Cadmium, manganese, nickel and lead contents in surface sediments of the lower Ulla River and its estuary (northwest Spain)

The authors determined the total contents of cadmium, manganese, nickel and lead in 16 surface sediment samples along the last 7 km of the Ulla River and in its estuary. Prior to chemical analysis, the grain-size fractions below 500, 63 and 2 μm were separated. The metal concentrations were analysed in the fraction below 63 μm, and in selected samples from the clay fraction ( 2 μm). The soil samples were digested with a HF + HNO₃ + HCl mixture and the total concentrations of Cd, Mn, Ni and Pb were analysed with the AAS method. The highest contents of metals were found in the riverine sediments, near the town of Padrón, and in the estuary. The enrichment of metals in the sediments was mainly related to the proximity of the industrial sources, and to the fine particles transported and deposited in the sediments. The Ni and Mn contents found are considered very high, at some points reaching values of up to 357 mg kg⁻¹ and 2 110 mg kg⁻¹, respectively. Lead and Cd were mainly found within the range considered as natural background levels in the sediments of the Galician rias, with concentrations of 25-68 mg kg⁻¹ for Pb and 0.01-0.92 mg kg⁻¹ for Cd. The lower part of the Ulla River and its estuary present: l) moderate to high contamination levels of Mn and Ni; 2) moderate Pb pollution levels; and 3) no Cd contamination. The highest concentrations of metals were obtained in the river, near the wastewater discharges, and in the estuary, associated with fine particles.El contenido total de cadmio, manganeso, níquel y plomo se determinó en 16 muestras de sedimentos superficiales a lo largo de los últimos 7 km del río Ulla y en su estuario. Previamente a los análisis químicos, se realizó la separación granulométrica de los sedimentos en las fracciones inferiores a 500, 63 y 2 μm. La concentración de metales se determinó en la fracción inferior a 63 μm y, para algunas muestras, en la fracción arcilla ( 2 μm). La digestión del sedimento se realizó en una mezcla ácida de HF + HNO₃ + HCl y se analizó la concentración total de Cd, Mn, Ni y Pb por espectroscopia de absorción atómica. Los contenidos más altos en metales se encontraron en los sedimentos del río, en las inmediaciones de Padrón y en los del estuario. El enriquecimiento de los sedimentos en metales se ha relacionado con la proximidad a las zonas industriales y con el material fino transportado y depositado en los sedimentos. Se han encontrado contenidos muy altos de Ni y Mn con valores de 357 mg kg⁻¹ y 2 110 mg kg⁻¹, respectivamente. Las concentraciones de Cd y Pb son comparables a los valores establecidos como niveles naturales en los sedimentos de las rías gallegas: 25-68 mg kg⁻¹ para el Pb y 0.01-0.92 mg kg⁻¹ para el Cd. El sedimento de la parte baja del río Ulla y su estuario presentan niveles moderados-altos de contaminación para Mn y Ni, moderados para Pb y nulos para Cd. Las mayores concentraciones de estos metales en el sedimento fueron medidas asociadas con las fracciones finas ( 63 μm): cerca de Padrón, zona de influencia fluvial y, también, aunque con valores más bajos, en la desembocadura del Ulla, zona de influencia marina.Instituto Español de Oceanografí

Comparación entre el comportamiento mecánico a tracción, fractura y fatiga de armaduras de refuerzo fabricadas con distintos tipos de acero

