzed in tissues of 25 Common shelduck (Tadorna tadorna) from La Albufera Natural Park (NP) in Valencia (Eastern Spain), which were found dead due to a botulism outbreak. The objective was to assess Pb exposure in waterfowl, fourteen years after the implementation of the Real Decreto 581/2001, which banned the use of Pb ammunition for hunting activities in internationally relevant wetlands. For this purpose, this study measured the actual ingestion of lead pellets in Common shelduck from La Albufera de Valencia and provide data on Pb residue concentrations in different tissues of this species breeding in this NP. The Pb distribution pattern in tissues was bone > kidney > liver > brain > muscle, with Pb concentrations of 778.96 ± 998.64, 122.40 ± 89.18, 92.08 ± 57.65, 18.90 ± 16.30 and 15.13 ± 11.85 ng/g (wet weight), respectively. This work presents, as far as we are aware, the first published data on Pb concentrations in Common shelduck. The Pb levels detected were lower than those reported in other studies on Anatid species from Spanish wetlands, which may be explained by this ban. Moreover, lead concentrations found were below those levels for which any observable effect has been described for acute or chronic lead exposure. Image 1 • No Pb pellets were found in gizzards of Common shelduck from La Albufera Natural Park. • The ban of Pb ammunition in the wetland has reduced the Pb exposure in Anatid species. • Pb levels in tissues were lower than those found in other Anatid species in Spain. • Pb levels in Common shelduck were below those related to any observable effect. [ABSTRACT FROM AUTHOR]

Sampling, cost-effective analysis, diagnosis of sources of pollution and assessment of potential toxicological effects were included in the case study. Marine sediments collected from 24 points along the eastern Mediterranean coast of Spain (Comunitat Valenciana region) in 2010, 2011, 2012 and 2015 have been analysed for polycyclic aromatic hydrocarbons. Fluoranthene, pyrene, chrysene, benzo[ b ]fluoranthene and benzo[ a ]pyrene were the most found. An analysis of the relative abundance of selected PAHs revealed that petrogenic and mixed petrogenic/pyrogenic sources are predominant in the area. The total concentrations of the target compounds ranged from 14.7 to 615.3 ng/g dry weight. The effects range-low (ERL) guideline values were used to assess potential toxicological effects. Rarely adverse biological effects can be expected in the tested area. The level of pollution by PAHs in the area can be considered low, although occasionally high values can be found, particularly in areas with high population or ship traffic. Unlabelled Image • A guide for studying the persistence of PAHs in marine sediments is proposed. • Fluoranthene and pyrene relative abundance vs their source was tested. • Petrogenic and mixed petrogenic/pyrogenic sources are the predominant ones. • Rarely adverse biological effects can be expected in the tested area. • High population or ship traffic areas presented the highest contents. [ABSTRACT FROM AUTHOR]

Abstract: Occurrence of ochratoxin A (OTA) in ground roasted coffee from different brands and types available in Spain was assessed. Based on these data, exposure of the Catalan population to OTA through coffee consumption was estimated. Coffee samples were purchased in hypermarkets and supermarkets of twelve cities of Catalonia, Spain, and composite samples were prepared for analysis. OTA was extracted, cleaned-up by immunoaffinity columns, and detected by HPLC-fluorescence detection. Mean OTA content (n = 72) was 2.17 ± 0.79 ng/g (range 1.21–4.21 ng/g, 49% occurrence). An additional sampling was done by brands (n = 45), mean OTA contamination being 2.07 ± 0.61 ng/g (range 1.30–5.24 ng/g, 95% occurrence). Coffee consumption data were obtained by means of a food frequency questionnaire. Mean coffee consumption per capita was 11.58 ± 8.73 g/person/day. OTA daily intake (DI) was estimated by means of deterministic and probabilistic methods. In both cases, estimated DI (around 0.22 ng/kg bw/day) was below the latest PTDI value of 17 ng/kg bw/day suggested by EFSA. [ABSTRACT FROM AUTHOR]

Abstract: The contamination of wastewater and sewage sludge has been examined for three phosphodiesterase type V inhibitors sildenafil, vardenafil and tadalafil, active agents of Viagra®, Levitra® and Cialis®, respectively. Sensitive quantification methods based on solid-phase extraction (SPE) and pressurized liquid extraction (PLE) followed by high performance liquid chromatography – tandem mass spectrometry (HPLC–MS/MS) have been developed to analyse these compounds in wastewater and sewage sludge. Effluent water of nine sewage treatment plants (STPs) has been analysed to assess the impact of the phosphodiesterase type V inhibitors on the environment. One municipal STP (Tarragona, Spain) has been thoroughly studied over the year 2008 (i) with respect to the distribution of these compounds among influent and sewage sludge and (ii) the elimination efficiency. The developed methods allowed quantification at trace concentrations. Sildenafil was present in all investigated samples at the low ng/L and ng/g range, respectively. Tadalafil was not detected or below the limit of detection (LOQ) in effluent water taken in Spain but in sewage sludge (12 ng/g –  < LOQ). Vardenafil was present only in one sludge sample and between 5 ng/g and < LOQ in effluent water. The overall removal efficiency of the STP in Tarragona (Spain) is 68%, 69% and 80% for sildenafil, tadalafil and vardenafil, respectively. This study shows for the first time the determination of these compounds in wastewater and sewage sludge. [Copyright &y& Elsevier]

