A dynastic elite in monumental Neolithic society.

The nature and distribution of political power in Europe during the Neolithic era remains poorly understood1. During this period, many societies began to invest heavily in building monuments, which suggests an increase in social organization. The scale and sophistication of megalithic architecture along the Atlantic seaboard, culminating in the great passage tomb complexes, is particularly impressive2. Although co-operative ideology has often been emphasised as a driver of megalith construction1, the human expenditure required to erect the largest monuments has led some researchers to emphasize hierarchy3-of which the most extreme case is a small elite marshalling the labour of the masses. Here we present evidence that a social stratum of this type was established during the Neolithic period in Ireland. We sampled 44 whole genomes, among which we identify the adult son of a first-degree incestuous union from remains that were discovered within the most elaborate recess of the Newgrange passage tomb. Socially sanctioned matings of this nature are very rare, and are documented almost exclusively among politico-religious elites4-specifically within polygynous and patrilineal royal families that are headed by god-kings5,6. We identify relatives of this individual within two other major complexes of passage tombs 150 km to the west of Newgrange, as well as dietary differences and fine-scale haplotypic structure (which is unprecedented in resolution for a prehistoric population) between passage tomb samples and the larger dataset, which together imply hierarchy. This elite emerged against a backdrop of rapid maritime colonization that displaced a unique Mesolithic isolate population, although we also detected rare Irish hunter-gatherer introgression within the Neolithic population.

Microextraction with polyethersulfone for bisphenol-A, alkylphenols and hormones determination in water samples by means of gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry analysis.

In the present work, the suitability of polyethersulfone (PES) tube was assessed for the simultaneous sorptive microextraction of commonly found endocrine disrupting compounds in natural waters such as bisphenol-A (BPA), nonylphenol technical mixture (NP mix), 4-tert-octylphenol (4tOP), 4-n-octylphenol (4-nOP), 17ß-estradiol (E2) and 17α-ethynilestradiol (EE2). After the concentration of target compounds in the PES polymer, the analytes were recovered soaking the polymer with a suitable solvent (ethyl acetate or methanol), derivatized using N,O-bis(trimethylsilyl)trifluoroacetamide with 1% of trimethylchlorosilane (BSTFA+1% TMCS) and determined by gas chromatography-mass spectrometry (GC-MS). The analysis was also performed without derivatization step by means of liquid chromatography-tandem mass spectrometry (LC-MS/MS). Extraction parameters (addition of MeOH, ionic strength, extraction speed and time and desorption time) were evaluated and the optimum conditions were fixed as follows: 150 mL water samples containing a 10% (w/v) of sodium chloride and using 5 tubular PES sorbent fibers (1.5 cm length×0.7 mm o.d.). Equilibrium conditions were achieved after 9 h, with absolute extraction efficiencies ranging from 27 to 56%. On the whole, good apparent recoveries were achieved (68-103% and 81-122% for GC-MS and LC-MS/MS, respectively) using deuterated analogues as surrogates. Achieved quantification limits (LOQs) varied between 2-154 ng/L and 2-63 ng/L for all the compounds using GC-MS and LC-MS/MS, respectively. The effect of organic matter was evaluated previous to apply the final method to the analysis of estuarine and wastewater real samples. The comparison of both methods showed that overall, PES-LC-MS/MS provided shorter sample preparation time and better LODs, but PES-silylation-GC-MS allowed the simultaneous determination of all the studied compounds with adequate repeatability and accuracy.

Low serum concentrations of 25-hydroxyvitamin D in children and adolescents with systemic lupus erythematosus

We evaluated the concentrations of 25-hydroxyvitamin D [25(OH)D] in children and adolescents with juvenile systemic lupus erythematosus (JSLE) and associated them with disease duration and activity, use of medication (chloroquine and glucocorticoids), vitamin D intake, calcium and alkaline phosphatase levels, and bone mineral density. Thirty patients with JSLE were evaluated and compared to 30 healthy individuals, who were age and gender matched. Assessment was performed of clinical status, disease activity, anthropometry, laboratory markers, and bone mineral density. The 30 patients included 25 (83.3%) females and 16 (53.3%) Caucasians, with a mean age of 13.7 years. The mean age at diagnosis was 10.5 years and mean disease duration was 3.4 years. Mean levels of calcium, albumin, and alkaline phosphatase were significantly lower in patients with JSLE compared with controls (P<0.001, P=0.006, and P<0.001, respectively). Twenty-nine patients (97%) and 23 controls (77%) had 25(OH)D concentrations lower than 32 ng/mL, with significant differences between them (P<0.001). Fifteen patients (50%) had vitamin D levels <20 ng/mL and 14 had vitamin D levels between 20 and 32 ng/mL. However, these values were not associated with greater disease activity, higher levels of parathormone, medication intake, or bone mineral density. Vitamin D concentrations were similar with regard to ethnic group, body mass index, height for age, and pubertal stage. Significantly more frequently than in controls, we observed insufficient serum concentrations of 25(OH)D in patients with JSLE; however, we did not observe any association with disease activity, higher levels of parathormone, lower levels of alkaline phosphatase, use of medications, or bone mineral density alterations.