The use of austenitic stainless steels as rebar is an option increasingly used in reinforced concrete structures exposed to aggressive environments and especially those that have to work in marine environments. The same is true for duplex stainless steel rebars, although nowadays they have a lower use, mainly due to the fact that their inclusion in the reinforced concrete standards was delayed 10 years compared to austenitic stainless steel ones, and consequently their in-service behavior is not as well known. A study of the mechanical properties, including fracture toughness, fatigue behaviour and corrosion resistance in saline alkaline environments of austenitic (AISI 304LN and 316LN) and duplex (D2205) stainless steel reinforcing bars was performed in this work. Bars made on a high ductility carbon steel (B500SD) that are normally used to reinforce concrete were also characterized and used as a comparison. Stainless steel reinforcing bars show mechanical properties at least similar but usually higher than one of the best carbon steel re-bars (B500SD), along with a significantly higher ductility and, of course, much better corrosion behaviour in saline alkaline environments.El uso de aceros inoxidables austeníticos como armaduras de refuerzo es una opción cada vez más utilizada en estructuras de hormigón armado expuestas a ambientes agresivos y especialmente en las que han de trabajar en ambientes marinos. Lo mismo cabe decir de las armaduras de acero inoxidable dúplex, si bien su uso es menor, debido sobre todo a que su inclusión en la normativa aplicable al armado de hormigón se retrasó 10 años con respecto a los inoxidables austeníticos y, consecuentemente, su comportamiento en servicio es menos conocido. En este trabajo se analiza el comportamiento mecánico, incluyendo fractura y fatiga, así como la resistencia a la corrosión en medios que simulan un hormigón contaminado de cloruros, de armaduras fabricadas tanto con aceros inoxidables austeníticos (304LN y 316LN) como dúplex (D2205). Asimismo se han caracterizado armaduras convencionales de acero al carbono (B500SD) como comparación. Las armaduras de acero inoxidable muestran unas propiedades mecánicas similares e incluso superiores a las de acero al carbono, exhibiendo además una ductilidad y una resistencia a la corrosión en un medio alcalino salino claramente ventajosas

The 4G/5G PAI-1 polymorphism influences the endothelial response to IL-1 and the modulatory effect of pravastatin

BACKGROUND: Increased plasminogen activator inhibitor (PAI-1) levels lead to impaired fibrinolytic function associated with higher cardiovascular risk. PAI-1 expression may be regulated by different inflammatory cytokines such as interleukin-1alpha (IL-1). Several polymorphisms have been described in the PAI-1 gene. AIM: We examined the influence of the 4G/5G polymorphism in the promoter region on IL-1alpha-induced PAI-1 expression by human umbilical vein endothelial cells (HUVEC) in presence or absence of pravastatin. METHODS AND RESULTS: Genotyped HUVEC were incubated with IL-1alpha (500 U mL(-1)) in presence or absence of pravastatin (1-10 microm). PAI-1 expression was analyzed by real time polymerase chain reaction (PCR), and PAI-1 antigen measured in supernatants by ELISA. IL-1alpha increased PAI-1 secretion in a genotype-dependent manner, and higher values were observed for 4G/4G compared with both 4G/5G and 5G/5G cultures (P < 0.05). Preincubation of HUVEC with 10 microm pravastatin significantly reduced IL-1-induced PAI-1 expression in 4G/4G HUVEC compared with untreated cultures (177.5% +/- 24.5% vs. 257.9% +/- 39.0%, P < 0.05). Pravastatin also attenuated the amount of secreted PAI-1 by 4G/4G HUVEC after IL-1 stimulation (5020.6 +/- 165.7 ng mL(-1) vs. 4261.1 +/- 309.8 ng mL(-1), P < 0.05). This effect was prevented by coincubation with mevalonate, indicating a dependence on HMG-CoA reductase inhibition. CONCLUSIONS: The endothelial 4G/5G PAI-1 genotype influences the PAI-1 response to IL-1alpha and the modulatory effect of pravastatin. As increased PAI-1 levels have been linked to cardiovascular disease the observed endothelial modulation by pravastatin may have potential clinical implications

Protective effect of the G-765C COX-2 polymorphism on subclinical atherosclerosis and inflammatory markers in asymptomatic subjects with cardiovascular risk factors