The article presents the study which explores the distribution of perfluorinated compounds (PFCs) levels on human liver and breast milk in Catalonia, Spain. Samples were analyzed by solid-phase extraction and ultra-performance liquid chromatography tandem mass spectrometry. It notes that liver samples accumulated high PFCs and perfluorooctanesulfonate (PFOS) concentration. It was observed in the study that PFCs are bound to the protein fraction in blood.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are globally distributed, persistent, toxic, and are found in human blood and serum. Exposure pathways are not well characterized. To better understand indoor dust ingestion as a potential pathway for human exposure, we determined the concentrations of these compounds in dust collected from 10 houses, 38 apartments, 10 day care centers, 10 offices, and 5 cars. Samples were prepared using a rapid extraction and cleanup method and analyzed using LC-MS/MS. PFOS and PFOA were found in dust samples from all microenvironments and their concentrations were significantly positively correlated to each other. Highest median concentrations were seen in offices (PFOS: 110 ng/g dry weight) and apartments (PFOA: 93 ng/g dw). Adult and toddler dust ingestion exposures were estimated and compared to dietary exposure data from Canada and Spain. Results show that diet is the most important exposure route, but in a worst case scenario, dust ingestion may also be significant. [ABSTRACT FROM AUTHOR]

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) were determined in breast milk from women living in the vicinity of a new hazardous waste incinerator (HWI) in Catalonia, Spain. The results were compared with the levels obtained in two previous surveys carried out in 1998 (baseline study) and 2002. The current concentrations of PCDD/Fs in breast milk ranged from 45 to 143 pg/g fat (2.8 to 11.2 pg WHO-TEQ/g fat), while total PCBs ranged from 114 to 617 pg/g fat (2.8 to 17.6 pg WHO-TEQ/g fat). PBDE concentrations (sum 15 congeners) ranged from 0.57 ng/g fat to 5.9 ng/g fat, with a mean value of 2.5 ng/g fat. A general decrease of the concentrations for PCDD/Fs and both planar and total PCBs was observed. Regarding to PBDE concentrations in breast milk, similar levels between the 2002 and the present study were noted. The levels of PCDD/Fs and PCBs in milk of women living in urban areas were higher than those corresponding to the industrial zones (38% and 40%, respectively). However, the current PBDE levels were slightly lower (13%) in the urban than in the industrial zone. For PCDD/Fs and PCBs, the current decreases are in accordance with the reduction in the dietary intake of these pollutants found in recent studies carried out in the same area of study. [Copyright &y& Elsevier]

Mercury (Hg) speciation and partitioning have been investigated in a river-reservoir system impacted by the Almadén mining activities, the world''s largest Hg district. This study is the first to simultaneously investigate Hg dynamics from above the mining district and into the La Serena Reservoir (3219 Hm3), being the third largest reservoir in Europe and the largest in Spain. Water, sediment and biota were sampled at different seasons during a 2-year study from the Valdeazogues River, which flows east–west from the mining District, to La Serena Reservoir. Simultaneously, a comprehensive study was undertaken to determine the influence of some major physico-chemical parameters that potentially influence the fate of Hg within the watershed. Concentrations of dissolved Hg in water were below 0.14 µg/L, whereas particulate Hg ranged from 0.1 to 87 µg/g, with significant seasonal variation. Total Hg concentrations varied from 7 to 74 µg/g in sediment from the Valdeazogues River, while in sediments from La Serena Reservoir were below 2 µg/g. On the other hand, methyl-Hg reached concentrations up to 0.3 ng/L in water and 6 ng/g in sediment from La Serena Reservoir, whereas maximum concentrations in Valdeazogues River were 5 ng/L and 880 ng/g in water and sediment, respectively. The distribution of Hg species in the Valdeazogues River–La Serena Reservoir system indicated a source of Hg from the mine waste distributed along the river. Total Hg in water was strongly correlated with total dissolved solids and chlorophyll a concentrations, whereas organic carbon and Fe concentrations seem to play a role in methylation of inorganic Hg in sediment. Total Hg concentrations were low in fish from Valdeazogues River (0.8–8.6 ng/g, wet weight) and bivalves from La Serena Reservoir (10–110 ng/g, wet weight), but most was present as methyl-Hg. [Copyright &y& Elsevier]