Intersex condition and molecular markers of endocrine disruption in relation with burdens of emerging pollutants in thicklip grey mullets (Chelon labrosus) from Basque estuaries (South-East Bay of Biscay).

Endocrine disrupting chemicals (EDCs) interfere with the functioning of the endocrine system, causing reproductive and developmental disturbances in aquatic wildlife. Appearance of intersex gonads and elevated plasma levels of vitellogenin in male fish are well known biomarkers of exposure to xenoestrogenic EDCs. In the present study, intersex condition and transcription levels of vtg and cyp19a1b were assessed in five thicklip grey mullet populations from the Basque coast (Bay of Biscay). Levels of EDCs (estrogenic hormones, polycyclic musks, bisphenol-A, phthalates, alkylphenols and pesticides) were determined in water and fish bile. Intersex gonads were observed in three out of five mullet populations. Vtg and cyp19a1b were up-regulated in mullet populations with relatively higher EDCs load. Phthalates and pesticides were the most abundant EDCs in bile, followed by alkylphenols, musks, bisphenol-A and estrogenic hormones. Statistically significant correlations were found between concentrations of individual and total EDCs in bile and water samples and transcription levels of vtg and cyp19a1b.

Serum 25-hydroxyvitamin D and biochemical markers of bone metabolism in patients with juvenile idiopathic arthritis

Our objective was to evaluate the concentrations of serum 25-hydroxyvitamin D [25(OH)D], serum calcium, serum phosphorus, alkaline phosphatase, and parathormone (PTH) in patients with polyarticular juvenile idiopathic arthritis (JIA) and to associate them with disease duration and activity, bone mineral density and use of medications. In a cross-sectional and controlled study, 30 patients with polyarticular JIA were evaluated and compared to 30 healthy individuals matched for age and gender. Clinical status, anthropometry, laboratory markers in both patients and controls, and bone mineral density, only in the patients, were measured. Of the 30 patients included in the study, 23 (76.7%) were female and 16 (53.3%) non-Caucasian; mean age was 14 years (range = 4 to 20 years). Mean disease duration was 5 years (range = 1 to 12 years). The mean concentrations of serum albumin-corrected calcium (9.04 ± 0.41 mg/dL) and alkaline phosphatase (153.3 ± 100.1 IU) were significantly lower in patients with JIA than in controls (P < 0.0001 and P = 0.001, respectively). No differences in 25(OH)D, PTH or serum phosphorus were observed between JIA and control subjects. Regarding 25(OH)D concentration, 8 patients (26.7%) and 5 controls (16.7%) had 25(OH)D concentrations compatible with deficiency (lower than 20 ng/mL) and 14 patients (46.7%) and 18 controls (60%) had concentrations compatible with insufficiency (20-32 ng/mL). These values were not associated with disease activity, use of medications or bone mineral density. We observed a high frequency of 25(OH)D insufficiency and deficiency in the study sample. The compromised bone metabolism emphasizes the importance of follow-up of JIA patients.

Solid-phase extraction combined with large volume injection-programmable temperature vaporization-gas chromatography-mass spectrometry for the multiresidue determination of priority and emerging organic pollutants in wastewater.