BACKGROUND: Cyclooxygenase (COX)-2, a key regulatory enzyme in prostanoid synthesis, plays an important role in inflammatory processes. The -765G>C COX-2 polymorphism has been associated with lower promoter activity in vitro and reduced levels of C-reactive protein (CRP) in atherosclerotic carriers of the C allele. However, its pathophysiological relevance in vivo has not been fully elucidated. METHODS AND RESULTS: We assessed the -765G>C polymorphism and COX-2 expression in 220 asymptomatic subjects free of cardiovascular disease, in relation to global vascular risk, carotid intima-media thickness (IMT), and inflammatory markers (fibrinogen, C-reactive protein [CRP], von Willebrand factor [vWF] and interleukin-6 [IL-6]). Genotype frequencies were: CC (7.7%), CG (34.5%), GG (57.7%). Among hypercholesterolemic subjects (n=140), C allele carriers had lower COX-2 expression (p<0.05), reduced carotid IMT (p<0.01) and diminished levels of inflammatory markers CRP, vWF and IL-6 (p<0.05), as compared to GG homozygous subjects. The association between carotid IMT and COX-2 polymorphism remained significant after adjusting for cardiovascular risk factors and inflammatory markers (p=0.008). CONCLUSIONS: In asymptomatic hypercholesterolemic subjects the C allele of -765G>C COX-2 polymorphism was associated with lower COX-2 expression, and reduced subclinical atherosclerosis and systemic inflammation compared with GG homozygous, thus conferring atherosclerosis protection in this cardiovascular risk population

On conditional skewness with applications to environmental data

The statistical literature contains many univariate and multivariate skewness measures that allow two datasets to be compared, some of which are defined in terms of quantile values. In most situations, the comparison between two random vectors focuses on univariate comparisons of conditional random variables truncated in quantiles; this kind of comparison is of particular interest in the environmental sciences. In this work, we describe a new approach to comparing skewness in terms of the univariate convex transform ordering proposed by van Zwet (Convex transformations of random variables. Mathematical Centre Tracts, Amsterdam, 1964), associated with skewness as well as concentration. The key to these comparisons is the underlying dependence structure of the random vectors. Below we describe graphical tools and use several examples to illustrate these comparisons.The research of Félix Belzunce, Julio Mulero and José María Ruíz is partially funded by the Ministerio de Economía y Competitividad (Spain) under Grant MTM2012-34023-FEDER. Alfonso Suárez-Llorens acknowledges support received from the Ministerio de Economía y Competitividad (Spain) under Grant MTM2014-57559-P

Ejercicio interlaboratorio de bioensayos marinos para la evaluación de la calidad ambiental de sedimentos costeros. IV. Ensayo de toxicidad sobre sedimento con crustáceos anfípodos

9 páginas, 2 figuras, 3 tablas.[EN] Interlaboratory variability was studied for the bioassay using crustacean amphipods. Nine series of data were obtained from different laboratories using four different species (Ampelisca brevicornis, Corophium volutator, Corophium multisetosum and Microdeutopus gryllotalpa), all previously used for sediment toxicity assessment in Spain. Results were studied for interlaboratory variability and according to different confounding factors. The coefficients of variation were similar to those previously reported for this bioassay and sample classification was homogeneous among the laboratories that successfully completed the exercise. No significant tendencies related to test species were identified and it seems that the factor most critically affecting test results and the classification of samples is storage time before testing.[ES] Se estudió la precisión interlaboratorio del bioensayo con crustáceos anfípodos. Se recogieron nueve series de datos procedentes de distintos laboratorios europeos y de cuatro especies distintas (Ampelisca brevicornis, Corophium volutator, Corophium multisetosum y Microdeutopus gryllotalpa), todas ellas usadas previamente para la caracterización de la toxicidad de sedimentos en España. Esos resultados se estudiaron para evaluar la variabilidad interlaboratorio de acuerdo a las diferentes especies y los distintos tiempos de almacenamiento de las muestras antes del ensayo. Los resultados mostraron coeficientes de variación similares a los encontrados en estudios previos y permitieron una clasificación homogénea de las muestras entre los laboratorios que completaron el ejercicio con éxito. No se identificaron tendencias significativas debidas al uso de distintas especies y, al parecer, el factor que puede afectar más críticamente la clasificación de las muestras y, por lo tanto, el uso de los resultados para la toma de decisiones, es el tiempo de almacenamiento de los sedimentos previamente al desarrollo del ensayo.This study was carried out under a joint research project between CEDEX and the University of Cádiz. Part of the work was funded by the Spanish Ministry of Science and Technology REN2002_01699/TECNO). The first author was supported by a grant (FPI) from the Spanish Ministry of Education and Science.Peer reviewe

Antioxidant vitamins increase the collagen content and reduce MMP-1 in a porcine model of atherosclerosis: implications for plaque stabilization

Degradation of extracellular matrix, particularly interstitial collagen, promotes plaque instability and contributes to restenosis after vascular injury. We have explored the effects of vitamins C and E on the collagen content and metalloproteinase-1 (MMP-1) expression after angioplasty in hypercholesterolemic pigs. Iliac angioplasty was performed on 18 minipigs divided into three diet groups: a normal-cholesterol (NC), a high-cholesterol (HC) and a high-cholesterol plus vitamins C+E (HCV). Four weeks later, after sacrifice, the vascular collagen content and MMP-1 protein expression, along with the plasma caseinolytic activity and lipid peroxidation, were measured. MMP-1 was also determined in arterial rings stimulated with native low-density lipoproteins (LDL) isolated from experimental groups. Cholesterol-rich diet augmented plasma lipid peroxidation (P<0.05), reduced the collagen content and increased vascular MMP-1 expression after injury (P<0.05). Enhanced caseinolytic activity (identified as MMP-1) was also observed in HC plasma samples and in supernatants from arterial rings incubated with HC-LDL. Vitamins C and E markedly increased neointimal collagen content (P<0.01), reduced the hypercholesterolemia-induced changes in vascular MMP-1 (P<0.05) and diminished plasma and ex vivo caseinolytic activity. Vitamins C and E may help stabilize atherosclerotic plaque after angioplasty and favor vascular remodeling by increasing collagen content and reducing vascular MMP-1 expression in porcine hypercholesterolemia

Different expression of MMPs/TIMP-1 in human atherosclerotic lesions. Relation to plaque features and vascular bed

BACKGROUND: Proteolytic imbalance might determine arterial remodeling and plaque destabilization in atherosclerotic vessels. The aim of this study was to examine differences in the patterns of metalloproteinases (MMPs) and MMP inhibitor (TIMP-1) expression in advanced human atheromas, both in relation to the plaque features and the vascular bed involved. METHODS AND RESULTS: Immunohistochemistry for MMP-1, -3, -9 and TIMP-1 as well as the collagen content were measured in vascular sections from patients undergoing peripheral revascularization (carotid n=11, femoral n=23) and aorto-coronary bypass surgery (mammary arteries n=20, as controls). Increased expression of all MMPs was detected in atherosclerotic as compared with control sections (P<0.01). Aneurysmal plaques showed a significant increase of MMP-1 and-3 and a reduction in total collagen (P<0.05) in relation to occlusive lesions. Calcification areas in atherosclerotic plaques were consistently associated with increased TIMP-1 expression (P<0.01). Finally, MMP-9 expression was higher in occlusive lesions from carotid than femoral arteries (P<0.01). CONCLUSIONS: Aneurysm lesions expressed higher MMP-1 and-3 expression than occlusive plaques, and MMP-9 was mainly detected in carotid as compared with femoral arteries. TIMP-1 was associated with arterial calcification. These differences in the MMPs/TIMP-1 expression might determine the evolution of advanced atherosclerotic plaques and contribute to its vulnerability