In the present work the simultaneous extraction for the multiresidue determination in wastewater samples of organic compounds such as polychlorinated biphenyls (PCBs), polybrominated biphenyls (PBBs), pesticides, polycyclic aromatic hydrocarbons (PAHs), phthalate esters (PEs), alkylphenols (APs), bisphenol A (BPA) or hormones included in different lists of priority and emerging pollutants because of their action as endocrine disrupting compounds (EDCs) was developed. Different solid phase extraction (SPE) variables such as the nature of the solid phase (Oasis-HLC, C18 and Lichrolut), the sample volume, the addition of MeOH and NaCl, the pH of the water phase and the volume of the eluent solvent were optimized in order to analyze simultaneously the priority and emerging families of pollutants mentioned above. Good recoveries were obtained for Milli-Q water (80-120%), however, since the use of deuterated analogues and dilution of the sample did not correct the matrix effect, additional SPE clean-up step using Florisil® cartridges was necessary to obtain good results for wastewater samples (80-125%). In order to improve the limits of detection (LODs), large volume injection (LVI) using programmable temperature vaporizer (PTV) coupled to gas chromatography-mass spectrometry (GC-MS) was also optimized. Since analytes losses in the case of the most volatile congeners occurred during the derivatization step and no separation of the derivatized and the non-derivatized analytes was possible during SPE elution, two different injections were optimized for each analyte group. LODs were in good agreement with those found in the literature and relative standard deviations (RSDs) were in the 10-25% range for Milli-Q and 12-30% for wastewater samples. The method was finally applied to the determination of target analytes in three different wastewater treatment plants (WWTPs, Bakio, Gernika and Galindo (Spain)) and in one water purification plant (WPP) in Zornotza (Spain).

Inmovilización covalente de ß-galactosidasa de A. fonsecaeus sobre sílice aminada / Covalent immobilization on aminated silica of ß-galactosidase from A. fonsecaeus

La ß-galactosidasa semipurificada del A. fonsecaus fue inmovilizada covalentemente sobre sílice aminada activada con glutaraldehído. Se estudió la influencia del área específica del soporte, de la concentración de proteínas y del PH de inmovilización sobre los rendimientos del proceso. Se demostró que el área específica más efectiva fue de 122 m2 (aproximadamente 250A) y que la concentración de proteínas y el PH óptimo de inmovilización fueron de 1,6 g/l y 8,6 respectivamente. La enzima inmovilizada tiene una zona de PH óptimo para la hidrólisis del orto-nitrofenil ß-D-galactopiranósido (ONPG) semejante a la enzima libre. Los resultados obtenidos utilizando la ß-galactosidasa purificada de A. oryzae son comparables a los resultados obtenidos con los preparados semipurificados de ß-galactosidasa de A. fonsecaus. Este estudio crea las premisas para el empleo de la ß-galactosidasa de esta nueva fuente microbiana, en la inmovilización covalente sobre otros soportes utilizables en procesos industriales, para los que las propiedades de esta enzima sean relevantes

Inmovilización covalente de ß-galactosidasa de A. fonsecaeus sobre derivados celulósicos del maíz: comparación con la ß-galactosidasa del A. oryzae / Covalent immobilization on corn cellulose derivative of ß-galactosidase from A. fonsecaeus: comparison with ß-galactosidase from A. oryzae

La ß-galactosidasa del A. fonsecaeus con actividad específica entre 19-24 U/mg, a concentraciones de 1,6-3,3 g/l y PH 8,6 fue inmovilizada covalentemente sobre derivados celulósicos del maíz (DCM), con altos rendimientos (667 U/g de DCM). El mayor porcentaje de enzima inmovilizada y los valores superiores de actividad enzimática por gramo de soporte, se obtuvieron con el empleo de DCM de 0,8 mm. Fueron determinadas algunas características cinéticas de la ß-galactosidasa inmovilizada de A. fonsecaeus y A. oryzae en reactor antidifusional utilizando ortonitrofenil-ß-D-galactopiranósido (ONPG) y lactosa como sustrato. La enzima de A. fonsecaeus presenta valores de Km aparente inferiores a la de A. oryzae en forma inmovilizada, contrario a lo que ocurre en forma libre. La hidrólisis continua de soluciones de lactosa en reactores de columna empacada con DCM ß-galactosidasa de ambos microorganismos, produjo resultados similares y comparables a los obtenidos en otros sistemas reportados. La enzima inmovilizada del A. fonsecaeus fue muy estable; los tiempos de vida media a 35-C y 50-C, fueron de 240 y 80 días respectivamente. La enzima inmovilizada puede ser empleada para la hidrólisis continua de la lactosa del suero lácteo a 50-C y PH 4,5 con una productividad de 0,9 g de lactosa/g de DCM-enzima/hora.